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ANTHRACENE AND ANTHRAQUINONE
J^*
ANTHRACENE AND
ANTHRAQUINONE
^t
.V
BY
E BARRY BARNETT, B.Sc.(Lond.), F.I.C.
LECTURER IN ORGANIC CHEMISTRY AT THE SIR JOHN CAbS TECHNICAL INSTITUTE;
FORMERLY RESEARCH CHEMIST TO LEVINSTEIN, LTD. ; AND WORKS
MANAGER OF THE STOCKTON-ON-TEBS CHEMICAL WORKS, LVD.
NEW YORK
D. VAN NOSTRAND COMPANY
EIGHT WARREN STREET
1921
PRINTED IN GREAT BRITAIN
^;Vs
2qs
PREFACE
It is now over forty years since Auerbach published his
"Das Anthracen und seine Derivate,"* and during this
period, and more particularly during the last fifteen years,
enormous advances have been made in our knowledge of
the chemistry of the anthracene derivatives. Much of the
research which has been carried out has appeared only in
the form of patent specifications, and for that reason has
escaped the attention which it merits. It seemed, therefore,
that a short account of the anthracene derivatives would
not be without value, more especiall}^ as many of the most
valuable fast dyes belong to this class of compound. At
the urgent request of several friends the author has there-
fore arranged his own private notes on the subject in book
form, and trusts that the appearance of this volume will
lead to greater attention being paid to anthraquinone
chemistr}' in this country than has been the case up to the
present. Many of the claims made in the patent literature
require elaborating and confirming (or contradicting), and
as several anthraquinone derivatives are now manufactured
in this country, work of this nature would be suitable for
senior students in universities. Such research would be of
the utmost value at the present time, when serious attempts
are being made to manufacture the very valuable anthra-
quinonoid dyes in this country.
In the following pages wiU be found a fairly complete
account of the work which has been published up to
November, 1920, on the derivatives of anthracene and
* Second German edition, 1880. English translation by Sir William Crookes
of first German edition, 1877.
V
vi PREFACE
anthraquinone ; but an account of naturall}- occurring
anthracene derivatives, such as chrysarobin, etc., has
purposely been omitted, as an up-to-date account of these
substances has recently appeared elsewhere.* References
have been given liberally, although it is not claimed that
those cited form a complete bibliography of the subject.
All references given have been read by the author in the
original with the exception of a few German patents which
have been granted during or siftce the war, and which at
the time of going to press are not available in the Patent
Office librar5\ For such patents the author has been
compelled to rely on the very inadequate abstracts pub-
lished in j ournals such as the Chemisches Zentralhlatt, Chemi-
ker Zeitung, and Journal of the Society of Chemical Industry.
The introduction of new systems of notation is not to be
encouraged as a rule, but after mature consideration the
author decided to make use of his own modification of
Pfaff 's system. The best excuse he can offer for this is the
very considerable saving in the cost of composing which it
has effected. In cases where the straight line notation is
not suitable, the formulae have been reproduced by means
of blocks.
The author wishes to take this opportunity of expressing
his thanks to Mr. J. W. Cook, B.Sc, for much valuable help
while the book was passing through the press.
E. DE BARRY BARNETT.
Sir John Cass Technical Institute,
Jewry Street, Aldgate, E.C. 3,
yannary, 192 1.
* Perkin and Everest, "Natural Organic Colouring Matters."
CONTENTS
CHAPTER I.— INTRODUCTION
Historical sketch, i. Dyeing, 5. Commercial names, 7. Colour and con-
stitution, 8. Nomenclature, lO.
CHAPTER II.— ANTHRACENE AND ITS
HOMOLOGUES
Anthracene, 14. Structure, 18. Oxidation, 19. Paranthrene, dianthrene, 24.
Homologous anthracenes, 26.
CHAPTER III.— SIMPLE DERIVATIVES OF
ANTHRACENE
Hydroanthracenes, 39. Halogen compounds, 41. Action of nitric acid on
anthracene, 50, Sulphonic acids, 61. Hydroxyanthracenes, 64. Amino-
anthracenes, 67. Nitriles and carboxylic acids, 69. Aldehydes and
ketones, 70.
CHAPTER IV.— THE ANTHRAQUINONES AND
DIANTHRAQUINONYLS
i.2-Anthraquinone, 73. 1.4-Anthraquinone, 73. 9.10-Anthraquinone, 73.
Homologous anthraquinones, 79. Reduction products, 80. Action of
Grignard's solution, 85. Dianthraquinonyls, 90. Anthradiquinones, 92.
Anthraflavones, 94.
CHAPTER v.— ANTHRONE, ANTHRANOL AND
ALLIED PRODUCTS
Anthrone and anthranol, 96. Hydroxyanthrone and anthraquinol, 108.
Dianthryl and its derivatives, 114. Tautomerism, 118.
vii
VUl
CONTENTS
CHAPTER VI.— ANTHRAQUINOxNE RING
SYNTHESES
I. From aromatic monocarboxylic acids .....
II. From phthalic acid by the direct method ....
III. Phthalic acid synthesis .......
PACK
125
127
130
CHAPTER VII.— THE BENzAnTHRAQUINONES
I.
II.
III.
IV.
V.
(7«^.-Benzanthraquinone (Naphthanthraquinone)
//«.-Benzanthraquinone (Naphthacenquinone)
//«.-Benzanthradiquinone (Xaphthacendiquinone)
irafis-disaMg-.-Dihenza.uihraqumone (Dinaphthanthraquinoue)
/j«.-Dibenzanthraquinone (Dinaphthanthraquinone)
143
145
152
154
156
CHAPTER VIII.— THE ALDEHYDES, KETONES,
AND CARBOXYLIC ACIDS
I. Aldehydes IS9
II. Ketones 160
III. Carboxylic acids 162
CH.\PTER IX.— THE NITRO, NITROSO, AND
HALOGEN ANTHRAQUI NONES
I. Nitro compounds ......... 167
II. Nitroso compounds ......... 169
III. Halogen compounds . . . . • • • .170
CHAPTER X.— THE SULPHONIC ACIDS,
MERCAPTANS AND SULPHIDES
I.
II.
III.
Sulphonic acids
Sulphinic acids
Sulphenic (Sulphoxylic) acids .
IV.
V.
VI.
VII.
VIII.
Mercaptans
Selenophenols .
Sulphides
Bisulphides
Diselenides
IX.
Thianthrenes .
176
180
181
182
185
186
187
188
188
CONTENTS ix
CHAPTER XL— THE AMINOANTHRAQUINONES
AND DIANTHRAQUINONYLAMINES
Reduction of nitre groups, 192. Replacement of negative groups, 195.
Replacement of halogen atoms, 196- Replacement of nitro groups, 198.
Replacement of hydroxyl groups, 200. Replacement of sulphonic
acid groups, 205. Hofmann's reaction, 206. Alkylation and arylation,
207. Tinctorial properties, 210. Acylaminoanthraquinones, 212.
Ureas and thioureas, 219. Addendum, 223. Nitration, 223. Nitra-
mines, 226. Halogenation, 227. Dianthraquinonylamines, 231.
CHAPTER XII.— THE HYDROXY AND AMINO-
HYDROXY ANTHRAQUINONES AND ETHERS
I. The hydroxy compounds ........ 236
Replacement of sulphonic acid groups, 239. Replacement of nitro
groups, 241. Replacement of halogen atoms, 247. Replacement
of amino groups, 249. Direct oxidation in alkaline solution, 252.
Direct oxidation in acid .solution by concentrated sulphuric acid or
oleum, 256 ; by nitrosyl sulphuric acid, 260 ; by various oxidising
agents, 263. Reduction of polyhydroxy compounds, 264. Miscel-
laneous methods, 266. Properties and reactions, 267. Tinctorial
properties, 271. Halogenation, 273. Sulphonation, 276. Nitra-
tion, 279.
II. The aminohydroxy compounds ....... 282
III. The ethers 285
CHAPTER XIII.— PYRIDINE AND QUINOLINE
DERIVATIVES
I. Pyridanthrones ......... 290
II. Anthraquinone quinolines ........ 293
III. Anthraquinone phenanthridones ...... 297
IV, Pyranthridones ......... 297
V. Flavanthrones ......... 300
CHAPTER XIV.— THE ACRIDONES, XANTHONES,
AND THIOXANTHONES
I. The Acridones . 305
II. The Xanthones . . . . . . . . • 3»5
III. The Thioxanthones 317
CONTEXTS
CHAPTER XV.— THE BENZANTHRONES
I. Simple benramh^one^ ....
II. Complex beiizamhrones ....
Violan thrones, 329. ;>tf-Violamhrones, 331.
Helianthrones, 333. Pyranthrones, 335.
Cyanthrones, 332.
320
327
1.
II.
CHAPTER XVI.— THE CVCLIC AZINES AND
HYDROAZINpS
Mixed amines and hydroazines ......
Simple axines and hydroazines ......
340
342
CHAPTER XVII.— MISCELLANEOUS HETERO-
CYCLIC COMPOUNDS
1. The Pjtidazineanthrones
II. The Pyrimidoneanthrones
III. The Ox.vzines
IV. The Thi.izines
V. The Carbazols
VI. The ?\Trolanthrones
VII. The Pyrrazols
VIII. The Ind.izols
IX. The Imidiuols
X. The Oxazols
XI. The Isoxazols
XII. The Thiophenes
XI II. The Thiazols
XIV. The ut'-Thiazolanthrones
XV. The Cffroxene derivatives
XVI. The Ccerthiene deri%-atives
XVII. The Coeraniidine derivatives
XVIII. Miscellaneous compounds
353
354
355
358
360
362
363
364
36s
368
369
370
371
374
37S
379
380
CHAPTER XVIII.— MISCELLANEOUS
COMPOUNDS
1. Arsenic compounds .....
II. .\ceanthrenequinones .....
III. Diazonium salts ......
IV. Azo, azimino, and azoxy compounds
V. Hvviroxylamines, hydrazines and hydrazo compounds
Addenda
Index to German Patents
Index to Authors .
Index to Subjects
382
383
3S5
3S7
3^
393
401
419
424
\
ABBREVIATIONS
Literature.
A. Annalen der Chemie.
A. ch. Annales de Chimie et de Physique.
A. P. United States of America Patent.
Am. American Chemical Journal.
Am. Soc. Journal of the American Chemical Society.
B. Berichte der Deutschen Chemischen Gesellschaft.
Bl. Bulletin de la Societe Chimique de Paris.
C. Chemisches-Zentralblatt.
C. r. Comptes rendus de I'Academie des Sciences.
Ch. Z. Chemiker-Zeitung (Cothen).
D.R.P. Patentschrift des Deutschen Reiches.
E.P. English Patent Specification.
P.P. French Patent Specification.
F.T. Zeitschrift f. Farben- u. Textil-Industrie.
F.Z. Farbe-Zeitung.
G. Gazetta chimica itaUana.
J. Jahresbericht der Chemie.
J. pr. Journal fiir praktische Chemie.
M. Monatshefte der Chemie.
Mon. Sci. Moniteur Scientifique.
Pat. Anm. Patent Anmeldung.
Proc. Proceedings of the Chemical Society.
R. Receuil des travaux chimiques des Pays-Bas.
R.G.M.C. Revue General des Matidres Colorantes.
Soc. Journal of the Chemical Society.
Z. Zeitschrift fiir Chemie.
Z. ang. Zeitschrift fur angewandte Chemie.
Firms.
Agfa. Aktien-Gesellschaft fiir Anihn Fabrikation, Berlin-Treptow.
B.A.S.F. Badische Anihn- u. Soda-Fabrik, Ludwigshafen a/Rh.
By. Farbenfabriken vorm. Friedr. Bayer u. Co. Elberfeld u. Leverkusen.
Cas. Leopold Cassella u. Co., G.m.b.H. Frankfurt a/lVL
G.E. Chemische Fabrik Griesheim-Elektron, Frankfurt a/M.
K. Kalle u. Co. Aktien Gesellschaft, Biebrich a/Rh.
M.L.B. Farbwerke vorm. Meister Lucius u. Briining, Hochst a/M.
Wed. Wedekind u. Co. G.m.b.H., Uerdingen.
W.t.M. Chemische Fabrik vorm. Weiler-ter-Meir, Uerdingen.
xi
ANTHRACENE
AND ANTHRAQUINONE
CHAPTER I
INTRODUCTION
HiSTORICAI. vSkETCH
Anthracene was first discovered in 1832 by Dumas and
Laurent, who obtained it from the higher boihng fractions
of coal tar and named it " paranaphthalene," although
Laurent, who investigated the substance more closely a
few years later, changed the name to anthracene. In
1857 I'ritzsche also obtained anthracene from coal tar, and
seems to have prepared it in a purer state than Dumas
and Laurent ; and a few years later, in 1862, Anderson
also described its isolation and the preparation from it of
several derivatives. In 1866 the first synthesis of anthracene
was published, as in this year Limpricht obtained it by
heating benzyl chloride with water at 180'', and Bert helot
showed that anthracene is obtained by the pyrogenic de-
com]josition of many simpler hydrocarbons.
About this period some doubt was thrown on the belief
that anthracene was really a single chemical compound,
and Fritzsche regarded it as a mixture of two substances,
which he named photene and phosene. That anthracene
should be regarded as a mixture is hardly surprising in view
of the fact that it is not a particularly easy compound to
obtain in a state of purity, and at the period in question
ver>' little was known of, the constituents of coal tar.
I I
2 ANTHRACENE AND ANTHRAQUINONE
The first ^ructural formula which was proposed for
anthracene was diie to Graebe and Liebermann, who pro-
posed both the forniida now assigned to phenanthrene and
also what is now known to be the correct formula. They
discussed the merits of both of these, but regarded the
phenanthrene formula as being more in accordance with
the then known facts. Shortly after, however, the discovery
of phenanthrene rendered tlie second alternative almost
certain, final confirmation being obtained by the synthesis
of anthracene derivatives from phthalic acid and phenols,
and of anthraquinone itself from benzoyl benzoic acid.
Further proof of the presence of two benzene rings lies in
the fact that whereas nitroanthraquinone on oxidation
gives nitrophthalic acid, the corresponding aminoanthra-
quinone gives phthalic acid itself. The oxidation of anthra-
cene to anthraquinone was first described by Laurent, who
named the product " paranaphthalose," or, at a later date,
" anthracene." Anderson also prepared anthraquinone and
named it " oxanthracene," the modern name, " anthra-
quinone," being introduced by Graebe and Liebermann.
Up to the year 1868 anthracene was regarded merely as
a chemical curiosity, but in that year Graebe and Liebermann
made the discovery that alizarin 3delds anthracene when
distilled over zinc dust, and hence that alizarin was to be
regarded as a derivative of anthracene. 1 This epoch-
making discovery came at an opportune moment, as in
1856 Perkin had started making Mauveine on a commercial
scale, and other synthetic dyes such as Magenta, Nichol-
son's Blue, Methyl Violet, Saffranine, and Bismarck Brown
had rapidly rewarded the labours of those investigating the
possibility of obtaining dyewares from coal products.
The verj' great success that had recently attended other
researches made with a view to obtaming synthetic d3'es,
naturally led to hopes that alizarin might also be made by
an artificial process, and these expectations were fulfilled
^ The formula of alizarin had been previously determined by Strecker,
who, however, had not published his results in any journal, although he
mentioned the matter in his text-book of inorganic chemistry, published
in 1866.
INTRODUCTION 3
in a remarkably short space of time, as in the same year
synthetic aUzarin was prepared m Germany by Graebe and
lyiebermann, and in the following year the technical process
for its manufacture from anthraquinone sulphonic acid was
patented independently by Caro, Graebe and lyiebermann, ^
and by Perkin.^
The successful manufacture of alizarin naturally led to
the investigation of other polyhydroxyanthraquinones, and
during the following years several of these were described,
but although some of them were found to be of value as
dyes, their importance from a technical standpoint was
relatively small. The investigation of alizarin and its de-
rivatives led to the preparation of its quinoline, Alizarin
Blue X, by Prud'homme in 1877, and ten years later
Peter Bohn discovered that fresh hj^droxyl groups could
be introduced into the molecule by direct oxidation. The
immediate result of this discover}^ was the technical manu-
facture of Alizarin Green X and Alizarin Indigo Blue, but
simultaneously, although independently, R. E. vSchmidt
discovered that the reaction was a very general one in the
anthraquinone series, and that by it many hydroxyanthra-
quinones could be prepared. It is difficult to overestimate
the importance of this discovery, as it rendered available
compounds which have proved to be of the utmost value
as starting-out substances. Among other valuable dj-es
which were discovered as a direct result of hydrox3-anthra-
quinones being made easily available may be mentioned
Alizarin Cyanine Green and Alizarin Saphirol. Both of
these discoveries were due to R. E. vSchmidt, the former
being obtained in 1894 and the latter in 1897. To
R. E. Schmidt is also due the credit of the discovery in 1903
that the presence of mercury during the sulphonation of
anthraquinone leads almost exclusivel)' to the formation
of o-sulphonic acids, but Iljinsky seems to have made the
same discover}- independently and almost simultaneously.
In a patent applied for in 1894 an insoluble product is
' Patent applied for on June 25, 1S69.
* Patent applied for on June 26, 1869.
4 ANTHRACENE AND ANTHRAQUINONE
described as being obtained by heating anthrachr3-sazin
with concentrated aqueous ammonia for fifteen hours at
150-200°, and it is claimed that this substance acts as a
brownish black vat d3-e. ^ This seems to be the first occasion
on which the possibility of vat dyeing with anthraquinone
derivatives was taken into consideration, and it is truly
remarkable that the discovery- should have been delayed so
long. At that period, of course, vat dyeing was not a
common method of applying a colouring matter, but it was
well known that the indophenols could be applied in this
way, and in the case of indigo, vat d^-eing had been carried
out since almost prehistoric times. The d^-estuff described
in the patent proved to be of no technical value, and no
further interest seems to have been taken in the matter
for some seven 5'ears. In 1901, however, Bohn discovered
Indanthrene and Flavanthrene, and the great value of
these d^-estuffs led to an immediate search for other
vat d5'es containing the anthraquinone ring S3'stem. Success
was soon achieved, as Anthraflavene was discovered by
Isler in 1905, and P3'ranthrene b3^ Scholl in the same 3'ear,
whereas the next 3-ear saw the discover3^ of Violanthrene
b3' Ball3\ Since that time the discovers' of new anthra-
quinonoid vat d3'es has been continuous, although during
the last tw-o or three 3-ears there has been a ver3' remarkable
falling ofi' in the number of patents taken out. This falling
off in the patent claims is not, however, confined to the
anthraquinone series, but is ver3' noticeable throughout the
whole of the chemical industr3^ It does not denote an3'
slackening of research, nor does it point to exhaustion of
the subject, but is to be attributed to the formation of the
" Interessengemeinschaft " among the leading German
firms having removed practicall3' all competition, with the
result that the firms interested prefer to preserv^e their dis-
coveries as trade secrets, and thus avoid furnishing rival
concerns in other coimtries with information. The de-
preciated value of the mark rendering protection in foreign
countries somewhat costh- is also, no doubt, to some extent
1 M. L. B., D. R. p. 83,068.
INTRODUCTION 5
responsible for the policy of secrecy. Up to the present the
British firms which are now interested in the manufacture
of vat d^-es have applied for ver}^ few patents. This, how-
ever, is not at all surprising, as they have naturally been full}-
engaged in reducing " known " processes to a workable form.
The chief workers on anthraquinone have been Lieber-
manu, R. E. Schmidt, Bally, Bohn, Ullniann, and vScholl.
Liebermann worked almost continuously on the subject
from 1868 right up to the time of his death in igi6. Ullmann
has been responsible for much very useful synthetic work,
but in recent years the beautiful work of Scholl must be
regarded as taking first place. The names of R. E. vSchmidt,
Ball}^ and Bohn are found comparatively little in the
literature, as their discoveries are usually patented by the
firms with which they are associated. The same remark
also applies to Isler, Iljinsky, and others.
Dyeing
Any detailed description of either the theory or practice
of dyemg would be completeh- out of place in a volume of
this description, but a few ver\- brief notes concerning the
more important types of dyestuffs may prove useful to the
reader who has not studied tinctorial chemistry.
An acid dye is usually a sulphonic acid, and is applied
to the fibre from an acid or neutral bath. In the anthraqui-
uone series the most important acid dyes are Alizarin Cj-anine
Green and Alizarin Irisol, although several others are used.
They are almost exclusively used for colourmg wool and
have Httle or no affinit}- for vegetable fibres.
A basic dye is a salt of an amine. In the anthraquinone
series the basic dyes which have been described are of no
importance. Basic dyes are used for dyeing silk and wool,
and often give extremeh- bright shades.
A mordant dye is a dye which can only be fixed on the
fibre by means of a metallic oxide, usually the oxide of
aluminium, chromium, tin, or iron, although nickel and
magnesium are also sometimes used. In this case the colour
6 ANTHRACENE AND ANTHRAQUINONE
developed is due to salt formation taking place between the
metallic oxide and the dyestuff, although exactly how the
salt or " lake " becomes fixed to the fibre is not known.
All mordant dyes contain h3^droxyl groups and, as wall be
seen later, the positions occupied b}^ these groups is of
great importance. Mordant dyes usually give different
shades according to the mordant used, alizarin being a
t^'pical dye of this type.
Sometimes when a fibre is dyed* with an acid dye, after-
treatment with a solution of sodium bichromate or chromium
fluoride alters the shade and renders it much faster. The
change is brought about by salt formation, so that such
dyes can be regarded as mordant dyes in the widest sense.
In their case it should be noted that the " mordant " is
applied after the dyestuff itself, w^hereas in the case of the
true mordant dyes the mordant is applied first and then the
colouring matter. Mordant dyes can be applied to both
animal and vegetable fibres.
A vat dve is an insohible coloured substance which,
however, is readily reduced to a soluble substance which
has affinity for the fibre and which is readily reoxidised on
exposure to the air. The soluble reduction product or " vat, "
may either be colourless, as is the case with indigo, or it
may be highly coloured, as is almost always the case where
anthraquinone derivatives are concerned. The colour of
the " vat," however, has no relation to the colour of the
dye itself, as the finished shade is only developed by sub-
sequent oxidation by exposing the dyed fibre to the air.
All anthraquinone derivatives in which there are two cyclic
carbonyl groups in suitable positions, not necessarily form-
ing part of the same ring, give easily oxidised reduction
products when reduced in alkaline solution. Not all anthra-
quinone derivatives, however, are vat dyes, as a vat dye
is only obtained when the reduction product has affinity
for the fibre.
Vat dyes can be applied either to animal or vegetable
fibres, but the use of the anthraquinonoid vat dyes is almost
completely confined to cotton dyeing, as the vats are usually
INTRODUCTION y
too strongly alkaline to be used for wool. Vat dyeing is
almost always carried out with the yarn, as \\ilh piece
goods penetration is not sufficienth- good to allow satis-
factory results to be obtained. Vat dyes, however, are
largely used in printing, and are often well adapted for obtain-
ing discharge effects, i.e. where a white pattern is obtained
by dicliarging the d}'e.
Vat dyeing is somewhat expensive, but the shades ob-
tained are usually ver>^ fast. Vat dyeing is largely used in
the preparation of the best quality shirtings and upholstery
materials.
The commercial tiames given to dyes were formerly purely
fancy names, and names containing works like anthracene
were not given with a view to representing chemical con-
stitution— Anthracene Red, for example, being a disazo
dye in no waj- connected with anthracene. Now, however,
a much more sensible system is adopted, as the various
manufacturing firms have registered trade names for different
types of dyes, the individual d}-es being distinguished by
a word and initials denoting the shade given. This method
of nomenclature has been carried out most systematically
in the case of the antliraquinone vat dyes, the following
being a list of the chief registered names applyhig to
this class of dye, together with the name of the firm
registering. 1
REGISTERED NAME. FIRM.
Algol 2 Bayer & Co.
Caledon Scottish Dyes, Ltd.
Chloranthrene 3 British Dyestuffs Corporation, Ltd.
Helindon Meister Lucius and Briinning.
Hydranthrene L. B. Holliday & Co., Ltd.
Indanthrene Badische Anilin u. Soda Fabrik.
' Some Cibanon colours (G.C.I.B.) are anthraquinonoid vat dyes con-
taining sulphur.
- Also Leucol.
3 Duranthrene was used by Levinstein, Ltd., before their amalgamation
with British Dyes, Ltd.
8 ANTHRACENE AND ANTHKAQUINONE
Colour and Constitution
Tlie relation of colour to constitution will be treated in
detail, so far as our present knowledge permits, in connection
with the different classes of anthraquinone derivatives,
but at this point attention may be drawn to a few generalities
which have been found to apply to the simple derivatives in
which only one anthraquinone residue is present. The
colour referred to is in every casQ the colour of the finely
divided substance, or the colour of its solution in some
indifferent solvent, and is not the colour obtained by dye
trials. The usual conventional method of considering the
shade to " deepen " when it passes successively from yellow
to orange, red, violet, blue, and green is employed, the
reverse charge being a " lightening " of the shade,
Anthraquinone itself is practically colourless, and the
entrance of nitro groups and halogen atoms has but a vei}^
slight effect, although bromine atoms deepen the colour
rather more than chlorine atoms. The entrance of a
hydroxyl group, however, has a ver}- considerable influence,
although the auxochromic effect is almost completely
destroj'Cd by replacing the hydroxyl hydrogen atom by
an alkyl, aryl, or acyl group. As would be expected, the
sulphydrate group has a similar but more marked influence
than the h^^droxyl group.
The influence of a primarj^ amino group is much greater
than that of a hydroxyl group, and in this case replacement
of one aminohydrogen atom by an alkyl or ar^^l group
increases its auxochromic character, the influence of an
aryl group in this direction being considerabty greater
than that of an alkyl group. On the other hand, replacing
one amino hydrogen by an acyl group decreases its auxo-
chromic character, although by no means destroying it,
and at the same time confers powerful tinctorial properties,
so that the acyl amino anthraquinones can be used as vat
dyes.
The above facts are well illustrated by the following
compounds : —
INTRODUCTION
OH
NH.,
NHCH3 NHPh NHCOCHj
1
1
1
1
1
Yellow. Brick red. Bluish red. Violet red. Yellow.
The influence of a group is always much greater when
in the a-position than when in the j3-position.
When two or more groups are present their effect is more
or less additive, but when they are in the para- position to
one another they seem to reinforce one another, a property
which has been made use of to a considerable extent. The
following formulae represent the reinforcing effect of a
second substituent in the para- position : —
NHCOPh NHCOrh
NH,
NH,
1
1
1
Brick red.
NH,
OH
Bluish red.
NHCH.
Yellow.
NHPh
NHCOPh
Red.
NHPh NHPh
NH2 NH2
Violet. Bluish violet.
NH2 NHCH3 NHPh
Blue. Greenish blue. Green.
The above rules are very general in their application and
render it possible to predict the colour of a simple anthra-
quinone derivative with considerable accuracy. Where
the more complicated compounds are concerned, however,
the state of our knowledge at present hardly justifies the
drawing of conclusions, although, as will be seen in the
sequel, regularities can often be detected.
10 ANTHRACENE AND ANTHRAQUINONE
Nomenclature
The ten positions in the anthracene ring are numbered
as shown, although when dealing with monosubstitution
products it is often more convenient to denote the i, 4, 5,
and 8 positions by the Greek letter a, the 2, 3, 6, and 7
positions by the Greek letter j3, and the 9 and 10 positions
b)^ the prefix meso- or ms- :
8orc< dorms lorc<
5oro( lOorms 4orc(,
In the case of the more complex condensed derivatives
this system is insufficient, and the following notation has
been proposed by Scholl.i
Compounds which when written in the ordinary waj^
contain a straight line of rings are called linear {lin.),
whereas those which when written in this wa}- do not
contain a straight line of rings are denoted as angular [ang).
When the Hue of rings is twice bent the terms cis-bisangrdar
and /mws-bisangular are employed. The following examples
will make this clear : —
Linear. Angular.
cis -Bisangular . ^ra;; s-Bisangulax .
For greater accuracy- condensed systems are regarded
as anthracene derivatives and the fused-on rings as sub-
stituents. The anthracene ring is numbered as usual,
beginning with that a-carbon atom which takes part in the
^ B. 44, 1235 ; 1662.
INTRODUCTION
II
formation of a fused-on (" aufgepropfte ") ring, or is nearest
such a ring. The following examples illustrate this system.
7( Y ] y
5 CO ^
1.9-Benzanthronc. 2.9 Naphthaiithronc.
2.3-Pyridiuoantlira-
quinone.
3 (N) . 4 Pyridino- 1 2-benzanthra-
quinone.
If two or more independent fused-on rings are present
the simplest takes the lowest numbers, isocj-clic rings
having preference over heterocyclic ones.
The positions in the fused-on ring are numbered by
beginning with the carbon atom nearest the lowest numbered
carbon atom of the anthraquinone ring, the rings being
specified by the usual prefixes such as Bz., Py, Nt, etc.
When the rings are heterocyclic it is often more convenient
to denote the positions of substituents by Greek letters.
8-Nitro[5.61Bz.-i-chlor- Bz.-i-chlor-Py-a-hydroxy- 2.9-Naphthanthrone-
1.2.5.6-dibenzanthra- 3(N)-4-pyridino-i,9-benz- Nt-2-sulphonic acid,
quinone [1.2] BZ..3- anthrone - 6 - sulphomc
sulphonic acid. acid.
If two independent anthraquinone rings are present the
above system is applied, but the positions in one anthra-
quinone ring and its attached groups are denoted by plain
12 ANTHRACENE AND ANTHRAQUINONE
figures, and the positions in the other anthraquinone ring
and its groups b}- dashed figures :
With more highly condensed sj-stems any system of
numbering becomes ver}^ cumbersome, and it is best to use
the formula.
For denoting the position of substituents in simple
derivatives of anthracene and anthraquinone the author
has for man}- years employed an adaptation of Pfaff's system.
In this anthracene is denoted by three vertical lines of
equal length and anthraquinone by two lines of equal length
with a shorter line between them :
8 9
8
6 o
5 10 4
Anthracene.
6 3
5 4
Anthraquinone.
The same system is adopted when dealing with more
complex linear bodies, such as naphthacenquinone, naphtha-
cendiquinone, dinaphthanthraquinone, etc., a short line
always representing a ^am-quinone ring :
1.4.9.10-Anthradi-
quinone.
2.3-Benzanthraquinone.
/i/;-Benzanthraquinone
/i;/-Dibenz-i.4.5.8
anthradiqiiinone.
INTRODUCTION 13
This sjstem has its limitations as it is not well adapted
for denoting benzanthrones and other derivatives in which
an ws-carbon atom forms part of a fused-on ring. It, how-
ever, is easily and rapidly written and is perfectly satis-
factory in cases where the simpler derivatives of anthracene
and anthraquinone are concerned. Its use when making
notes will be found a great saving of time.
CHAPTER II
ANTHRACENE AND ITS HOMOLOGUES
Anthracene. — Coal tar is, of course, the only source of
anthracene which is of an}' practical importance, the hydro-
carbon being first isolated by Dumas i in 1832. Dumas
named it " paranaphthalene," and obser\^ed that it was
oxidised by nitric acid to a yellow crj-stalline substance.
Xo synthesis of anthracene that is of any practical im-
portance as a method of obtaining the h5'drocarbon has
yet been de\'ised, but numerous syntheses have been de-
scribed which have considerable interest from a theoretical
standpoint, and the chief of these will be briefl}- mentioned.
Anthracene has been obtained by several pyrogenic
methods, and these throw some light on the probable
mechanism of formation of the hydrocarbon during the
distillation of coal. Schultz 2 found that anthracene is
formed when turpentine vapour is passed through a red-hot
tube, and imder somewhat similar conditions it was obtained
by Letny 3 from Caucasian petroleum, by Liebermann and
Burg 4 from lignite tar oil, and by Atterberg 5 from wood
tar oil. o-Benz3d toluene also gives it when passed through
a red-hot tube,^ or, in better yield, when passed over lead
oxide below a red heat.'^
Toluene, benzene, or styrene, when mixed with ethylene
and passed through a red hot tube, give anthracene, ^ and in
connection with this it is interesting to notice that Kraemer
and Spilker ^ have foimd that meth\lated benzenes \\'ill
» A. 5, 10. 2 B. 7, 113. cy. Staudinger, B. 46, 2466.
3 B. 10, 1112 ; 11. 1210. « B. 11, 723.
« B. 11, 1222. 6 Dorp, A. 169, 216.
' Behr and Dorp, B. 6, 75-1 . « Berthelot, A. 142, 254.
9 B. 23, 3160; 3269.
14
ANTHRACENE AND ITS HOMOLOGUES 15
combiue quite readih' with styrene in the presence of sulphuric
acid to form phen}^ aryl propanes, which when passed
through a red-hot tube yield anthracene hydrocarbons, the
3'ields being in some cases as high as 63 per cent. It is not
impossible that the anthracene derivatives found in coal
tar have been formed by very similar reactions.*
Numerous syntheses of anthracene and its homologues
by means of aluminium chloride have been recorded. Thus
toluene when heated in a sealed tube with anh}-drous
aluminium chloride gives anthracene, and X3-lene gives
dimethyl anthracene, 1 but in all cases the yields are minute.
By condensing an aromatic hydrocarbon in the presence of
aluminium chloride with acetylene tetrabroniide,^ ethylidene
bromide or cliloride,^ vinyl bromide,"* perchloreth3'lene,5
meth}-lene chloride 6 or chloroform,'^ anthracene hydro-
carbons are obtained. In these syntheses it is probable that
a ^/zs-dih3'droanthracene is liist formed, which is then oxidised
at the expense of part of the halogen compound, or that
an ?«s-dichlordihydroanthracene is the first product, this
then splitting off two atoms of chlorine. These are not
evolved as such, but clilorinate part of the hydrocarbon or
react with the carbon bisulphide which is usually used as
a dilutant.
Perkin and Hodgkinson ^ and Schramm ^ have shown
that benzj-l chloride itself gives anthracene under the
influence of aluminium chloride, and Limpricht 10 and
Zincke 1 ^ have found that benzyl chloride, when heated under
pressure with water at 160°, gives a mixture of benz}-!
alcohol, benzyl ether and co-chlortolyl phenyl methane,
this latter yielding anthracene on distillation.
Jackson and White 12 have applied the method of Wurtz,
and by treating o-brombenzyl bromide with metallic sodium
* But compare R. Mej^er, B. 45, 1609 ; 46, 3183, who has obtained
anthracene by condensing naphthalene with acetylene.
1 Anschiitz, A. 235, 137. ^ A. 235, 157.
» A. 235, 299 ; B. 17, 165. * A. 235, 323.
5 Bl. [3] 19. 554- ' A- Ch. [6] 11, 264 ; Bl. 41, 323.
■ B. 18, 348. 8 soc. 37, 726.
9 B. 26, 1706. *- 1" A. 139, 308.
" B. 7, 276. >* B. 12, 1965.
i6 ANTHRACENE AND ANTHRAQUINONE
obtained a mixture of anthracene and dihj'droanthracene.
They state that the reaction is very slow when benzene is
used as a solvent, but becomes rapid in absolute ethereal
solution. Anthracene in 60 per cent, yield can be obtained
by the action of aluminium chloride on benzyl trichloracetate, 1
but in spite of the good 34eld this method does not seem to have
been applied to the study of other anthracene derivatives.
In the distillation of coal tar the anthracene passes over
with the fraction which boils between 280-400°. This
fraction has a specific gravity of about iioo and is known
as " anthracene oil " or " green oil " on account of its green
colour, although after standing in the air for some time the
colour usually changes to brown. The crude oil contains
only 5-10 per cent, of anthracene, and on cooling this is
deposited together with phenanthrene, carbazol, acridine,
and other impurities. The crude solid thus obtained con-
tains 15-25 per cent, of anthracene, but can be brought up
to 40-50 per cent, strength by hot or cold pressing and by
washing with solvent naphtha or creosote oil. It is in this
state that it is usually sold, sales always being effected on
a percentage basis, and the price at present (1920) being
quoted at gd. per unit per cwt., an increase of about 500 per
cent, over the pre-war price. Anthracene in this state is
quite suitable for conversion into anthraquinone, as if it
is reduced to a state of fine subdivision by distillation with
superheated steam and condensation of the vapours with fine
jets of water, oxidation with the calculated amount of
chromic acid converts the anthracene into anthraquinone
without to any great extent affecting the impurities. The
presence of any considerable quantity of methyl anthracene,
however, spoils the shade of the alizarin obtained, and the
presence of paraffins gives endless trouble by choking the
filters. It is for this latter reason that the crude anthracene
obtained by the distillation of mixtures of hard coal with
cannel-coal is not popular with dye-makers, and, of course,
low-temperature carbonisation also increases the content
of paraffins.
1 Delacre, C. r. 120, 155 ; Bl. [3] 13, 302.
ANTHRACENE AND ITS HOMOLOGUES 17
Numerous methods have been proposed for purifying
crude anthracene. For example, it can be recrystalHsed
from fatty acids such as oleic acid,^ or it can be washed
with acetone,- or liquid ammonia,-^ or sulphur dioxide. * By
far the best method, however, is washing with pyridine or
quinoline bases, ^ as this leaves a product containing
90-98 per cent, of anthracene. Graebe ^ obtained anthra-
cene free from carbazol by fusing with caustic potash, the
carbazol forming its potassium salt and the anthracene
bemg distilled off. This process has been the subject of
several patents'^ but does not seem to have been a com-
mercial success. Wirth ^ attacked the problem in a rather
different way, and claims that if crude anthracene is treated
with nitrous acid the anthracene is unaffected, whereas the
carbazol is converted into a nitroso compound which is
soluble in benzene and can therefore be removed b}' washhig
with this solvent.
When pure, anthracene is a colourless crystalline solid
which melts at 2i6"5° and boils at 351°. It has an intense
violet fluorescence, but this is complete!}- masked by small
quantities of impurities. This fluorescence is shown by all
anthracene derivatives in which each w^so-carbon atom is
in combination with only one monovalent element or group,
and may be due to double symmetrical tautomerism (see
p. 19).
Molinari 9 has prepared an ozonide of anthracene but
does not seem to have examined its decomposition products.
Schlenk, Appenrodt, and Thai 10 have found that when
ethereal suspensions of anthracene are shaken with sodium
powder a disodium addition compound is formed. In this
1 Renev and Erhart, D.R.P. 38,417.
- By., b.R.P. 78,861.
3 Welton, D.R.P. 113,291.
* By., D.R.P. 68,474.
* Chemische Fabriks-Actiengesellschaft in Hamburg, D.R.P. 42,053.
Clark, J. Ind. Eng. Chem. 1919, 204.
* A. 202, 22.
' A. G. fiir Teer- u. Erd-oUndustric, D.R.P. 111,359; By., D.R.P.
157,123 ; Agfa, D.R.P. 178,764.
8 D.R.P. 122,852.
» B. 40, 4160.
" B. 47, 473.
i8 ANTHRACENE AND ANTHRAQUINONE
the sodium atoms must be attached to the ms-carboii
atoms, as treatment with carbon dioxide leads to the forma-
tion of the sodium salt of dihydroanthracene dicarboxjdic
acid :
H Na H COONa
c
C
^6^4.^0611.1
CO.,
CoH4<()>C6H4
c
c
/\
/\
H Na
H COONa
Anthracene forms a well-cr3-stallised picrate with one
molecule of picric acid when treated with alcoholic solutions
of picric acid.i
Structure. — There is some doubt as to the disposition of
the fourth valency of the ;«esc>-carbon atoms in the anthracene
molecule, and the formula of anthracene can be written
either as a bridged ring or as a quinonoid compound :
CH CH
C6H4<' 5^)06114 C6H4^^C6H4
CH CH
Against the ortho-qmnonoid formula it ma}- be urged that
this would represent a coloured compound, whereas anthra-
cene is colourless. 2 Our present knowledge of the relation-
ship between molecular structure and the absorption of
light, however, is not sufhcienth- wide to allow much weight
to be given to arguments of this nature. On the other hand,
the formation of a disodium addition compound is much
more in accordance with the quinonoid structure, asSchlenk,
Appenrodt, and Thai 3 have found that in the case of other
hydrocarbons the formation of such compounds is closely
allied with unsaturation. Auwers,^ from a study of the
optical anomality of ;HS-amylanthracene and ms-amyl-
9.10-dihydro-anthracene, also concludes in favour of the
1 B. 7. 34; A. 139, 309
- Absorption spectrum. Baly Soc. 93, 162.
3 B. 47. 473. * B. 53, 941-
ANTHRACENE AND ITS HOMOLOGUES 19
quinonoid structure. The quinonoid structure, however,
indicates a type of isomerism among anthracene derivatives
which is totally unknown, as a monosubstitution product, for
example, should exist in two forms :
CH CH
C6H4^)>C6H3C1 and C6H3C1^)>C6H4
CH CH
The powerful iluorcscence of anthracene and of all its
derivatives in which the " bridge " remains intact points
to double symmetrical tautomerism, so that on the whole Ihc
dynamic formula :
CH CH CH
C6H//;>CcH, ^ CeH^^^CoH, ^ CeH4<;^J:CeH,
CH CH CH
is the best representation. In the following pages the
" bridge " formula is used as a matter of convenience ; but
its use is without prejudice, and it must be understood that
it probably merely represents the middle point of the
vibration.
It should be noted that anthracene compounds show a
marked capacit}- for forming addition compounds, e.g. with
picric acid. This capacity for forming addition compounds
apparently lies in the arrangement of the valencies of the
central ring, as destruction of the " bridge," e.g. by reduction,
is accompanied by complete loss of capacity to form a
picrate. Destruction of the bridge also leads to the dis-
appearance of fluorescence.
Oxidation. — The oxidation of anthracene and its de-
rivatives leads usually to anthraquinone or an anthraquinone
derivative ; but if one of the benzene rings is weakened by
the presence of hydroxy-1 or amino groups, this ring is usually
ruptured. Sulphonic acid groups, halogen atoms, alkyl
groups, carboxylic acid groups, etc., do not weaken the
ring, so that such derivatives of anthracene on oxidation
pass into the corresponding anthraquinone derivative, and
20 ANTHRACENE AND ANTHKAQUINONE
in many cases advantage has been taken of this for deter-
mining the position of substituents.
On the other hand, groups attached to the ms- carbon
atoms are usually eliminated on oxidation, so that ms-
substituted derivatives of anthracene give anthraquinone
on oxidation ; but Simonis and Remmert ^ have shown that
9-io-diphen3danthracene on oxidation does not give anthra-
quinone, the chief oxidation product being o-dibenzoyl-
benzene :
C«H
6^^i
CfiH
6^^i
CfiH
6X14N
.COCfiH
6^^5
^COC«Hr,
6^^5
and, curiousl}- enough, i.2-dimethoxy-9-io-diphenylanthra-
cene on oxidation gives dibenzo}^! veratrol :
I
C
(MeO)2C6H2
.COCfiH
>CfiH
e^^i
(MeO)2C6Ho<
6-»^-^5
^COCeHs
CeHs
Anthraquinone is a verj- stable substance and resists the
action to oxidising agents to a ver^" marked extent. Hence
although it is possible in some cases to rupture the centre
ring with the production of an o-benzo^-l benzoic acid or a
phthalic acid, the method is of no importance, as such
violent means have to be used that the phthalic acid is
usualh^ almost completely destro3'ed. Of course, if only
one of the benzene rings is weakened b}^ the presence of
hydroxyl or amino groups, it will be possible to obtain
phthalic acid from the substance, and this in many cases
gives useful information as to the position of substituents.
' ]}. 48, 2o8.
ANTHRACENE AND ITS HOMOLOGUES 21
Although anthraqiiinone is the final stable stage in the
oxidation of anthracene, by moderated oxidation it is some-
times possible to isolate lower oxidation products. Thus,
Schulze 1 oxidised anthracene with lead dioxide m boiling
glacial acetic acid solution and obtained anthraquinol,
and Kurt Meyer 2 has shown that under these circum-
stances the first product formed is acetoxj- anthrone, which
passes into anthraquinol by hydrolysis and subsequent
isomerisation :
H OCOCH., H OH OH
/
c c
'Z
c c c
II II I
O O OH
From ms-alk3'l dihydroanthracenes lyiebermann ^ was
able to obtain alkylh^'droxyanthrones by careful oxidation
with chromic acid :
H R
HO R
C
C
C6H4<(' ^C6H4
CHo
->
C6H40C
C
^Hj
O
and Bae^-er * obtained ;;?s-phenyl h3'drox}^anthrone b}'
the careful oxidation of ?«s-phenyl anthracene. In both
cases more vigorous oxidation leads to anthraquinone.
lyiebermann ^ also found that the moderated oxidation of
the ?«s-alkyl hydroxj^dihydroanthracenes led to «?s-alkyl
hydrox>'anthrones :
^ B. 18, 3036.
3 A. 212,' 67'; B. 13, 1596 ; 15. 452. 455. 462.
« A. 202, 54.
^ A. 212, roi.
22 ANTHRACENE AND ANTHRAQUINONE
HO R
HO R
C
C
CcH^. ^C6H4
CH2
->
C6H4<^ /C6H4
CO
As will be seen later, the moderated oxidation of the
anthranols readily leads to dianthrdnes :
OH
!
I
1
C C6H4 C6H4
C6H4<^,\C6H4 -> CO<^\c=C<^^^CO
C C6H4 LeH4
I
H
Kurt Mej^er,^ by Oxidising anthracene with one molecule
of lead dioxide in boiling glacial acetic acid, obtained a
mixture of anthranol acetate and hydrox3'anthrone acetate,
this latter substance being the main product when two
molecules of lead dioxide are used. 2 Similar results were
obtained by using
CeH.
OCOCH3
1
c
/V6H4
<-
CeH
CH
4<^,^C6H4
~>
H OCOCH3
\/
C
C6H4<(' yCeBi
CH
CH
C
O
manganese dioxide, eerie acetate, and vanadic acid, all in
boiling glacial acetic acid solution. With other solvents,
however, the course of the reaction is different, dianthrone
often being formed :
I A. 397, 73. 2 Cf. Schulze. B. 18, 3036.
ANTHRACENE AND ITS HOMOLOGUES 23
C6H4 C6H4 H H C6H4
HC^CH ^ 0=C<^^C-C<;^^C=0
CqH.4, C6H4 CgHi
The fact that Schiilze 1 obtained aiithraquinol by oxi-
dising anthracene in glacial acetic acid with lead dioxide
is obviously due to the fact that he treated his product with
alkali without first examining it, the effect of the alkali
being to split off the acetyl group from the acetox>'-
anthrone and then to enolise the hydroxyanthrone formed
(p. 108).
Kurt Meyer 2 has also found that halogens in aqueous
solvents below^ 25° oxidise anthracene very smoothly. In
this case oxidation probably takes place by alternate addition
and hydrolysis :
OH
I
C
H. -> C^-Ry^C^K^
H Br
H OH
C
C
C6H4<(' ^C6H4
c
c
c
I
H
O
II
c c c
C6H4<^V6H4 -> C6H4<^^C6H4 "> C6H4<^^C6H4
c c c
H Br H OH H OH
The further action of halogen brings about substitution
of the ;ns-hydrogen atom in the h>-droxyanthrone, subse-
quent hydrolysis leading to anthraquinone :
1 Loc. cit. ' A. 379, 73, 166.
c
CeH/^CeH^
C
/\
Br OH
24 ANTHRACENE AND ANTHRAQUINONE
000
II 11 II
C C
c c
/\ II
HO OH O
The action of nitric acid on anl^racene is discussed on
p. 50, but Dimroth,! b}'^ treating anthracene with nitric
acid in glacial acetic acid solution, obtained dianthrone :
CeH^ CeH^ H H C6H4
2CH<^^CH ~> OC/^C— C<^Vo
CeH^ C6H4 C6H4
Paranthrene, Dianthrene. — When solutions of anthra-
cene are exposed to direct sunlight or ultraviolet light,
polymerisation takes place, and an almost insoluble bimole-
cular 2 polymer is precipitated. This is known as paranthrene
or dianthrene, and as it readily reverts to the monomolecular
form when heated, its formation has been employed in the
laboratory' as a means of obtaining ver}^ pure anthracene.
The process, however, is a very inconvenient one to carr}^
out owing to the very slight solubility of anthracene itself.
The polymerisation of anthracene under the influence of
sunlight has been known almost since the discovery of
hj'drocarbon,^ and, in fact, gave rise to the old name
" photene," In more recent j-ears the reaction has formed
the subject of several investigations. Linebarger, Orndorff,
and Cameron * found that the polymerisation takes place
best in xylene solution,'and can also be effected in benzene,
toluene, alcohol, chloroform, and acetic acid, but will not
take place in carbon bisulphide or in ethylene dibromide.
' B. 34, 219.
2 Klbs, J. pr. [2] 44, 267.
2 Fritsche, Z. 1867, 290; Ernst Schmidt, J pr. [2] 9, 248; Graebe
and Liebermann, A., Suppl. VII., 264.
* Am. 14, 599.
ANTHRACENE AND ITS HOMOLOGUES 25
Weigert 1 and his students, and Byk 2 have examined the
reaction from a physico-chemical and thermodynamic point
of view, and have found that the amount of change is directly
proportional to the light energy absorbed.
The formation of bimolecular polymers by anthracene
derivatives has been studied b}" Fischer and Ziegler 3 and
by Weigert and Kummerer.* The former investigators
showed that a-methyl anthracene is much more rapidly
polymerised than either anthracene itself or j3-methylanthra-
cene. They also found that 1-4-methylchloranthracene,
a-chloranthracene, ms-monobromanthracene and a-chlor-
;«s-monobromanthracene all polymerise, whereas dihydro-
anthracene, dihydromethylanthracene and ws-dibromanthra-
cene do not. Weigert and Kummerer studied the action of
light on the anthracene monocarboxjlic acids and found that
all three acids are polymerised, but the a-acid is only poly-
merised slowly, whereas in the case of the ^-acid the action is
rapid. The ms-acid is also polymerised both in glacial acetic
acid solution and in alkaline solution. In the latter case the
action of light also causes rapid oxidation b}- atmospheric
oxygen, so that it is necessary' to work in evacuated vessels.
The bimolecular polymers are all colourless solids which
melt at fairly high temperatures, and either at the melting
point or at a slightly higher temperature revert to the
monomolecular form. They are not fluorescent, do not
form picrates, and on oxidation give the same products as
the monomolecular hj'drocarbons. In all probability their
structure is represented bv the formula :
C6H/V6H4 CeH/^CaH,
Dianthrene itself melts at 244*^ and is depolymerised
at 272°.
1 B. 42, 850 ; 1783 ; Ann. der Phys., 24, 55, 243 ; Z. f. Elektrochemie,
14, 591 ; Z. f .physikal, Chemie, 51, 297 ; 53.' 385 ; '63, 458.
* B. 42, 1 145 ; Z. f. physikai. Chemie, 62, 454.
3 J. pr. [2] 86, 289. * B. 47. 898.
26 ANTHRACENE AND ANTHRAQUINONE
Homologous Anthracenes
i-Methylanthracene. — Ve^ little information is avail-
able with reference to this substance, although it has been
described by two investigators. Birukoff i obtained it by
condensing phthalic acid with ^-cresol and then distilling
the resulting i-methyl-4-h5^droxyanthraquinone with zinc
dust. He describes it as melting at 199-200° and giving a
quinone which melts at i66-i67°.« O. Fischer 2 repeated
Birukoff's work and obtained a hydrocarbon which melted
at about 200°, but which on oxidation gave anthraquinone
itself, and which he therefore concluded consisted chiefly
of anthracene, the methyl group having been split off as
methane during the distillation with zinc dust. Fischer
also observed that the mother liquor from the recr^-staUisation
of the hydrocarbon contained a substance of very low
melting point which on oxidation gave a quinone melting at
about 170°, but he did not investigate it further. He, how-
ever, prepared i-meth^^anthracene by distilling i-metltyl-
4-chloranthraquinone, obtained from phthalic acid and
^^-chlortoluene, with zinc dust and described it as melting
at 85-86°, and giving a quinone which melted at 170-171°.
At first sight the melting-point seems extremely low, and
reminds one of the compounds of uncertain composition
which have been obtained by Elbs ^ by the alkaline reduc-
tion of methylanthraquinones in which a meth}^ group is in
the a-position to one of the carbonyl groups ; but Lavaux ^
has obtained what he describes as i.8-dimethylanthracene,
m.p. 86°, although the composition of this substance cannot
be said to be proved. The low melting point of the a-deriva-
tive is also to be expected from analog}' with the correspond-
ing naphthalene h5^drocarbons. Thus naphthalene itself
melts at 79° and j3-methylnaphthalene at 32-5°, whereas
a-methylnaphthalene melts at — 20°, and i.6-dimethyl-
naphthalene is also liquid at the ordinary temperature.
The bimolecular form of a-methyl anthracene melts at 246°.
1 B. 20, 206S. 2 j_ pr. [-2] 83, 201.
=> B. 20, 1365 ; J. pr. [2] 41, 12.
* C. r. 139, 976 ; 140. 44 ; 150, 1400 ; Bl. [4] 7, 539-
I
ANTHRACENE AND ITS HOMOLOGUES 27
2-Methyi.anthracene. — This is a much more important
compound than the isomeric i-methjdanthracene and, as
it is much more readily obtained, it has been much more
carefully investigated. It seems to be the parent hydro-
carbon of many naturally occurring anthracene derivatives,
and is obtained from them by distillation with zinc dust.
Thus Ciamician ^ obtained it from colophonium, and
lyiebermann 2 and Jowett and Pother ^ from chrysarobin
and emodin. It is present in coal tar and has been isolated
from this source b}^ Schulz ^ and Bornstein, •'' and Waschen-
dorff 6 has obtained it from the pitch left from the distillation
of commercial aniline oil. Its formation by the pyrogenic
decomposition of h3'drocarbons seems to be quite common,
as Schulz '^ has obtained it by passing turpentine vapour
through a red-hot tube, and O. Fischer,^ Schulz, ^ and
Weiler 10 have obtained it b}" similar means from ditolyl-
methane and ditolylethane.
Elbs 11 has obtained it by the prolonged boiling of the
phenyl X3dyl ketone obtained by condensing benzoyl chloride
with p-xylene, and Gresley ^^ has obtained it by condensing
phthalic anhydride with toluene and then distilling the
ketonic acid over zinc dust.
A rather interesting synthesis has been carried out by
Kraemer and Spilker,i3 who find that methyl benzenes, in
this case w-xylene, condense with styrene in the presence of
sulphuric acid to form diaryl propanes :
CgHqCH : CHo+CcH4(CH3)2 -» CgHoC— CH2C6H.1CH3
I
CH3
and these when passed through a red-hot tube apparently
split off a carbon atom and yield an anthracene derivative.
1 B. 11, 269. * A. 183, 162 ; 212, ^4. s Soc. 81, 15S1.
* B. 10, 1049, 5 B. 15, 1821.
" B. 10, 1481. It must be remembered that this observation was pub-
lished in 1S77. It is highly improbable that any anthracene derivatives
could be obtained from modern commercial anihne oil.
' B. 10, 118. 3 B. 7, 1195 ; J. pr. [2] 79, 555-
9 B. 10. 118. 10 B. 7. 1185.
'1 J. pr. [2] 35. 471 ; 41, 1,1 ; B. 17. 2848.
"* A. 234, 238. " 12 B. 23, 3169 ; 3269.
28 ANTHRACENE AND ANTHRAQUINONE
lu the case in question a 63 per cent, yield of 2-methyl-
anthracene was obtained. This reaction suggests a possible
explanation of the presence of meth3^1 anthracene in coal
tar.
2-Methylanthracene can, of course, be obtained by the
distillation of methylhydrox^-anthraquinones over zinc
dust,i but this method is of theoretical rather than of
practical importance. It is most readily obtained b}^ the
reduction of the coi responding qumone,^ and as this is
readily obtained from phthalic anhydride and toluene,
the h3'drocarbon is easily available.
The melting point of 2-methylanthracene given in the
literature is ver}' variable, most investigators giving it as
198-204°. Probably the figures given by O. Fischer, ^
viz, 203° (uncor.) and 207*^ (cor.), are the most reliable.
The latter figure is also given b)^ Limpricht and Wiegand,"*
Kraemer and Spilker,^ and Scholl.^
Orndorff and Megraw"^ find that when its solutions are
exposed to sunlight 2-methyl anthracene passes into a non-
fluorescent bimolecular form which melts at 228-230° with
simultaneous reversion to the monomolecular form.
Methanthrene. — In addition to a- and jS-methyl-
anthracene a third isomer has been described by Oudemas,^
who states that he obtained a hydrocarbon with the formiila
C15H12 by distilling podocarpinic acid with zinc dust. He
gives the melting point of the h5^drocarbon as 117°, and
states that on oxidation it gives a quinone, C15H10O2, which
melts at 187°, and which is slowly reduced by sulphurous
acid. It seems improbable that Oudemas's compound was
an anthracene derivative at all.
Dimethyl Anthracenes. — The chemistry of the
dimethyl anthracenes is far more complicated than would
seem to be the case at first sight, and in spite of numerous
investigations comparatively little really reliable data is
1 Nietzki, B. 10, 2013 ; Niementowski, B. 33, 1633.
2 Limpricht and Wiegand, A. 311, i8i ; Scholl, M. 39, 237.
3 J. pr. [2] 79, 555. * A. 311, iSi.
6 B. 23, 3169 ; 3269. 6 M. 39, 237.
' Am. Soc, 22, 154. « A. 170, 243 ; J. pr. [2] 9, 416.
ANTHRACENE AND ITS HOMOLOGUES 29
forthcoming. As Ivavaux ^ has pointed out, nearly all the
reactions which lead to dimethyl derivatives are capable
of yielding more than one isomer, and nearly all these re-
actions have to be carried out under conditions under which
there is considerable danger of methyl groups wandering.
In addition the isomers have a great tendency to form
eutectic mixtures which are extremel}- difficult to recognise
as such, and which can only be separated into their con-
stituents by special means.
Several uivestigators have described a dimethyl anthra-
cene melting at 225°, and givmg on oxidation a quinone
melting at 156-160°. Thus Waschendorff and Zincke 2
obtained it from the heavy fractions of connnercial aniline
oil ; Aiischiitz 3 obtained it by treating toluene with sym-
tetrabrom-ethane and aluminium chloride, and also by
treating toluene with aluminium chloride. '^ P'riedel and
Crafts 5 obtained it b}- the action of methylene chloride
and aluminium chloride on toluene, and by the action of
aluminium chloride on toluene also obtained a dimetli>-l
anthracene. The melting point of this latter substance
thc}^ give as 231°, but find that it gives a quinone melting
at 160°. Elbs and Wittich ^ from toluene, chloroform, and
aluminium chloride obtained a dimethyl anthracene melting
at 215-216° and giving a quinone melting at 161-162° ; but
Lavaux has shown that the melting point of their compound
was too low owing to the presence of a little monometh}l
anthracene.
Lavaux '^ has shown that all these so-called dimethyl
anthracenes are really eutectic mixtures, and from them he
has isolated two distinct dimethyl anthracenes, one melting
at 244*5° and the other melting at 240°. In addition, from
the product of Friedel and Crafts reaction he has isolated
a third ver^- soluble isomer which melts at 86°. This last
he seems to assume to be i.8-dimethylanthracene, but does
not appear to have investigated in detail.
1 C. r. 146. 137. 2 B. 10. 1481.
3 A. 235, 171 ; B. 17, 2816. * A. 235, 181.
B A. Ch. [r.] 11. 265 ; Bl. 41. 323. 6 B. 18, 348.
' C. r. 139, 976 ; 1*0, 44 ; 152, 1400 ; Bl. [4] 7, 539.
30 ANTHRACENE AND ANTHRAQUINONE
The compound melting at 244-5° seems to be identical
with the dimeth}^ anthracene obtained by Anschiitz and
Roniig 1 by distilling the condensation pioduct of toluene
and ethylidene bromide over zinc dust. On oxidation it
gives a quinone melting at 236-5°, and also a methyl anthra-
quinone carboxylic acid and an anthraquinone dicarboxylic
acid. The nieth}^ anthraquinone carbox3dic acid was
reduced by zinc dust and ammonia to methylanthracene
carboxylic acid, and from this it can be concluded that the
methyl group is in the ^-position, as Elbs ^ has shown
that a-methyl anthraquinones do not give the corresponding
anthracene derivative by reduction in alkaline solution.
Further, Lavaux showed that the meth}^ anthracene
carbox3dic acid, by loss of carbon dioxide, gave ^-methyl-
anthracene.
Lavaux ^ fomid that his anthraquinone dicarboxylic
acid on fusion with caustic potash * gave a mixture of
isophthalic acid and terephthalic acid, but no phthalic acid.
The only anthraquinone carboxylic acids which could
give this are the 2.6- and the 2.7-acids, and Lavaux con-
cluded that his acid was anthraquinone-2. 7 -dicarboxylic
acid, and consequently that the dimeth^d anthracene which
melted at 244-5° was 2.7-dimethyl anthracene.
Seer ^ by heating ;»-methyl benzojd chloride with
aluminium chloride to 140° obtained a mixture of three
dimeth}-l anthraquinones, of which the main product
melted at 235-236°. By the action of ;«-methylbenzoyl
chloride on m-:xylene in the presence of aluminium chloride
he obtained a tolyl xylyl ketone which ' when boiled
(b.p. 315-320°) for five days & gave a dimethyl anthracene
which melted at 243°, and which on oxidation gave a quinone
melting at 235-236°. Seer's products are presumably
1 A. 235, S17; B. 18, 662.
2 J. pr. [2] 15, 121 ; B. 20, 1365.
» C. r. 141, 354 ; 14.3, 687.
* In the anthraquinone series these fusions are often ver^- troubles ome
to carry out. In the case in question, for example, it was necessary to
maintain a temperature of 260° for 300 consecutive hours.
* M. 32, 143.
» C/. Elbs, J. pr. [2] 33, 1S5.
ANTHRACENE AND ITS HOMOLOGUES 31
identical with the products obtained by Lavaux. The fact
that the tolyl x^-lyl ketone gave an anthracene derivative
is proof that one nieth>l group is in the ortho- position
to the carbonyl group, and if it is assumed that nieth}!
groups have not wandered there are only two alternatives
for the structure of the ketone and the dinieth>-l anthracene
derived from it :
CO
CH3
CH3 ^•' ^ CH3
CH,
i
CH3 r T Y >CH:
1.7-Dimethylanthracene. 26 Dimcthylanthraceue.
Lavaux, however, has proved conclusively that it is
either the 2.6- or the 2.7- compound, and hence Seer con-
cludes that it must be 2.6-dimeth3-l anthracene.
Lavaux has also investigated the second isomer of his
eutectic mixture. This on oxidation gives a methyl anthra-
quinone carboxylic acid which can be reduced to a meth\l-
anthracene carboxylic, this latter by loss of carbon dioxide
passing into j3-methyl anthracene. By further oxidation
an anthraquinone dicarbox\lic acid is formed and this
by fusion with caustic potash gives a mixture of phthalic,
isophthalic, and terephthalic acids, and consequently must
be either the 1.6- or the 1.7- dicarboxylic acid. Lavaux
considers the former alternative the more probable, and
consequently designates the dimethyl anthracene which
melts at 240° as i.6-dimethyl anthracene. The corre-
sponding quinone melts at 169°.
The production of an anthracene derivative by means
of methylene chloride is obviously preceded by the pro-
duction of a dihydroanthracene, subsequent oxidation being
brought about at the expense of part of the methylene
chloride. In the case of chloroform a dichlordihydroanthra-
ceue is the intermediate product, this passing into the
32 ANTHRACENE AND ANTHRAQUINONE
anthracene by loss of two atoms of chlorine. This chlorine
is not evolved as such during the reaction but chlorinates
part of the toluene or reacts with the carbon disulphide used
as a dilutant.
The structure of the dimethyl anthracene described b}'
Dewar and Jones ^ as being obtained by heating toluene
with nickel carbonyl and aluminium chloride is very doubt-
ful. They describe it as 2.6-dimeth5d anthracene and state
that it melts at 215-216° and give* a quinone which melts
at 159-160°. Seer 2 suggests that it may be 2.7-dimethyl
anthracene, but it seems much more probable that it is a
rather impure eutectic mixture.
Other heteronuclear dimethyl anthracenes have also
been described. For example, van Dorp ^ by heating
X34yl chloride with water to 210° obtained a dimethyl
anthracene which melted at 200°, and on oxidation gave a
quinone melting at 153°. van Dorp's products were
probably complex mixtures, as he states that he made his
xylyl chloride from xjdene which boiled at 136-139°,
and which on oxidation gave a mixture of isophthalic and
terephthalic acids, the former " in prepondering amount."
The chloride itself he describes as boiling at 190-200° and
" consisting chiefly of the desired chloride."
Of the four possible homonuclear dimethylanthracenes
neither the 1.2- nor the 1.4- isomers have been described,
although Gresly * and Heller ^ prepared 1.4-dimethyl
anthraquinone from /)-xylene and phthalic acid thc}^ do
not seem to have reduced it to the anthracene com-
pound.
Klbs and Eurich 6 condensed phthalic anhydride with
o-x>'lene and obtained 3-4-dimethylbenzoylbenzoic acid, the
position of the methyl groups being proved b}^ F. Me3^er,''
who, by fusion with caustic potash, obtamed a mixture of
benzoic acid and 2. 3-dimethyl-i -benzoic acid. The ketonic
acid by loss of water passed into a dimethylanthraquinone
1 Soc. 85, 216. 2 M. 33, 143. 3 A. 169, 207.
« A. 240, 240. 6 ]3, 43^ 2892.
« B. 20. 1361 ; J. pr. [2] 41, 5. ' B. 15. 637.
ANTHRACENE AND ITS HOMOLOGUES 33
which melted at 183°.* This might be either i.2-dimcth3-l-
anthraquinone or 2-3-dimethylanthraquinone ; but since
toluene jaelds exclusively j3-methylanthraquinone one is
j ustilied in assuming that the reaction takes a similar course
in the case of o-xylene, the product in this case being
2.3-dimethyl anthraquinone. That this is correct has been
proved by the fact that the dicarboxylic acid obtained from
it b}^ Elbs b}^ oxidation melts at 340°, whereas the di-
carboxylic acid obtained by Scholl ^ by the oxidation
of i.2-benzanthraquinone (naphthanthraquinone) melts at
267-268°. As Scholl's acid must be anthraquinone 1.2-dicar-
boxylic acid, it follows that Elb's acid nmst be the 2.3-dicar-
boxylic acid. Both acids readily yield cyclic anh3"drides,
which shows that no wandering of the methyl groups can
have taken place. Elbs and Enrich reduced the dimethyl-
anthraquinone by zinc dust and ammonia and obtained
2.3-dimethylanthracene, m.p. 246°.
vSeveral investigators have prepared 1.3-dimetliyl-
anthracene, but their descriptions are so conflicting that it
is very doubtful if the substance has ever been obtained
pure.
Elbs 2 found that benzoyl mesitylene on heating does not
pass into a dimethyl anthracene : but Louise, 3 by passing
benzyl mesitylene through a red-hot tube obtained two
dimethylanthracenes, viz. one which melted at 218-219°
and gave a quinone which melted at 170°, and one which
melted at 71° and gave a quinone which melted at 157-158°.
It is rather difficult to see how two dimethylanthracenes
could be produced from benzyl mesit3'lene unless an impure
sample of mesitylene were used, or unless a wandering of
the methyl groups takes place either during the passage of
the benzyl mesitylene through the red-hot tube, or, more
probably, during the preparation of the benzyl compound.
Louise's quinone, which melts at 170°, is not identical with
Lavaux's i.6-dimethylanthraquiuone (m.p. 169°), as the
* Limpricht, A. 312, 99, gives the melting point as 200", and Heller, B.
43, 2891, as 205-206°.
* B. 44, 2002 ; O.R.P. 2.(1,624.
« J. pr. [2] 35, 487 : 41, 12. => A. ch. [6] 187.
3
34 ANTHRACENE AND ANTHRAQUINONE
latter investigator has done a mixed melting point deter-
mination. Tlie very low melting point of the second
isomer would be in agreement with the assumption that it
was the dihydro compound, but Louise's analysis is not in
agreement with this explanation. The low melting point
might, of course, also be explained by the presence of the
methyl group in the a-position (cf. a-meth34anthracene,
p. 26), and at first sight it would seem possible that the
compound was the unknown ' i .4-dimethylanthracene.
This, however, can hardly be the case, as i .4-dimethylanthra-
quinone 1 melts at 118°. Louise considers that the hydro-
carbon which melts at 71° is really 1.3-dimethylanthracene,
as he has prepared 2 1.3-dimethylanthraquinone from
benzoyl mesitylenic acid, and finds that it melts at 157-
158°.*
Totally different results have been described by other
investigators. Gresly ^ distilled xyloylbenzoic acid with
zinc dust and obtained what he described as 1.3-dimethyl-
anthracene melting at 202-203°, but did not oxidise it to
the quinone. He obtained the corresponding quinone,
however, by loss of water from the xyloylbenzoic acid, and
gives its melting point as 180°. Birukoff * condensed
2.4-dimethyl benzoic acid with gallic acid in the presence of
sulphuric acid and obtained i.3-dimeth3d-6.7.8-trihydroxy-
anthraquinone. This by distillation with zinc dust gave a
dimethylanthracene which melted at 220-226°, and which
on oxidation gave a quinone melting at 112°. Birukoff
obtained his dimethyl benzoic acid from commercial
xylidine, and as the condensation with gallic acid gave a
yield of only two per cent, it is not improbable that the
reaction was taking a different course to that intended.
Kraemer and Spilker ■'"' condensed st3'rene with un-
symmetrical trimethyl benzene (pseudocumene ?), and by
1 Gresly. A. 234, 240.
2 A. ch. [6] 6, 233.
* Elbs, J. pr. [2] 33, 319, obtained 1.3-dimethylanthraquinone from
m-xylene and phthalic anhydride, and gives the m.p. as 162°. B. A. S. F.
in D.R.P. 200,335 refer to 1.3-dimethylanthraquinone, m.p. 159-163°.
« A. 234, 246.
* B. 20, 870. » B. 23, 3169 ; 3260.
ANTHRACENE AND ITS HOMOLOGUES 35
passing the product through a red-hot tube obtained a
dimethylanthracene. This, unfortunately, cannot be com-
pared with the dimethylanthracenes described by other in-
vestigators, as, owing to a misprint, Kraemer and wSpHker give
the melting point of their product as 298 uncor. = 235° cor.
Tremethylanthracenes. — Excluding ms - compounds
there are sixteen possible trimethylanthracenes. Of these
very few have been prepared, and in view of the very con-
tradictor}^ results obtained in the case of the dimethyl
compounds the structures allotted to the trimethyl com-
pounds can only be accepted with some reserve pending
further investigation. As the trimethylanthracenes are
of very little interest they will be treated very briefly.
Gresly 1 by distilling 2.4.5-trimetli3dbenzoyl benzoic
acid with zinc dust obtained 1.2.4-trimethylanthracene, m.p.
243°, the quinone melting at 161° ; and Elbs - has repeated
this work with almost exactly similar results, his melting
points being 244° and 162°. The same compounds have
also been obtained by Wende ^ by condensing durylic acid
with gallic acid by means of sulphuric acid and then dis-
tilling the trimeth3'ltrihydroxy anthraquinone with zinc
dust. By this means he obtained 1.2.4-trimethylanthracene
and from it the quinone by oxidation. He gives the melting
points as 236° and 157-160°.
Elbs 4 has obtained 1.3.6- and i.4.7-trimeth3danthracenes
by heating 2.^.2'.^'- and 2.5.2'.5'-tetrameth3'lbenzophenone.
He finds that the}^ melt at 222° and 227°, the corresponding
quinones melting at 190° and 184°.
In the case of the trimethylanthracenes it is noticeable
that methyl groups in the a-position do not seem to cause
any fall in the melting point. This phenomenon cannot at
present be compared with the behaviour of the corresponding
naphthalene derivatives, as very few trimethylnaphthalenes
have been described, but 1.4-dimethylnaphthalene is a
liquid and melts at —18°.
Tetramethylanthracenes. — Friedel and Crafts ^ by
I a. 234, 2^8. 2 J.,pr. [2] 41, 121. ^ B. 20, 867.
* J. pr. [2] 35, 482 ; 41, 141 ; B. 19, 408. » a. ch. [6] 11, 2O7.
36 ANTHRACENE AND ANTHRAQUINONE
treating w-xylene with methylene chloride and aluminium
chloride obtained a tetramethylanthracene which melted
at 162-163°, and which on oxidation gave a quinone which
melted at 204-206°. From pseudocumene and methylene
chloride they obtained the same substance and also a
tetramethylanthracene melting at 290°, and a hexamethyl-
anthracene melting at 220°. Friedel and Craft's first com-
pound (m.p. 162-163°) is probably identical with the 1.3.5.7-
tetramethylanthracene obtained by Seer 1 by the action
of aluminium chloride on the cliloride of mesitylenic acid :
COCl
cioc
and subsequent reduction by distillation with zinc dust.
Seer also obtained the same tetramethyl compound directly
from xylyl mesityl ketone by the action of heat. He
agrees with Friedel and Crafts as regards the melting point
of the hydrocarbon (163-164°), but gives the melting point
of the quinone as 235°.
Anschiitz,2 by heating w-xylene with acetylene tetra-
bromide and aluminium chloride, or by heating xylene in a
sealed tube with aluminium chloride, obtained a tetramethyl
compound which melted rather indefinitely at 280°, and
gave a quinone melting at 228-230°. Dewar and Jones ^
by heating m-xylene with nickel carbonyl obtained a
tetramethyl anthracene which melted at 280°, and gave a
quinone melting at 228-230°. This they conclude is
i.3.5.7-tetrameth3danthracene, on the ground that the
action of nickel carbonyl in the cold leads to 2.4-dimethyl-
benzaldehyde. On their own showing, however, it is very
improbable that the aldehyde is formed as an intermediate
product when anthracene compounds are produced, as
although benzene and nickel carbonyl gives anthracene,
they were unable to obtain anthracene from benzaldehyde.
Seer * has repeated the work of Friedel and Crafts, and
1 M. 33, 33. 2 A. 235, 173. » Soc. 85, 21G. * M. 33, 33.
ANTHRACENE AND ITS HOMOLOGUES 37
by a slight variation in the experimental conditions lias
obtained a very small quantity of a tetramethylanthracene
which melted at 281°. He concludes that the product
obtained by Friedel and Crafts consisted mainly of 1.3.5.7-
tetramethylanthracene (m.p. 162-163°) with a little 1.3.6.8-
tetramethylanthracene (m.p. 281°). The products obtained
by Dewar and Jones and by Anschiitz are probably also
1 .3.6,8-tetrametliylanthracene.
Other Anthracene Homoi^ogues. — There seem to be
no records of attempts to prepare homologous anthracenes
by the Friedel and Crafts' reaction, but Lippmann, Pollok,
and Fritsch,! by the prolonged boiling of anthracene with
benzyl cliloride in carbon bisulphide solution in the presence
of zinc dust, claim to have obtained mono- and di-benzyl
anthracenes. The former of these was also obtained by
Bach 2 by benzylating anthraquinol. The monobenzyl
compound melts at 119° and the dibenzyl compound at
239-240°. Both on oxidation give anthraquinone, so that
the benz^d groups must be attached to the w^s-carbon atoms.
The dibenz5'l compound gives a monobrom substitution
product, which when treated with basic substances such
as potassium acetate, potassium carbonate, pyridine, or
quinoline, loses hydrobromic acid and passes into two new
compounds. These Lippmann regards as dibenzalanthracene
and 6ts-dibenzalanthracene and assigns them the formula? :
C CIiC6H5 C — CHCgH5 — CHCgH.5 — C
CfiHZ >C6H4 and CgHZ | >C6H4 CgHZ 1 >C6H4
C CHCgHs C — CHCgHg — CHCgHg — C
Dibenzalanthracene, 6Js-Dibenzalanthracene,
m.p. 236°. m.p. 184°.
It is surprising that the bimolecular compound should
melt at such a much lower temperature than the mono-
molecular form, and in any case the formulae can only be
accepted with some reserve pending further confirmation.
Other ;«s-homologues of anthracene have also been
described, but they are invariably obtained by indirect
1 M. 23. 672 ; 25, 793'. » B. 23, 1570.
38 ANTHRACENE AND ANTHRAQUINONE
methods. Thus, Jiingermann i obtained wis-diamyl anthra-
cene by reducing the product obtained by the action of
amyl-magnesium bromide on amylh3^droxy anthrone :
HO CgHn CgHn
CO C c
C6H4< >C6H4 -^ CeH/ >C6H4 -» CeH/NCeH^
C C C
HO CsHn HO Crjlu CgHn
It melts at 132-137°. Other homologous anthracenes have
been obtained by similar methods, and will be referred to
elsewhere. Wis-Diphen3dantliracene has been obtained by
Simonis and Remmert 2 by treating o-brombenzyltriphenyl
carbinol with concentrated sulphuric acid :
Ph Ph
H^l^/Br •.
C6H4<( CgHs -> C6H4<(|y^6H4
nOH V
Ph Ph
and by a similar reaction the same investigators have pre-
pared i.2-dimethoxy-w/s-diplienylanthracene.
1 B. 38, 2868. - B. 48, 208.
CHAPTER III
SIMPLE DERIVATIVES OF ANTHRA-
CENE
Hydroanthracenes
A CONSIDERABLE uumber of hydroaiitliraceiics have been
described, although none of them are of any particular
interest. They arc almost invariably obtained by the
reduction of the anthracenes, although some of the lower
members can be conveniently obtained by the partial
dehydrogenation of the higher members, a method chiefly
developed by Godchot.i
The reduction of anthracene and its derivatives can be
effected by various reducing agents. Liebermann 2 and
his co-workers made extensive use of hydriodic acid and
red phosphorus, and by varying the concentration of the
acid and the temperature and time of heating were able to
obtain di-, tetra- and hexahydroanthracenes. More recently
O. Fischer and Ziegler 3 have found that i-methyl-4-chlor-
anthracene can be reduced to a dihydro compound by
simply passing a stream of hydriodic acid gas through its
boiling solution in glacial acetic acid. The ease with which
this reduction takes place is probably exceptional, as
O. Fischer and Reinkober * have found that ^-method-
anthracene is quite unaffected by treatment in this wa3^
Sodium amalgam ^ in conjunction with ethjd or amyl
alcohol has been used by several investigators, and, like
1 A. ch. [8] 12, 468 ; Bl. [4] 1, 701 ; C. r. 139, 605 ; 141. 1029 ; 142,
1202.
* A. Suppl. VII., 257 ; 212, 5 ; B. 1, 187 ; 9, 1202,
' J.pr. [2]86, 289.
* J. pr. [2] 92, 51.
5 Bamberger and Lodter, B. 20, 3076 ; Padova, C. r. 148, 290 ; Wie'and,
B. 45, 492.
39
40 ANTHRACENE AND ANTHRAQUINONE
hydriodic acid, seems to produce hydroantliracenes in which
the ws-carbon atoms are affected, as the reduction products
are non-fluorescent, do not form picrates, and, so far as an}'
information is available, do not polymerise to bimolecular
compounds when their solutions are exposed to direct
sunlight.
Catalytic reduction of anthracene by hydrogen in the
presence of finely divided nickel at 200-250° has been studied
by Godchot 1 and by Ipatjew, Jacowlew and Rakitin,^
and often leads to products which differ from those obtained
by hydriodic acid or by sodium amalgam. Thus the tetra-
hydroanthracene obtained by means of h^'-driodic acid melts
at 101-103°, is not fluorescent, and gives no picrate, whereas
that obtained by reduction by h3^drogenation in the presence
of nickel melts at 89°, shows a blue fluorescence, and gives
a picrate.
The hydroanthracenes as a rule are colourless soHds
which melt below 100°, and which are more or less fully
dehydrogenated by passing through a red-hot tube. They
reduce sulphuric acid to sulphur dioxide, although Godchot 3
states that octahydroanthracene gives a sulphonic acid in
which sulphonic acid group is attached to one of the
/>/s-carbon atoms.
Of the individual members, only one dihydroanthracene,
C14H12, is known. This melts at 108-5°, and is dehydro-
genated when shaken in benzene solution with finely divided
palladium. 4 Two tetrahydroanthracenes, C14H14, are
known, which melt at 101-103° and at 89°. The former
is obtained by means of hydriodic acid, and the latter by
catah^tic reduction. As the latter is fluorescent and gives
a picrate the ?HS-carbon atoms are probably intact. Two
hexahydro compounds, C14H16, have been described. One
is obtained by reduction with hydriodic acid and melts at
63°, and boils at 290°. The other is obtained by loss of
water from octahydroanthranol ^ and melts at 66*5°, and
1 A. ch. [8] 12, 468 ; Bl. [4] 1, 701 ; C. r. 139, 605 ; 141, 1029 ; 142,
1 202.
2 B. 40. 1289 ; 41, 997. 3 Bl. [4] 1, 701. * Wieland, B. 45 492.
5 Godchot, C. r. 142, 1203 ; A. Ch. [S] 12, 468.
SIMPLE DERIVATIVES OF ANTHRACENE 41
boils at 303-306°. The method of formation renders it
almost certain that the ;«s-carbon atoms are intact, and
this is supported by the blue fluorescence of the compound.
An octahydroanthracene, C14H18, has been prepared by
catalytic reduction. It melts at 71°, gives a picrate, and
shows a green fluorescence. Hence, in all probability the
wzs-carbon atoms are intact, although Godchot 1 brings
forward some arguments to the contrary, e.g. it gives hexa-
hydroanthrone on oxidation Nvith chromic acid. Deka-
hydroanthracene, C14H20, melts at y;^° ; dodekahydro-
anthracene, C14H22, boils at 140-150° at 15 mm. ; and
perhydroanthracene, C14H24, melts at 88° and boils at
270°. None of them form picrates, and none of them are
fluorescent.
Halogen Compounds
The action of chlorine and bromine on anthracene has
been studied by many investigators, but often with contra-
dictory results. The reactions which take place are some-
what compUcated, as their course is very largely dependent
on the solvent used and on the temperature at which the
experiment is carried out, but as a rule the first compound
formed is an addition compound which readily splits out
halogen acid to give halogen anthracenes, in which one or
both of the nieso- hydrogen atoms have been substituted.
The resulting halogen anthracenes then again form addition
compounds with more halogen atoms, and these again lose
halogen acid, substitution now taking place in the benzene
rings. The case is complicated by the fact that in addition
to place isomerism the addition compounds also exliibit
geometrical isomerism of the cis-trans type.
Diel ~ by passing chlorine gas over anthracene, first at
the ordinary temperature and then at 230°, obtained a
dichloranthracene tetrachloride, C14H8CI2.CI4. This melted
with decomposition at 141-145°, and when treated with
alcoholic caustic soda passed into a tetrachlor anthracene,
m.p. 220°. By treating anthracene at 200° with chlorine
1 Bl. f4] 1, 121. * B. 11, 173.
42 ANTHRACENE AND ANTHRAQUINONE
in the presence of antimony pentachloride, he obtained hexa-,
hepta-, and octa-chlor anthracene, the former passing into
tetrachloranthraquinone on oxidation. The passage of a
hexachlor anthracene into a tetrachloranthraquinone shows
that two of the chlorine atoms are attached to the wis-carbon
atoms, and, as the tetrachloranthraquinone is quite different
from that sj^nthesised from tetrachlor phthalic acid, the
remaining four chlorine atoms must be heteronuclear.
Their exact positions have not beea determined, but Diel's
hexachloranthracene was probably a mixture, as he gives the
melting point as 320-330°. Meyer and Zahn 1 have shown
that ;»s-dichloranthracene tetrachloride when heated de-
composes into 2.3.9. lo-tetracliloranthracene, so that the
chief constituent of Diel's hexachlor compound was pro-
bably 2.3.6.7.9. lo-hexachloranthracene.
Diel also studied the action of bromine on anthracene and
found that when heated to 120° in the presence of a trace
of iodine a hexabromanthracene was formed, whereas at
200° he obtained a mixture of heptabrom- and octabrom-
anthracene. The hexabrom- and the heptabrom- compounds
on oxidation gave respectively tetra- and penta-brom-
anthraquinone. Anderson 2 also studied the action of bromine
vapour on anthracene, and working at the ordinary tempe-
rature he obtained what he thought was an addition product
(anthracene hexabromide, Ci4HioBr6) ; but Graebe and
Liebermann ^ have proved it to be dibromanthracene
tetrabromide. When heated alone it gives tribromanthra-
cene, and when treated with alcoholic potash tetrabrom-
anthracene. Hammerschlag ^ found that the final product
of the action of bromine vapour on anthracene at the ordinar}-
temperature was tetrabromanthracene tetrabromide. This
on heating alone to 180° lost one molecule of hydrobromic
acid and two atoms of bromine, and yielded a penta-
brom anthracene giving a tribromanthraquinone on oxida-
tion. On treatment with alcoholic caustic soda, on the
other hand, it lost tv/o molecules of hydrobromic acid and
1 Page 44. 2 A. 122, 304.
» A. Suppl. VII, 304. * B. 10, 1212.
SIMPLE DERIVATIVES OF ANTHRACENE 43
passed into hexabromanthracene, from which tetrabrom-
anthraquinone was obtained by oxidation.
Very similar reactions take place when wis-dichloranthra-
cene is treated with bromine vapour, 1 addition and substitu-
tion products being formed, which when heated alone lose
both bromine and hj-drobromic acid, whereas only hydro-
broniic acid is lost by treatment with alcoholic caustic alkali.
More definite information as to the positions of the
bromine atoms has been obtained by Kauffler and Imhoff.2
They treated w/s-dibromanthracene with bromine vapour
and obtained a dibromanthracene tetrabromide. From
this they obtained a tribromanthracene, m.p. 171°, which
on oxidation gave 2-bromanthraquinone, and a tetrabrom-
anthraccne, m.p. 20)8-300°, which on oxidation gave a di-
bromanthraquinone (m.p. 289-290°), which was identical
with the 2.6-dibromanthraquinone obtained from the
corresponding diaminoanthraquinone by the diazo reaction.
When anthracene is treated with chlorine or bromine in
carbon bisulphide solution ^ the first action is the formation
of a very unstable addition compound, anthracene dilialide,
wliich then splits off halogen acid and yields ;;is-halogen
anthracene, the second wzs-hydrogen atom being replaced in
the same way.^ The action of chlorine on anthracene in
chloroform and benzene solution was first studied by
Schwazer,^ who obtained first ;;is-dichloranthracene, which
by the further action of chlorine passed into dichloranthra-
cene dichloride. This on heating did not split off free
halogen, but at 170° lost one molecule of hydrocliloric acid
and gave trichloranthracene. ]\Iore recently Meister Lucius
and Briining 6 have re-examined the action of chlorine on
anthracene in chloroform and in benzene solution. They
state that Schwazer's dicliloranthracene dichloride is really
1 Schwazer, B. 10, 376; Hammerschlag, B. 19, 1106.
* B. 37, 4708.
' Perkin, Bl. [i] 27, 464 ; Chem. News, 34, 145 ; Graebe and Lieber-
mann, A. Suppl. VII. 257; B. 1, 186; Anderson, A. 122, 306; O. Fischer,
and Ziegler, J. pr. [2] 86, 291.
* Meyer and Zahn, A. 396, 166.
5 B. 10, 376. Cf. Radulescu, C. 190S (2), 1032.
« D.R.P. 283,106.
44 ANTHRACENE AND ANTHRAQUINONE
a mixture of anthraquinone tetracliloride (m.p. i8o°) and
dichloranthracene dichloride (m.p. 139-140°) :
CI CI
\/ CI
c c
C6H4<(' ^C6H4 C6H4<' ^C6H4Cl2
C C
CI
CI CI
Thej' find that low temperatures and the use of cliloro-
form as a solvent favours the formation of the former;
whereas higher temperatures, certain carriers, such as
phosphorus pentachloride, and the use of benzene as a
solvent, favour the formation of the latter. By chlori-
nating anthracene or ws-dichloranthracene in chloroform
suspension at 2°, or in tetrachlorethane at —10° to —15°, they
obtain pure anthraquinone tetrachloride, whereas almost
pure dichloranthracene dichloride is obtained by clilori-
nating in benzene at 60°. In a later patent 1 they claim
that clilorination in chloroform in the presence of iodine
or in sulphuryl chloride leads to dichloranthracene hexa-
chloride and dichloranthracene octachloride.
Hammerschlag,2 by treating anthracene in benzene
solution with chlorine, obtained a dichloranthracene tetra-
chloride which yielded a tetrachloranthracene when treated
with alcoholic potash. This latter on oxidation gave a
dichloranthraquinone which melted at 205°.
Meyer and Zahn ^ have repeated Hammerschlag's work,
and state that Hammersclilag's tetrachloride was impure.
They were unable to obtain any isomeric forms of dichlor-
anthracene tetrachloride, and state that their product is
identical with that obtained by Liebermann and lyinden-
baum 4 by treating " nitrosoanthrone " with phosphorus
pentachloride. On heating it does not split off free halogen
like the corresponding bromo- compound (see below), but
parts with two molecules of hydrochloric acid, and forms
1 D.R.P. 284,790. 2 B. 19, 1106. 3 A. 396. 166. « B. 13, 158S.
SIMPLE DERIVATIVES OF ANTHRACENE 45
tetracliloranthracene. An isomeric tetrachloranthracene is
also formed by treatment with alcoholic caustic potash.
The tetrachloranthracene formed by the action of heat must
be 2.3.9.10-tetrachloranthracene, as on oxidation it yields
2.3-dichloranthraquinone, the structure of which is known
by its synthesis from 3.4-diclilorphthalic acid.i The iso-
meric tetrachloranthracene obtained by the action of
alcoholic caustic potash must be 1.3.9.10-tetrachloranthra-
cene, as on oxidation it gives a dicliloranthraquinone which
is not identical with 1.2-dicliloranthraquinone obtained
from 3.4-dichlorphtlialic acid, nor with 1.4-dichloranthra-
quinone obtained from 3.6-dichlorphthalic acid. 2
CI CI ^^ 01
KOH >r Heat
<■ CcHK >C6H4Cl4
—CI
CI (il CI
I— CI
-CI
B}^ heating anthracene or ^HS-dibromanthracene in
cliloroform solution with bromine, Meyer and Zahn 3 obtained
a dibromanthracene tetrabromide. This when heated and
when treated with alcoholic caustic potash gives the same
tribrom- and tetrabrom-anthracene as Graebe and Lieber-
mann * obtained from their tetrabromide, but Meyer and
Zahn's bromide (a-compound) differs widely in its physical
properties from Graebe and Liebermann's product (j3-
compound). Thus Meyer and Zahn's tetrabromide melts
at 134°. whereas Graebe and Liebermann's product melts
at 182°. The substances differ also in their crystalline
form and solubility. The most marked difference, however,
is in their behaviour towards light, for whereas Graebe and
Liebermann's compound is unaffected, Meyer and Zahn's
compound loses four atoms of bromine and passes into ms-
dibromanthracene. The reaction, however, takes place only
in benzene solution or, ver^' slowly, in chloroform solution.
1 Ullmann, A. 381, 27. " Ullmann, A., 381. n, 26.
« A. 398, t60. « A. Suppl. VII., 304.
46 ANTHRACENE AND ANTHRAQUINONE
Me^'er and Zahn have also obtained a dichloranthracene
tetrabromide which is sensitive to light and which is iso-
meric with the compound obtained by Schwazer i and by
Hammerschlag.2 The isomerism is probably geometrical,
Meyer and Zahn's compounds being the cis- form and Graebe
and Liebermann's, Schwazer's and Hammerschlag's being
trans- forms. This is in agreement with the great ease with
which a- compounds lose bromine, and also with the general
rule that the trans- isomer has the higher melting point. 3
In connection with the above it is interesting to notice
that Radulescu,^ by heating anthraquinone with a large
excess of phosphorus pentachloride, has obtained a hexachlor
compound to which he ascribes the formula :
CI CI
.H
CI
,H
^Cl
CI CI
He states that it exists in two stereoisomeric forms, one
melting with decomposition at 185°, and one melting with
decomposition at 149°. Both on heating give the same
trichloranthracene.
Kurt Me^-er and Zahn ^ have also studied the chlorina-
tion of anthracene in other solvents. They find that in
water or dilute acetic acid the action of chlorine at tempe-
ratures below 25° is chiefly an oxidising action, hydroxy-
anthrone (anthraquinol) and anthraquinone being formed,
whereas at higher temperatures ws-dicliloranthracene is
produced. In alcoholic solution the action is very similar,
alkox3^antlirone and anthraquinone being produced in
dilute solutions, whereas from concentrated solutions ms-
1 B. 10, 376. 2 B. 19 1 106.
' Stewart, " Stereochemistrv " (1919), p. 107.
* Bull. Soc. Stii. Buciiresci, 17, 29; C. 1908 (2), 1032.
'- A. 396, 166.
SIMPLE DERIVATIVES OF ANTHRACENE 47
dicliloranthracene can be obtained. Ether has much the
same effect as carbon bisulphide, anthracene dichloride and
mono- and di-cliloranthracene being produced. When
glacial acetic acid is used as a solvent they find that the chief
products are anthraquinone and dichloranthracene tetra-
chloride.
Liebermann 1 and Schilling 2 have prepared numerous
chloranthracenes by reducing the corresponding chloranthra-
quinones with zinc dust and ammonia. ^ They firid that,
as in the case of the cliloranthraquinones the a-chloranthra-
cenes melt at considerabh' lower temperatures than the
corresponding ^- compounds.
Liebermann finds that the a-chloranthracenes readily
give addition products with chlorine, whereas the j3- com-
pounds only give them with difficulty, as the chlorine atom
in the j3-position seems to facilitate the substitution of the
;«s-hydrogen atoms. The ease with which a-chlor- com-
pounds form addition products is borne out by O. Fischer and
Ziegler,4 who obtained a dibromide from i-chlor-4-methyl
anthracene by treating it with bromine in carbon bisulphide
solution :
H Br
C
Y ^ci
H Br
According to a patent ^ by Meister, Lucius, and Briining,
although the ;;is-dicliloranthracene polyhalides lose halogen
acid when treated with alcoholic caustic potash, they
do not do so when treated with aqueous alkali unless
benzyl sulphanilic acid is present. By means of this re-
agent they obtain pentachlor- and hexachloranthracene, and
suggest their use as yellow pigments.
» B. 47. loii. * B. 46, 1066.
' Cf. Fischer and Zieeler, J. pr. [2] 86, 291.
* J- pr- [2] 86, 291. "^ * D.R.P. 282,818.
48 ANTHRACENE AND ANTHRAQUINONE
The clilorination of anthracene and of 9.10-dichlor-
anthracene by the action of sulphuryl chloride in the presence
of an inert solvent, e.g. nitrobenzene at 100°, has been in-
vestigated and it is claimed 1 that in both cases the product
is 2.9.10-trichloranthracene.
Very little work has been done on the halogenation of
the homologous anthracenes, but O. Fischer and Reinkober -
have studied the action of bromine and chlorine on j8-methyl-
anthracene. With bromine they claim to have obtained
a pentabrom substitution product, but with chlorine they
obtained impure substances which seemed to be mixtures of
compounds containing five, six, nine, and ten chlorine atoms.
I/ippmann and PoUok 3 endeavoured to chlorinate
anthracene by treating it with sulphur chloride in petroleum
ether solution. They claim that prolonged action leads
to ws-dichloranthracene, but that an intermediate com-
pound, Ci4Hc,S2Cl, is first formed. This, they state, on
oxidation yields anthraquinone and on reduction takes up
two atoms of hydrogen. To the addition compound and its
reduction product they assign the formulae :
CI— S : S CI— SH— SH
I I
c c
^6^4^ /C6H4 »^ C6H4<(' |^C6H4 j
CH CH
but as they state themselves that the addition compound is
iinaffected by boiling alcoholic potash, these formulae can
hardly be accepted pending some independent confirmation.
In addition to methods depending on the direct chlorina-
tion of anthracene, chloroanthracenes can be obtained by
other methods. Graebe and Liebermann * heated anthra-
cene to 200° with a mixture of phosphorus pentachloride and
oxychloride and obtained what appeared to be a mixture of
trichlor- and tetrachloranthracene. More recently this
reaction has been examined by Radulescu,^ who finds that
1 M.L.B., D.R.P. 292,356. 2 J. pr. [2] 92, 49.
' B. 34. 276S. * A. 160, 126.
■• Bull. Soc. Stii. Fincuresci, 17, 29. C. 1908 (2), 1032.
SIMPLE DERIVATIVES OF ANTHRACENE 4(3
the first product is anthraquiiione tetrachloride (red needles,
m.p. 139°, with decomposition), and that this on heating then
passes into dichloranthracene dicliloride and tricliloranthra-
cene :■
CI CI 01 CI
I I
c c
C6H4<^j>C6H, -> CoH^^I^CeH^Cl^ C^Ki<^^C^ll,Cl
C C C
I I
CI CI CI CI
As stated on p. 46, he finds that the use of larger
quantities of phosphorus pentacliloride leads to the forma-
tion of two stereoisomeric licxachlor compounds.
As alread}^ stated (p. 47), lyiebermann, Schilling, and
O. Fischer and Ziegler have prepared cliloroanthracenes by
reducing the corresponding chloroanthraquinones with zinc
dust and ammonia. Kircher 1 endeavoured to obtain
1,2.3.4-tetrachloranthracene in the same way from tetra-
cliloranthraquinone, but during reduction two chlorine atoms
were lost, so that the product was a dichloranthracene.
This, Kircher states, gave a dichloranthraquinone on oxida-
tion which gave alizarin on fusing with caustic potash.
From this he concluded that his reduction product was 1.2-
dicliloranthracene ; but Ullmann and Billig 2 have since
proved it to be 2.3-dicliloranthracene, as its oxidation product
is identical with the dicliloranthraquinone obtained from
4.5-dichlorphthalic acid. Although Kircher was unable to
obtain tetrachloranthracene by the reduction of tetrachlor-
anthraquinone, he succeeded in obtaining it by heating
tetrachlor-o-benzoyl benzoic acid with hydriodic acid to 220°.
Very little is known of the chloranthracene sulphonic
acids, but ;ns-dichlorantliracene-^-suiphonic acid is said to
be obtained by sulphonating ;»s-dichloranthracene with
chlorsulphonic acid, preferably in the presence of some
neutral solvent such as chloroform,^ or with oleum. *
1 A. 238. 346. ^ » A. 381 26.
» B.A S.F.. D.R.P. 260,562. * M.L.B.. D.R.P. 292,590.
4
50 ANTHRACENE AND ANTHRAQVINONE
It has recently been found that 9.10-dichloranthracene,
when treated in the cold with nitric acid and an inert solvent,
forms an addition compound with one molecule of the acid.i
This addition compound apparently has the formula :
HO CI
C
CfiH4< yC^H.^^
NO2 CI
and on heating to 90-95° is decomposed into antiiraquinonc.
The formation of such addition compounds seems to be
connnon to nearly all derivatives of 9.10-dichloranthracene.
Action of Nitric Acid on Anthrackne
The action of nitrous and nitric acids on anthracene was
first studied by Liebermann and his co-workers 2 and by
A. G. Perkin,3 and also at a later date by Dimroth * and
others. The somewhat complicated reactions which take
place have more recently been fully investigated by Meisen-
heimer,5 who has established the constitution of the various
products formed, and also the mechanism of the reactions
which lead to them. He has to a large extent confirmed the
experimental results obtained by Liebennann and A. G.
Perkin, but has shown that their interpretations of the
reactions involved were usualh^ quite erroneous.
Although the exhaustive action of nitrous or nitric acid
on anthracene leads, as would be expected, to anthraquinone,
the moderated action leads to several interesting compounds,
including a mono- and a dinitro- compound in which the
nitro groups are attached to the ins- carbon atoms. Nitro
derivatives of anthracene in which the nitro groups are
attached to benzene nuclei are as yet unknown.
1 M.L.B., D.R.P. 296,019. 2 B. 13, 1584 ; 14, 467.
8 Soc. 59, 644; 61, 866.
• B. 20, 974 : 33, 3548 ; 34, 221. D.R.P. 127,399.
» A. 323,205; 330, 133.
SIMPLE DERIVATIVES OF ANTHRACENE 51
If anthracene is suspended in acetic acid and then
treated with exactly one molecule of nitric acid, the lirst
action is one of addition, g-hydroxy-io-nitro-g.io-dihydro-
anthraccne being obtained (dihydro-nitro-anthranol) :
H OH
C
c
H NO2 ♦
L/ieberniann and Lindemann 1 described this com-
pound as being obtained by the action of nitrous oxides of
anthracene, and named it " salpetersaiireanthracen ; " but
Meiscnheimer failed to obtain it, and pointed out the pro-
bable cause of the error on the part of Liebermann (see p. 52).
The hydrox3'l group in this compound is excessively reactive,
so that in the presence of acetic acid it is at once acetylated,
the acetyl derivative being formed :
H OCOCH,
C
CgHix /C6H4
C
y
H NO2
If this compound is treated with hydrochloric acid the
corresponding cliloride is obtained, whereas with nitrous
acid it yields the nitrite, a somewhat unstable substance
which, like the other esters, yields the methoxy compound
very readily when treated with methyl alcohol.
H ONO H OCH;i
c
C
C6H40C6H,
->
C6H4<^yC6H4
C
c
/\
-
/\
H NOo
H NO2
1 U. 13.
15S4.
52 ANTHRACENE AND ANTHRAQUINONE
It was probably this nitrite that Liebermann and Linde-
mann obtained, as it corresponds very closely in its properties
with their " salpetersaiireanthracen," although differing con-
siderably in composition. Liebermann, however, states in
his paper that the sample aualj-sed was recrystallised from
benzene, and Meisenheimer has pointed out that under these
conditions the nitrite is decomposed into nitroanthrone,
which differs but slightly in composition from the substance
analysed. The formation of the nitrite was no doubt due to
Liebermann having generated his oxides of nitrogen from
arsenious acid and* nitric acid (D=i'33), as under these
conditions it is very difficult to prevent nitric acid being
carried over. If this were the case the nitric acid would
cause the formation of Meisenheimer's acetate, which would
then be precipitated as the nitrite by the nitrous acid.
The formation of dihydronitroanthranol as the primary
product of the action of nitric acid on anthracene is con-
firmed by the study of the action of nitric acid on ethyl
dihydroanthracene, and Meisenheimer has shown that in this
case the first action of the nitric acid is to oxidise the dihydro-
compound to ms-ethy\ anthracene :
H C2H5 C2H5
LfiH,
C«H
6^-»-4
CfiH,
CfiH
Q^^i
H H H
This then adds on nitric acid to form «iS-ethyl-nitro-
anthranol, but the influence of the etlijd group has been to
render the hydroxyl group much less reactive, so that the
free hydroxy- compound is stable and can be isolated.
HO C2H5
C,;H.
CfiHi
H NO2
1
SIMPLE DERIVATIVES OF ANTHRACENE 53
If nitric acid is added to nitroantliranol acetate the nitrate
is not obtained, as the action of an excess of nitric acid causes
a different reaction to take place ; but Meisenheimer was able
to prepare the nitrate by nitrating anthracene in chloroform
solution. If any attempts are made to hydrolyse these
esters, loss of water takes place at once with the formation
of ;«s-nitroanthracene :
H OH H
C C
C C
H NO2 NO2
a perfectly stable substance which melts at 145-146°,
and which distils in vacuo at over 300° without decomposi-
tion. On reduction it gives the corresponding amino com-
pound. 1 The nitro- compound can also be obtained directly
by the nitration of anthracene in acetic acid solution in the
presence of acetic anhydride, but it is more easily obtained
by the hydrolysis of the acetate.
Perkin 2 nitrated anthracene in the presence of methyl
alcohol, and obtained a compound which he named anthra-
cene methyl nitrate. Other alcohols, such as ethyl alcohol,
propyl alcohol, and iso-butyl alcohol, gave similar products,
and these are luidoubtedly formed by the action of the
alcohol on the nitroanthranol nitrate or nitrite first formed :
H 0X0 H OCH3
\/ \/
C C
^e^K /C6H4 -> CeHiv /CeH^i
H NOo H XO2
They are very readil}^ hydrolysed by alkali and simulta-
neously lose water, the product being ;»s-nitroanthracene.
If anthracene in glacial acetic acid is treated with zh
>■ D.R.P. 127,390. - - Soc. 59, 648 ; 61, S<.r..
54 ANTHRACENE AND ANTHRAQUINONE
molecules of nitric acid instead of with one molecule, the
reaction takes a somewhat different course and two unstable
substances are formed. One of these is soluble in hot alkali,
and Meisenheimer has identified it as nitroanthrone ; a
compound first obtained by Perkin i by the action of nitric
acid on anthracene in the presence of iso-hntyl alcohol
under certain conditions, and more lately and in good yield
by Kurt Meyer 2 by nitrating anthrone in acetic acid :
O
II
c
C
H NO2
The other substance is insoluble in alkali, but is left behind
as a decomposition product. Meisenheimer obtained it in the
pure state by fractional precipitation from chloroform by the
addition of petroleum ether, and identified it as trinitro-
dihydroanthracene :
H NO2
C
c
NOo NOo
It might be argued that this compound was a nitrous
ester and not a true trinitro- compound. If it were an ester
one would expect it to react with methyl alcohol in the same
way as nitroanthranol nitrite (p. 51) ; but methyl alcohol has
no effect on it. With alkali it splits off one.nitro group
and at the same time loses a molecule of water, the product
being wjs-dinitroanthracene. This is a stable compound
melting at 294°, which has also been obtained by Perkin, ^
together with the mononitro compound, by nitrating anthra-
cene in nitrobenzene solution. He did not recognise it,
1 Soc. 61, 868. 2 A. 396, 150. ^ goc. 59, 637.
SIMPLE DERIVATIVES OF ANTHRACENE 55
however, as dinitroanthracene, and appears to have satisfied
himself with identifying it as being identical with the
" nitrosonitroanthracene " previously obtained by Lieber-
mann and Landshoff.i
The composition of the above trinitro- compound
receives support from the investigation of the action of nitric
acid on ethyl-dih^'droanthracene carried out by Meisen-
heimer. As stated previously, the first product formed is
ethyl nitroanthranol :
HO C2H5
\/
C
C
H NO2
This forms stable alkali salts from which it is reprecipitated
as such by acetic acid, although mineral acids cause an im-
mediate loss of water and formation of ethyl nitroanthracene :
C2H5
I
C
C6H4<( j /C6H4
N02
a stable compound melting at 135°.
The further action of nitric acid on ethyl anthracene
takes two directions. In the first, oxidation takes place
with the production of ethyl nitroanthrone :
O
II
c
C6H4<^^CcH,
C
/\
C2H5 NO2
1 B. 14, 470.
56 ANTHRACENE AND ANTHRAQUINONE
while in the second place the nitrous acid thus generated
combines with the ethyl nitroanthracene formed simultane-
ously to produce trinitrodihydroethylanthracene :
C2H5 NO2
Cc^4\ /CfiH
NO2 NO2
This corresponds exactl}^ to the trinitro compound obtained
from anthracene. It cannot be a nitrous ester as it is stable
towards alkali, and can in fact be warmed with 30 per cent,
methyl alcoholic caustic potash without undergoing decompo-
sition.
Liebermann and LandshofE 1 nitrated dih5^droanthracene
and obtained a substance which the}' named h^-droanthracene
nitrite, and to which the}' ascribed the formula :
H H H H
C
C6H4< >C6H4 or CeH^/^CeH,
C C
ONO ONO ONO NO2
It seemed ver}^ improbable that dih^-droanthracene would
react differently towards nitric acid than anthracene itself,
especially as ethyl dih3'droanthracene reacts in the same way
as anthracene, and Meisenheimer therefore re-examined the
point and found that Liebermann's and Landshoff's " hydro-
anthracene nitrite" is really nothing but a mixture of
nitroanthrone and trinitrodih3-droanthracene.
It was mentioned on p. 51 that lyiebermann and
Lindemann - studied the action of nitrous acid on anthracene
and obtained a substance which they named " salpetersaure-
anthracen." Under somewhat different conditions and by
i^B. 14, 467. ^ B. 13. 1585 ; 14, 4S4 ; 33, 3547-
SIMPLE DERIVATIVES OE ANTHRACENE 57
using nitrous oxides carefully freed from nitric acid, they
obtained a different compound, which they named " unter-
salpetersaureanthracen." This has also been re-investigated
by Meisenheimer, who confirms Liebermann and Linde-
mann's results, but finds the compound is most readily
obtained if the nitrogen dioxide is generated by heating lead
nitrate. He considers that the compound is sj/m-dinitro-
diliydroanthracene, and that it is formed by the addition
of two (single) molecules of nitrogen dioxide :
H NO2
C
C6H4\ yC6H4
c
H NO2
With reference to this it should be noted that a similar
reaction takes place between stilbene and nitrogen dioxide : 1
H H
CgHsCH^CHCeHs -> CgHsC CCeH,,
I I
NO2 NO2
The action of alkali on the various nitration products of
anthracene is very interesting.
As stated on p. 53, the esters and ethers of nitro-
anthranol when treated with alkali pass into ws-nitro-
anthracene. This, by the further action of alkali, passes into
anthraquinone-monoxime,2 a compound which was obtained
by Perkin b3^ this method, but which, curiously enough, he
did not identify, although he prepared an acetj'l derivative : ^
H OH O
I I II
c c c
C6H4<(!^C6H4 -> CcH4<(^\c6H4 or C6H4<^\CoH4
C C C
I I II
NO2 .^ NO NOH
i B. 34, 3540. « A. 328, 232. » sqc. 59, 644 ; B. 16, 2179.
58 ANTHRACENE AND ANTHRAQUINONE
The change is obviously due to the wandering of an
oxygen atom, and although it seems curious at first sight,
it is by no means unique. Thus i-nitro-naphthalene-
3.8-disulphonic acid when boiled with aqueous caustic soda
passes into i.4-nitrosonaphthol-3.8-disulphonic acid : 1
S NO.
S NO
— S
OH
and dinitro-, trinitro-, and tetranitronaphthalene also give
nitronitroso- compounds under the influence of alkali. 2
sjym-Trinitrobenzene and sywi-trinitrotoluene behave in a
somewhat similar manner.
Meisenheimer ^ has made a very careful study of the
action of potassium methoxide on ws-nitroanthracene.
He finds that the first action is one of addition, the product
being :
H OCH3
C6H4<^^C6H4
C
N^^
\0K
By the action of potassium hypobromite on this compound
he obtained :
H OCH3
CcH^^^^^CeH^
C
» B. 28, 1535-
Br NO2
2 B. 32, 2S76, 3528 ; D.R.P. 127.295.
8 A. 323, 205.
SIMPLE DERIVATIVES OF ANTHRACENE 50
which by loss of hydrobromic acid gave methoxynitro-
anthracene. By treating this with potassium methoxidc
and then with sodium hypobromite he got :
CHoO OCH,
CH3O OCH3
c
C
and
11^0
N
\o
K
c
Br NO2
This last compound he oxidised to dimethoxyanthrone.
On treating it with mineral acids, however, it was instan-
taneously h3'drolysed to anthraquinone oxime.
Trinitrodihydroanthracene under the influence of alkali
loses a nitro group and passes quantitatively into dinitro-
anthracene :
H NO2
C
CeH^^CeH., ->
C
NO2 NO2
H NO2
\/
C
C6H4<r y>C6H4
c
HO NO2
-> C6H4<^
NO2
I
c
C6H4
c
I
N02
and dinitrodihj'droanthracene by a very similar reaction
gives mononitroanthracene :
r H OH 1
H NO2
\/
C
C6H4<^CcH4
C
/\
H NO2
<-'6H4'C '>C6H4
c
H NOo
H
I
C
-^ C6H4<;^;>C6H4
c
I
N02
Nitroanthrone dissolves in alkali to form a coloured
solution from which it is reprecipitated by acetic acid in
6o ANTHRACENE AND ANTHRAQUINONE
the original colourless form. If, however, a mineral acid is
used to liberate it from its salts it can be obtained in a less
stable red form. This can be preserved in a vacuum in the
dark for some months, but under the action of light slowly
reverts to the colourless form. These Meisenheimer con-
sidered corresponded to the normal and aci- forms :
O O
c
c
C
C
H NO2
11^0
Colourless.
Red.
and Hantzsch 1 claims to have isolated a third, yellow,
variety which is very unstable and rapidly passes into the
red form. He ascribes to it the formula :
OH
\^4\ i /C6H4
NO2
This compound was described by Perkin,^ but Meisen-
heimer 3 has shown that Perkin's substance was really pure
nitroanthrone (colourless variety) .
Kurt Meyer 4 has re-examined the subject, but has failed
to obtain the labile compound described by Hantzsch. He
has, however, confirmed the existence of the two isomerides
described by Meisenheimer, and although he agrees with the
anthrone formula for the colourless variety, he considers
that Meisenheimer' s red unstable substance is not the aci-
(nitrolic) form, but is nitroanthranol :
1 B. 42. 121C. - See. 61, 868.
8 A. 330, 153. * A. 396, 137.
SIMPLE DERIVATIVES OF ANTHRACENE 6i
O OH
II I
c c
C6H4<^NC6H4 C6h/J^CoH4
c c
H NO2 NO2
Colourless. Red.
The latter compound should give an acetyl derivative,
and although Meisenheimer failed to obtain one, Meyer has
been able to do so by treating it with acetyl chloride in
pyridine solution. He has also obtained a benzoyl derivative
by the same means.
It might be argued that the latter anthranol formula
represents a fluorescent compound, whereas nitroanthranol
shows no fluorescence. The nitro- group, however, has a
great influence in hindering fluorescence, so that this objec-
tion does not hold good, and it is fairly certain that Meyer's
interpretation of the isomerism is the correct one.
The question of anthrone-anthranol isomerism will be
found more fully discussed on p. 119.
SuLPHONic Acids
The anthracene sulphonic acids can be obtained either
by sulphonating anthracene or by the reduction of the
corresponding anthraquinone sulphonic acid.
As regards the sulphonation of anthracene, the literature
is very confusing, and even now it is not at all clear exactly
what takes place. Linke,i by sulphonating anthracene
claimed to have obtained two dift'erent monosulphonic
acids, each of which gave a difterent hydroxyanthracene when
fused with caustic potash. Ivieberniann,2 however, repeated
lyinke's work and failed to obtain any monosulphonic acid
the conditions specified by Linke always leading to disul-
plionic acids. Graebe and Liebermann,2 and Liebermann
and Rath, 3 however, obtained a monosulphonic acid by
» J. pr. [2] 11, 227. * A. 212, 43 ; B. 11, 1C13. ^ B. 8, 246.
62 ANTHRACENE AND ANTHRAQUINONE
sulphouation. These latter observers distilled the sodium
salt of their acid with potassium ferrocyanide and saponified
the resulting nitrile. They thus obtained an anthracene
carboxylic acid which gave a soluble barium salt and which
melted rather indefinitely at 260°. On oxidation it gave the
corresponding anthraquinone carboxylic acid, m.p. 282-284".
There can be but little doubt that the sulphonic acid they
obtained was anthracene-i -sulphonic acid. Thc}^ give no
details of the sulphonation process except to state that it
was carried out at as low a temperature as possible.
On the other hand, the Societe Anon^ane des Matieres
Colorantes 1 sulphonate anthracene at a tem^jerature of
120-135°, with an acid of 67 per cent, strength (53° Be.),
and obtain yields of 60 per cent, of anthracene- 1 -sulphonic
acid. They state that the same product is formed when tlie
sulphonation is carried out at 140-150° with sodium bi-
sulphate or nitre-cake instead of with sulphuric acid. 2 They
also state that a certain quantity of three different disulphonic
acids is formed at the same time, and that one of these, by
heating with hydrochloric acid under pressure, is hydrolysed
and converted into anthracene or anthracene monosul-
phonic acid. None of these acids seem to have been in-
vestigated, but the one that is hydrolysed is probably an
a-sulphonic acid, as sidphonic acid groups in the a- position
are much more readily removed than those in the j8- position.
More recently Bayer and Co. 3 have described the sulphona-
tion of anthracene by chlorsulphonic acid in glacial acetic
solution at 95°, and claim to obtain a yield of 50 per cent, of
anthracene- 1 -sulphonic acid and 30 per cent, of anthracene-
2-sulphonic acid. Helf ter ^ has carried out some in-
vestigations with the monosulphonic acid made by the
French process and has prepared the sulphochloride. This
is remarkably stable for a sulphocliloride and can be boiled
with water for a few minutes without it undergoing decom-
position. In order to convert it into the sulphamide he
apparently found it necessary to heat it in a sealed tube for
1 D.R.P. 72,226 ; 7^.961; 76,280. 2 D.R.P. 77,^1 r.
3 D.R.P. 251,695. ' ^ B. 28, 2256.
SIMPLE DERIVATIVES OF ANTHRACENE 63
four hours at 150° with alcohoHc ammonia. By reduction
with zinc and ammonia or with sodium sulphite he obtained
the sulphinic acid.
Liebermann 1 by sulphonating anthracene obtained two
disulphonic acids which he separated by taking advantage
of the different sohibilities of their lead and sodium salts.
These on fusion with caustic alkali gave two different
liydroxyanthracenes, the acetyl derivatives of which Lieber-
niann oxidised and then hydrol3^sed, and thus obtained
anthrarufin and chrj^sazin. He therefore concluded that
the two sulphonic acids were the 1.5 and the 1.8 isomers,
and states that a high temperature during sulphonation
favours the formation of the former.^ This deduction,
however, is hardly justified, as caustic fusion is notoriously
unreliable as a method of determining constitution, and at
high temperatures hydroxyl groups have a great tendency
to wander to the a- position. It is true that Lampe ^ has
obtained the two disulphonic acids by the reduction of the
corresponding anthraquinone sulphonic acids, and states
that they are the same as those obtained by Liebermann ;
but the description he gives of the acids is not full enough
to justify this statement, and it must therefore be accepted
with some reserve until further information is forthcoming.
It seems reasonably certain that under some conditions
anthracene is sulphonated in the a- position, while it is
equally certain that under other conditions it is the /3-
position that is attacked. In the naphthalene series exactly
the same phenomenon is encountered, as when sulphonated
below 80° the a-sulphonic acid is almost the sole product,
whereas above 80° the ^- isomer predominates, and on heating
with sulphuric acid the a- acid is converted into the ^- acid
by the wandering of the sulphonic acid group. Tliis wander-
ing must be regarded as hydrolysis and subsequent sulpho-
nation, and the conditions specified in the patented process
for the manufacture of anthracene-i -sulphonic acid would
favour hydrolysis. It is, of course, quite possible that
sulphonation first takes place at the ms- carbon atoms, but
1 A. 212, 43 ; B. 11, 1C13. « B. 12, 182. » B. 42, 1413.
64 ANTHRACENE AND ANTHRAQUINONE
no anthracene ws-sulphonic acids seem to have been
described.
The reduction of the anthraquinone sulphonic acids can
be carried out with hydriodic acid and phosphorus, i or with
zinc and ammonia. 2 Reduction must, however, not be more
vigorous than is necessary, as otherwise the sulphonic acid
group may be spUt off. This is particularly likely to happen in
the case of the a-sulphonic acid, Liebermann and Hormann,^
by reducing anthraquinone sulphonic acid, obtained an
anthracene sulphonic acid which on fusion with caustic
potash gave an hydroxyl compound the acetyl derivative
of which melted at 139°, i.e. was probably i-acetoxy anthra-
cene. It is improbable that I^iebermann and Hermann
were using anthraquinone-i -sulphonic acid, as it is only
in recent years that this has been available, and it must
therefore be concluded that the production of i-hydroxy-
anthracene was due to a wandering of the hydroxyl group
during the alkali fusion. This receives confirmation from
the fact that Liebermann and Bischoff * reduced com-
mercial anthraquinone sulphonic acid with hydriodic acid
and then distilled the sodium salt of the resulting anthracene
sulphonic acid with potassium ferrocyanide. On hydro-
lysing the resulting nitrile they obtained an acid which
melted rather indefinitely at over 280° and which gave an
insoluble barium salt and was undoubtedly anthracene-
2-carboxyUc acid. It was accompanied by a small quantity
of an isomeric acid which gave a soluble barium salt and
which Liebermann ^ has since recognised as anthracene-
a-carboxyhc acid, and which, as he has proved, was derived
from the small amount of anthraquinone-a-sulphonic acid
always present in commercial samples of the ^- acid.
Hydroxyanthracenes
Hydroxyanthracenes, in which the hydroxyl groups are
attached to the ;»s-carbon atoms, the anthranols and anthra-
1 A. 212, 43 ; B. 12, 589. 2 B. 13, 47.
3 B. 15, 1807 ; 37. 70 ; 38, 2863. D.R.P. 21,178 (Agfa).
* B. 13, 47. * B. 37, 646.
SIMPLE DERIVATIVES OF ANTHRACENE 65
quinols, differ very considerably in their properties from
those in which the hydroxyl groups are attached to the
benzene rings. These wzs-compoimds are almost invariably
obtained by the reduction of the corresponding anthra-
quinone, and will be described in Chapter IV.
The hydroxyanthracenes, in which the hydroxyl groups
are situated in the benzene rings, are known as anthrols to
distinguish them from the anthranols, in which the hydrox>d
group is attached to one of the 7«s-carbon atoms. They
can be obtained by the reduction of the corresponding
hydroxyanthraquinones, e.g. with zinc dust and ammonia ;
but simultaneous loss of one or more of the nuclear hydrox^d
groups is ver)^ apt to take place, so that the anthrol obtained
often contains fewer hydroxyl groups than the anthra-
quinone derivative from which it was made.i A nmch more
generally useful method, however, is the fusion of the corre-
sponding anthracene sulphonic acids with caustic potash,
although, as the sulphonic acid groups are very firmly held,
a rather high temperature is necessary. This method has
been largely developed b}' Liebermann and his students, 2 and
has been applied not only to the sulphonic acids obtained
by sulphonating anthracene, but also to the anthracene
sulphonic acids which are readily obtained by the reduction
of the corresponding anthraqumone sulphonic acids. A
third method which is sometimes useful, although limited
in its application, consists in the reduction of derivatives
of i.2-anthraquinone or 1.4-anthraquinone. Both these
substances are true quinones, and their reduction apparently
can be readily effected without danger of simultaneous loss
of hydroxyl groups. So far, however, the method has been
very little applied. ^
As would be expected, the anthrols resemble the phenols
1 Cf. pp. 264-266; Lagodzinski, A. 342, 104; B. 28, 1533.
2 Liebermann, B. 11, 1610. Liebermann and Boeck, B. 12, 185,
1613. Liebermann and Hormann, B. 12, 589. Schiiler, B. 15, 1807.
R. E. Schmidt, B. 37, 70. Dienel, B. 38, 2863. Lampe, B. 42, 1414.
Liebermann, A. 212, 43. Linke, J. pr. [2] 11, 227. Agfa, D.R.P.
21,178.
3 Lagodzinski, B. 39, 1717; A. 342, 59. Dienel, B. 39, 930. Has-
linger, B. 39, 3537. Pisovschi, B. 41, 1436.
5
66 ANTHRACENE AND ANTHRAQUINONE
very closely in their deportment. Thus they are soluble
in caustic alkali, give nitroso compounds i with nitrous acid,
and in alkaline solution couple with diazo- solutions to produce
h}-droxy azo compounds.^ The corresponding alkyl ethers
are very readily prepared, it being sufficient to saturate the
warm alcoholic solution with hydrochloric acid gas. 3 By
this procedure the alk3iated anthrol is usually obtained in
almost quantitative 3ield, whereas the phenols of the
benzene series are almost unaffected?. The naphthols can
be alk^'lated by saturating their alcoholic solutions with
hydrogen chloride, but the reaction takes place with some
difficulty and the fields are poor.
The following anthrols have been described : —
Position
M.p.
Acetyl derivative,
Methyl
Ethyl
of OH.
m.p.
ether, m.p.
ether, m.p.
I
_
152° decomp.
128-130° decomp.
70°
69°
2
Decomp. at 200°
198°
175-178°
145-146°
1.2
—
131° decomp.
145°
1.4
■ — ■ — •
169°
— ■
—
1-5
Rufol > 265° decomp.
196-198°
224°
179°
1.8
Chrysol 225° decomp.
184°
198°
139°
2-3
— Decomp. 180°
155-160°
204°
? ?
Flavol 260-270°
254-255°
"
229°
Flavol was described by Schiiler,* who reduced com-
mercial anthraquinone disulphonic acid to anthracene disul-
phonic acid and then fused this with caustic potash. It is
probably either 2.6-dihydrox3' anthracene or 2.7-dihydroxy
anthracene, or it may be a mixture of the two.
Of the anthracene mercaptans very little is known, but
Heffter,^ by reducing anthracene-/S-sulphinic acid with zinc
and hydrochloric acid, obtained anthracene-j3-mercaptan.
Kehrmann and Sava,^ by treating its lead salt with dimethyl
sulphate, obtained dimethyl-j8-anthraquinonyl sulphonium
salts.
' Dienel, B. 39, 930. Lagodzinski, A. 342, 59.
- Lagodzinski, B. 39, 1717. Agfa, D.R.P. 21,178.
' Liebermann and Hagen, B. 15, 1427 ; B. 21, 2057. Dienel, B. 38,
2863. Lampe, B. 42, 1413.
« B. 15, 1807. 6 B. 28. 2263. 6 B. 45, 2898,
SIMPLE DERIVATIVES OF ANTHRACENE 67
Aminoantpiracenes
Methods iuvolviug the reduction of nitro groups are not,
as a rule, available for the preparation of anthramines, as
anthracene is only nitrated with difficulty, and the ws-nitro-
anthracenes are the only known nitro compounds. The anthr-
amines, however, are fairly easily prepared by other methods.
Wis-Anthramine (ws-aminoanthracene) was first prepared
by Goldmann 1 by heating anthranol with concentrated
aqueous ammonia at 200°, and later was prepared by
Meisenheimer 2 and Dimroth ^ by the reduction of ms-nitro-
anthracene with tin and Itydrochloric acid, or with zinc
dust and ammonium chloride. It is a rather unstable
substance, which melts indefinitely at about 115°. When
treated with acetic anhydride at the ordinary temperature
it gives a stable monoacetyl derivative (m.p. 273-274°),
whereas when treated with boiling acetic anhydride it readily
gives a diacetyl derivative (m.p. 159°). N-Arylanthramines
have been prepared by Padova * by heating anthranol with
excess of primary aromatic amines, such as aniline and a- and
j3- naphthylamine.
The B^-anthramines are best obtained from the anthrols
by heating with aqueous ammonia, ^ calcium chloride am-
monia,^ or acetamide,"^ but 0- and p-Simmo anthrols and
0- and /)-diamino anthracenes are more readily obtained b}-
the reduction of the corresponding nitrosoanthrol,^ or the
hydrox}^ or amino azo- compound. ^
Anthramines can also sometimes be obtained by reducing
the corresponding aminoanthraquinone, e.g. Romer 10
obtained ^-anthramine by heating j8-aniinoanthraquinone
with hydriodic acid and phosphorus ; but the method is not
^ B. 23, 2522; A. 330, 165; By. D.R.P. 127,399.
= B. 33, 3548.
» B. 34, 220.
* C. r. 149. 217.
•" Liebermann and Bollert, B. 15, 8i6.
« Pisovschi, B. 41, 1434. Liebermann, loc. cit. (footnote).
' Liebermann and Bollert, B. 15, 226; A. 212, ^6. Dienel, P.. 38,
28G3. Liebermann, li. 41, 1434 (footnote).
« Dienel, B. 38, 930. Lagodzinski, A. 342, 73.
* Pisovschi, B. 41, 1434. Lagodzinski, B. 39, 1717. A. 342, 75.
" B. 15, 223.
68 ANTHRACENE AND ANTHRAQUINONE
a satisfactor}^ one, and Graebe and Blumenfeld i failed to
reduce a-aminoanthraquinone to a-antliramine.
The antliramines are very weak bases, and consequently
are scarcely soluble in hydrochloric acid, although salts can
be precipitated by adding an acid to the ethereal solution of
the anthramine. These salts, however, are at once hydro-
lysed by water. 2 They give monoacetyl derivatives on
prolonged boiling with acetic anhydride, and in this way
the B2-anthramines differ from ws-anftiramine, this latter,
as stated on p. 67, readily yielding a diacetyl derivative.
The primary anthramines pass with great ease into the
dianthramines, boiling for a short time with glacial acetic
acid being sufficient to bring about the change; but in the
case of a-anthramine the reaction is considerably slower
than with jS-anthramine.s The primar>^ anthramines react
very readily with methyl iodide and pass directly into
quaternary ammonium salts, C14H9N (€113)31, from which
the quaternary base can be liberated by means of silver
oxide. This when boiled with water, or, more readily, when
heated with water to 120-130°, loses methyl alcohol, and
passes into the dimethylanthramine.4
The anthramines do not seem to be readily diazotised,
although Pisovschi ^ states that he obtained aminoazo
anthracene by treating a-anthramine with amyl nitrite in
alcoholic solution. Bollert,^ on the other hand, states that
j3-anthramine when treated in alcoholic solution either with
nitrous acid or amyl nitrite yields (Ci4H9NH)2NO. In
Bollert's compound, however, it is not improbable that one
of the ws-hydrogen atoms had been affected.
The following simple anthramines have been described : —
Position of NHj.
M.p.
Acetyl derivative, m.p.
I
2
1.4
ms.
119"
236-237°
About 113°
198°
240°
322°
( Monoacetyl, 273-274°
I Diacetyl, 115°
1 B. 30, iiiS. 2 Liebermann and Bollert, B. 15, 226; A. 212. 56.
3 Bollert, B. 16, 1634. Dienel, B. 38, 2863. * Bollert, B. 16. 1634.
5 B. 41. 1434. « B. 16, 1634.
SIMPLE DERIVATIVES OF ANTHRACENE 69
NiTRILES AND CARBOXYWC AcIDS
The ms-nitrile of anthracene has not been described, but
several nuclear nitriles have been prepared. They are
usually best obtained by distilling the potassium salts of
the corresponding sulphonic acids with potassium cyanide. 1
They are of no particular interest, and, like the naphtho-
nitriles, are very difficult to hydrolyse.
Anthracene-ws-carboxylic acid (anthroic acid) was first
obtained by Graebe and Lieberniann ~ b}^ heating anthra-
cene under pressure with carbon3'l chloride at 180°, and at
a later date Behla ^ and Liebermann and Zsuffa * showed
that if the temperature is raised simultaneous chlorination
takes place, the product being ?«s-clilor anthroic acid. The
yields of anthroic acid obtained by this method are very poor,
but more recently Liebermann and Zsuffa ^ have obtained
it in eighty per cent, yield b}' heating anthracene with
oxalyl chloride to 160-170°. If oxalyl chloride is used in
conj miction with aluminium chloride the yield of anthroic
acid falls to about thirty per cent., but aceanthrene quinone
is simultaneously formed in sixty per cent. 3'ield :
and this, on careful oxidation in neutral or alkaline solution,
gives anthracene-i.Q-dicarboxylic acid.^ The behaviour of
anthracene homologues and halogen substitution products
* towards oxalyl chloride is very similar.'
The anthroic acids are somewhat unstable, and lose
carbon dioxide readily when heated, loss of carbon dioxide
commencing at 150° in the case of anthroic acid itself. On
oxidation the 7ns- carboxyl group is lost, anthroic acid itself
being quantitatively converted into anthraquinone. As
1 Liebermann and Rath, B. 8, 246. Liebermann and Bischoff, B. 13, 47.
Liebermann and Pleus, B. 37, 646. Dienel, B. 39, 932.
» A. 160, 137; B. 2. 678. 8 B, 18, 3169: 20, 704.
^ B. 44, 202. s B. 44, 202.
« B.A.S.F., D.R.P. 280,092. ' B. 45. 1213.
70 ANTHRACENE AND ANTHRAQUINONE
would be expected from stereochemical considerations, the
anthroic acids are only esterified with the utmost difficulty,
prolonged heating of the silver salt with the alkyl iodide
under pressure usuall}' being necessary.
The nuclear carboxylic acids cannot be obtained directly
by the oxidation of the methyl anthracenes, as simultaneous
oxidation of the ws-carbon atoms always takes place, the
product invariabh' being an anthraquinone carboxylic acid.
These, however, are readily reduced* to the anthracene
derivative, e.g. by zinc dust and ammonia, and the reduction
of the anthraquinone carboxylic acids forms the easiest
means of obtaining the anthracene carbox3dic acids, i The
acids can also be obtained by the hydrolysis of the nitriles,
and this method has been applied in several instances by
Liebermann and his students.
The following nuclear carboxylic acids have been
described : —
Position of GOGH.
M.p. of acid.
I
245°
2
—
1-3
Above 330°
1.4
320° approx.
2-3
345°
1.2.4
Aldehydes and Ketones
No aldehydes of the anthracene series have been described,
and ver}' little is known of the ketones. Perrier 2 condensed
anthracene with benzo}^ chloride in the presence of alumi-
nium chloride, and obtained three compounds, having melting
points of 75°, 143°, and 203°. Lippmann and Fleisser,^ and
lyippmann and Keppich * also obtained three compounds,
viz. a monobenzoyl derivative melting at 148°, a dibenzoyl
1 Elbs, B. 20, 1363; J. pr. [2] 41, 6, 121.
B. 30, 1 1 18. Lavaux, C. r. 14.3, 687.
' B. 33, 816. 3 B. 32, 2240.
Graebe and Blumenfeld,
* B. 33, 3086.
SIMPLE DERIVATIVES OF ANTHRACENE 71
derivative melting at 158°, and a tribenzoyl derivative
melting over 300°. All three componnds gave antlira-
quinone on oxidation, and hence it would appear that in all
of them the benzo}-! groups are attached to the ws-carbon
atoms. It is somewhat difficult, however, to account for
three benzoyl groups. In a later paper Lippniann and
Pollok 1 claim that better 3'ields of the monobenzoyl com-
pound, anthraphenone, are obtained by warming anthracene
with benzoyl chloride and zinc dust in carbon bisulphide
solution for 480 consecutive hours.
1 13. 34. 2766.
CHAPTER IV
THE ANTHRAQUINONES AND
DIANTHRAQUINONYLS
ThKoretically six monoquinones might be derived from
anthracene, viz. four homonuclear quinones :
o o o
:0
:0
:0
o
0
.2-Anthra
i.4-Anthra»
2.3-Anthra-
9.10-Anthra
quinone.
quinone.
quinone.
quinone.
and two heteronuclear quinones
O
O
O
O
1 .5-Anthraquinone. 2 .6-Anthraquinone.
Of these 9.10-anthraquinone is by far the most important
and is what is ordinaril}^ understood by the term " anthra-
quinone." Of the other isomers 1.2-anthraquinone and 1.4-
anthraquinone have both been prepared, but 2-3 anthra-
quinone is unknown, and the same apphes to the heteronuclear
quinones.
^3
ANTHRAQUINONES—DIANTHRA QUINONYLS 73
In addition to the monoquinones there is a possibility
of the existence of numerous diquinones, some of which are
known, and a triquinonc has also been described.
1.2-Anthraquinone
This was obtained by Dienel 1 and I.agodzinski 2 by
oxidising 2-amino-i-anthrol with ferric chloride and hydro-
chloric acid. It crystallises from water in red needles,
which melt with decomposition at 185-190°. It is not
volatile with steam, and on reduction with zinc dust and
acetic anhydride passes into i. 2 -diacetoxy anthracene. Like
all a-diketonic compounds it condenses with o-phenylene
diamine to form an azine, Lagodzinski ^ endeavoured to
obtam 2.3-anthraquinone by oxidising 2 ^-dihydroxy anthra-
cene, but without success.
1 .4-ANTHRAOUINONE
This was first described almost simiiltaneously by
DieneH and Ivagodziuski,^ both of whom obtained it by
oxidising 4-amino-i-anthrol with ferric chloride, and shortly
after Pisovschi 6 obtained it by oxidising 1.4-diamino
anthracene. It forms ^^ellow needles which, according to
Dienel, melt at 206°, whereas Pisovschi states that the com-
pound darkens at 210° and melts with decomposition at
218°. Like all true ^-quinones it is very volatile. It is
converted into quinizarin by reduction with zinc dust and
acetic anhydride, and subsequent oxidation and hydrolysis. '^
9 . 10 - AnTHR AOUINONE
Synthetic methods for building up the anthraquinone ring
are discussed in Chapter VI., and although the synthesis
from phthalic acid is useful in the laboratory, the only method
of any technical importance is the oxidation of anthracene.
In the laboratory the oxidation is best brought about by
1 B. 39, 930. • B. 27. 1438; 28, 1422; A. 342, 59.
3 B. 28. 1533. * B. 39. 931. 5 B. 39, 1717.
«* B. 41, 1430. ' Pienel, B. 39, 931. Haslinger, B. 39, 3537.
74 ANTHRACENE AND ANTHRAQUINONE
an excess of chromic acid in boiling glacial acetic acid
solution,! but on the manufacturing scale the cost of the
acetic acid is prohibitive, and in addition sufficient chromic
acid must be used not only to oxidise the anthracene but
also to oxidise the impurities present. The acetic acid
method, however, gives quantitative results, and is uni-
versally used for the estimation of anthracene in commercial
samples of the hydrocarbon.
Anthracene can be oxidised by aqueous solutions of
chromic acid (bichromate and sulphuric acid) provided it
is first reduced to a state of fine subdivision, and this method
has the advantage that the anthracene is attacked more
readily than the impurities, so that it is only necessar}^ to
use the calculated amount of chromic acid. In order to
reduce the anthracene to the desired physical condition it
is sublimed in a current of superheated steam and the
vapour condensed by fine jets of water. The paste thus
obtained is oxidised with sodium bichromate and sulphuric
acid, and the chromic acid regenerated from the liquors
electrically. 2 The crude anthraquinone, the purit3^ of whicii
depends, of course, on the grade of anthracene used, is
filtered off, washed, dried, and then dissolved in concentrated
sulphuric acid at 130°. Tliis treatment does not affect the
anthraquinone, but sulphonation of most of the impurities
takes place, and at the same time the acridine is converted
into the soluble sulphate. The acid solution, without
cooling, is run into boiling water, when the anthraquinone
is precipitated, and the sulphonated impurities and the
acridine sulphate dissolve. It is necessary to run the hot
acid solution into boiling water, as otherwise the anthra-
quinone separates as a fine sludge, which is very difficult to
filter. After washing the anthraquinone is quite pure
enough for all ordinary purposes, but can be further purified
by sublimation or by recrystallisation, e.g. from tetrachlor-
ethane, aniline, nitrobenzene or nitrotoluene.^
^ Kopp, Monit. Sci. [3] 8, 1159. Graebe and Liebermann, ibid. [3]
9, 421.
* By. D.R.P. 252,759. This patent describes a continuous electrical
recovery process. ^ Sadler & Co., D.R.P. 137,495.
A NTHRA Q UINONES—DIA N THRA Q UINON YLS
/.~)
Further purification can be effected if desired by reducing
the anthraquinone to the alkali soluble anthraquinol, filter-
ing off impurities and then oxidising the clear alkaline
solution with atmospheric ox^^gen. On a technical scale
it is stated that the reduction can be effected with finely
divided iron and alkali. i
In addition to the chromic acid method, several other
processes have been described for oxidising anthracene to
anthraquinone. Thus, Hofmann, Ehrhart, and Schneider 2
have described the oxidation with potassium chlorate in
the presence of a trace of an osmium salt, and Hofmann,
Quoos, and Schneider 3 have described the oxidation by
sodium nitrate or clilorate in the presence of a large excess
of molten crystallised magnesium chloride. They state
that the reaction starts at 125°, and is almost quantitative
at 300°, whereas without the magnesium chloride no anthra-
quinone at all is formed, even at 330°. Hofmann and
Ritter * have described the oxidation at the ordinary
temperature by the use of aqueous sodium hypochlorite in
the presence of a trace of an osmium salt, and Hofmann
and Schumpelt 5 have described the oxidation by potassium
chlorate in formic acid solution.
The electrolytic oxidation of anthracene has been
described, and quantitative yields with a current efficiency
of almost 100 per cent., have been claimed by carrying out
the oxidation in 20 per cent, sulphuric acid suspension in
the presence of a little eerie sulphate as a catalyst. ^
Several patents have been granted for the use of nitric
acid and oxides of nitrogen under various conditions. The
action of nitric acid in the presence of a solvent such as nitro-
benzene, with or without the use of mercury as a catalyst,
has been investigated by the Chemische Fabrik Griesheim-
Elektron, and good results claimed.'^ Probably ms-miro-
^ Lewis and Gibbs, A. P. 1,293,610 (191S).
- B. 45, 3334 ; 46, 16G9.
^ B. 47, 1991. Hofmann, D.R.P. 277,733.
^ B. 47, 2238.
=* B. 48, 821.
8 E.P. I9,i78«2.
" D.R.P. 283,213; 284,083-4; 284,179. Cf. A.P. i,ii9.54<^'
76 ANTHRACENE AND ANTHRAQUINONE
compounds are first formed and then pass into anthra-
quinone.
The use of oxides of nitrogen has been described in several
patents, and is of considerable interest in view of the read}-
production of these by the catalytic oxidation of ammonia.
The Badische Anilin u. Soda Fabrik claim the use of nitrogen
dioxide in the presence of a suitable solvent such as nitro-
benzene, i and the Aktien Gesellschaft Griinau, Landshoff u.
Meyer,2 claim oxidation by nitrogen "dioxide at a tempe-
rature of 100-200°, preferably at 200°, and state that an
improved quality of anthraquinone is obtained if the anthra-
cene is mixed with zinc dust or other substance which will
destroy nitric acid. 3
In addition to the experiments of Hofmann and his
students referred to on p. 75, Meister, Lucius, and Briinning
have developed the use of chlorates, and in two patents *
claim the use of the chlorates of iron, nickel, cobalt, man-
ganese, and chromium.
Attempts have been made to carr}^ out the oxidation
with oxygen, and it has been stated that anthracene can be
oxidised in aqueous suspension at 170° with oxygen under
pressure if a suitable catalyst is used.^ The best catalyst
is said to be cupric oxide, but nickel, cobalt, iron and lead
compounds are also effective. The oxidation in the vapour
phase has also been described, the Barrett Co. (New York) ^
claiming oxidation by air or oxj-gen by passing anthracene
vapour over a vanadium catalyst at 300-500°.
The use of ozone has also been claimed.'^
Anthraquinone is a yellow cr>^stalline soHd which melts
at 280°. 8 It can be sublimed fairly easily, but is not nearly
as volatile as most /)-quinones, and in this respect differs
1 D.R.P. 268,049.
* D.R.P. 234,289 ; 254,710.
2 M.L.B., i3.R.P. 256,623 (taken over from Akt. Ges. Griinau, Lands-
hoff u. Meyer).
* D.R.P. 273,318-9.
6 M.L.B., D.R.P. 292,681.
6 E.P. 134,52218.
' Heinemann, E.P. 5514^^.
8 Phillipi, M. 33, 373. Kempf, J. pr. [2] 78, 257. The melting point
usually given in the hterature, viz. 278°, is too low.
A NTHRA QUINONES~DIA NTHRA Q UINON YLS 77
sharply from the isomeric 1.4-anthraquinone. It is a very
stable substance and is only attacked by oxidising agents
with great difficulty, and then yields phthalic acid. Its
behaviour towards reducing agents is discussed in detail
elsewhere, but attention may here be drawn to the fact that
the formation of a deep red solution by reduction in the
presence of alkali (zinc dust and ammonia or caustic soda,
or sodium hydrosulphite and caustic soda) serves as a con-
venient test for anthraquinone, and as the " vat " is very
easily oxidised by air or weak oxidising agents, such as
hydrogen peroxide, reduction and subsequent oxidation is
often a convenient method of getting rid of impurities.
Anthraquinone hardly behaves like a true quinone, nor
does it behave like a true ketone. It forms no phenyl
hydrazone, and only reacts with hydroxylamine to form a
monoxime. Even this monoxime is only formed with great
difficulty,! and it is only obtained directly by heating
anthraquinone with alcoholic solutions of hydroxylamine
hydrochloride in sealed tubes at 180°. Indirectly, however,
both the monoxime 2 and the monophenyl hydrazone 3 can
be obtained fairly easily by treating dibromanthrone with
h3-droxylamine or phenyl hydrazine. The monoxime melts
at 224°. The phenyl hydrazone is identical with the azo-
dye obtained by coupling benzene diazonium salts with
anthranol in alkaline solution.
Although the anthraquinone itself only undergoes oxime
formation with the greatest difficulty, this is not the case
when chlorine atoms are present in the a- position, and
Fremid and Achenbach ^ have found that i-chloranthra-
quinone gives a monoxime quite easily, and that 1.5-dichlor-
anthraquinone readily forms both monoximes and dioximes.
The monoximes of i-chloranthraquinone and of 1.5-dichlor-
anthraquinone both exist in two isomeric forms, of which
one gives an isoxazole, whereas the other does not, and the
dioxime also exists in two forms. The isomerism is
2
> Goldschmidt, B. 16, 2179. Cf. Schunck and Marchlewski, B. 27, 2125.
2 Kurt Meyer, A. 396, 165.
' Kaufler and Suchanck, B. 40, 51S.
* B. 43. 3251-
I
^% ANTHRACENE AND ANTHRAQUINONE
probabl}- geometrical, although, in the case of the oxime of
i-chloranthraquinone positional isomerism is not impossible :
HON NOH
II II
C CI C CI
CO CO
Gives no isoxazole. Gives isoxazole.
»
The formation of isoxazoles by one isomer and not by
the other is in agreement with Victor Meyer's observation i
that one of the oximes of o-chlorbenzophenone will give an
isoxazole whereas the other will not.
Freund and Achenbach have also studied oxime forma-
tion with other a- derivatives of anthraquinone. They
find that erythroh^^droxy anthraquinone will give no oxime,
whereas its alkyl and ar}^ ethers give monoximes with
difficulty, and anthrarufin dimeth^^l ether will give a mon-
oxime. No oxime could be obtained from 1.5-diamino
anthraquinone or from i-chlor-5-amino anthraquinone.
Although the carbonyl oxygen atoms in anthraquinone
are not very reactive, they readily enter into the formation
of new rings and, as will be seen in the sequel, some of these
ring compounds have proved to be very valuable dyestuffs.
Staudinger 2 has found that anthraquinone will react with
diphenyl ketene, but only with difhcult}^ and analj-sis and
molecular weight determinations point to the formula :
Ph— C— Ph
^6^i\^y^G^4
Ph— C— Ph
for the product. The substance obtained, however, forms
colourless needles which melt at 302-303°, and in view of the
lack of colour vStaudinger is doubtful of the quinonoid formula.
J B. 25, 1498 ; 3293- ■ B. 41, 1362.
ANTHRAQUINONES—DIANTHRAQUINONYLS 79
Goscli 1 has found that aiithraquinone condenses with
aldehyde ammonia if heated with it for six hours at 220°.'
The product mehs at 281°, and he ascribes to it the formula :
H— C— CHO
c
C6H4<(^(
-6^4
C
li
H C
CHO
Bayer & C0.2 state that if anthraquinone is boiled with
primar}' aromatic amines and a condensing agent such as
boric acid, products are obtained in which both the carbonyl
oxygen atoms have been replaced b}^ ArN: groups. They
state that the reaction is facilitated by the presence of
reducing agents, such as stannous chloride, but do not
describe the resulting compounds in detail. Ver^^ similar
products seem to be obtained from anthraquinone-jS-sul-
phonic acid, 3 but as these are practically insoluble in dilute
caustic soda, it would seem that the sulplionic acid group
had also reacted. This is supported by the analytical
figures given for the condensation product with _/)-toluidine.
These point to the presence of three toluido groups, and are
in approximate agreement with the formula C35H33O2N3VS.
Anthraquinone, when fused with caustic potash, yields
benzoic acid,^ and caustic fusion has been applied in some
cases for determming the constitution of anthraquinone
derivatives. Owing to the stability of the anthraquinone
ring, however, the method is rather tedious to carr^- out,
and in the case of dimethyl anthraquinone I^avaux found it
necessary to heat to 260° for three hundred consecutive hours.
Homologous Anthraouinones
The alk}-! anthraquinones are of no great importance,
and have not been studied in detail. Most of the methyl
1 Soc. Ill, Gio. - D.R.P. 148,079. 3 By. D.R.P. 136.872 ; 147,277.
* Graebe and Liebermann, A. 160, 129.
So ANTHRACENE AND ANTHRAQUINONE
anthraquinones have been already mentioned in connection
with the methyl anthracenes. The most important is j3-
meth3'l anthraquinone, and this can be obtained by the
oxidation of the j3-methyl anthracene obtained from coal
tar, or from toluene by the phthalic acid method. When
treated with caustic alkali it gives anthraflavone. P- Ethyl
anthraquinone and ^-propyl anthraquinone were prepared
by Scholl 1 from ethyl benzene, and propyl benzene, but are
of no great interest. Of greater interest are the benzanthra-
quinones (naphthanthraquinones) , and these are treated in
a separate chapter.
Reduction Products. — Unlike true quinones, 9.10-
anthraquinone and its derivatives are not reduced by
sulphurous acid or the sulphites. 2 They are, however,
readily reduced by other reducing agents, such as hydriodic
acid, stannous chloride or tin and hydrochloric acid, zinc
dust and caustic soda or ammonia, sodium hydrosulphite,
etc., and a considerable variety of products can be obtained
according to the conditions under which the reduction is
carried out. In studying the reduction of anthraquinone
derivatives it must be borne in mind that the partial reduc-
tion of the cyclic carbonyl groups often has a great influence
on the stability of groups attached to the nucleus, so that
such groups are frequently split off. 3
Rosentiel 4 seems to have been the first to make use of
hydriodic acid and phosphorus, but Liebermann ^ and his
students made a much more thorough examination of the
reaction. They found that when the reduction is carried
out in open vessels the product formed depends on the
concentration of the acid, on the temperature used, and on
the time of heating, but that as a rule reduction cannot be
taken beyond the dihydro-anthracene stage.' Bj' working
1 M. 32, 687.
2 In the abstracts published by the Chemical Society statements will
sometimes be found, e.g. Soc. 94 (i), 786, that anthraquinone derivatives
are reduced by sodium hydrogen sulphite. Reference to the original or to
the Zentralblatt, however, will show that in these cases the abstractor has
wrongly translated " hydrosuhit " as " hydrogen sulphite."
3 For example see pp. 179, 265.
* C. r. 79. 764.
^ A. 212, 5. B. 9, 1202; 10, 607; 11, 1610; etc.
C6H4N
ANTHRAQUINONES—DIANTHRAQUINONYLS 8i
in sealed tubes, however, they were able to obtain more highly
hydrogenated substances, i By carrying out the reduction
with a more dilute acid, less fully reduced products are
obtained, and it is possible to isolate the anthraquinol,
anthrone and hydroxydihydroanthracene compounds : 2
OH H H H H
1 \/ \/
c c c
C6H4 -> C6H4<^^C6H4 -» CfiH^^^CeH^
C CO C
I /\
OH HO H
Anthraquinol. Anthrone. Hydroxydihydro-
anthracene.
Compounds of this last type are somewhat unstable, and
very readily lose a molecule of water.
Liebermann 3 has more recently studied the mechanism
of the reduction of anthraquinone compounds with h}- driodic
acid, and has isolated several addition compounds containing
iodine and hydriodic acid.
Much more interesting results have been obtained with
other reducing agents. Thus Liebermann,* by reducing
anthraquinone with tin and hydrochloric acid, obtained
anthrone in good yield ; and more recenth' Kurt Meyer 5
has improved the method by using tin and hydrochloric
acid in boiling glacial acetic acid. Zinc dust and ammonia
or caustic soda has been emploj-ed by a very large number
of investigators, 6 and if the reaction is carried sufficienth-
far, almost invariably leads to the anthracene derivative, this
being one of the most convenient methods of preparing
anthracene derivatives from the corresponding anthra-
quinone compounds, as there is no danger of the production
of more highly hydrogenated derivatives. It is not applicable,
' See Chapter III.
- Liebermann and Pleus, B. 35, 2923.
=» B. 37. 3341; 38. 1784.
' B. 20, 1854.
» A. 397. 55.
» E.g. Elbs, J. pr. [2] 41, 6, i2i ; B. 20, 1365. Lampc, B. 42, 1414, etc.
R. E. Schmidt, B. 37, 70.
6
82 ANTHRACENE AND ANTHRAQUINONE
however, to anthraquinone derivatives in which there is
a methyl group in the a- position, as Elbs i has found that
these on alkaHne reduction pass into hj-drocarbons in which
one of the ms- carbon atoms seem to be affected. These are
monomolecular and form picrates, and Elbs considers that
they are probably formed by the loss of a molecule of water
between the methyl group and the ws-hydrox}-l group of
the anthranol, e.g.
OH CH,
Moderated reduction with zinc dust and an alkali leads
first to the anthraquinol,^ and Perger 3 has found that
further reduction leads to the wks-hydroxydihj'droanthracene,
which b}' loss of water passes into the anthracene. The
course of the reduction is, therefore, very similar to that
pursued in the case of hydriodic acid.
Schulze 4 has repeated Perger's work, and finds that in
addition to hydroxydihydroanthracene, anthrapinacone is
also formed :
C6H4 OH OH C6H4
CH2<^\c C<(^CHo
which by loss of water passes into dianthr\'l :
Ct}H4 C6H4
CH^C— CACH
C6H4 C6H4
This Liebermann and Gimbel ^ managed. to obtain direct
from anthraquinone by reduction with tin and hydrochloric
acid ; and more recently Eckert and Hofmann ^ have repeated
Liebermann's work and find that much better yields are
1 J. pr. [2] 41, <), 121 ; B. 20, 1365.
* Graebe and Liebermann, A. 160, 126. Liebermann, A. 212, 65.
Romer and Schwazer, B. 15, 1040.
» J. pr. [2j 23. 127. * B. 18. 3034. * B. 20. 1854. « M. 36. 497.
ANTHRA Q UINONES—DIANTHKA Q UINON YLS 83
obtained if the reduction is carried out in the presence of
a trace of a platinum salt.
Hans Me3'er,i by reducing anthraquinone with zinc and
caustic soda under pressure at a high temperature, has
obtained dianthrol, which by prolonged heating with
hydrochloric acid passes into the ketonic isomer, dianthrone.
caustic alkali causing the reverse change :
CoH, CgHt HCi CoH, H H e,M,
HO— Cf->C— Cf^C— OH NaOH 0=C< >C-C< )C=0
^1)^4 C6H4 C6H4 C6H4
Dianthrol. Dianthrone.
This latter on reduction in glacial acetic acid v\itli liu
and hydrochloric acid gives tetrahydrodianthrol, which
passes into dianthryl very readily by loss of water : 2
pj ^6^4 H H C6H4 -^j- CoH4 C0H4
HO c„H4 C,H4 OH ^^jj^ ^.^^^
From a commercial point of view alkaline sodium hydro-
sulphite (Na2S204) is the most important reducing agent for
anthraquinone derivatives, as it readily converts them into
the soluble vats, these being readih- oxidised to the original
substance on exposure to the air. The reaction has been
examhied by Grandmougin,^ who has found that the reduction
product is the anthraquinol :
OH
I
C
C
I
OH
As will be seen later, the anthraqiiinone vat dyes often
1 B. 42, 143. M. 30, 165.
* M. 36, 497.
> J. pr. [2] 76, 138; R.G.M.C. 12, 44.
84 ANTHRACENE AND ANTHRAQUINONE
CH,-
contain two or more anthraquinone groups, either or both
of which may become reduced in the vat.
The alkaline reduction of anthraquinone derivatives is
sometimes hindered by the presence of substituents in the
a-position. The abnormal behaviour of anthraquinone
derivatives in which there is a methyl group in the a-
position has already been mentioned, and Seer i has shown
that none of the following compounds will give " vats " :
CHs NHCHaCfiHg W CH,
I
CHc
I
-CH.
CeHsCHoNH
CeHgCO.
\
CH2C6H5
I
/
N
C6H4[/>]CH3
C6H5CH2^
In the case of this last compound it is curious to notice that
the dicarbox34ic acid obtained by oxidation :
COOH
can be reduced in alkaline solution.
The use of amalgamated zinc and hydrochloric acid has
been advocated by Clemmensen,^ who claims that by this
means both anthraquinone and alizarin can be reduced to
dihydro- and hexahydro-anthracene.
The results obtained with other reducing agents will be
foimd discussed in the chapter dealing with the anthrones
and dianthr>d derivatives ; but mention may be made here
of the fact that all hydroxyanthraquinones when distilled
with zinc dust yield anthracene, a reaction which has
1 M. 31, 379; 33, 33, 546; 34, 579.
« B. 47, 684. Cf. By., D.R.P. 296,091 ; 301,452; 305,886.
A NTHRA Q UINONES—DIA NTHRA Q UINONYLS 85
proved of the utmost value in the study of naturally occurring
anthraquinone compounds.
Action of Grignard's vSolution. — Anthraquinone reacts
with either one or two molecules of magnesium alkyl halides,
the products being alkyl hydroxy anthrone and dialkyl-
dihydroxydihydroanthracene :
R OH
R OH
c
C
C6H4<^P>C6H4
CO
CeH^^CcH^
C
R OH
With magnesium ar}-l haHdcs the reaction is similar,
anthraquinone, for example, reacting with two molecules of
phem'l magnesium bromide to form : 1
HO Ph
C
c
/\
HO Ph
In these compounds in which an ar^-l and a hydroxy- 1
group are attached to each ;;js-carbon atom, the hydroxyl
groups are ver}- reactive and are readity replaced by chlorine
by treatment with alcoholic hydrochloric acid, 2 and can be
methylated by methyl alcohol and hydrochloric acid. The
dichloro compounds thus formed are not ver}^ stable, and on
treatment with potassium iodide readily spUt off their
chlorine and pass into sym-diaryl anthracenes. By starting
with a diar^'l anthrone and treating this with an ar>4 mag-
nesium bromide, a compound containing three ar^'l groups
1 C. r. 138, 327, 1251 ; 139. 9; 150, 1290; Bl. [3] 33, 1104. Clarke,
B 41, 935. Am. Soc. 33, 1966.
* Loc. cit.
86 ANTHRACENE AND ANTHRAQUINONE
and a hydrox>'l group attached to the two ws-carbons is
obtained,! e.g.
Ph Ph
C
c
/\
Ph OH
In these the hydrox}^! group is very easily etherilied by
alcohol and h3'drochloric acid, but a fourth ar^d group
cannot be attached to the 7»s-carbon atom unless this ar>'l
group contains an amino group or a phenolic hydrox3'l
group 2 (see p. 89).
By treating anthraquinone with a molecule of magnesium
benzyl chloride, HaUer and Padova 3 obtained benzyl
hydroxy anthrone, which under the influence of hydro-
chloric acid readily lost a molecule of water and passed
into benzylidene anthrone, the same compound being also
obtained b}' condensing anthrone with benzaldehyde :
^O ^^sCeHg CHCeHg
C C CH2
C6H4<()CoH, Z^ CeH.^CeH, S^J^"^ CeH^^CgH,
CO C CO
o
Benzylidene anthrone was also obtained by Levi * and
by Bach ^ by benzylating alkaline solutions of anthraquinol
with benzj'l bromide and subsequently treating the benzyl
hydrox}^ anthrone with concentrated sulphuric acid, and
their description of the substance is in close agreement with
that given b}- Haller and Padova. Tschilikin,^ however,
has recently prepared the substance by treating anthraquinol
with dimethylphenj'lbenzyl ammonium chloride (leuco-
1 C. r. 139, 9- ' C. r. 140, 2S3, 343. =» C. r. 141. 857.
* B. 18, 2152. 5 B. 23. 1567. « B. 47, 1055.
A NTHRA Q UINONES-^DIA NTHRA Q UINON YLS 87
trope D) and gives the melting point as 117° in place of the
126-127° found by Ivcvi, Bach and Haller, and Padova.
Tschilikin obtained benzylhydroxy anthrone simidtaneously.
By treating anthraquinone with two molecules of
magnesium methyl iodide, Guyot and Stahling 1 obtained
a dimethyl dihydroxy derivative which, like its phenyl
analogue, is very readily methylated by alcohol and hydro-
chloric acid. Both the hydroxy compound and its methyl
ether are decomposed by heat :
CPI;, OH CH3 OCH3
C C
CH3 OH
CH3 OCH3
^
1
CHo
CH2
C
C
CoH,<^\c6H,
C
c
CH3 OH
CH3 0CH3
the reaction being exactly similar to that midergone by the
benzyl derivative described on the previous page.
Similar compormds were obtained by treating phenyl
methoxy anthrone with an alkyl magnesium iodide and then
boiling the resulting substance with glacial acetic acid :
CaHg OCH3 CeHg OCH3
C C
CeH / XoH, -> C6h/\c6H4
c c
CH3 OH
CHo
* Bl. [3] 33, 1 144. Cf. Clarke, B. 41, 935; Am. Soc. 33, 1966 (corre-
sponding ethyl compounds). ,
88 ANTHRACENE AND ANTHRAQUINONE
Haller and Guyot i have studied the action of Grignard's
solutions on other anthrones. Starting with diphen^-l-
anthrone they treated this with magnesium phenyl bromide,
and obtained a triphenyl hydroxy' dihydroanthracene, which
on reduction with zinc and acetic acid gave triphenyl
dihydroanthracene :
Ph Ph Ph Ph Ph Ph
\/ \/ \/
C C . C
CeH^/ \C6H4 -^ CgH^/ >C6H4 -> CgH^/ \C6H4
CO c c
Ph OH Ph H
This latter compound they were also able to sjmthesise by
treating the methyl ester of triphenylmethane-o-carboxylic
acid with magnesium phen3-l bromide :
Ph Ph Ph Ph
Q \/ \y
C.OCH3 C— OCH3 c
C,-H,<^yCeH, -^ C6H4<^C6H5 -> C6H4<^C6H4
C C C
/\ /\ /\
Ph H Ph H Ph H
This latter synthesis closely resembles the synthesis of
?«s-diphenylanthracene by Simonis and Remmert.2 These
investigators found that o-brombenzyl triphenyl carbinol
loses hydrobromic acid ver^^ readily when treated with
sulphuric acid and passes into 7>2S-diphenylanthracene :
H Ph Br Ph
\;/ I
c c-
C6H4<^/C6H5 -> C6H4<^|^CgH4
C C
/\ 1
Ph OH Ph
1 C, r. 139, 9. - B. 48, 20S. C/. C. r. 138. 1252 ; 140. 1461.
ANTHRA Q UINONES—DIA N THRA Q UINON YLS 89
and i.2-dimethoxy-wis-diphenylanthracene can be obtained
in a very similar manner :
HO Ph H Ph
C C
(CH3O) oC6H2<(^C6H5 -> (CH3O) 2C6H2<^|)>C6H4
c c
^\ I
Ph OH Ph
As stated on p. 86, the h5'drox}'l group in triphenjd
hydrox}- dihydroanthracene cannot be replaced by an ar>'l
group, but these compounds react readily with compounds
of the type ArX when Ar is an ar}d group and X an hydroxyl
or primar}^ secondary or tertiary- amino- group. The con-
densation is brought about by boiling in glacial acetic acid
solution, 1 and leads to compounds of the type :
Ph Ph
C
C
Ph ArN(CH3)2
The diphenyl dihydrox}- dihydroanthracene which is
obtained b}- the action of magnesium phen3-l bromide on
anthraquinone will also condense with tertiar}^ amines.
The products are compounds of the type :
Ph CeH^N^Ieo
C
C
Ph C6H4NMe2
and exhibit geometrical isomerism. 2
' Haller and Guyot, C. r. 140, 283. ^ C. r. 140, 283, 343.
90 ANTHRACENE AND ANTHRAQUINONE
The dihj-droxy compound can also be converted into
the dichlor- compound by means of alcohohc hydrochloric
acid, and from this the chlorine is readil}- spht off by potassiimi
iodide, the product being ws-diphenyl anthracene :
Ph OH
Ph CI
Ph
\/
\/
1
C
C
C
C6H4<^C6H, -> C6H4<0>C6H4^
- CeH,<|>
C
C
C
/\
y\
1
Ph OH
Ph CI
Ph
C«H.
From this it will be seen that the use of Grignard's solu-
tion forms a convenient means of synthesising both complex
and simple derivatives of anthracene in which the meso-
carbon atoms are involved. A considerable number of such
compounds have been prepared by Haller and his co-workers,
for details of which reference must be made to the literature. ^
The DlANTHRAQUmONYLS
The dianthraquinonyls are the anthraqmnone analogues
of diphem-l and are not to be confused with the dianthra-
quinones (p. ii6). There are three possible isomeric di-
anthraquinonyls, viz. i.i'-dianthraquinonyl, 2.2'-dianthra-
quinonyl, and i.2'-dianthraquinonyl, but neither this
last-named substance nor any of its derivatives have been
described :
i.i'-Dianthraquinonyl. 2.2'-Dianthraqumonyl.
The dianthraquinonyls can, of course, be built up from
diphenyl by the phthalic acid s^-nthesis, and this method is
discussed on p. 135. The results, however, are not satis-
factory-, and the dianthraquinon3'ls are much more readily
1 Bl. [3] 25, 315; Bull. Soc. ind. Mulhaus, 72, 268.
A NTHRA Q UINONES—DIA NTHRA Q UIXON YLS 91
obtained by reactions which lead to the union of two anthra-
quinone residues. In some cases the union of two anthra-
quinone molecules can be effected by oxidation, and this is
particularly the case when h3'drox3'l groups are present in
the molecule. Thus er5-throhydrox5^ anthraquinone on
fusion with caustic potash gives i.i'-diliydrox>"-2.2'-dianthra-
quinonyl,! the structure being proved by its giving a fur-
furane derivative by loss of water, and by its giving 2.2'-
dianthr}d on distillation with zinc dust. 2 In the case of
quinizarin, dianthraquinonyl formation takes place more
readily, heatmg with aqueous sodium carbonate at 120°,
sufficing to produce a tetrahydroxy dianthraquinonyl. 3
This also gives 2.2'-dianthryl on distillation with zinc dust,
and as it passes into a furfurane derivative by loss of water
it must be i.4.i'.4'-tetrah3-drox3--2.2'-dianthraquinonyl.*
The oxidation of hydrox^-anthraquinones by hypochlorites
usuaU}- leads either to halogenation or to complete rupture
'of the ring s^'Stem, but Scholl 5 has foimd that alizarin can
be oxidised to i. 2.1'. 2 '-tetrahydrox3'-3. 3 '-dianthraquinonyl
by treatment under suitable conditions with potassium
hj'pochlorite and caustic potash. The proof of the structure
of the product rests on its conversion into a furfurane deriva-
tive by loss of water, and into 2.2'-dianthr>'l by distillation
with zinc dust.
Dianthraquinonyls can be obtained from the anthra-
quinone diazonium salts b}^ treatment with copper powder
or with cuprous salts. Thus diazonium sulphates when
warmed with cuprous chloride or bromide in aqueous
solution or suspension pass very readil}' into the dianthra-
quinonyl, provided that no very considerable quantity of
halogen acid is present,^ and diazonium sulphates can also
be converted into the dianthraquinomd by treating them with
copper in the presence of acetic anhydride.'^
« By., D.R.P. 167.4G1.
2 Scholl, B. 52. 2254.
3 By., D.R.P. 146,223.
* SchoU, B. 52, 2254.
5 B. 52, 1829; D.R.P. 274,784. « B.A.S.F., D.R.P, 215.006.
' SchoU, B. 40. 1696. B.A^.F., D.R.P. 184,495. Cf. Knoevenagel,
B. 28, 2049
92 ANTHRACENE AND ANTHRAQUINONE
Although all the above methods of preparing dianthra-
quinonyls have proved useful, the most general method
consists in heating a halogen anthraquinone with copper
powder, either alone or in the presence of some indifferent
solvent such as nitrobenzene or naphthalene, i Both a-
and ^- halogen compounds can be used, and although, as
would be expected, the reaction takes place most rapidly in
the case of the iodo- compounds, both chlor and brom com-
pounds can be used, and in many cas^s give yields amounting
to 70-80 per cent, of the theoretical. If the halogen atom is
in the a- position and there is also an amino group in the
ortho- position to it, dianthraquinonyl formation is accom-
panied by the production of a flavanthrone, and in order to
avoid this the amino group must be protected by the use of
the benzylideue derivative. 2
The dianthraquinonyls themselves are of no great im-
portance, their chief interest lying in their relation to the
helianthrones (p. 333) and fiavanthrones (p. 301). They
are readily nitrated, but the nitration products have not been
studied in detail. 3 Methyl groups when present can be
oxidised to carboxyl groups. *
The Anthradiquinones
Polyhydroxy anthraquinones in which two hj'droxyl
groups are in the para- positions to one another, e.g. quini-
zarin, readily yield anthradiquinones when oxidised. The
oxidation can be brought about in concentrated sulphuric
acid solution by means of various oxidising agents such as
manganese dioxide, arsenic acid, lead dioxide, etc., but
under these conditions simultaneous hydroxylation by oxida-
tion is very apt to occur, & Lesser, ^ and Dimroth and
1 SchoU. B. 40. 1696; 43, 355, 1738; 44, 1086; 51. 452; M. 32. 687.
Seer, M. 34, 631. Benesh. M. 32. 447. Eckert and Tomaschek, M. 39, 843.
UUmann. B. 45. 689; 49. 740, 2161 ; A. 399. 332; D.R.P. 248,999.
B.A.S.F., D.R.P. 180,157; 241,472.
2 SchoU, B. 51, 452. Ullmann, A. 399, 332. D.R.P. 248,999.
=> SchoU, B. 43, 355, 1738.
* SchoU, B. 40. 1696.
^ By., D.R.P. 66.153 ; 68.113; 68,114; 68,123; 69.842
« B. 47. 2526.
A NTHRA Q UINONES—DIA NTHRA Q UINON YLS 93
Schnitzel obtained 1.4.9.10-anthradiquinone by oxidising
quinizarin with lead dioxide, the former investigator using
benzene as a solvent, whereas the latter worked with glacial
acetic acid solutions. It is a not very stable substance which
melts at 211-213° when rapidly heated, the bath being
preheated to 205°. When its aqueous suspensions are
heated it undergoes decomposition with simultaneous
oxidation and reduction, part being reduced to quinizarin
at the expense of another part, which becomes oxidised to
phthalic acid.
All the anthradiquinones are true quinones and, like
1.4-anthraquinone, show the usual quinone reactions. Thus,
1.4.9.10-anthradiquinone is rapidly reduced to quinizarin
by sulphurous acid, it adds on a molecule of h5'drochloric
acid to form 3-chlorquinizarin, and when warmed with
concentrated sulphuric acid takes up a molecule of water and
passes into purpurin. This last reaction is a somewhat
important one, for, as will be seen later, the formation of
many polyhydroxyanthraquinones is probably due to the
addition of the elements of water to a diquinone.
When _^-diaminoanthraquinone or _/)-h3^droxyamino-
anthraquinone is treated with sodium chlorate and hydro-
chloric acid 2.3-dichlor-i.4.9.io-anthradiquinone is obtained,
simultaneous chlorination and oxidation taking place, and
diaminoanthrarufin under similar treatment yields tetra-
chlor-i.4.5.8.9.io-anthratriquinone.2
The anthradiquinones when treated with phenols yield
violet or blue mordant dyes, which are probably similar in
nature to phenoquinone. Up to the present i. 2. 9.10-
anthradiquiiione has not been isolated, but Dimroth and
Schultze have obtained a straw-yellow solution b}" oxidising
alizarin suspended in a mixture of equal volumes of glacial
acetic acid and ether with lead dioxide. This solution
exhibits all the properties of a true quinone, viz. it liberates
iodine from potassium iodide, is at once reduced to alizarin
by sulphurous acid, and gives chloralizarin when treated
with hydrochloric acid. It undoubtedh' consists of a solution
1 A. 411, 345. ' M.L.B., D.R.P. 258,556.
94 ANTHRACENE AND ANTHRAQUINONE
of 1.2.9.10-anthradiquinone, but the quinone is so unstable
that it was found impossible to isolate it.
Anthraflavones
If ^-meth}'! anthraquinone is fused with caustic potash,
or better if it is heated with alcoholic caustic potash, a yellow
vat dye is obtained. 1 This has come into fairly general use
under the name Authraflavone G, and! was originally believed
to have the structure :
although Scholl 2 showed that neither /3-ethylantliraquinone
nor j8-propylanthraquinone gave an}' trace of an authra-
flavone compound when treated with caustic potash. A
compound of the structure shown above would pass on
oxidation into a new complex containing a third quinonoid
group, whereas Ullmann and Klingenberg 3 found that the
oxidation product consisted onl}- of anthraquinone-j8-car-
boxylic acid. Further, they pointed out that authraflavone
adds on a molecule of bromine without au}^ evolution of
hydrobromic acid, and that the dibromo- product thus
obtained is quantitatively changed back to authraflavone b}'
treatment with diethylaniline. These facts all point to
authraflavone being really dianthraquinonyl eth3dene, and
this is in agreement with the observation of Ullmann and
Klingenberg, 4 that authraflavone is obtained when cu-
dibrom-^-methyl anthraquinone is heated with dimethyl-
aniline, or better with dieth3daniline.
The stilbene structure has been full}' confirmed by the
work of other investigators. Thus, Hepp, Uhlenhuth and
1 B.A.S.F., D.R.P 179.893; 199,756. Bohn, B. 43, 1001.
- M. 32, 690. ' B. 46, 712. * Loc. cit.
A NTH R A Q UINONES—DIA NTHRA Q UINON YLS 95
Romer 1 obtained anthraflavone by heating w-dibrommethyl
anthraquinone with sodium iodide in acetone solution, or by
treating it with copper powder; 2 and UUmann^ has employed
this method for preparing dicliloranthraflavone from 2-chlor-
3-dibrommethyl anthraquhione.
Scholl ■* condensed phthalic acid with j3- methyl naphtha-
lene, and from the 3-methyl-i.2-benzantliraquinonc thus
obtained he got an anthraflavone which no doubt had the
structure
CO
-CH=CH
CO
although vScholl gave it c\ clic formula in conformity with the
then belief that anthraflavone contained a seventh ring.
Scholl's product was a vat dye, and gave reddish shades of
yellow. A vat dye which gives orange shades is said to be
obtained b}- adding bromine to a boiling solution of i-chlor-
4-niethyl anthraquinone in nitrobenzene. & The constitution
of the dye is unknown, but it ma}- be a stilbene derivative.
1 B. 46. 709. M.L.B., D.K.P. 260,662 ; 267,546.
2 Cf. Eckert, iM. 35, 300. ^ B. 47, 560.
* M. 32. 997. * M.L.B., D.R.P. 259,881.
CHAPTER V
ANTHRONE, ANTHRANOL, AND
ALLIED PRODUCTS
These are all reduction products of anthraquinone and
several of them have been mentioned already. Many of
them, however, are of considerable importance, and as they
exhibit extremely interesting dynamic isomerism they will
be discussed in some detail.
Anthrone and Anthranol
Anihrone itself was first obtained by Liebermann i by
the moderated reduction of anthraquinone with h3^driodic
acid or with tin and hydrochloric acid in glacial acetic acid
solution. More recently the experimental details of this
latter method have been improved by Kurt Meyer, 2 but as a
rule the reduction is best carried out by means of copper or
aluminium bronze ^ and concentrated sulphuric acid at
30-40°. This last process has been investigated b}^ Eckert
and Pollak,4 who find that the first product formed is the
anthraquinol (hj^droxy anthrone ?), the anthrone then being
formed by further reduction.
Baeyer & obtained ms-phenyl anthrone by heating tri-
phenylmethane-o-carbox34ic acid with dehydrating agents :
H Ph H Ph
COOH CO
1 A. 212, 5 ; B. 20, 1854. » A. 397. 55.
3 B.A.S.F., D.R.P. 190,656; By., D.R.P. 201,542.
^ M. 38, II ; 39. 839. ^ a. 202. 54.
96
ANTHRONE AND ANTHRANOL 97
and Bistrzycki and Ulffers 1 have prepared hj-droxy-
anthrone and one or two other anthrone derivatives by this
method, although the reaction is often compHcated by
phthalide formation.
A somewhat similar synthesis of more complex anthrone
derivatives has been worked out by Haller and Guyot.2
They condensed 4'-dimethylaminobenzophenone-i-carboxylic
acid with dimethylaniline by boiling in acetic anhydride :
CO <?6M«NMe2
c
COOH ^ ^
0
CO
The phthalide thus formed they reduced to the corre-
sponding triphenylmethane carbox}4ic acid, which, on boiling
with phosphorus oxychloride in dimethylaniline solution, lost
a molecule of water and passed into an anthrone derivative :
COOH " CO
The same investigators ^ obtained ws-diphenylanthrone
by condensing phthalyl tetrachloride with benzene in the
presence of aluminium chloride :
COCl CO
CCI3 C
Ph Ph
and also by condensing dichloranthrone or phenylchlor-
anthrone with benzene
CO CO
C6H4<^CcH4 -> CfiH/VeH^
C c
/\ /\
CI Ph ^ Ph Ph
1 B. 31. 2799. ' Bl. [3] 25, 315. » C. r. 121. 102.
98 ANTHRACENE AND ANTHRAQUINONE
Baeyer i had previously obtained the same compound by
heating phenyl hj'droxyanthrone with benzene and sulphuric
acid although he did not describe it in detail.
Anthrone itself is a colourless crystalline compound which
does not exhibit fluorescence, and which melts at I54°.2
It is insoluble in cold alkali, but dissolves on heating owing to
its conversion into the enolic form (anthranol), and when
boiled with acetic anhydride it form§ the acetyl derivative
of this latter compound.
Anthrone is not readily attacked by mild oxidising
agents in the cold, and is only attacked comparatively
slowly on heating, the reaction being most rapid in those
solvents which favour enolisation. Goldmann 3 has studied
the action of chlorine and bromine on anthrone. He finds
that bromine gives first a monobrom compound (m.p. 148-
151° decomp.), and then a dibrom compound (m.p. 157°).
In both of these the halogen atoms must be imited to a
m^so-carbon atom, as both give anthraquinone on oxidation.
As was to be expected, chlorine reacts similarly, but much
more vigorously, so that onl}^ the dichlor compound could be
isolated. The same dichloranthrone (m.p. 132-134)° had
previously been obtained by Thorner and Zincke * by
treating o-methylbenzophenone with chlorine :
CO CO
,<^C,-H, -> C6H40C
CH, CCL
Nuclear chloranthrones have been obtained by Eckert
and Tomaschek ^ by reducing chloranthraquinones with
copper powder and concentrated sulphuric acid. Padova ^
has found that anthrone reacts with phosphorus penta-
chloride, but the product he obtained was probably dianthryl,
as it melted at 298-300" and contained no chlorine. The
1 A. 202. 65.
* Kurt Meyer, A. 397, 55. Liebermann, A. 212, 7, gives the melting
point as 167-170*.
3 B. 20, 2436; 21, 1176. * B. 10. 1478.
5 M. 39, 839. 6 C. r. 149. 217.
ANT H RONE AND A NTH R A NO L 99
alk}'! chloranthrones are obtained by the action of phos-
phorus pentachloride on the products obtained by alkylating
hydroxy anthranol (anthraquinol),i and Liebermann and
his students 2 have more recently found that the use of
phosphorus pentachloride is superfluous, as the reaction is
easily brought about by cold hydrochloric or hydrobromic
acid. The halogen atoms in the halogen anthrones are
extremel}' reactive, so that monobromanthrone is converted
into hydroxy^anthrone by aqueous solvents, 3 and into
methoxyanthrone by methyl alcohol.'^ Ammonia does not
convert it into an amino compound, but into bromdianthrone,
but arylamino anthrones are obtained b}- treatment with
primary aromatic amines. ^ Copper powder converts it into
dianthrone.6
Anthrone reacts normall}- with nitroso dimethyl aniline,*^
and Padova ^ has found that with benzaldehyde it gives
phenj'lmethylene anthrone, and with benzophenone chloride ^
it yields diphenylmeth^-lene anthrone :
CHPh CPho
C C
C6H4\/C6H4 C6H4N. ^C(;H4
c c
• • « •
o o
It does not, however, react with aniline, dimethyl-
aniline or with benzophenone itself. With benzo-trichloride,
however, it gives phen3'ldichlormethyl anthrone, ^ which
when heated with pyridine splits off a molecule of hydro-
chloric acid and passes into phenylchlormethylene anthrone :
' A. 212. 67. B. 13, 1596; 15. 452, 455. 462. C. r. 121. 102.
"- B. 37, 3337.
3 A. 379, 45.
< A. 323. 23G ; 379, 45. Cf. also B. 38, 2868.
« A. 396, 133, 145.
« A. 396, 143.
' B. 40, 525. Cf. B. 32, 2341 ; 33. 959 : 34, iiS, 3047.
8 C. r. 141. 857. Cf. Weitz, A. 418, 29.
' C. r. 143, 121. In the abstract of this paper pubhshed by the Chemical
Society (Soc. 90, (i) 741), " chlorure de benzophenone " is mistranslated
as " chlorobenzophenone."
100 ANTHRACENE AND ANTHRAQUINONE
c *c
C C
• • • •
o o
Padova 1 also found that anthrone reacts with chloro-
form in alcoholic solutions of caustic potash to form a com-
pound :
CgH, C6H4
O =C<^^C =CH— C^C— OH
C6H4 C6H4
and Friedlander 2 and Kalle & Co.^ have obtained vat dyes
by condensing it with isatine dichloride and dibromoxy-
thionaphthene :
C6H4 NH C6H4 S
CO<(^)>C =C<(^)>C6H4 CO<'^C =C<f ^C6H4
C6H4 CO C6H4 CO
Meerwein * has studied the condensation of anthrone
with unsaturated j3-diketonic compounds and finds that in
the case of benzal malonic ester and benzal aceto acetic ester
addition takes place verv^ readily :
/COCH3
COOEt
C6HgCHCH(COOEt)2
C6H5CHCH<^
CH
C6H4\ /C6H4
CO
CH
C6H4^^C6H4
CO
Attempts to hj^drolyse such compounds usually lead to
the formation of anthrone, but in the case of the addition
compound with benzalmalonic ester the hydrol3'sis could be
effected by means of sulphuric acid in glacial acetic acid
solution and lead to :
1 C. r. 140. 290. " B. 42, 1060.
3 D.R.P. 193.272. * J. pr. [2] 97, 284.
ANTHRONE AND ANTHRANOL loi
CeHgCHCH.COOH
1
CH
CO
Meerwein also found that anthrone forms an addition
compound with benzalacetophenone.
The formation of benzanthrones from anthrones is an
extremely important reaction, and is treated in detail in
Chapter XVI.
Kurt Meyer i has found that dibromanthrone reacts
easily with hydroxylamine and yields anthraquinone mon-
oxime ; and Haller and Guyot 2 have shown that dichlor-
anthrone condenses with dimeth34aniline in the presence of
anhj'drous aluminium chloride to form a compoimd
Me2NC6H4 C6H4NMe2
C
CO
Liebermann and Mamlock 3 found that bromanthrone reacts
very readih" with resorcinol by simply boiling in benzene
solution, no condensing agent being required. Under these
conditions one would rather expect the hj'droxyl groups of
the resorcinol to react with the production of a phenolic
ether ; but as the product gives a triacetyl compound it must
be regarded as a triphenyl methane derivative :
H C6H3(OH)2 C6H3(OH)2
c c
CeH^^CgH^ or C6H4<(|)>C6H4
C C
II I
O OH
As the compound apparently is not fluorescent the first
formula is the more probable. The triacetyl derivative,
1 A. 396. 152. = C. r. 136. 535. => B. 38. 1796.
102 ANTHR-iCEXE AXD AXTHRAOUIXOXE
which must conespand to the second formula, is ^; rough-
flaorescent.
In phenylchloranthrone the reactivity of halogen atom
is, as would be e^)ected, greater than it is ia the case of
brom-anthrone. With resordnol condensation takes place
in exactly the same way as vdth bromanthrone, but in the
case of the simpler phenols, such as phenol and cresol.
the reaction is different, the h\-drox\-l group reacting viixh the
halogen atom and at the same time condensation taking
place with the carbonyl group ; products of the stnictine :
Ph OR
C
C
X\
RO OH
being obtained.^
In the case of alcohols the hydrox\-l group reacts with
the halogen atom, but simiiltaneous condensation with the
carbonyl group does not take place, so that the products are
alkoxyanthrones.
The structure of phenylchloranthrone is ver\- similar to
that of triphem-lmethyl chloride, a compound which it
resembles in many of its reactions. It is therefore not
impossible that when treated with metals it might form a
compound 'amilaT to triphenyl methyl. Liebermann 2 and
his co-workers have found evidence that this is actually the
case, and Sdblenk,* by boiling phenyl chloranthrone in
petroleum ether solution with copper bronze, obtained a
yeUow crystalline powder which, in the absence of air, gave
a red solution in ether. The molecular weight was found to
be 400, a figure which corresponds to about 33 1 per cent, of
C20H13O and 66| per cent, of C40H26O2. vSchlenk has pointed
out that if the bridge formiila for anthracene is correct
wfs-di^henyl anthracene is really a derivative of the imknown
hexaphenylethane :
1 B. 38, iSoo. * B. 37. 3337 i 38, 1799. * A. 394. 3340.
ANTHRONE AND ANTHRANOL 103
C6H4 CeHg CgHs
CeHs-Cf-^C-CeHs CeHg-C^l^C-CeHs
C0H4 CgHr, CgHs
Diphenylanthracene. Hexaphenyl ethane.
and consequently might readily form a compound containing
two trivalent carbon atoms. He was unable, however, to
bring about this change.
ms-Nitroanthrone is formed when anthracene is treated
with nitric acid under certain conditions,! and also when
anthrone is nitrated in glacial acetic acid solution. 2 On
reduction it loses ammonia, anthrone and anthraquinol
being formed respectively when the reduction is carried out
in acid and alkaline solution. 3 The corresponding ms-
amino anthrone has never been obtained pure, but by
reducing phenyl-azo-anthranol Kurt Meyer * obtained an
impure substance which lost ammonia very readily and
formed anthraquinol. This was probabl}^ amino anthrone,
but owing to its instability it could not be purified sufficiently
for analysis.
The chlorine atoms in dichloranthrone are capable of
reacting witli nuclear hydrogen atoms under the influence of
aluminium chloride, and by this means Haller and Guyot ^
have prepared tetramethyl and tetraethyl diaminodipheu}!
anthrone from dichloranthrone (anthraquinone dichloride)
and dimethyl and diethyl aniline ;
CI CI MegNCsH^ CgHiNMeo
\/ \y
c c
C6H4<^^C6H4+2C6H5NMe2 -> C6H4<^C6H4
CO CO
In the case of aryl chlor anthranones the reactivity of the
chlorine atom is very much greater, and by condensing phenyl
chloranthrone with benzene m the presence of aluminium
chloride diphenyl anthrone is produced, a compound
' Perkin, Soc, 59. 648 ; 61, 866. * Kurt Meyer, A. 396, 150.
' A. 396, 133. * Loc. cit. ^ C. r. 136, 535.
104 ANTHRACENE AND ANTHRAQUINONE
which had been previously obtained by them by con-
densing phthalyl tetrachloride with benzene and aluminium
chloride,! and by Bae5^er by condensing phenyl hydroxy
anthranol with benzene in the presence of sulphuric acid : 2
Ph Ph CI Ph
CCI2 C C
C6H,<^^0+C6Ho -> C6H,<^CoH4 <- C6H6+C6H4<^C6H4
CCI2 CO * CO
t Ph OH
\/
C
CoH6+C6H4<(^C6H4
CO
Starting with this substance several interesting syntheses
have been carried out.
Liebermann and Lindenbaum * found that it was ver^-
readily reduced by zinc and acetic acid to the corresponding
hydrocarbon, and that by treating this latter with bromine
one, and onl}^ one, of the hydrogen atoms attached to the
;;is-carbon atom could be replaced :
Ph Ph Ph Ph
C
C
CeH.^CeH^ -> C,Jl^0C,il,
C
C
/\
/\
H H
H Br
The bromine atom in this compound is very reactive
and is readily replaced by hydroxyl and methoxy groups
by treatment with water or alcohol. The most interesting
reaction undergone by the compound is its behaviour when
1 c. r. 121, 102.
2 A. 202, 65. B. 38, 1799.
* Liebermann and Lindenbaum give it the formula CsjHjg and show-
two extra hydrogen atoms. Such a compound would only be formed by
loss of bromine and not by loss of bydrobromic acid, and the above formula
is the more probable.
ANTHRONE AND ANTHRANOL 105
heated, as it melts at 214-216° with evolution of hydro-
bromic acid and almost immediately solidifies, the same
change being brought about by heating with neutral solvents
of high boiling point, such as naphthalene. The resulting
compound contains no bromine, and undoubtedly has the
structure :
It is an extraordinarily stable substance which forms
slightly yellow cr3'Stals which are practically insoluble in
all media and which do not melt at 360°. It is hardly
attacked by boiling concentrated sulphuric acid.
Anthranol and its derivatives are to be regarded as
enolic tautomers of the corresponding anthrones (p. 118).
They are much more sensitive to oxidation than to corre-
sponding anthrones, and are usuall}' attacked by atmo-
spheric oxygen. Anthranol itself on moderated oxidation
passes into dianthrone, but the arylamino-anthranols pass
into the corresponding anil : 1
OH
O
C«H.
C«H. -> C6H4<^C6H,
C
NPh
NHPh
Goldmann 2 has studied the behaviour of anthranol
when heated in alkaline solution with ethj^l iodide and has
isolated three products. The first of these is anthranol
ethyl ether (wzs-ethoxy anthracene). It reacts violently
with bromine, but at —20° forms an mistable addition
1 A. 396. 147. * B. 21. 1 178. 2505.
io6 ANTHRACENE AND ANTHRAQUINONE
compound which evolves hydrobromiue acid at 0°, and
passes into a more stable dibrom compound. This on
oxidation 3delds, first, the monoeth}^ ether of B2:.-brom-
anthraquinol and then bromanthraquinone. and hence
must contain one bromine atom attached to the ws-carbon
atom and one attached to one of the benzene rings.
The second compound isolated b}^ Goldmann is a ver}^
stable substance melting at 136°. It is unaffected b}^
bromine, boiling aqueous caustic «potash and alcoholic
hydrochloric acid at 180°. It is very stable to both oxidising
and reducing agents, but by boiling with chromic acid in
glacial acetic acid solution it can be oxidised with difficulty
to anthraquinone. When heated with hydriodic acid and
phosphorus in a sealed tube it is reduced to tmsym-diethyl
dihydroanthracene, and must, therefore, be diethylanthrone :
Et Et Et Et
CO CH2
It is interesting to observe the diificult}- with which this
reduction is effected in view of the fact that the correspond-
ing diaryl compounds, e.g. diphenylanthrone, are very
readily reduced to the i/HSj^m-diaryldihydroanthracenes by
boiling with zinc and glacial acetic acid.i
The third compound isolated by Goldmann melted at
77°, and on moderated oxidation yielded C-ethyl hydroxy
anthrone, a compound previously obtained by lyiebermann 2
by the ethylation of hydroxy anthrone. It must, therefore,
be the ethyl ether of ethyl anthranol :
C2H5
./
C.H./ >C«H
.5J.X4
\
'6-^4
C
OC2H6
^ B. 38. 1799. =« A. 212, 70.
ANTHRONE AND ANTHRANOL 107
Hallgarten 1 has carried out similar experiments with
methyl iodide, »so-amylbromide and benzyl chloride, but
has only been able to obtain the dialkylanthrones. These,
like the diethyl compound, can only be reduced with
difficulty.
Kurt Meyer 2 and his co-workers have carried out some
very interestmg experiments on the action of diazonium
salts on the anthranol ethers. They lind that, contrar^^ to
the belief usually held, diazonium salts often couple quite
readily with phenolic ethers and even with unsaturated
aliphatic hj-drocarbons. The coupling is greatly facilitated
by the presence of negative substituents such as nitro
groups and halogen atoms, when in the ortho or para position
to the diazo group, but is hindered by negative groups m
the phenolic ether. Positive groups, especially alkoxy
groups, in the phenolic ether greatly facilitate the coupling
when m the meta position. In the case of the phenolic
ethers derived from phenols and naphthols, dealkylation
does not take place, the product being an alkox3^azo com-
pound. When anthranol methyl ether is used, however,
dealk3'lation does take place. Meyer suggests that the
first stage of the reaction consists in the formation of an
addition compound, which then passes into the azo com-
pound either by loss of water, or, in the case of anthranol
methyl ether, by the loss of a molecule of methyl alcohol :
MeO OH
\/
C
0
• •
C
C
H N : NAr
C6H4<^C6H4
c
N . NHAr
Methylanthranol methyl ether also couples with dizaonium
salts, and it is probable that the mechanism of the reaction
is somewhat similar :
^ B. 21, 2508.
* B. 47, 1741. e/. A. 898. 74; B. 52, 1468.
io8 ANTHRACENE AND ANTHRAQUINONE
CH3O OH Q
CgH^s
OCH3
I
c c
c c
I /\
CHo CHo N : NAr
^6^'i\ /CeH.i
CH3 N : NAr
Hydroxyanthrone and Anthraquinol
Hydroxyanthrone is to be considered as the tautomeric
(ketonic) form of anthraqtdnol, although in this case the
transformation of one isomer into the other is very slow, so
that solutions only attain equilibrium after prolonged boiling
(p. 121). Kurt Meyer 1 obtained hydrox3^anthrone by
treating bromanthrone with water, and found it to be a
colourless, non-fluorescent crystalline substance which melted
at 167°. He obtained the acetate by treating bromanthrone
with anhydrous potassium acetate and boiling glacial acetic
acid, and also by oxidising anthracene in boiling glacial
acetic acid solution with two and a half molecules of lead
dioxide,2 or by treating it in aqueous suspension with
chlorine or bromine below 25°. It is enolised b}^ hydro-
chloric acid and by sodium acetate, and also dissolves in
hot alkali owing to its conversion into the enolic form.
The ketonic form is quite stable in the air, and is onl}'-
attacked by mild oxidising agents when heated, oxidation
being probably preceded by conversion into anthraquinol.
On the other hand, it is readily reduced to anthranol by zinc
and glacial acetic acid at the ordinary temperature.
The methyl ether (methoxy anthrone) is obtained by
the action of methyl alcohol on bromanthrone 3 and is
enolised by caustic soda.
lyiebermann ^ endeavoured to prepare alkoxy anthranols
by heating alkaline solutions of anthraquinol with alkyl
halides, but instead he obtained stable compounds which
1 A. 379, 63. » A. 397, 76. ^ a. 323. 236.
* A. 212, 67. B. 13, 1596 ; 15, 452, 455, 462.
A NTH RONE AND ANTHRANOL
109
must be regarded as C-alkyl hydroxy anthrones for the
following reasons : —
(i) On reduction with hydriodic acid and phosphorus
they are converted quantitatively into ms-alkyl dihydro
anthracenes, which on oxidation with chromic acid first pass
back into the original alkylhydroxy anthrone and then into
anthraquinone. The composition of the alkyl diliydro-
anthracenes is almost identical with that of the various
hydroanthracenes, as will be seen from the following table,
so that elementary' analysis is not sufficient to establish
definitely that the products still contain the alkyl group : —
Ethyl dihydro
anthracene.
Carbon
Hydrogen
92-3
77
Butyl dihydro
anthracene.
91-5
8-5
Amyl dihydro
anthracene.
91 "2
8-8
Tetra hydro
anthracene.
92-3
77
Hexa hydro
anthracene.
913
87
Liebermann, however, carried out quantitative oxidations
by chromic acid, and by weighing the amount of anthra-
quinone formed, established beyond doubt that the sub-
stances were not hydroanthracenes.
(2) On treatment with phosphorus pentachloride (one
molecule) a vigorous reaction takes place and the hydroxyl
group is replaced by a chlorine atom. A similar replace-
ment is also brought about ver}' readily by cold hydro-
chloric or hydrobromic acid.i
(3) Although the hydroxyl group cannot be acetylated
in the ordinary way, Liebermann found that by treating
the chloride with anhydrous sodium acetate he was able to
obtain an acetyl compound, although he failed to obtain it
in a state of purity. This difficulty of acetylation is in
harmony with the fact that the C-phenyl hydroxy anthranol
obtained by Baeyer 2 by oxidising ms-phenyl anthracene
does not give an acetyl derivative.
(4) When reduced by zinc dust and ammonia, alkyl
dihydroanthranols are formed which very readil}- split off
water and pass into wzs-alkyl anthracenes :
1 B. 37, 3337-
A. 202, 5^.
no ANTHRACENE AND ANTHRAQUINONE
HO R
\/
C
HO R
c
R
1
C
H
c
o
C6H4<J>C6H4
C
/\
H H
-H2O r^ TT
>C6H,
C
I
H
The reaction here is exactly analogous to the reduction of
anthraquinone to anthracene carried out by Perger.i It
has received confirmation by Iviebermann,^ who alkylated
Perger's hydroxy dihydro anthracene and obtained sub-
stances which readily passed into ms-alkyl anthracenes by
loss of water, and which on moderated oxidation yielded
alkyl h^^droxy anthrones :
R
R OH
\/
C
C6H4< 1 >C6H4
c
/\
H H
o
C
I
H
R OH
\/
C
C6H4<^C6H4
c
• •
O
The above reactions were all obtained with the ethyl,
propyl, ^'so-butyl and iso-amyl compounds, but when
alkaline solutions of hydroxy anthranol were heated with
methyl iodide the reaction took a different course and a
methyl compound was obtained which formed methyl
iodide when heated with hydriodic acid, and which did not
react with phosphorus pentachloride. Its melting point
(187°) was also higher than the melting points of its homo-
1 J. pr. [2] 23. 137. * A. 212. G7. B. 13. 1596; 15, 452, 455. 462
A NTH RONE AND ANTHRANOL iii
logues. Obviously this is an 0-metliyl compound (methoxy
anthrone) :
H OMe
\/
C
CO
On one occasion, however, liebermann i obtained an
isomeric substance which melted at 98°, and which behaved
like a C-methyl compound, but he was unable to repeat his
experiment.
It will be noticed that methoxy anthrone can be con-
sidered as tautomeric with anthraquinol monomethyl ether :
H OMe OMe
\/ I
C C
C6H4<Q>C6H4 C6H.,<(^C6H4
CO c
I
OH
and this tautomerism is discussed on p. 121.
Kurt Meyer 2 has investigated the methylation and
ethylation of anthraquinol by means of methyl and ethyl
sulphate. With methyl sulphate he obtained a mono-
methyl ether (m.p. 164°), and a dimethyl ether (m.p. 202°),
and with ethyl sulphate a mono- and a di-eth)'l ether and also
Iviebermann's C-ethyl hydroxy' anthrone.
The formation of C-alkyl compounds by the alkylation
of hydroxy anthranol is ver>' similar to the formation of
C-alkyl compounds from sodio-acetoacetic ester. In this
latter case Saar has proposed that the transition from the
enolic to the ketonic state and vice versa is so rapid that as
soon as a molecule of one form enters into a reaction the
equihbrium is restored by the rearrangement of a molecule
of the other form. In the case of the hydroxy anthranols
this theory is not applicable, as Kurt Meyer has shown that
1 B. 21. 1 175. * A. 379, 47.
112 ANTHRACENE AND ANTHRAQUINONE
the transition from the anthrone to the anthranol form and
vice versa is slow. Claissen's theory that in the case of
acetoacetic ester O-alkyl compound is first formed, and that
this is at once rearranged into the C-alkyl compound, is
hardly tenable in view of the fact that O-alkyl compounds of
acetoacetic ester have been obtained and have been found to
be stable substances, and the same objection of course
applies to the monoalkyl ethers of anthraquinol. In the
case of acetoacetic ester Michael has proposed that alkylation
is preceded by addition, and in the case of the alkylation of
anthraquinol this theory also furnishes the best explanation
of the formation of C-alkyl compoimds :
ONa
CfiHZ^CaH
NaO R
\/
C
NaO R
.6x14
C
1
ONa
C6H4<' ^C6H4
c
/\
NaO Br
-> C6H4
6^4
o
The production of the 0-methyl compound is to be
ascribed to the predominance of the " normal " reaction in
this case :
0|Na IICH3
C
I
ONa
OCH3
I
C
CfiH
6^4
C
I
ONa
C6H4
The alkyl and aryl hydroxy anthrones can also be
obtained by the action of Grignard's solutions on anthra-
quinone, and this method of formation is discussed on p. 85.
The hydrox}'! group of the arj-l hydroxy anthrones is
very reactive and, as is pomted out elsewhere (p. 85), is
readily replaced by chlorine or bromine by treatment with
halogen acid. The carbonyl group is also reactive and
A NTH RONE AND ANTHRANOL 113
Haller and Gu3''0t 1 have found that in some cases heating
with concentrated sulphuric acid and an aromatic hydro-
carbon such as benzene or toluene is sufficient to cause
condensation to take place :
Me2NC6H4 OH Me2NC6H4 OH
C C
CO C
Ph OH
The anthraquinols are the enolic forms of the hydroxy
anthrones and are of great importance, as they are readily
soluble in dilute alkali and the alkaline solutions are very
rapidly oxidised b}- the air or by weak solutions of h3^drogen
peroxide with the formation of the corresponding anthra-
quinone. The msoluble vat dyes are always applied to the
fibre in the form of their anthraquinol derivative (" vat " or
" leuco- compound "), the insoluble dyestuif being subse-
quentl}^ precipitated on the fibre by exposure to the air or
by after-treatment with a mild oxidising agent,
Anthraquinol itself was first prepared by Graebe and
Liebermann - by the reduction of anthraquinone with zinc
dust and caustic soda, and more recently Grandmougin ^
has shown that the reduction is better effected with sodium
hydrosulphite in alkaline solution, the reducing agent alwa3^s
used in vat d3-eing. Owing to the ease with which the
anthraquinols are oxidised b3^ the air their isolation is a
matter of some difficult3-, and for this reason Liebermann *
introduced the method of carrying out the reduction with
zinc dust in boiling glacial acetic acid solution in the presence
of anhydrous sodium acetate. Under these conditions the
anthraquinol is acetylated as soon as formed, and as the
acet3'l derivatives are quite stable the3' can easih^ be purified.
They can be hydrol3'sed b3- alkali, but owing to the sensitive-
ness of the free h3^droxy compounds it is necessar3^ to work
1 C. r. 137. 606. » A. 160. 126.
' J. pr- [2] 76, 138; B. 39, 3963. * B. 21, 436, 1172.
8
114 ANTHRACENE AND ANTHRAQUINONE
in an inert atmosphere if pure products are to be obtained.
The behaviour of the anthraquinols when alkylated with
alkyl halides and with dimethyl and dieth}l sulphate has
already been described (p. iii).
DlANTHRYL AND ITS DERIVATIVES
Dianthryl is the hydrocarbon formed b}- the imion of
two anthracene residues by their ws-carbon atoms, and corre-
sponds to anthracene in much the same way that diphenyl
corresponds to benzene :
CgH^ C6H4
CH^C— C^CH
^6^4 C6H4
Theoretically five other dianthryls are possible which
may be represented as A[9][i]A, A[9][2]A, A[i][i1A,
A[i][2]A and A[2][2]A, where A indicates an anthry (C14H9)
group, and the numbers indicate the carbon atoms at which
junction is effected. These compounds do not seem to
have been described as yet, although some of the corre-
sponding quinones of the three last are well known. Di-
anthryl was first obtained by Schulze 1 by the action of
dehydrating agents on anthrapinacone :
C6H4 OH OH C6H4 C6H4 C6H4
CH,/Nc_C<^^CH., -^ CH^V— C^CH
C6H4 CgH^j C6H4 C^Hi
and Liebermann and Gimbel 2 soon afterwards found that
it could be obtained direct from anthraquinone by reduction
with tin and hydrochloric acid in glacial acetic acid solution.
More recently Eckert and Hofmann ^ have improved the
experimental details by carrying out the reduction with tin
and hydrochloric acid in glacial acetic acid solution in the
presence of a trace of a platinum salt, and claim to have
obtained excellent yields.
1 B. 18. 3035- * B. 20, 1854. =» M. 36. 497-
ANTHRONE AND ANTHRANOL 115
Dianthryl is a colourless fluorescent compound which
melts at 300°. When nitrated in acetic acid solution it
gives a dinitro compound,^ and as this on oxidation gives
anthraquinone, the nitro groups must be attached to the
;;K-carbon atoms. The dinitro compound is quite stable,
and melts at 337° decomp. On reduction the dinitro com-
pound gives the corresponding diamino- compound (m.p.
307-309° decomp.), which by gentle oxidation passes into
the di-imide, the tautomerism of which is discussed on p. 124.
Dianthranol corresponds to dianthr^'l in the same way
that anthranol corresponds to anthracene :
HOC^C— C^-^COH
C6H4 CgH^
It was first prepared by Hans Meyer - by the reduction
of anthraquinone with zinc and caustic soda under pressure
at a high temperatiure, and more recently Eckert and Hof-
mann ^ have obtained it by the alkaline hydrolysis of the
diacetate obtained by oxidising dianthryl with lead dioxide
in glacial acetic acid solution :
Ce^i CuH4 CyH4 C,jH.i
CHf-^C— Cf-^CH ^ CHaCO.OC^^C— C;^^;CO.COCPL,
^6^4 C,5H4 C6H4 C6H4
^6^4 CeH4
It melts rather indefinitely at 230°, its diacetyl com-
pound melting at 273° and its dimethyl ether at 245°, It is
easily oxidised to anthraquinone by chromic acid, but
mild oxidising agents, such as ferric chloride, alkaline
potassium permanganate or iodine in potassium iodide
convert it into dianthraquinone : *
1 B. 20.243^ - B. 42, 143; M. 30, 165; Kinzlberger c1- Co., D.R. p. 221,210.
3 M. 36, 497. * B. 42, 143.
ii6 ANTHRACENE AND ANTHRAQUINONE
CqH.4^ C6H4
O : C/Nc=c/Nc : O
C6H4 CeH.,
It has been stated that ;;z^so-ethers of hydroxylated
dianthranols are formed when mandeHc acid is heated with
p3-rocatechol or hydroquinone at 200-300°, although in the
case of resorcinol the product is dih^^droxydfphenyl methane
carboxyHc acid.^ The course of the reaction is not clear,
and the results claimed cannot be unreservedh' accepted
without further confirmation.
Diant krone is the tautomeric form of dianthranol, just
as anthrone is the ketonic form of anthranol, and the two
isomers are interconvertible b}^ the action of acids and
alkalis (see p. 124). It is obtained by the action of copper on
bromanthrone,2 and Dimroth ^ has obtained it in quantitative
jneld by the action of ferric chloride on anthranol, and in
smaller 3'ield by the action of nitric acid on anthracene :
C6H4 jj C6H4 H H C6H4
2 O : C< >C< -> O : Ci >C— C< >C : O
C6H4 C6H4 C6H4
Padova '^ has also claimed that it is obtained in good
34eld when dianthranol is oxidised with phenanthraquinone.
Orndorff and Bliss ^ have described a compotmd which
they obtained by the action of simlight on benzene solutions
of anthranol, and by boiling benzene solutions of the same
substance. This the}' regarded as a bimolecular polj-mer
of anthranol, and named it dianthranol, but there is little
doubt that their substance was reall}- dianthrone.
Dianthrone melts rather indefinitely at 245-255°, and is
insoluble in cold alkali.
Dianthraquinone is readil}- obtained b}' the oxidation of
dianthranol, Eckert and Hofmann ^ finding that it is
produced by the sulphuric acid hydrol3-sis of dianthranol
1 H. von Licbig, J. pr. [2] 78, 93. ^ A. 379, 44.
3 B. 34, 210. Cf. Scholl, B. 44, 1075. ^ C. r. 149. 217.
» Am. 18, 453- * M. 36, 497.
A NTH RONE AND A NT H RANG L 117
diacetate, although more readih' obtained by oxidising
dianthranol in alkahne solution with potassium persulphate
or hydrogen peroxide, ^ or, according to Kinzlberger & Co.,
by potassium permanganate : 2
^6^4 C6H4 CqH^ C6H4
HOC Ac— C(^^COH -> O : C<^^C=C<^^C : O
C6H4 C6H4 C6H4 C6H4
Padova ^ has stated that it is also obtained when di-
anthranol is oxidised by amyl nitrite in pyridine solution ;
but according to Meyer, Bondy and Eckert ^ the substance
obtained by Padova was really only a mixture of anthra-
quinone and unchanged dianthranol. Eckert and Toma-
schek 3 have studied the chlordianthraquinones. These
thej' obtained by oxidising the chlordianthranols with
potassium persulphate, and found that they are oxidised by
atmospheric ox\'gen under the influence of light to more
highly condensed compounds, e.g. —
CO ci
CO CI
Kurt Meyer ^ endeavoured to prepare aminoanthrone
b)' the action of ammonia on bromanthrone, but always
obtained brom-dianthrone, which b}' treatment with copper
powder or when heated alone lost hydrobromic acid and
passed into dianthraquinone :
C6H4 Br H C6H4 C6H4 C6H4
O : C Ac— C<^^C : O -> O : C Ac : C Ac : O
^6^4 C6H4 C6H4 CgHi
1 M. 33. 1447. - D.R.P. 223,210.
=" C. r. 148, 290. ^ ' M. 33, 1447.
5 M. 39, 839. • A. 396, 133.
ii8 ANTHRACENE AND ANTHRAQUINONE
Tautomerism
Kurt Meyer ^ lias studied the question as to what extent
anthranol and anthrone compoimds can be considered to
be tautomeric :
OH O
I 11
C G
Q)H4<' yC6H4 ^ C6H4\ /CeHi
C C
H H H
Anthranol. Anthrone.
He points out that the formation of soluble alkali salts
with hot caustic alkali and the formation of acetyl deriva-
tives point to the enolic formula, whereas the insolubilit}'
in cold alkali points to the ketonic formula. Also Padova 2
has prepared condensation products with aldeh3'des and
ketones (see p. 99), and Kaufler and Suchannek ^ have
found that anthranol will not react with phenyl isocyanate.
These facts point to the ketonic (anthrone) formula, as does
also the absence of, or very slight, fluorescence shown by
the compounds.
Kurt Me^-er found that if an alkaline solution of Lieber-
niann's anthranol is acidified below —5° with dilute sul-
phuric acid an isomeric substance separates out, which
crystallises in yellow needles which melt at 120° when
suddenly heated, whereas the original substance is colourless
and melts at 154°.* The new substance has a very strong
fluorescence and is easily soluble in cold aqueous alkali.
On keeping it slowly changes back to the original substance,
the change being much more rapid when the substance is
amorphous than when it is crj^stalline. It is readil}^ soluble
in most media, giving 3^ellow solutions with a strong blue
fluorescence, but these fairly rapidly lose their colour and
^ A. 379. 37-
2 C. r. 141, 857; 143, 121.
^ B. 40, 518.
* Liebermann (A. 212, 7) gives the melting point as 167-170°.
ANTHRONE AND ANTHRANOL 119
fluorescence, especially when boiled, and the colourless
solutions on cooling deposit the original colourless sub-
stance.
Kurt Meyer therefore concludes that the colourless form
(m.p. 154°) is anthrone, and the yellow fluorescent form
anthranol :
OH
CO
^6^4^ /C6H4 CgH.i
OHo C
>CcH4
H
Anthrone. Anthranol.
In the solid state each of these can exist, but in solution
a state of equilibrium is reached, the change from enolic to
ketonic form being accelerated by the presence of a trace of
hydrochloric acid. At the equilibrium point the ketonic
state is always predominant in the case of the unsub-
stituted substances, but depends to some extent on the
solvent. It seems that glacial acetic acid favours the
enolic form more than other solvents, whereas chloroform
and acetone are especially active in favouring the ketonic
form.
The enolic but not the ketonic form is readily oxidised
by bromine to the non-fluorescent dianthrone, and as the
velocity of the change from ketone to enole is low, it is
possible to estimate the amount of enole present by titration
with bromine solution. This Kurt Meyer 1 has done by
using the disappearance of fluorescence to determine the
end point, as this is ver}- easily seen when the solution is
strongly illuminated by an iron-arc. He compared various
derivatives and determined the per cent, of enole present at
the equilibrium point in i per cent, alcoholic solution at the
ordinary temperature.
Equihbrium is also set up on fusion, and if anthrone is
1 A. 396, 140.
120 ANTHRACENE AND ANTHRAQUINONE
melted and then suddenty cooled it is foimd to be partiaUy
soluble in cold alkali.
Compound.
Per cent enole.
Anthrone
. . II
Nitroanthrone . .
.. 3
Phenylanthrone
. . 30
A nilidoanthrone
. . 80
Hydroxy^anthrone
f . 96
In pyridine solution all the above seemed to be completely
enolised.
Kurt Meyer 1 has noted the following differences between
the reactions of anthranol and anthrone : —
(i) Anthranol is readil}' attacked by mild oxidising agents
such as ferric chloride, bromine, am^^l nitrite, etc., whereas
anthrone is not attacked in the cold and only with difficult}-
on heating. As anthrone is most readily oxidised in those
solvents which favour the change to the enolic form, it is
probable that oxidation onh^ takes place subsequent to
enolisation. It is noticeable that the oxidation product is
always the ketonic dianthrone and never the enolic dianthra-
nol, this being the case even when the oxidation is carried
out with potassium ferricyanide in alkaline solution.
(2) Anthranol couples with diazonium solutions to yield
azo- dyes, whereas the anthrone does not. Kurt Meyer 2
has examined these with a view to determining whether
they are enohc or ketonic, but has been unable to come to
any definite conclusion. He obtained the same product
by coupling phenyl diazonium chloride with anthranol as
he obtained by condensing dibromanthrone with phenj-l
hydrazine. He obtained two isomeric benzoyl derivatives,
however, one of which must be ketonic, as he obtained it b}'
condensing dibromanthrone with benzoyl phen^-l hydrazine.
The other isomer he obtained by coupling diazotised anUine
with anthranol, and then benzoylating the azo dye. This
latter must be enohc, and by comparing the properties of the
two benzoj'-l derivatives Meyer formed the opinion that the
» A. 379. 37.
« A. 396. I5-J.
ANTHRONE AND ANTHRANOL 121
parent azo- dye was probably enolic. Kauffler and Such-
annek,! and more recently Cliarrier,^ on the other hand,
prefer the ketonic (hydrazone) formula. 3
(3) Anthranol condenses with nitroso dimethyl aniline
to form an anil, whereas anthrone does not.*
Kurt Meyer ^ has also examined the isomerism of anthra-
qninol :
OH
I O
c c
OH . H OH
Anthraquinol. Hydroxyanthrone.
which is obviously enolic, as it is soluble in cold aqueous
alkali, is fluorescent and is ver^- readily oxidised. If its
alkaline solutions are acidified at a low temperature it is not
precipitated in the ketonic form, nor is it ketonised by
boiling with alcoholic hydrochloric acid. Meyer was imable
to convert it into h^-droxA-anthrone, but succeeded in
preparing this latter substance by treatmg bromanthrone
with water :
H Br H OH
C
C6H4\/C6H4 "> C6H4<^^C6H4
CO CO
He found it to be colourless, non-fluorescent and stable
to atmospheric ox>'gen. Unlike anthraquinol it is only
attacked by bromine on heating, and even then the reaction
is slow, and it is readily reduced by zinc and acetic acid to
anthranol, whereas anthraquinol is not. It is insoluble in
cold alkali, but is enolised to anthraquinol by boiling alcohoUc
alkali. The intercon version of the isomers in this case is much
1 B. 40, 518. 2 G. 45, 502.
' For absorption spectrum see Sircar, Soc. 109, 762.
* B. 40. 525- * A. 379, 44.
122 ANTHRACENE AND ANTHRAQUINONE
more difficult than in the case of anthrone and anthranol,
so that solutions do not reach the equilibrium point imtil
after being submitted to prolonged boiling, imless a catalyst
such as h^'drochloric acid or sodium acetate is present. This
difficulty of interconversion renders the behaviour of the
substances when heated different. Thus anthranol when
heated slowly shows no sharp melting point owing to its
gradual conversion into anthrone, whereas anthraquinol
melts sharply at i8o°, and hydroxy anthrone at 167°, and
on further heating both decompose into anthrone, anthra-
quinone and water, without apparently first imdergoing
any interconversion. An exactly similar isomerism is
exhibited by methox}- anthrone and anthraquinol mono-
methyl ether. Here the ketonic form is obtained b}' the
action of methyl alcohol on bromanthrone,i and is enolised
by warm dilute alkali, the enolic form being obtained
direct by the action of methj-l iodide or dimeth5'l sulphate
on anthraquinol. 2 This on oxidation gives dimethox}"-
dianthrone, which cannot form an enolic isomer as it has no
labile hydrogen atom : ^tt
H OMe
C6H4C
/\c«H
6^ A
OH -^
Sr.
NaOH
OH
C
I
OMe
C6H4 OMe OMe C6H4
^CO
« A. 323, 236.
oc<Q>c
C6H4 C6H4
« A. 376, 47.
ANTHRONE AND ANTHRANOL 123
Baeyer 1 obtained phenyl anthrone by heating tri-
phenyl methane-o-carboxyhc acid with sulphuric acid.
Ph H Ph H
COOH CO
This is obviously ketonic, as it is not fluorescent, is in-
soluble in cold alkali, and is not oxidised by cold alcoholic
bromine. 2 It dissolves in hot alkali, and if the solution is
cooled to —5° and acidified with dilute sulphuric acid, the
enolic form separates out. This is strongl}- fluorescent,
soluble in cold alkaU, and is readih- oxidised by bromine,
or by air when in alkalme solution. It is much less stable
than anthranol itself, and on keeping rapidly reverts to the
ketonic form.
Kurt jNIeyer ^ endeavoured to prepare amino anthrone,
but was unable to obtain it in a pure state. However, he
was able to prepare ar3'lamino anthrones by treating brom-
anthrone with primary- aromatic amines and found that
they exhibit the same keto-enole tautomerism. As was to
be expected, the ketonic form is non-fluorescent, and is not
sensitive to bromine, whereas the enolic form, obtained from
the ketonic form by boiling with a catalyst, such as hydro-
chloric acid or sodium acetate, is fluorescent and sensitive
to bromme. In most solvents the enolic form predominates,
but in glacial acetic acid it is the ketonic form which is
predominant. On oxidation the enolic form \ields the anil,
and it is curious to note that whereas the monoanil is deep
red, the dianil is only yellow :
0
NPh
c
CgH4<0>CcH,
c
C
C6H4<Q>CoH4
C
NPh
Deep red.
» A. 202, 54.
* A.
396,
133
NPh
YeUow.
* Loc. ciU
124 ANTHRACENE AND ANTHRAQUINONE
Dianthrauol and dianthrone exhibit the same form of
isomerism as anthranol and anthranone. Thus, Hans
Meyer i prepared dianthranol by reducing anthraquinone
with zinc and caustic soda imder pressure, and foimd that it
was ketonised by prolonged boiling with alcohohc h^'dro-
chloric acid, the reverse change being brought about by
caustic potash :
CgH^ C6H4 HCl CgH^ rt H C6H4
HOC^C— C^COH KOH O : C<^^C— C^^C : O
CsH^ C6H4 C6H4 CeH^
and Ktut Meyer 2 has found that ms-anthramine when oxidised
by amyl nitrite,^ or by other oxidising agents such as bromine,
gives an imide (m.p. 205°), which is partially isomerised on
melting or when boiled with sodium acetate or aqueous
caustic potash, and is completely isomerised by alcoholic
potash :
C6H4 H H C6H4 C6H4 C6H4
HX : C^^C— C<(^C : NH -> H^N.C^C— C^C.NHa
C6H4 C6H4 C6H4 C6H4
This latter compoimd melts rather indefinitely at 324-
334°, and was obtained by Gimbel 3 by nitrating and reducing
dianthr>-l. So far the reverse change has not been brought
about.
1 B. 42, 143. 2 B. 46, 29. ^ B. 20, 2433.
CHAPTER VI
ANTHRAQUINONE RING SYNTHESES
The synthetic methods which have been employed for the
production of anthracene derivatives, and the oxidation of
these to the corresponding anthraquinones, are described
elsewhere, 1 and in this chapter only those methods will be
treated by which an anthraquinone is formed without the
previous production of an anthracene derivative. Some of
the methods to be described have proved to be of the greatest
assistance in the study of the more complex anthraquinone
vat dyes ; but special methods of building up these complexes
will only be mentioned very shortly, as they are more con-
veniently treated in detail when dealing with the special
classes of compounds involved.
I. P'rom Aromatic Monocarboxywc Acids
When aromatic monocarbox>-lic acids are heated with
dehydrating agents, such as phosphorus pentoxide or an-
hydrous zinc chloride, loss of two molecules of water between
two molecules of the acid often takes place with the pro-
duction of an anthraquinone derivative :
COOH <^°
HOO
CO
The production of anthraquinone itself by this method
was achieved by Behr and van Dorp 2 by heating benzoic
acid with phosphorus pentoxide, but the yieldsare exceedingly
1 Chapter II. » B. 7. 16, 578.
125
126 ANTHRACENE AND ANTHRAQUINONE
poor. The reaction takes place much more readily if a
hydroxy benzoic acid is used in place of benzoic acid, and
in some cases quite satisfactory yields are obtained by
heating the hydroxy acid with concentrated sulphuric acid.
Thus vSchunck and Romeri foimd that when m-hydroxy-
benzoic acid is heated with concentrated sulphuric acid a
mixture of various dihydroxy anthraquinones is formed in
42 per cent, yield. Of the isomers fornled anthraflavic
acid is the most plentiful (82 per cent.), the remainder con-
sisting chiefly of anthrarufin and a little 1.7-dihydroxy
anthraquinone. They contradict Rosentiel's statement 2
that iso- anthraflavic acid is also formed. Other hydroxy
benzoic acids behave in a similar way to w-hydroxy benzoic
acid, e.g. 2-methyl-3-hydroxy-i-benzoic acid gives 1.5-
dimethyl dnthraflavic acid,^ and gallic acid gives rufigallol.*
The above method can be extended by heating a molecular
mixture of two different aromatic monocarboxylic acids
with a dehydrating agent, although, as would be expected,
this procedure often results in a complex mixture of various
anthraquinone derivatives. As examples of this method
may be mentioned the production of dimethyl anthragallol
by Birukoff,5 by heating a mixture of benzoic acid and
gallic acid with concentrated sulphuric acid, of trimeth3'l
anthragallol by Wende 6 from durylic acid and gallic acid,
and of anthragallol itself from benzoic acid and gallic acid.'^
The yields, however, are very poor ; Birukoff, for example,
obtaining only a yield of two per cent. When, however,
gallic acid is condensed with a hydroxy benzoic acid better
results are obtained, e.g. gallic acid when condensed with
2-methyl-3-h3^droxy-i -benzoic acid and with 2-methyl-5-
Itydroxy-i-benzoic acid gives respectively 5-meth3d-i. 2.3.6-
tetrahydroxy anthraquinone and 5-methyl-i.2.3.8-tetra-
hydroxy anthraquinone. ^
There would seem to be some possibility that the above
1 B. 10, 1225 ; 11, 969. 1225. 2 B 10, 1033. 3 K., D.R.P. 87,620.
* Robiquet, A. 19, 204 (18^6). Schiff, A. 163. 218.
6 B. 20, 870. « B. 20, 867.
' Seuberlich, B. 10, 38. Auerbach, Ztg. 1882, 910.
8 K., D.R.P. 87,620.
ANTHRAQUINONE RING SYNTHESES 127
method of forming the anthraqiiinone ring could be carried
out by a catal5'tic method, e.g. by passing the vapour of the
aromatic monocarboxyhc acid over a suitable catalyst, such
as precipitated silica or aluminium or calcium phosphate,
although no such method has been recorded.
II. From Phthalic Acid by the Direct Method
It is usually best to build up anthraquinone derivatives
from phthalic acid in two steps, by first forming the phthaloyl
derivative (o-benzo}-l benzoic acid), and then subsequently
closing the anthraquinone ring by treatment with a de-
hydrating agent. This method is treated in detail in the
next section mider the heading " Phthalic Acid Synthesis,"
and in the present section onl}- those methods will be men-
tioned by which an anthraquinone derivative can be obtained
from phthalic acid in one step. The method is confined to
the production of Itydroxyanthraquinones.
In some cases phthalic acid will condense with a phenol
to form a hj-drox^^ anthraquinone simply under the in-
fluence of heat, no dehydrating agent or catalj^st being used.
Thus, Baeyer and Drewson ^ obtained 4-methylerythro-
hydroxy anthraquinone by heating phthalic anhydride with
^-cresol for two days at 160-200°, and more recently Ull-
mami 2 has found that when phthalic anhydride is heated
with /)-clilorphenol a mixture of 4-chlorer3'throh3-droxy
anthraquinone and of o-hydroxychlorbenzojd benzoic acid
is obtained. As a rule, however, the condensation only
takes place in the presence of a condensing agent such as
sulphiuric acid, although, as will be seen, boric acid or alu-
minium chloride are often effective.
When sul])huric acid is used as a condensing agent
phthalein formation takes place simultaneous!}', so that
the yields obtamed are often extremely poor. Baeyer and
Caro, and Liebermann and his students have studied the
condensation of phthaHc anhydride with various phenols
in the presence of concentrated sulphuric acid, and have
1 A. 212, 345. * D.R.P. 282,493.
128 ANTHRACENE AND ANTHRAQUINONE
obtained various li3'droxy authraquinones, such as erythro-
hj-droxyantliraquinoue mixed with a little /3-hydroxyanthra-
quinone from phenol itself, i alizarin and hystazarin from
P3-rocatechol,2 and quinizarin from hydroquinone.3 The
yields, however, never exceeded 5 per cent, of the theoreti-
cally possible, and Birukoff * states that the condensation of
phthahc anhydride with _/)-cresol gives a jdeld of only i J per
cent, of 4-meth3derythrohydrox}'anthraqui»one. It should
be noted that during the condensation of phthalic anhydride
with ^-chlorphenol simultaneous replacement of the chlorine
atom by hydroxjd takes place, the product being quinizarin.
In this case the yield obtained is nearly 10 per cent, of that
theoretically possible, and prior to the discovery of the
direct oxidation of anthraquinone to quinizarin this was the
best method of preparing the substance. ^
The condensation of phthalic anhydride with phenols
under the influence of concentrated stdphuric acid has been
extended to the preparation of 3-methyl quinizarin from
phthalic anhydride and meth3'lh3'droquinone by Nietzki,^
and to the preparation of various heteronuclear methyl-
dihydroxy authraquinones from s-meth^'l phthalic acid and
pyrocatechol and h^-droquinone b>- Niementowski,' but the
yields are imsatisfactory.
By using chlorphthalic acid in place of phthalic acid,
heteronuclear chlorh}- droxy authraquinones can be obtained,
and it has been claimed ^ that hydroquinone condenses readily-
under the influence of concentrated sulphuric acid with
chlorinated phthahc acids, in which not more than one
chlorine atom is in the otiho- position to a h\'drox3'l group.
The reaction is described as taking place readily with 3-
chlorphthalic acid, and particularly readily in the case of
4.5-dichlorphthalic acid, but as failing completeh- in the case
of 3.6-dichlorphthalic acid and tetrachlorf^hthalic acid.
1 Baeyer and Caro. B. 7, 972 ; 8, 152.
2 Baeyer and Caro, B. 7, 972 ; 8, 152. Schoeller, B 21, 2503.
^ Grimm, B. 6, 972; Baeyer and Caro, B. 7. 972.
* B. 20, 2068.
5 Liebermann, B. 10, 608 ; A. 212, 10.
« B. 10. 2011. ' B. 33, 1631.
8 M.L.B., D.R.P. 172,105.
\
\.
ANTHRAQUINONE RING SYNTHESES i2Q
Crossley i has investigated the condensation of 4-amino-
phthalic acid with hydroquinone in the presence of sulphuric
acid at 170-100°, and finds that the main product is 1.4.6-
trihydrox^-anthraquinone, although some 6-aminoquini-
zarin is also formed. Here apparently the amino group is
replaced by hydroxyl, but the results must be accepted with
some reserve, as Crossley states that his 1.4.6-trihydroxy
compound did not melt at 300°, whereas Dimroth and Fick 2
give its melting point as 256°.
In some cases the yield of hydrox^^anthraquinone is
greatly improved by carr^'ing out the condensation with
concentrated sulphuric acid in the presence of boric acid,
and by this means it has been claimed ^ that quinizarin
can be obtained in 75 per cent, yield from phthalic anhydride
and either hydroquinone or ^-chlorphenol. In this case the
improved yield is no doubt due to the formation of a boric
ester hindering phthalein formation, but there is no informa-
tion available to say whether boric acid has a similar bene-
ficial influence on the condensation of phthalic anhydride
with other phenols.
Boric acid alone at about 210° can also bring about the
condensation between a phthalic acid and a phenol. Thus,
Dimroth and Fick * obtained i.2.4.6-tetrahydrox}'anthra-
quinone by heating 4-hydrox3'phthalic acid with hydroxy-
quinol triacetate and boric acid in benzoic acid solution.
In the same way they obtained i.4.6-trihydrox\benzoic acid
from hydroxj'phthalic acid and quinol, and i-methyl-
3.5.8-trihydrox\'anthraquinone from coccinic acid and quinol
diacetate.
As will be seen later, anhydrous aluminium chloride is
almost invariably used in the synthesis of anthraquinone
derivatives by the indirect method. In some cases, however,
it leads to the anthraquinone compound in one step, and it
has recently been found that hydroxyanthraquinones can
be obtained by heating phthalic anhydride with phenols,
naphthols, anthrols or hydroxy anthranols at 180-250° in
1 Am. Soc. 40, 404. * A. 411, 330.
' By., D.K.P. 255,031. « A. 411, 325.
P
130 ANTHRACENE AND ANTHRAQUINONE
the presence of auhydrous aluminium chloride, i The
reaction is best carried out by using a great excess of phthalic
anhydride as a solvent. By this meaas hystazarin is ob-
tained from pyrocatechol, no alizarin being formed.
III. Phthalic Acid Synthesis
This extremely important method of building up anthra-
quinone derivatives consists in first forming a phthaloyl
derivative (o-benzoyl benzoic acid) by condensing phthalic
anhydride with an aromatic compound, usually in the presence
of anhydrous aluminium chloride, and then closing the
anthraquinone ring by treatment with a dehydrating agent,
such as concentrated sulphuric acid :
CO CO CO
C6H4<(^0+C6H6 -^ Ceil,(^C,li, -> C6H4<^C6H,
CO COOH CO
As the method is of very general application, and as the
yields are often almost theoretical, it has met with vei}'
extended use, and many investigations have been carried
out with a view to determining the optimum conditions.
The first step of the process, viz, the formation of the
ketonic acid, is brought about by anhydrous aluminium
chloride, and usually starts at or about the ordinary tem-
peratmre, although as a rule is only completed by heating on
the water bath for 6-12 hours, viz. imtil the evolution of
hydrochloric acid gas ceases. In carrj^irig out the reaction
it is absolutely essential to use a whole (double) molecule of
aluminium chloride, as although the action of the chloride is
catalytic, it combines with the ketonic acid to form an addi-
tion compound, and is thus rendered inoperative. 2 Hence, if
less than a molecular proportion is used the yields obtained
are proportionally small. As a rule, the best solvents to use
during the condensation are carbon bisulphide or light petro-
leum, but in some cases the use of a different solvent give«-
more satisfactory results. These will be discussed when d
ing with the various classes of substance which have b
1 By., D.R.P. 298,345. * Heller and Schiilke, B. 41, 3627
ANTHRAQUINONE RING SYNTHESES 131 ^33
found to undergo the condensation. As a rule, the best pro- \
cedure is to add i part of powdered ahiminium chloride to (j
i|-2 parts of solvent, and then to add all at once an equimo- *'
lecular mixture of finely powdered phthalic anhydride with
the substance with which it is to be condensed. The reaction
sets in either at the ordinar^^ temperature or on gently warm-
ing and is completed by boiling under a reflux condenser
mitil no more hydrochloric acid is evolved. Water is then
added to destroy the aluminium chloride, and the solvent
removed by distillation with steam. It is not generally
necessary to purify the ketonic acid before converting it into
the anthraquhione derivative, but if desired to do so it
will often be found that the most satisfactory results are
obtained by cr^'Stallising the ammonium salt.
In carr^'ing out the above condensation it must be
remembered that the aluminium chloride may bring about
side reactions. Thus, if alkoxy groups are present in the
molecule, partial or complete dealkylation will almost
certainly be brought about, and if methyl groups are present
intramolecular or intermolecular wandering of these may
take place. The same remark also applies to some extent
to halogen atoms, so that conclusions as to the orientation
of groups in the finished product can only be drawn with
great caution and, as far as possible, should be confirmed by
independent methods. As the ketonic acids are stable
substances it is often possible to introduce new groups into
:he molecule before closing the anthraquinone ring.
For closing the anthraquhione ring concentrated sulphuric
cid (six to ten parts) is usualh' employed, but the ease with
hich water is lost varies ver\' much with the individual
mpounds. Thus, naphtho^-l benzoic acid loses water at
5-50°, whereas benzoyl benzoic acid requires a temperature
( about 120°, and in other cases the reaction only takes place
"v temperatures of 150° or above. W^hen this is the case
ilphonation frequently takes place simultaneously. If the
^tonic acid becomes sulphonated it is usualh^ impossible to
se the ring at all, whereas if ring formation precedes
)honation the finished product is a sulphonic acid.
\
^
132 ANTHRACENE AND ANTHRAQUINONE
When trouble is experienced through sulphonation taking
place it will often be found advantageous to use oleum con-
taining from 10 to 30 per cent, of free anhydride in place of
concentrated sulphuric acid, as if this is done it is usually
possible to work at a much lower temperature, and by
selecting suitable conditions it will often Ije found possible
to close the ring without appreciable sulphonation taking
place. 1 In any case the addition of boric acid is frequently
advantageous, and the same remark applies when ordinary
concentrated sulphuric acid is being used.
In addition to the danger of sulphonation taking place,
the use of sulphuric acid has the drawback that it often
demethylates methoxy groups when these are present, even
when they have escaped the hydrolytic action of the aluminium
chloride, and also in some cases brings about simultaneous
oxidation. Thus,- Gresly 2 condensed phthalic anhydride
with pseudo-cuniene and obtained a trimethj'l benzoyl
benzoic acid which, when heated with oleum, gave dimeth3^1-
anthraquinone carboxylic acid and not the trimethylanthra-
quinone as expected.
In order to avoid such side reactions phosphorus pent-
oxide can be used in place of sulphuric acid,^ and Elbs * hcs
used phosphorus pentoxide in conjunction with sulphuric
acid. In this latter case it is difficult to see what advantage
phosphorus pentoxide and sulphuric acid can have over
oleum, unless phosphoric acid has a beneficial action re
sembling that of boric acid.
Another method of closing the ring which has of^n
proved of value in obstinate cases consists in reducing he
ketonic group and thus obtaining the diphenyl methue
derivative. The ring can then often be closed by meanpof
sulphuric acid or oleum, zinc chloride or sodamide, and he
1 Bentley, Gardner and Weizmann, Soc. 91, 1630. Bentley and V>iz.
mann, Soc. 93, 435. Harrop, Norris and Weizmann, Soc. 95, 12 12. Wgch
and Weizmann, Soc. 97, 687. Bentley and Weizmann, Soc. 105, 748.
HeUer and Schiilke, B. 41. 3627. Mettler, B. 45, 800. Gresly, A. 234 • i.
* A. 234, 238. Cf. also UUmann, A. 388, 217. er
' Behr and van Dorp, B. 7, 578. Bentley and Weizmann, Soc. ' lor,
M.L.B., D.R.P. 194,32s. -'
* J- pr- [2] 41, 122.
(
ANTHRAQUINONE RING SYNTHESES 133
lesulting antlirone then oxidised to the anthraquinone.
This method has often proved useful in the S3'nthesis of
the more complex anthraquinone derivatives, and is also
often of service when it is desired to introduce a new group
before closing the ring.i
H0MO1.OGOUS Anthraouinones. — The phthalic acid syn-
thesis originated in an observation by Friedel and Crafts, 2
that small quantities of anthraquinone were present in the
products formed by the action of anhydrous aluminium
cliloride on phthalic anhydride in benzene solution, and at
a later date 3 they extended their investigations to the
products formed from toluene and xylene, and at the same
time pointed out that acetic anhydride behaves in much the
same way as phthalic anhydride, acetic anh^'dride and
benzene giving acetophenone when treated with aluminium
chloride. Previous to this Biircker * had showTi that
succinic anhydride will condense with benzene in the presence
of aluminium chloride to give /3-benzoyl propionic acid.
The preparation of anthraquinone ^ itself from benzene
and phthalic anhydride has been investigated in great detail,
as at one time it was proposed to manufacture anthraquinone
by this process, although the scheme was abandoned on
account of the cost of the aluminium chloride. 6 The yields,
however, are excellent, about 97 per cent, of the theoretically
possible, and there is no difhculty in closing the anthra-
quinone ring by heating the benzoyl benzoic acid Avith
ordinary- concentrated sulphuric acid at 125-150°. If oleum
is used instead of concentrated sulphuric acid, simultaneous
sulphonation takes place with production of anthraquinone-
/3-sulphonic acid.' The condensation of the phthalic
^ Gresly, A. 235, 238. Bistrzycki and Schepper, B. 31, 2793. Scholl,
B. 44, 1075. M. 32. 687. Limpricht, A. 309, 121. Weitz, A. 418. 29.
Seer, M. 33, 540.
« Bl. 41, 323.
» A. ch. [6] 14, 446.
* A. ch. [5] 26, 435.
0 Friedel and Crafts, A. ch. [6] 14, 446. Pechmann, B. 13, 1612.
Haller and Guyot, C. r. 119, 139. Gresly, A. 234, 238. Graebe and Ull-
mann, A. 291, 9. Elbs, J. pr. [2] 41, x. Heller, Z. ang. 19, 669. Heller
and Schulke, B. 41, 3627. Rubidge and Qua. Am. Soc. 36, 732.
8 HeUer, Z. ang. 19, 669.
' Liebermann, B. 7, 805.
134 ANTHRACENE AND ANTHRAQUINONE
anhydride with benzene is most conveniently effected by
using a large excess of the hydrocarbon as a solvent, and the
same is true when meth}^ anthraquinones are being prepared
from toluene or the xylenes.
From toluene i the main product obtained is )S-methyl-
anthraqiiinone, from o-xylene 2 2.3-dimethyknthraquinone,
from m-xylene 3 i.3-dimeth3'lanthraquinone and from p-
xylene ^ 1.4-dimethylanthraquinone. Pseudo-cumene gives
i.2.3-trimethylanthraquinone,5 although, as has alread}''
been pointed out, the final closing of the ring b^^ means of
sulphuric acid is apt to be accompanied by simultaneous
oxidation of one methyl group to carbox>d. Scholl ^ has
prepared ethyl, propyl and ^so-prop^d anthraquinone from
phthalic anhydride and ethyl, propjd, and iso-propyl benzene.
Condensation between phthalic anhydride and naphthalene '
takes place with great ease, and the resulting naphtho}^
benzoic acid loses water very readily when warmed to
45-50° with concentrated stdphuric acid, the product being
i.2-benzanthraquinone. This compound and its derivatives
are treated in greater detail in Chapter VII., but here it maj-
be pointed out that so easily does naphthalene condense with
phthalic anhydride that the reaction may be carried out in
benzene, toluene or X3dene solution without the solvent being
attacked, provided no excess of phthalic anh3'dride is used.
Benzene, in fact, is the best solvent to employ.
Anthracene ^ also condenses readily \\ith phthalic
anhj^dride, and here again benzene is the best solvent
provided an excess of phthalic anhydride is avoided.
1 Friedel and Crafts, A. ch. [6] 14, 446. Limpricht, A. 299, 300.
Limpricht and Wiegand. A. 311, 181. Heller and Schulke, B. 41, 3627.
Elbs, J. pr. [2] 41, 4.
» F. Mej'er, B. 15, 636. Limpricht. A. 312, 99- Elbs, J. pr. [2] 41, 6 ;
B. 20, 1361. HeUer, B. 43, 2891.
3 F. Meyer, B. 15, 637. Gresly. A. 234, 238. Elbs, J. pr. [2] 41, 13;
B. 20, 1364. Scholl, B. 43, 353.
* Gresly, A. 234, 238. Elbs, J. pr. [2] 41, 27. Heller, B. 43, 2892.
6 Gresly, A. 234, 238. Elbs, J. pr. [2] 41, 122.
« M. 32, 687.
' Elbs, B. 19, 2209. Gabriel and Colman, B. 33, 448. Heller and
Schulke, B. 41, 3627. Heller, D.R.P. 193-961.
8 HeUer and Schulke, B. 41, 3O27 ; 45, 669. Heller, D.R.P. 193.961.
Cf also Schaarschmidt, B. 49, 381.
ANTHRAQUINONE RING SYNTHESES 135
Treatment of the product with dehj'dratmg agents, however,
does not lead to an anthraquiuone, but to rupture of the mole-
cule with formation of anthracene and phthalic acid, so that
the phthalo^'l group is probably attached to the ws-carbon.
Phthalic anh3'dride will also condense with phenanthrene, 1
and the phenanthroyl benzoic acid, when treated with phos-
phorus pentoxide, gives an anthraquiuone derivative which is
probably 1.2.3.4-dibenzanthraquinone and has the structure
CgH^— C— COv
I II /CeH^, although this has never been proved.
CeH4— C— CO^
Elbs 2 and Kaiser ^ were only able to condense one
molecule of phthalic anhydride with one molecule of di-
phenyl, thus obtaining phenylbenzoyl benzoic acid which
they could not transform into an anthraquiuone derivative.
Scholl 4 at a later date reinvestigated the subject and suc-
ceeded in closing the ring by heating phenyl benzoyl benzoic
acid alone at 340°, or with aluminium or zinc chloride at
150°. In both cases, however, the 3'ields were very poor.
Benzoyl benzoic acid itself is readily and quantitatively
reduced to the diphen^-l methane derivative by ammonia
and zinc dust in the presence of copper sulphate, but in the
case of phen3-l benzo^d benzoic acid the 3-ield by this method
was only 15 per cent. By using a mixture of caustic soda,
ammonia, ammoniacal copper sulphate and zinc dust,
however, Scholl obtained an almost quantitative yield
of the phenyl diphenyl methane carbox}-lic acid, although
the reaction was slow and required 144 hours. From this
compound he was unable to spht out water b}" means of
siilphuric acid, owing to sulphonation taking place, but b}-
heating with zinc chloride or sodamide at 190° he obtained
phenyl anthrone, from which /3-phenylanthraquinone was
obtained by oxidation. Scholl 5 also succeeded in con-
densing one molecule of diphenyl with two molecules of
phthalic anhydride, and from the product he obtained 2.2'-
dianthraquinonyl.
1 M.L.B., D.R.P. 194,3".?. * J- V^- W 41, I45-
3 A 2.57, 95. « B. 44, 1075. • B 44, 1086.
i36 ANTHRACENE AND ANTHRAQUINONE
>
Scholl found that o-ditohl i will also condense with two
molecules of phthalic anh^^dride, but a dimethj-l dianthra-
quinonyl can only be obtained from the product with the
utmost difficulty. As it gives no p3'ranthrone it must be
3.3'-dimethyl-2.2'-dianthraquinonyl. ^-Ditohd, on the con-
trary'', will only condense with one molecule of phthalic
anh3^dride, and the product tends to pass into a phthalide,
rather than into an anthraquinone.2 By reduction, de-
hydration, and subsequent oxidation, however, i-methyl-
4-/)-tolyl anthraquinone can be obtained. ^
as-Dix^dyl (2.4.2'.4'-tetramethyl diphenyl) condenses
with two molecules of phthalic anhydride to produce a
mixture of phthalo3dic acids. From these 2.4.2'.4'-tetra-
methyl-i-i'-dianthraquinonyl 4 can be obtained by treat-
ment with concentrated sulphuric acid at ioo°.
Halogenated Anthraquinones. — Homonuclear halo-
gen anthraquinones can be formed by the phthalic acid syn-
thesis either by condensing phthalic acid with an aromatic
halogen compound, or b}^ condensing a halogenated phthalic
acid with an aromatic h\'drocarbon. Heteronuclear halogen
anthraquinones are, of course, obtained when a halogenated
phthalic acid is condensed with an aromatic halogen com-
pound. Halogen compounds are also sometimes obtained
by halogenating the benzoyl benzoic acid and then closing
the ring. By this last method Mettler ^ obtamed a dichior-
dihydrox}- anthraquinone by chlorinating the dihydrox3'
benzoyl benzoic acid obtained by the oxidation of fluor-
esceine, and then closing the ring, and i-amino-4-chlor-
anthraquinone has been obtained by preparing 3-acetyl
amino benzophenone-3'-carbox3dic acid and- then treating
with dehydrating agents. ^ The method, however, has been
very little developed.
The formation of homonuclear halogen anthraquinones
from phthalic anhydride and aromatic halogen compoimds
has been fairly fully investigated. Chlorobenzene ' and
' B. 44, 109J. 2 Scholl, B. 44, 1091.
' Seer, M. 33, 540, * Scholl, B. 43, 512.
6 B. 35, 800. 6 Agfa, D.R.P. 254,091.
' M.L.B., D.R.P. 75,288.
ANTHRAQUINONE RING SYNTHESES 137
bromobenzcne 1 lead to the corresponding ^-halogen
anthraquinones, and ^-chlortoluene leads, of course, to i-
metliyl-4-cliloranthraquinone.2 From o-chlortoluene Heller
and Scliiilke 3 obtained a methylchloranthraquinone which
on oxidation and subsequent loss of carbon dioxide passed
into jS-chloranthraquinone, thus showing that the product
was either i-methyl-2-chlor-anthraquinone or 3-methyl-
2-chloranthraquinone. Ullmann ^ proved the latter of these
to be correct by oxidising it to the corresponding carbox}'lic
acid and then condensing with aniline. The resulting
anilidoanthraquinone carbox^dic acid by loss of water
passed into an acridone which was neither anthraquinone-
i.2-acridone nor anthraquinone-2.1 -acridone, and hence
must have been anthraquinone-2.3-acridone.
The condensation of phthalic anhydride with 0-, m-, and
p-bxova. toluene has been studied by Heller, ^ who finds that
in each case a mixture of methylbrombenzoylbenzoic acids
is formed, but that from each of these mixtures the same
methyl brombenzoyl benzoic acid can be isolated and that
this by loss of water passes into 2.3-methylbromanthra-
quinone. From this it is clear that in the case of m- and
;5)-bronitoluene the aluminium chloride has caused either the
methyl group or the bromine atom to wander, and as the same
phenomenon is not observed in the cases of the correspond-
ing chlortoluenes, it is probable that it is the bromine atom
that has changed its position. The wandering of bromine
atoms under the influence of aluminium chloride has, of
course, long been known ; Roux,^ for example, having
shown that aluminium chloride is capable of converting
a-bromnaphthalene into j8-broninaphthalene.
The condensation of 3.6-dichlorphthalic acid and 2.4-
dichlorphthalic acid with aromatic hydrocarbons has been
studied by several investigators,"^ without any results of
1 Ullmann, A. 380, 337.
a Heller and Schiilke. B. 41, 3627. Heller, B. 45, 792.
» HeUer and Schulke, B. 41, 3627. HeUer, B. 45, 792.
* B. 47. 553.
6 B. 47. 792. • A. ch. [6] 12. 334.
' Harrop, Norris and Weizraann, Soc. 95, 12 12. Ullmann and Billig,
A. 381. I. Le Royer, A. 238, 356, Ree, A. 234, 239.
138 ANTHRACENE AND ANTHRAQUINONE
particular interest being recorded, altliough it is worth
noting that the ketonic acid obtained from 3.6-dichlorphthalic
acid and w-xylene only passes into the anthraquinone with
the utmost difficulty, and yields of over 5 per cent, could
not be obtained. 1 Tetrachlorphthalic acid h^as also been em-
ployed for preparing homonuclear tetrachloranthraquinone.2
A large number of heteronuclear chloranthraquinones
have been obtained by Hofmann 3 by condensing various
chlorphthalic acids with aromatic halogen compoimds, but
they are of no particular interest.
Hydroxyanthraquinones. — Phthalic acid as a rule
will not condense with free phenols under the influence of
aluminium chloride to produce a hydroxy benzoyl benzoic
acid, as a phthalein is usually the sole product, although
recently Ullmann and Schmidt * have found that in many
cases a good yield of the hydroxybenzo}'! benzoic acid can
be obtained if the condensation is carried out in tetra-
chlorethane solution. It is too early to say if this method
is a general one and is applicable to all phenols, but from
the results already published its value is obvious. When
phthalic acid itself is used the carbonyl group prefers the
ortho- position with reference to the hydroxyl group, although
small amounts of other isomers are formed simultaneously,
and when tetrachlorphthalic acid is employed it is exclusively
the ortho- position which is taken. It is interesting to notice
that the condensation of phthalic anhydride with _/)-chlor-
phenol under the influence of aluminium chloride leads
to a mixture of _/>-clilorhydroxybenzoyl benzoic acid and
i.4-h5'drox\xhloranthraquinone, the conversion of the former
into the latter being completed by warming with concen-
trated sulphuric acid,^ whereas as already stated the direct
condensation of phthalic anh3^dride with ;/!)-chlorphenol by
sulphuric acid leads only to quinizarin.^
^ Harrop, Norris and Weizmann, Soc. 95, 12 12.
* Kircher, A. 238, 344. ^ M. 36, 805.
* Ullmann and W. Schmidt, B. 52, 2098. Ullmann and Conzetti,
B. 53, 830. Ullmann, D.R.P. 292,066.
6 Ullmann, D.R.P. 282,493.
' Liebermann, A. 212, 10; B. 10. 608. By., D.R.P. 255,031. See
also pp. 128, 129.
ANTHRAQUINONE RING SYNTHESES 139
The condensation of phthalic anh5'dride with phenols
can often be brought about with satisfactory results by
first niethylating the hydrox^'l groups, as this hinders
phthalein formation. During the condensation, however,
the aluminium chloride usuall}- causes partial or complete
demethylation, and methoxy groups which escape hydrolysis
by the aluminium chloride are usually demethylated during
the closing of the anthraquinone ring. This method was
used by Lagodzinski,i who obtained quinizarin from quinol
dimethyl ether, and hystazarin from veratrol, but Nourri-
son 2 had previously shown that ^-hydroxy anthraquinone
coidd be obtained from anisol. It has also been used to a
considerable extent by Weizmann * and his students, who
have obtained various hydrox}^anthraquinone derivatives
by condensing phthalic acid or a methox}^ phthahc acid,
such as hemipinic acid \nth aromatic hydrocarbons or
phenolic ethers.
The preparation of hydroxy anthraquinones from phenols
can also be effected without protecting the hydroxyl
groups if boric acid is used in place of aluminium chloride.
This method was first introduced b}'^ Deichler and Weiz-
mann, * who obtained hydroxy naphthoyl benzoic acid by
heating a-naplithol with phthalic anhydride and boric acid
at 190°, and has been extended by Weizmann and his
students, 5 who have prepared numerous hydroxy- anthra-
quinone derivatives from phthahc acid or hydroxy phthalic
acid and various phenols such as the cresols. Frey 6 has
used the method for condensing various dichlorphthalic
acids with hydroquinone, Hovermann "^ has condensed
tetrachlorphthalic acid with hydroquinone, and Dimroth
and Fick ^ have condensed phthalic acid, 4-hydroxyphthalic
1 B. 28. 117; A. 342. 90.
« B. 19, 2105.
' Bentley. Gardner and Weizmann. Soc. 91, 1630. Bentley and
Weizmann. Soc. 93, 435. Walsch and Weizmann, Soc. 97, 687. Bradbury
and Weizmann, Soc, 105, 2748. Cf. also Bistrzycki and Schepper, B. 31,
2793-
* Deichler and Weizmann, B. 36, 547.
* Bentley, Gardner and Weizmann. Soc. 91, 1630.
« B. 45, 1358.
' B. 47, 1210. « A. 411, 315
140 ANTHRACENE AND ANTHRAQUINONE
acid and coccinic acid (6-metliyl-4-hydrox}'plithalic acid)
with hydroquinone and hydroxyli3-droqiiinoue. In the case
of hydroxy hydroquinone they find it best to use the triacetyl
derivative, and find that the reaction takes place most
easily when benzoic acid is used as a solvent.^ Even by the
use of boric acid as a condensing agent phthalein formation
camiot be altogether avoided, a phthalein, for example,
being the sole product formed when 4-hydrox}- phthalic acid
is condensed with o-cresol.
Schaarschmidt i condensed phthalic acid with a-anthrol
by the use of boric acid, but was imable to close the ring.
MisCELL-\NEOUS SUBSTANCES. — Carhoxylic acids can
sometimes be obtained b}- the phthalic acid synthesis,
although the method has not been developed to any extent.
The preparation of dimethyl anthraquinone carboxylic acid
by Gresly 2 has already been mentioned, and the prepara-
tion of anthraquinone-^-carboxy-lic acid by oxidising toluj'l
benzoic acid and then closing the ring has been the sub-
ject of a patent. 3 It is claimed that oxidising the methyl
group before closing the ring leads to a much purer product,
Graebe and Blumenfeld,* and Graebe and Leonhardt.^
obtained anthraquinone a-carboxylic acid from hemi-
mellitic acid and benzene in the usual way, but in some cases
the presence of the carboxyl group seems to hinder the
closing of the ring. Thus, Heller and Schiilke ^ condensed
phthalic acid with _/)-chlortoluene and then oxidised the
meth}l group to carboxyl, but were unable to dose the ring
although before oxidation the ring closed quite easily, and
the}- experienced no difficulty in oxidising i-methyl-4-chlor-
anthraquinone to the corresponding carbox^-lic acid.
One or two tertiary amino anthraquinones have been
obtained by the phthalic acid s^mthesis, as Haller and
Guyot '^ have found that phthalic anhydride will condense
with tertian- aromatic amines which have a free para-
1 B. 49, 3S1. - Seep. 132.
' M.L.B., D.R.P. 80,407. * B. 30, 1116.
« A. 290, 231. « B. 41, 3627.
" Bl. [3] 25, 166; C. r. 119, 139. Cf. Societe anonyme des Matieres
Colorantes, D.R.P. 108,8^7; 112,913; 112,297; 114.197-S. Also
Weitz, A. 418. 29.
ANTHRAQUINONE RING SYNTHESES 141
position such as dimethyl aniHne, diethyl aniline and ethyl
benzyl aniline, and Scholl and Neovious 1 have condensed
two molecules of phthalic anhydride with one molecule of
carbazol.
Thianthrene and thiodiphenylatnine will also condense
with either one or two molecules of phthalic anhydride, and
the rings can be closed b}- means of zinc cliloride or concen-
trated sulphuric acid. 2
One or two variations of the usual phthalic acid synthesis
have been described although they have not led to any
important results. Thus, Louise 3 condensed benzoyl
chloride with mesitylene and then oxidised one of the methyl
groups of the resvdting trimethyl benzophenone to carboxyl.
The monocarboxylic acid thus obtained when treated with
dehydrating agents passed into 1.3-dimethylanthraquinone.
Ivimpricht * endeavoured to carry out a somewhat
similar synthesis. He condensed phthalic acid with 0-
x^'lene and then oxidised both methyl groups to carbox^-l.
He then condensed the resulting benzophenone tricarboxylic
acid wdth toluene, but subsequent treatment with a de-
hydrating agent failed to give a diquinone. Methods of this
nature would seem capable of further development and
should lead to interesting results.
"^fci
^ B. 44, 1249. * Scholl and Seer, B. 44, 1233.
' A. ch. [6] 6, 233. « A. 312. 99.
CHAPTER VII
THE BENZANTHRAQUINONES
There are two possible anthraquinones in which one of
the benzene rings has been replaced by a naphthalene
ring, viz. —
CO
CO
I
and both are known. In the literature they are usually
designated respectively as naphthanthraquinone and
naphthacenquinone ; but this nomenclature is open to
many objections, and it is much better to adopt Scholl's
system and denote them as 1.2-benzanthraquinone or
awo'.-benzanthraquinone (I) and 2.3-benzanthraquinone or
lin . -benzanthraquinone (II) .
Compounds containing five rings have also been pre-
pared, and of course the isomerism in this case becomes
more complicated. Most of the derivatives described up
to the present, however, are linear, the parent quinone (III)
being named dinaphthanthraquinone, although here again
it is preferable to adopt SchoU's system of nomenclature
and designate it as /m.-dibenzanthraquinone or 2.3.6.7-
dibenzanthraquinone —
CO
CO
in
142
THE BENZANTHRAQUINONES 143
Compounds of this nature are, of course, capable of forming
numerous mono-, di-, and tri-quinones, and several such
derivatives have been isolated.
/m«s-6iS««jg'.-Dibenzanthraquinone or 1.2.5.6-dibcnz-
anthraquinone (IV) has also been synthesised, but its
derivatives have not been studied.
I. ang.-BENZANTHRAOUINONE (NaPHTHANTHRAQUINONE)
a«^.-Benzanthraquiuone is extremely easily obtained
from naphthalene by the phthalic acid synthesis, ^ either
by using carbon disulphide as a solvent, 2 or, preferably,
by carrying out the reaction in benzene or toluene solution,
as the phthalic anhj^dride condenses with the naphthalene
so readily that the solvent remains unaffected provided
no excess of phthalic anh3-dride is used.^ The structure
of the quinone \vas proved by Scholl,-* who showed that
oxidation with potassium chlorate, nitric acid, chromic
acid or potassium permanganate and sulphuric acid led
to anthraquinone-i.2-dicarbox>dic acid, yields of 75 per cent,
being obtainable when the oxidation is carried out with
permanganate.
a«g.-Benzanthraquinone is a powerful vat dye (Sirius
Yellow G) and has considerable affinity for vegetable
fibres although used chiefly as a pigment. On reduction by
distillation with zinc dust ^ or by boiling with zinc dust and
ammonia ^ it 3'ields the parent hydrocarbon (a«g.-benz-
anthracene), which reverts to the quinone when oxidised.
Verv' few homologues of awg.-benzanthraquinone have
been described. From a-methylnaphthalene Scholl '
obtained a monomethyl compound which was probabh''
3-methyl-i.2-benzanthraquinone. ^-Methyl naphthalene also
readily condensed with phthalic anhydride, but the resulting
methylnaphthoyl benzoic acid would not pass into a quinone,
1 See p. 134.
* Graebe, A. 340, 249. Elbs, B. 19, 2209. Gabriel and Colman, B 33.
448.
3 Heller and Schulke, B. 41, 3627, Heller, D.R.P. 193,961.
* B. 44, 2992 ; D.R.P. 241,624. * Graebe. A. 340, 249.
« Elbs, B. 19, 2209. 1 M. 32, yy6.
144 ANTHRACENE AND ANTHRAQUINONE
so that in this case it is probable that the carbonyl group
had become attached to the a-carbon atom which was next
to the meth}-! group.
From a-chlomaphthalene and phthaHc anhydride Heller ^
obtained 3-chlor-i.2-benzanthraquinone, but ^-chlomaphtha-
lene led to a chlor-2.3-benzanthraquinone. Graebe and
Peter - condensed 3.6-dichlorphthahc acid with naphthalene,
but the closing of the anthraquinone ring was accompanied
b}^ sulphonation, so that dichlor-i.2-benzanthraquinone
sulphonic acid was obtained. As naphthanthraquinone
itself is not sulphonated under similar conditions it is probable
that the sulphonic acid group enters the benzene and not
the naphthalene ring.
The hydroxy- a;z^.-benzanthraquinones have been very
little investigated. Scholl 3 condensed phthahc anhydride
with i-meth3-l-2-methosy- naphthalene and then, after
reducing the ketoni< acid, closed the ring and final!}- oxidised
to the quinone. As the quinone when oxidised gave anthra-
quinone-i.2-dicarbox\-lic acid, the methox}- and meth}-!
groups must be in the benzene ring, and the quinone probably
has the structure I.
CO
OCH3
CH3
CO
I
By demethylating the free hydroxy- compound coiild be
obtained, but it was found impossible to replace the hydrox^-l
group by an amino group. If, however, the methyl methox\-
naphtho}-! benzoic acid was demethylated there was no
difficulty in replacing the hydroxyl group by an amino group,
and the anthraquinone ring could then be closed by the
action of dilute oleum. By this means Scholl was able to
obtain an amino meth^-l benzanthraquinone in which the
amino group could be replaced by chlorine or iodine in the
1 B. 45, 669. Cf. G.C.I.B., D.R.P. 230,455. * A. 340, 265.
9 M. 33, 507.
THE BENZANTHRAQUTNONES 145
usual way. The iodo compound when heated with copper
powder gave a dimethyl di-benzanthraquinonyl (II), and
the fact that this gave no pyranthrone dye when fused with
caustic potash supports Scholl's views as to the position of
the methyl groups.
When fl«^.-benzanthraquinone is nitrated ^ two mono-
nitro compounds (IV^ and Y) are formed :
CO
m
CO
V
The structure assigned to these is based on their behaviour
when reduced, as one of them (IV) gives a pyrrol derivative
whereas the other (V) gives an amino compound. As this
amino compound gives no vat dye either when fused with
caustic potash or when heated with antimony pentachloride,
it is extremely improbable that the amino group is in the
anthraquinone ring, and as the nitro group invariably enters
the naphthalene ring in the a-position formula V is reasonably
certain.
II. /iU.-BENZ.\NTHRAQUINONE (NaPHTHACENEQUINONE)
\\'hen phthaUc anhydride is condensed with succinic
acid by heating with sodium or potassium acetate, a sub-
stance is formed which is now known to be ethine diphtha-
lide (I) although it was originally regarded as bisdiketo-
hydrindene 2 —
C=CH CO CO CO
C6H40O j O0C6H, C6H4/ >CH-CH/ }C,H,
CO CH—C CO CO
I II
1 Scholl, B. 44. 2370.
2 Gabriel and Michael, B. 10, 1559. Gabriel, B. 17, 2531. Gabriel and
Leupold, B. 31, 1159. Roser, B. 17, 2619. Cf. also B. 10, 391, 2199 ; 11,
1007.
10
146 ANTHRACENE AND ANTHRAQUINONE
Nathanson, 1 and Gabriel and Leupold 2 have shown that
this substance undergoes a remarkable rearrangement when
treated with sodium methylate, both the lactone rings being
opened and loss of two molecules of water subsequently'
taking place between the carbox}^ groups and the hydrogen
atoms of the aliphatic chain, with the formation of bisdiketo
hydrindene (II) and iso-eihme diphthalide, the ketonic
form of this latter substance being identical with dihydro
/*'«.-benzanthradiquinone :
OH CO ^ Op 99
CO OH ' CO CO
fso-Ethinediphthalide or dihydro-ZfM.-Benzanthradiquinone.
Enolic form. Ketonic form.
Dihydro-/i7?.-benzanthradiquinone is, of course, also the
ketonic form of dihydrox\^-/w.-benzanthraquinone.
The above rearrangement is fairly general and is shown
also by the condensation product obtained by heating
phthalic anhydride with acetic acid and sodium or potassium
acetate, although in this case the formation of only one
compound is possible, viz. diketohydrindene :
OH
C=CHCOOH
C6H4<^0 ->
CO
OH
I
.C=CH2
C6H4\ +CO0
XOOH
C
-^C6H4<^^CH
CO
Diketohydrindene.
Enolic form.
As would be expected, this compound is formed directly
by the action of metallic sodium on a mixture of ethyl
phthalate and ethyl acetate, 3
Kaufmann * by oxidising diketohydrindene obtained
two products, one of which he regarded as bisdiketohydrin-
dene, although it differs completely from Nathanson's
1 B. 26.2582. ' B. 31, 1 160.
» Wislicenus, B. 20, 593 ; A. 246, 347 ; 252, 72. « B. 30, 382.
THE BENZANTHRAQUINONES 147
product, and the other of which he named indenigo and
ascribed to it the formula :
CO CO
C6H4^^C =Cv ^C6H4
CO CO
although Gabriel and Leupold ^ have since shown that
indenigo is almost certainly identical with their uo-ethine
diphthalidc.
The reduction of jso-ethine diphthalidc was also effected
by Gabriel and Leupold, 2 who thereby obtained two hydro-
carbons, viz. C18H12, which they named naphthacene
(/i'n.-benzanthracene), and its dihydro compound C18H14
(dihydronaphthacene or dihydro-^nz.-benzanthracene) . Both
on oxidation give /w.-benzanthraquinone (naphthacen-
quinone). This latter substance forms yellow needles
which melt at 294°, and when fused with caustic potash is
decomposed into benzoic acid and j3-naphthoic acid.
Nothing is known of the homologues of /m.-benzanthra-
quinones, and in fact, up to the present the hydroxyl de-
rivatives are the onl}' ones which have been studied in any
detail. By treating tso-ethine diphthalidc with phosphorus
pentachloride Gabriel and Leupold obtained 1.4-dichlor-
2.3-benzanthraquinone. In this the chlorine atoms are
fairly reactive, so that boiling for ten minutes with aniline
sufficed to convert it into the dianilido compound.
The hydroxy derivatives have been studied chiefly by
Weizmann and his students, although Liebermann and
Voswinckel,3 by heating i-methyl-3-hydroxybenzene-4.5.6-
tricarbox}'Hc acid to 200° with succinic acid and potassium
acetate, obtained a substituted ethine diphthalidc which by
treatment with sodium methylate gave a dimethyltetra-
hydroxy-/i«.-benzanthraquinone :
CHj OH CO
^ " "10H
OH CO CH3
' B. 31, 1272. ' Cf. also Deichler and Weizmann, B. 36, 547.
» B. 37, 3344-
148 ANTHRACENE AND ANTHRAQUINONE
This very closely resembled the substance obtained by
heating carminic acid to 200° in the air, although owing to
the insolubility of the substance in all solvents except
caustic alkali the identification could not be made
complete.
Deichler and Weizmann ^ found that phthalic acid would
condense with a-naphthol when heated inr the presence of
boric acid, and the resulting i-hydroxy-2-o-naphthoyl
benzoic acid when heated with concentrated sulphuric acid
passed into i-hydroxy-2.3-benzanthraquinone, and the
synthesis of hydroxy /m.-benzanthraquinones by this method
is fairly general. Thus Deichler and Weizmann 2 condensed
phthalic acid with i-naphthol-4-, 5-, and 8-sulphonic
acids, and Bentley, Friedl, Thomas, and Weizmann ^ ex-
tended the method to 1.5-dihydroxy naphthalene. In this
latter case two molecules of phthalic acid condensed with
one molecule of the naphthol; but subsequent treatment
with sulphuric acid led to the closing of only one ring, as
the second phthaloyl group split off and was replaced by a
hydroxyl group, the final product obtained being 4-hydroxy-
Bz.-i.2-dihydroxy-2,3-benzanthraquinone.
Hydroxy derivatives have also been obtained by con-
densing 4-hydroxy phthalic acid, 4 3-methoxy phthalic acid,^
and hemipinic acid ^ with naphthols, and nitro-hydroxy
compounds have been obtained from nitrophthalic acid,'
and chlorhydroxy compounds from 3.6-dichlorphthalic
acid and tetrachlorphthalic acid.^ In some cases the
closing of the anthraquinone ring can only be effected by
very drastic treatment, such as heating to 130° with oleum
containing 70 per cent, of free anhydride, and under these
conditions sulphonation and hydroxylation often take place
simultaneously. To some extent this can be avoided by
dissolving the naphthoyl benzoic acid in concentrated
sulphuric acid and boric acid, and then adding oleum
slowty.
1 B. 36, 547. ^ D.R.P. 134,985. => Soc. 89, 115 ; 91. ^5^8.
* Orchardson and Weizmann, Soc. 89, 115. ^ Ibid.
6 Bentley, Friedl, and Weizmann, Soc. 91, 1588. ' Ibid.
^ Harrop, Norris, and Weizmann, Soc. 95, 279.
THE BENZANTHRAQUINONES 149
Hydrox}'! groups can also be inserted into the molecule
b}' direct oxidation with oleum and boric acid, nitrosyl
sulphuric acid, or by fusion with caustic potash and potassium
chlorate, and by this means i.4-dihydrox3-2.3-benzanthra-
quinone (iso-ethinediphthalide) has been obtained from
i-hydrox3'-2.3-benzanthraquinone.i
When sulphonic acid groups are present in the molecule
they can be replaced by hydrox^-l groups by fusion with
caustic alkali, although this method has been ver\' little
appUed.- Weizmann ^ records one case in which an amino
group is replaced by hydrox^d by fusion with caustic alkali,
but as a rule he appears to find it best to carr^- out the
replacement by means of the diazo- reaction.*
Halogen atoms when present in a hydrox}'naphthoyl
benzoic acid are often replaced by hydroxyl groups when
the ring is closed, and Weizmann has obtained several
hydroxy- 1.2-benzanthraquinones b}- brominating the
hydrox^-naphthojd benzoic acid and then closing the
ring. 5 Under suitable conditions it is usually possible
to obtain a certain amount of the bromohydroxy- quinone
at the same time, and chlorine atoms seem to be much more
firmly bound than bromine atoms, as i-hydrox\--4-chlor-
naphthoyl-(2)-o-benzoic acid, obtained by treating the
hydrox^-naphthoyl benzoic acid with sulphured chloride,
gives 1 .4-hydroxychlor-2.3-benzanthraquinone.6
As regards the relationship between the colour of the
hydroxy- compounds and the position of the hydrox}*! groups,
Weizmann ' considers that hydroxy 1 groups in the naphtha-
lene ring tend to deepen the colour, whereas when in the
benzene ring the tendency is rather to lessen it. Bal}- and
Tuck 8 have examined the absorption spectra of some of
1 Deichler and Weizmann, B. 36, 719. D.R.P. 138,324-5.
* Deichler and Weizmann, B. 36, 719. Bentley, Friedl, Thomas, and
Weizmann, Soc. 91, 411.
3 Soc. 91, 411.
* Deichler and Weizmann, B. 36, 2326.
* Orchardson and Weizmann, Soc. 89, 115. Bentley, Friedl, Thomas,
and Weizmann, Soc. 91, 4it. Harrop, Norris, and Weizmann, Soc 95, 279.
* Geigv, D.R.P. 226,230.
'> Soc. '91. 411.
» Soc. 91, 426.
150 ANTHRACENE AND ANTHRAQUINONE
the liydrox>^ compounds, but as ver>' few of the large number
of possible compounds have been described, the data avail-
able are insufficient to justify any generalisation.
Very few halogen derivatives other than hydroxy- halogen
compounds have been described, but Orchardson and
Weizmann,! by treating hydroxynaphthoyl benzoic acid
with phosphorus pentachloride, obtained th^e corresponding
chloro acid, from which i-chlor-2.3-benzanthraquinone was
obtained. At the same time they obtained a bright red
compound which they regarded as an isomeric chloro-
benzanthraquinone although their analytical figures hardly
support this assumption (found, Cl=ii'2 ; calculated,
Cl=i2"i). By brominating their chlornaphthoyl benzoic
acid Orchardson and Weizmann obtained a bromo com-
pound from which they obtained i-chlor-3-brom-2.3-benz-
anthraquinone, but could not obtain it in a pure
condition owing to the tendency to split off hj^drobromic
acid.
Heller, 2 by condensing phthalic acid with /3-chlomaphtha-
lene, obtained a chlornaphthoyl benzoic acid from which
a quinone was obtained by loss of water. This he originally
believed to be 4-chlor-i.2-benzanthraquinone, but at a
later date found that on oxidation it gave anthraquinone-
2.3-dicarboxylic acid, and hence must be Bz.-2-chlor-2.3-
benzanthraquinone.3 The preparation of the 1.4-dichlor
compomid by the action of phosphorus pentachloride on
tso-ethinediphthalide has already been mentioned.*
A mononitro compound was obtained by Gabriel and
lycupold 5 by nitrating //«.-benzanthraquinone, but they did
not determine the position of the nitro group. Deichler
and Weizmann, 6 by nitrating i-h3^droxy-2.3-benzanthra-
quinone, obtained i-hydrox>^-4-nitro-2.3-benzanthraquinone,
from which by reduction and diazotisation the dihydroxy
compotmd (tso-ethinediphthalide) was obtained, thus
determining the position of the nitro group. Further
^ Soc. 89, 115. Cf. Pickles and Weizmann, Proc. 20, 220.
* B. 45, 669. s B. 46, 1497. * Page 147.
? B. 31, 1272. « B. 36, 2326,
THE BENZANTHRAQUINONES 151
nitration led to a dinitro compound. The analj-tical
values found for both the mono- and the dinitro com-
pounds are in very poor agreement with the calculated
values, so that pending further investigation it cannot be
assumed that either compound was obtained in a state of
purity.
By nitrating methoxy naphthoyl benzoic acid Orchardson
and Weizmann ^ obtained a nitro compound but were unable
to convert it into the quinone, as sulphuric acid caused
decomposition.
Hydroxy amino derivatives have been obtained by
Deichler and Weizmann, 2 and by Bentley, Friedl and
Weizmann ^ by the reduction of the nitrohydroxy com-
pounds, although here again the analytical figures given
leave the purity of some of the substances described open
to doubt. Amino groups have also been introduced into
the molecule by coupling the hydroxy compounds with
benzene diazonium chloride and then reducing the azo
dye formed.^ Negative groups or atoms when present in
the molecule are usually fairly readily replaced by arylamino
groups by boihng with primar}^ aromatic amines, ^ although
in those chloro- compounds obtained from chlorinated
phthalic acid the data available point to its only being
those chlorine atoms which are in the a-position which
react in this way.
Amino groups can also be introduced into the molecule
before closing the anthraquinone ring, either by nitration
and reduction, or by forming an azo- dye and then reducing
this. In the case of 4-aniino-i-hydrox3'-naphthoyl
(2) -benzoic acid the formation of the quinone takes place
with very great ease, it being sufficient to boil with nitro-
benzene,^ and the same amino-h3'drox)' quinone is formed
1 Soc. 89, 115.
* B. 34, 2326.
» Soc. 91, 1588.
* Harrop, Norris, and Weizmann. Soc. 95, 279.
' Gabriel and Leupold. B. 31, 1272. Orchardson and Weizmann,
Soc. 89, 115. Bentley, Tfiomas, Friedl. and Weizmann, Soc. 91, 411.
Harrop, Norris, and Weizmann, Soc. 95, 279.
« Bentley, Friedl, Thomas, and Weizmann, Soc. 91, 411.
152 ANTHRACENE AND ANTHRAQUINONE
directly when the corresponding hydroxy nitrouaphthoyl
benzoic acid is reduced with zinc and acetic acid.i
The only amino-/w.-benzanthraquinone which contains
no other substituents to have been described up to the
present seems to be i-amino-2.3-benzanthraquinone,2 which
was obtained by heating the corresponding hydroxys com-
pound with aqueous ammonia at 200°. ^
III. /^w.-Bknzanthradiquinone (Naphthacendiquinone)
Of the numerous /iVi.-benzanthradiquinones which are
theoretically possible, only one, viz. 2.3-benz-i.4.9.io-
anthradiquinone, has been described up to the present.
This was obtained by Gabriel and lycupold 3 by oxidising
1 .4-dihydrox>'-2.3-benzanthraquinone (/so-ethinediphtha-
lide) with nitric acid, and Deichler and Weizmann * have
shown that the reverse change can be brought about by
mild reducing agents such as ammonium sulphide or ferrous
salts.
The reactions of the diquinone have not been studied
in any great detail, but from the investigations which have
appeared it would seem that one of the quinone rings is
somewhat easily ruptured. Voswinckel ^ has studied the
action of the halogens on the diquinone and has found that
treatment with chlorine leads to the addition of two chlorine
atoms with the formation of a dichloride (I), which when
warmed with caustic soda rmdergoes rupture of one ring
with the formation of a ketonic acid (III), although at the
same time a small quantity of tso-ethinediphthalide (IV)
is formed. Probably the first action of the alkali is to bring
about the formation of a ketone hj-drate ^ (H)^ subsequent
loss of two molecules of hypochlorous acid then taking
place.
^ Orchardson and Weizmann, Soc. 89, 115.
2 Bentley, Friedl, Thomas, and Weizmann, Soc. 91, 411.
' B. 31. 1272.
« B. 36. 719.
5 B. 38, 4015.
6 Cf. Zincke, B. 20. 3229.
THE BENZANTHRAQUINONES
153
CO OH
With bromine a somewhat similar reaction takes place,
but in this case the dibromide cannot be isolated although
Voswinckel obtained a monobromketone monohydrate :
HO OH
This is very readily decomposed with rupture of the quinone
ring, and apparently gives the same ketonic acid as is
obtained from the dichloride. On this point, however,
Voswinckel could not be absolutely certain, as the melting
points of the acids from the two sources differed somewhat,
that from the bromo- compoimd melting at 199°, whereas
that from the dichloride melted at 185°.
The bromo-compound is much more reactive than the
dichloride, and when treated with aqueous sodium acetate
is readily converted into iso-ethinediphthalide. As obtained
by this means, however, the substance is almost black, and
its appearance is not appreciably altered by several re-
crystallizations from nitrobenzene or ethyl benzoate, whereas
a single recr^-stallisation from pyridine suffices to convert
it into the usual red needles. The black substance may
possibly represent one of the numerous possible tautomeric
forms, but Voswinckel ^ inclines to regard it as quinhydrone
1 B. 42. 465.
154 ANTHRACENE AND ANTHRAQUINONE
in nature. The tendency of the diquinone to form ketone
hydrates is very considerable, and Voswinckel has found
that such compounds are very readily formed by boiling
with phenol in glacial acetic acid solution in the presence of
a little sulphuric acid. The following scheme shows their
chief reactions ^ : —
HO C6H4OH
HO C9H4OH
OH
CH3OOO OH
JNoOH
HOCeHs OH qq
Ph^\ /OCOCM3
C Ph
HO OH N^o
CH3COOC6H, Ph £.Q
By the action of bleaching powder on the diquinone
Voswinckel obtained an internal cyclic oxide which, when
treated with caustic soda, gave the same ketonic acid that
he obtained from the dichloride (formula III, p. 153).
The acid when prepared in this way melted at 199°.
IV. tmnS-bisang.-'DlBT.NZANTKRAQUlNONZ (DlNAPHTH-
anthraquinone)
trans - 6iS«wg.-Dibenzanthraquinone (1.2.5.6. - dibenz-
anthraquinone) has been S3'nthesised by Weitzenbock and
Klinger " as shown by the following scheme : —
1 Voswinckel, B. 42, 458, 4648.
' Weitzenbock and Ivlinger, M. 39, 315.
THE BENZA NTHRA Q U I NONES
O")
COOH
3-4-5-e-0iben2phenanihr8ne.
■Z-S-G-Dibenzcfnihrcucene
i-Z-5-6-Dibenzanihraciuinom
The closing of the rmgs in the diainiuo compound was
effected by Pschorr's method, i viz. by treating the diazonium
salt with copper powder. Two alternative reactions were
possible and both took place, both an anthracene and a
phenanthrene being formed. It should be observed that
in the dibenzphenanthrene obtained there are two carbon
atoms in the peri- position to one another, so that when
heated with aluminium chloride a highly condensed
hydrocarbon, indicated by the dotted line, should be
^ Pschorr, B. 29, 496.
156 ANTHRACENE AND ANTHRAQUINONE
obtained,! although this does not seem to have been
attempted.
trans-bisang.-'Dihenza.nthraqmD.one melts at 248-249°.
It should be a powerful vat dye judging from its structure,
but no information regarding its tinctorial properties has
been published.
V. /w.-DlBENZANTHRAQUINONE (DiNAPHTHANTHRAOUINONE)
By condensing p3'romellitic acid with benzene, Philippi 2
and, at a later date, Mihs and Mills ^ obtained two isomeric
ketonic acids, both of which when treated with sulphuric
acid gave /w.-dibenz-i.4.5.8-anthradiquinone (dinaphth-
anthradiquinone) :
CO CO
CO CO
Philippi 4 also found that pyromellitic acid wlU condense
with toluene, but he was unable to obtain a quinone from
the ketonic acid. Scholl & obtained the same diquinone by
a different means. He condensed the chloride of anthra-
quinone-^-carboxylic acid with naphthalene and then heated
the resulting 2-anthraquinonYl-i-naphthyl ketone with
aluminium chloride. Here ring formation might take place
in either of two directions, as indicated by the dotted lines in
foimulae I and II ; but as the product on oxidation gave a
diquinone monocarboxylic acid, which by loss of carbon
dioxide passed into Philippi's diquinone, the reaction in-
dicated by I must be that which actually takes place.
CO CO ^ ^ CO
CO
1 See pp. 324, 328. Scholl, A. 394, iii ; B. 44, 1656. ^ M. 82, 624,
» Soc. 101, 2194. 4 M. 34, 705. 6 A. 394, 159.
THE BENZANTHRAQUINONES 157
It will be observed that the substance represented by
I can be regarded as a benzanthrone, and for a matter of
fact vScholl found that when fused with caustic potash it
gave a bluish-black vat dye which is probably a highly
complex violanthrone.
A substance which is probably a dihydroxy derivative
of the above diquinone is said to be obtained by condensing
phthalic anhydride with /^^/co-quinizarin and then oxidising
the product, 1 and compounds of similar structure are claimed
as being obtained by using hydroxyanthracenes or other
/ci^co-hydroxyanthraquinones in place of /^^wco-quinizarin.
By reducing their diquinone Mills and Mills 2 obtained a
hydrocarbon and an anthrone, the latter on oxidation giving
a monoquinone, viz. /i«.-dibenzanthraquinone :
CO
CO
PhLlippi,3 however, has criticised Mills and Mills' work,
and has concluded that some of their reduction products
were impure. Russig ^ when studying the action of carbon
dioxide under pressure on naphthoquinol obtained, in
addition to i.4-dihydrox>'naphthalene-2-carbox>dic acid, a
yellow substance which was probably a i.4.5.8-tetraliydrox3-
/jw.-dibenzanthraquinone (III) and a green substance which
he regarded as 5.8-dihydrox\^-/2.'w.-dibenz-i.4.9.io-anthradi-
quinone (IV) :
HO CO OH CO CO OH
3H CO OH CO CO OH
m IV
By treating i.4-dih3^drox>'naphthalene-2-carboxylic acid
with sulphuric acid he obtamed the triquinone, hn.-dibenz-
1.4,5.8.9.10-anthratriquinone (V). By distilling his dihydroxy
1 By., D.R.P. 298,345. * Soc. 101, 2194. ^ M. 35, 380.
J. pr. [2] 62, 44. Cf. Hartenstein, Dissertation, Jena, 1892.
158 ANTHRACENE AND ANTHRAQUINONE
diquinone with zinc dust he obtained what appeared to be
the parent hydrocarbon, /m.-dibenzanthracene (VI).
CO CO CO
CO CO CO
V VI
The compHcated conjugation of carbonyl groups with
double bonds which appears to exist in the triquinone renders
it an interesting substance.
CHAPTER VIII
ALDEHYDES, KETONES, AND
CARBOXYLIC ACIDS
I. Aldehydes
Comparatively little is known of the aldehydes of the
authraquiiione series, as they are somewhat troublesome to
prepare, although several members have been described.
The direct oxidation of methyl groups to the aldehydic
group can be effected by means of manganese dioxide and
sulphuric acid,^ although, as in the aromatic series, there
is considerable difficulty in preventing the oxidation going
too far. Ullmann and Klingenberg 2 have endeavoured to
avoid this by carr>^ing out the oxidation by Thiele and
Winter's method, i.e. by oxidising with chromic acid in
glacial acetic acid solution in the presence of acetic anhydride
and concentrated stdphuric acid, and subsequently hydro-
lysing the resulting acetate, and by this means have pre-
pared anthraquinone-j3-aldehyde from j3-methylanthra-
quinone. The method, however, is verv- troublesome ov>'ing
to the very slight solubility of methylanthraquinone.
The cu-dihalogen methyl anthraquinones do not give
the aldehyde on hydrolysis with alkali, but do so readily
when heated with concentrated sulphuric acid to 130°, with
or without the addition of boric acid, and this forms the
most convenient method of preparmg the aldehydes. 3 It
has also been applied to the preparation i.i'-dianthra-
quinonyl-2.2'-dialdehyde from 2.2'-diclilormethyl-i.i'-di-
anthraquinonyl.4
1 Agfa, D.R.P. 267,081. » B. 46, 712.
' Ullmann. B. 47, 559 ; 49, 744. B.A.S.F., D.R.P. 174.984.
* B.A.S.F., D.R.P. 241,472.
^59
i6o ANTHRACENE AND ANTHRAQUINONE
Amongst other methods of preparing aldehydes may be
mentioned the preparation of i-mtroanthraqmnone-6-
aldehyde by Eckert i by the action of nitric acid on j3-anthra-
quinonyl-j3-acrylic acid, and of i-aminoanthraquinone-2-
aldehyde by KaHscher 2 by treating with acids the con-
densation products obtained by heating i-amino-2-methyl-
anthraquinone with aromatic nitro compoimds and alkalis,
with or without the addition of primary aromatic amines.
The anthraquinonyl aldehydes form oximes, semicar-
bazones, phenylhydrazones and azines (two molecules of
aldehyde with one molecule of hydrazine) in the usual way, 3
and with dimethyl aniline green dyes of similar structure
to malachite green are obtained. These are somewhat
yellower in shade than malachite green, are difficultly soluble,
and are not at all fast.
II. Ketones
Extremely little is known of the anthraquinone ketones,
and it seems that the only substances described so far are
anthraquinonyl aryl ketones. These are prepared by the
action of the chlorides of the anthraquinone carboxylic
acids on aromatic compounds such as hydrocarbons, chloro-
hydrocarbons, etc., in the presence of aluminium chloride.*
The chlorides of both anthraquinone-a-carboxylic acid and
anthraquinone-j8-carboxylic acid react, but the latter reacts
most readily. Ullmann ^ condensed the chloride of 2-chlor-
anthraquinone-3-carboxylic acid with benzene and then
converted the resulting chloranthraquinonyl phenyl ketone
into the corresponding aminoketone by his sulphonamide
process.6 From this by diazotising and then treating the
diazonium salt with copper powder he was able to close the
fluorenone ring :
1 M. 35, 290.
= A. P. 1,285,726-7 (1918)-
3 Ullmann and Klingenberg, B .46, 712. B.A.S.F., D.R.P. 240,520;
241,786.
4 Ullmann, B. 47, 566, Schaarschmidt, B. 48, 831.
5 B. 47, 566.
6 See p. 197.
KETONES
i6i
CO
CO
NH,
CO CO CO CO
The product was found to be a yellow vat dye, but the
tinctorial properties were very feeble.
Schaarschmidt ^ iiuds that the ketones derived from
anthraquinone-a-carboxy^lic acid react quite differently
from those derived from anthraquinone-^-carboxylic acid
when reduced in acid solution, e.g. with concentrated sul-
phuric acid and aluminium bronze. The latter compounds
behave quite normally and are converted into the colourless
anthrones, whereas the former give highly coloured products.
These are green when dissolved in sulphuric acid of over 50 per
cent, strength, but become violet when the solution is diluted.
They are insoluble in alkali, but behave like other anthra-
quinone compounds towards alkaline reducing agents.
Schaarschmidt regards the violet compotmd as the
pinacone and the green compound as its cyclic anhydride :
OH OH O
• I I /\
— c — c— — c — c-
!
Ar Ar
I
I
Ar Ar
I
Violet compound.
Green compound.
but this theory seems somewhat improbable, as it provides
no explanation of the failure of the ^-ketones to form similar
compounds. It is much more probable that condensation
has taken place between the ketonic carbonyl group and the
reduced cyclic carbonyl group, with the production of some
such structure as
1 B. 48, 972 ; 1226 : 49, 3SO.
n
i62 ANTHRACENE AND ANTHRAQUINONE
the change in colour in strongly acid solution being due to
the formation of a carbonium sulphate. It should be noted
that the a-methylanthraquinones behave abnormally when
reduced in alkaline solution.
III. Carboxylic acids
In a few cases anthraquinone carbox>4ic acids have been
built up by the phthalic acid synthesis, e.g. from hemi-
mellitic acid,i but as a rule it is much better to introduce
the carbox}-l groups into the molecule after the formation
of the anthracene or anthraquinone ring. In the case of
the a-carbox3'lic acids this can be done by treating anthracene
wdth oxalyl chloride and aluminium chloride and then
oxidising the resulting anthracene carbox3'lic acid or ace-
anthrenequinone,2 but the method is of no great importance.
As a rule the anthraquinone carboxylic acids are obtained
either by the hydrolysis of the nitriles or by the oxidation
of the meth}^ anthraquinones. The hydroh'sis of the
nitriles takes a perfectly normal course, and the method
has been made use of by several investigators. ^
In preparing carbox\dic acids by the oxidation of methyl
compounds, either the method anthraquinone can be used,
or the methyl anthracene can be oxidised, when simultaneous
oxidation of the methyl groups and quinone formation takes
place. This latter method has been utilised to a considerable
extent as a means of identifying the homologous anthracenes,
and references will be found in Chapter II.
The oxidation of methyl anthraquinones to the corre-
sponding carboxjdic acids can be effected by boihng with
chromic acid in glacial acetic acid solution ; but as a rule the
best results are obtained by heating to 200-230° in a sealed
tube with dilute nitric acid * (D=iioo), although in some
cases it is preferable to use other means. Thus i-nitro-2-
1 See p. 140.
^ See p. 69. Also Butescu, B. 46, 212.
» Dienel, B. 39, 932. UUmann, B. 49, 735, 746 ; A. 388, 205 ; D.R.P.
243,788.
* Elbs, J. pr [2] 41, 6, 121. Heller and Schiilke, B. 41, 3627. O. Fischer
and Ziegler, J. pr. [2] 86, 293.
CARBOXYLIC ACIDS 163
methyl anthraquinoue is only oxidised with difficult)-, and
when heated under pressure with nitric acid the yield of
carboxylic acid does not exceed 30 per cent. In this case
the oxidisation is best brought about by boiling with nitric
acid (0=1383) and slowly adding chromic acid.i
a-Methylanthraquinone and its derivatives are usually
rather stable towards oxidation, 2 and although the carboxylic
acid can usually be obtained by heating under pressure with
dilute nitric acid, it has been claimed that treatment with
chlorine in nitrobenzene solution at 160° gives the most
satisfactorj' results.^ In other cases it is claimed that oxida-
tion can best be effected by the use of oxides of nitrogen, ^
preferably in conjunction with some indifferent solvent.
The ease with which oleum, nitrosyl sulphuric acid and
manganese dioxide bring about hydroxylation w^ould point
to these reagents as being tmsuited for the purpose of
oxidising methyl groups to carbox^d groups. This, however,
is not altogether the case, as Ullmann ^ has found that
i-methyl-4-chloranthraquinone is oxidised to the carbox\dic
acid when heated with concentrated sulphuric acid or oleum
to 120°. In the case of 2-methyl quinizarin the correspond-
ing carboxylic acid, quinizarin-2-carboxy-lic acid, can be
obtained by oxidation with nitrosyl sulphuric acid in the
presence of boric acid.^
Instead of oxidising a meth3danthraquinone directly to
the carboxjdic acid it is, of course, possible to convert it
first into the aldehyde and then to oxidise this. As a rule
this method has but little advantage over those depending
on direct oxidation, but in some cases Ullmann ' has found
it useful, particularly when dealing with large quantities.
It seems probable that in many cases the benzanthrone
derivative is a suitable source of anthraquinone-a-carboxylic
» B.A.S.F., D.R.P., 229,394. Tcrres, B. 46, 1638.
^ Birukoff, B. 20. 2068.
3 B.A.S.F., D.R.P. 259,365.
* B.A.S.F., D.R.P. 250,742.
^ A. 388, 217. Cf. O. Fischer and Sapper, J. pr. [2], 83, 207. Gresly,
A. 234. 238.
« Ullmann, B. 52. 511, 2111 ; By., D.R.P. 273,341.
' B. 47, 561 ; 49. 735. 746.
i64 ANTHRACENE AND ANTHRAQUINONE
acids, as Perkin i has found recentl}'- that anthraquinone-i-
carboxyHc acid itself can be obtained in 85 per cent, yield
by oxidising benzanthrone with chromic acid in acetic acid
solution.
A few carbox>"Hc acids have been described in which the
carboxyl group is situated in the side chain, and is not
directly attached to the nucleus. Thus jS-(f)-anthraquinonyl
acrylic acid can be obtained from /3-dichlormethyl anthra-
quinone 2 or anthraquinone-/S-aldehyde 3 by heating w4th
sodium acetate and acetic anhydride.
The individual anthraquinone carboxylic acids are of no
particular interest, and for a description of them the reader
is referred to the original Uterature.* It should be noted,
however, that they aU lose carbon dioxide rather easily, so
that samples which have been purified by subhmation fre-
quently show a low melting point. ^ One of the most readily
accessible acids is anthraquinone- 1. 2 -dicarboxj'lic acid,
which is very easily obtained by oxidising 1.2-benzanthra-
quinone.6 Like the isomeric anthraquinone 2.3-dicarboxyHc
acid, it readily gives a cjxlic anhydride. From this latter
acid WiUgerodt and MaffelzzoU '' endeavoured to prepare
the anthraquinone analogue of indigo, but failed, as they
could not get the glycine. By fusing the acid with zinc
chloride and resorcinol they obtained anthraquinone fiuores-
ceine, which, however, was onl}' feebly fluorescent.
The halogen carboxylic acids can be obtained from a
halogenated nitrile by h3'drolysis, or from a halogenated
methylanthraquinone by oxidation. Dichloranthraquinone
1 Soc. 117, 706.
2 By., D.R.P. 282.265.
' Eckert, M. 35. 290.
* In addition to those already given, the following are the more im-
portant references : Limpricht and Wiegand, A. 311, 180. Weiler,
B. 7, 1 185. O. Fischer, B. 7, 1195. Liebermann and Rath, B. 8, 248.
Schiiltz, B. 10, 118, 1049. Nietzki, B. 10, 2013. Wachendorfi and
Zincke, B. 10, 1481. Ciamician, B. 11, 269. Hammerschlag, B. 11, 82.
Bomstein, B. 15, 1821. Liebermann and Clock, B. 17, 888. Elbs, B. 17,
2848; 20, 1361. Heller, B. 43, 2891. Elbs, J. pr. [2] 35, 471. O.Fischer,
J. pr. [2] 79, 561. Fischer and Reinkober, J. pr. [2] 92, 53. Seer, M. 32.
163. Eckert. M. 35, 299. Lavaux, C. r. 143, 687.
* Limpricht and Wiegand, A. 311. 180.
« Scholl. B. 44, 2992. D.R.P. 241,624 ; 243,077.
' J. pr. [2] 82, 205.
CARBOXYLIC ACIDS 165
carbox3'lic acids ^ can also be obtained by chlorinating the
anthraquinone carbox^-lic acids themselves in concentrated
sulphuric acid solution at 125°.
Nitrocarhoxylic acids can be obtained from nitro nitriles
or nitromethylanthraquinones by the usual methods, and
Eckert 2 obtained 6-nitroanthraquinone-i-carboxylic acid by
treating j3(2)-anthraquinonylacr5'lic acid with nitric acid,
and then oxidising the resulting nitro aldeh^'de.
Liebermann and Clock ^ nitrated anthraquinone-jS-
carboxj-lic acid and obtained a uitro acid, but did not
determine the position of the nitro group. Ullmann *
nitrated authraquinone-a-carboxyhc acid and obtained
5-nitroanthraquinone-i-carboxylic acid, the structure being
proved bj^ its preparation from 1.5-dinitroanthraquinone
through the nitro amino compoimd and nitro nitrile.
Acid chlorides and acid amides are obtained by the usual
means,^ e.g. by phosphorus pentachloride and ammonia.
They are much more stable than the corresponding com-
pounds of the benzene series. Thus Liebermann and Clock
foimd that the chloride of anthraquinone-jS-carboxyUc acid,
after remaining in contact with water at the ordinary
temperature for 120 hours, was only hydrolysed to the extent
of 7 1 per cent. The corresponding amide they found was
not hydrolysed by cold concentrated sulphuric acid or by
boiling dilute alkali, although it was hydrolysed by hot
concentrated alkali.
The anthraquinone nitriles can be obtained from the
anthraqtiinone sulphonates by heating with potassium
C3-anide or, in some cases, from the chloranthraquinones by
heating with cuprous cyanide and an indifferent solvent. ^
They can also be obtained from the anthracene sulphonates
by distilling these with potassium cyanide and then oxidising
the resulting anthracene nitrile. According to Ullmann,''
1 By., D.R.P. 255,121. 2 M. 35, 290.
3 b: 17. 891. * A. 388, 207.
* Liebermann and Glock, B. 17, 888. Graebe and 131umenfeld, B. 30,
1 1 16. Wilgerodt and Mafielzzoli, J. pr. [2] 86, 205. Seer, M. 32, 163.
Eckert, M. 35, 290.
6 M.L.B., D.R.P. 271,790 ; 275,517.
' A. 388, 204. Cf. Dienel. B. 39, 932.
i66 ANTHRACENE AND ANTHRAQUINONE
however, the product obtained from anthracene-a-sulphonic
by this method consists chiefly of anthraquinone itself.
The usual method of preparing the nitriles, however, is
by treating the diazonium salts with potassium cupro-
cyanide, although the yields obtained are often very poor,
e.g. Ullmann ^ obtained a yield of only i6 per cent, from
2-amino-i-chloranthraquinone. In some cases the poor
yield obtained is due to the reducing action of the cupro-
cyanide, and Terres 2 has found that the diazonium salt
from 2-methyl-i-amino anthraquinone when treated with
potassium cuprocyanide gives jS-methylanthraquinone.
A considerable number of nitriles have been prepared by
Schaarschmidt,3 who finds that their tinctorial properties
are very feeble, although this can be remedied to some
extent by halogenating.
1 B. 49. 735, 746. Cf. also A. 388, 203.
2 B. 46, 1646. 3 A. 405, 95.
CHAPTER IX
THE NITRO, NITEOSO, AND HALOGEN
ANTHRAQUINONES
I. The Nitro Compounds
When anthraqiiinone is nitrated the a-position is first
attacked exclusively, no /3-nitroantliraquinone being formed.
The preparation of a-nitroanthraquinone has been described
by several investigators, i the most recent descriptions being
those by Ullmann 2 and Lauth.3 Both of these last carry
out the nitration by the addition of nitric acid to anthra-
quinone dissolved in concentrated sulphuric acid, the former
specifying a temperature of about 50°. Ullmann states
that the crude product contains about 8 per cent, of dinitro
compounds, all of which, with the exception of the i.8-dinitro
compound, can be got rid of by recrystallisation from toluene.
In order to remove the i.8-dinitroanthraquinone he suggests
distillation m vacuo, ^ and gives the boiling point as 270-271°
at 7 mm. Lauth does not state the amount of dinitro
compounds formed under the conditions he uses, but as his
crude product melted at 218° instead of at 220° the quantity
must have been very small. This is in accordance with
the author's experience, who has prepared several pounds
of nitroanthraquinone in the laboratory by adding potassium
nitrate in 5 per cent, excess to anthraquinone dissolved in
concentrated sulphuric acid, the whole being allowed to stand
at the ordinary temperature for 48 hours.
The further nitration of anthraquinone leads to a mixture
1 Bottger and Petersen, A. 166, 147. Romer, B. 15, 1786. Graebe
and Blumenfeld, B. 30, 11 18.
2 A. 388, 203 » C. r. 137, 6G2. " D.R.P. 281,490.
167
158 ANTHRACENE AND ANTHRAQUINONE
of dinitro compounds. ^ According to a patent specification ^
this contains 60 per cent, of 1.5- and i.S-dinitroanthra-
qninone, the remainder being chiefly i.6-dinitroanthra-
qninone with small quantities of 1.7-dinitroanthraquinone
and very small quantities of 2.6- and 2.7-dinitroanthra-
quinone. Eckert,^ who gives full details of the nitration,
separated the isomers by fractional crystallisation from
glacial acetic acid and arrived at a different result. He
found 75 per cent, of the 1.5-dinitro compound, 10 per cent,
of the i.6-dinitro compound, and 5 per cent, each of the
1.7- and 1.8- isomers. Holdermann * nitrated anthraquinone
in the presence of mercury, but failed to detect any directing
influence.
j3-Nitroanthraquinone cannot be obtained by the nitration
of anthraquinone, but has been prepared by Kauffler ^ by
heating anthraquinone-j8-diazonium nitrate with copper
nitrite, 6 and by Scholl ' by nitrating j3-aminoanthraquinone
and then removing the amino group from the resulting
2-amino-3-nitroanthraquinone by the diazo- reaction. It is
much less reactive than a-nitroanthraquinone and does not
react with primary- aromatic amines, although it is readily con-
verted into^-methoxy anthraquinone by potassium methoxide.
The nitration of a-methylanthraquinone has been carried
out by O. Fischer and Ziegler.^ They obtained a mononitro
compound but did not determine the position of the nitro
group.
i|;!^The dinitration of /3-meth3'l anthraquinone has been
effected by Schaarschmidt,^ who fotmd that the product
contained 65 per cent, of 2-methyl-i.5-dinitroanthraquinone
and 30 per cent, of 2-methyl-i.8-dinitroanthraquinone.
By the nitration of 1.3-dimethylanthraquinone Scholl 'o
1 Fritsche, J. pr. [i] 106, 287. Bottger and Petersen, A. 160, 185 ;
B. 8, 16. Graebe and Liebermann, B. 3, 905. Romer, B. 16, 363.
* M.L.B., D.R.P. 167,699.
» M. 35, 297.
* B. 39, 1256.
5 B. 37, 63.
* Cf. Sandmeyer, B. 20, 1495 ; 23, 1630. Hantzsch and Blagden,
B. 33, 1544.
' Scholl, M. 32, 1037. Scholl and Eberle, B. 37, 4434.
» J. pr [2] 86. 292. 9 B. 45, 3452. lo B. 43, 353.
THE NITRO COMPOUNDS 169
obtained i.3-dimeth3'l-4-nitroantliraquinone and 1.3-
dimethyl-2.4-dinitroantliraquinone, and from 2.6-dimetliyl-
anthraquinone Seer ^ obtained 2.6-dimetliyl-i.5-dinitro-
anthraquinone. By nitrating 1.3.5.7-tetramethylanthra-
quinone Seer ^ obtained a mixture of the 4.8-dinitro com-
pound and the tetranitro compound.
The reduction of the nitro compounds to amino com-
pounds is discussed in the chapter deaHng with these latter
substances, the reduction being particularly easily effected
by boiling with aqueous sodium sulphide solution. The
change of dinitroanthraquinone into polyhydroxyanthra-
quinones when heated with concentrated sulphuric acid or
oleum, with or without the addition of sulphur, will be found
described on p. 242.
The nitro groups in the nitroanthraquinoiies, especially
when in the a-positions, are decidedly more reactive than is
usually the case with aromatic nitro compounds. Thus they
are often readily replaced by arylamino groups when boiled
with primary aromatic amines such as aniline,^ and are
very easily replaced by methoxy groups b}- treatment with
alcoholic solutions of potassium methoxide.^
II. The Nitroso Compounds
Scarcely anything is known of the nitrosoanthraquinones.
Walker ^ found that i-nitroanthraquinone-2-sulphonic acid,
when reduced with glucose in alkaline solution, gave the
corresponding hydrox3damine derivative, which on oxidation
passed into i-nitrosoanthraquinone-2-sulphonic acid. From
this the hydrox3lamine derivative could be regenerated by
reduction with glucose. As stated elsewhere,^ 1.5-dinitro-
anthraquinone when heated to 50° with oleum containing
30 per cent, of free anhydride passes into i-nitro-5-nitroso-
8-hydrox}-anthraquinone, reduction of this leading to the
corresponding diamine compound.
» M. 32, 158. 2 M. 33, i3. ' See p. 198. * See p. 287.
6 B. 35, 666. « Seep. 244. By., D.R.P. 104,282.
170 ANTHRACENE AND ANTHRAQUINONE
III. The Halogen Compounds
Direct Halogenation. — Anthraquinone itself is only
attacked by halogens with the greatest difficulty, although
Diehl,! by the action of bromine in the presence of iodine,
obtained di-, tri-, tetra-, and penta-brom compounds.
The attack takes place somewhat more readily when con-
centrated stdphuric acid or oleum is used as a solvent, and
it is claimed that under these conditions anthraquinone
can be chlorinated in steps. 2 The reaction is carried out
at a temperature of 60-130° and is facilitated by the use of
iodine as a catalyst. The entering halogen atom seems to
prefer the a-positions, as it is stated that a-chloranthra-
quinone is converted into 1.4.5.8-tetrachloranthraquinone,
whereas 2.6- and 2.7-dichloranthraquinone yield hexachlor
compounds.
According to another patent specification ^ anthraquinone
can be brominated at 50-60° when dissolved in oleum
containing 80 per cent, of free anhydride, and then leads to
a tetrabromanthraquinone (m.p. 295°) and a heptabrom-
anthraquinone (m.p. over 350°) ; but Eckert and Steiner ^
have repeated the work and have stated that the tetrabromo
compound is not formed.
The chlorination of anthraquinone can also be effected
by means of antimony pentachloride, and by this means
Diehl 5 obtained di-, tri-, tetra-, and penta-chlor compounds
although he did not determine the positions occupied by
the chlorine atoms. There can be no doubt, however, that
Diehl's tetra-chlor compound was 1.4.5.8-tetrachloranthra-
quinone. More recently Eckert and Steiner ^ have re-
investigated the action of antimony pentachloride on anthra-
quinone. By heating the two substances together in the
presence of a trace of iodine they w^ere able to obtain a
heptachlor compound, but all attempts to obtain an octa-
chlor compound failed, as further chlorination led to the
rupture of the anthraquinone ring and formation of perchlor-
1 B. 11. 179. 2 By., D.R.P. 228,901.
3 Bv.. D.R.P. 107,727. * M. 36, 269.
■* B. 11, 179. « M. 35, 175 ; 36, 269. B. 47, 2628.
THE HALOGEN COMPOUNDS 171
benzoyl benzoic acid and tetraclilorphthalic acid. The
heptachlor compound melted at 380°, and in view of the fact
that halogens first attack the a-positions, it would seem
probable that the unchlorinated position was a j8-position,
i.e. that the compound was 1.2.3.4.5.6.8-heptachloranthra-
quinoue. Eckert and Steiner, however, prepared this
compound from tetrachlorphthalic acid and 1.2.4-triclilor-
benzene and found that it melted at 302°, although by
heating with phosphorus pentachloride it was converted
into the isomeric compound melting at 380°. By heating
1.2.3.4-tetrachloranthraquinone with antimon}^ pentachloride
a mixture of the two heptachlor compounds was formed.
From the above facts it would seem that the chlorination of
anthraquinone leads first to 1.2.3.4.5.6.8-heptachloranthra-
quinone (m.p. 302°), which then passes into 1.2.3.4.5.6.7-
heptachloranthraquinone (m.p. 380°) by the wandering of
a chlorine atom. Reactions of this type are not new, as
it has long been known that a-bromnaphthalene passes into
j3-bromnaphthalene under the influence of aluminium chloride.
When methyl anthraquinones are halogenated the
halogen atom can enter either the nucleus or the side chain,
which reaction takes place depending on the conditions of
the experiment, although owing to the paucity of the data
available it is impossible to draw any very definite con-
clusions as to the conditions which favour each t5'pe of
reaction. Ullmann ^ finds that when /S-methyl anthra-
quinone is heated on the water bath with sulphur\'l chloride
in nitrobenzene solution, 2-methyl-i-chloranthraquinone is
formed in 80 per cent, yield. On the other hand, sulphur\'l
chloride at 175° appears to convert /3-methylanthraquinone
into jS-dichlormethylanthraquinone. 2
jS-Methylanthraquinone when chlorinated in nitrobenzene
solution at 100° with molecular chlorine yields nuclear
methylcliloranthraquinones,3 whereas with chlorine at 175°
halogenation seems to take place in the side chain.* The
action of bromine at 1^0-175°, with or without a solvent
1 B. 49, 737. Agfa, D.R.P. 269,249. * B.A.S.F., D.R.P. 216,715.
» Agfa. D.R.P. 293,156. * B.A.S.F., D.R.P. 216,715.
172 ANTHRACENE AND ANTHRAQVINONE
such as nitrobenzene, seems to be very similar, UUmann
and Klingenberg,! and Hepp, Uhlenhuth, and Romer ^
obtaining ^-dibrommethylanthraquinone, and Eckert ^ ob-
taining jS-tribrommethyl anthraquinone, although unable
to obtain the jS-monobrommeth3'l anthraquinone described
in the patent literature.* Among other similar results may
be mentioned the preparation of a»-dibcom compoimds
from 2-methyl-i-chloranthraquinone and from 2-methyl-3-
chloranthraquinone by Ullmann,^ b}" the action of bromine
at 160-170° in nitrobenzene solution. These brominations
can be carried out in open vessels and the yields are often
excellent.
The presence of an amino group in the anthraquinone
nucleus greatly facilitates the entrance of halogen atoms,
and use has been made of this in the preparation of
nuclear halogen anthraquinones. Thus Ullmann ^ was
able to prepare 1.3-dibromanthraquinone by brominating
S-aminoanthraquinone and then removing the amino group
from the resulting 2-amino-i.3-dibromanthraquinone in the
usual way by diazotising and reducing. ^
Retrogressive Substitution. — Halogen atoms when
in the a-position are fairh- easily removed by reduction,
whereas those in the j3-position are much more firml}- bound.
Retrogressive substitution, therefore, sometimes forms a
convenient method of preparing the lower halogenated
compounds and also furnishes some indication of the
positions occupied by the halogen atoms. Kircher ' reduced
1.2.3.4-tetrachloranthraquinone with zinc dust and ammonia
and obtained a dichloranthracene (m.p. 255°), which on
oxidation gave a dichloranthraquinone (m.p. 261°), which he
believes to be 1.2-dichlor anthraquinone, but which Ullmann ^
has since shown to be 2.3-dichloranthraquinone. More
recently- Ullmann ^ has found that chlorine atoms when in
the a-position, but not when in the jS-position, can be removed
by heating the compound, e.g. in nitrobenzene solution, with
potassium acetate and a trace of copper powder. Thus,
1 B. 46, 712. - B. 46, 709. 3 M. 35, 299.
* B.A.S.F., D.R.P. 216,715. ' B. 47, 558 ; 49. 737- * B. 49, 2157.
' A. 238, 344 « A. 381. 26. • B. 45, 687.
THE HALOGEN COMPOUNDS 173
although /S-chloranthraquinone is unaffected, a-chloranthra-
quinone is reduced to anthraquinone itself, and i-metliyl-
4-chloranthraquinone to a-methylanthraquinone. In the
case of 1.2.3.4-tetrachloranthraquinone only two chlorine
atoms are removed, the product being 2.3-dicliloranthra-
quinone.
Replacement of Group. — Amino groups are usually
quite readily replaced by halogen atoms by first preparing
the diazonium salt and then treating this with cuprous
halide in the usual way.^ In some cases, however, there is
a tendency for the cuprous halide to form a dianthraquinonyl
derivative. 2
Hydroxyl groups can be replaced by chlorine atoms by
treatment with phosphorus trichloride, phosphorus penta-
chloride or phosphorus oxy-chloride.^ The cjxlic carbonyl
groups are unaffected.
Niiro- groups either in the a-position or in the jS-position
can be replaced by chlorine atoms by dissolving the nitro
compound in some suitable solvent such as trichlorbenzene,
and then treating it at 160° with chlorine.'* Meth3-1 groups
if present are simultaneously chlorinated, but in the case of
nitroanthraquinone sulphonic acids, the sulphonic acid
groups are replaced before the nitro groups.
Sulphonic acid groups^ either in the a-position or in the
j3-position, are verj- readily replaced by chlorine or bromine
atoms, and in many cases this reaction forms the most
convenient means of preparing halogen anthraquinones.
The reaction can be brought about by heating to 170° with
thionyl chloride,^ nitro groups if present remaining un-
affected ; but it is much more convenient to treat a boiling
aqueous solution of the sulphonic acid with molecular or
nascent chlorine or bromine. ^ The nascent chlorine can
1 Kauffler, B. 36. 60. SchoU, B. 40, 1696 ; 43. 354. Laube. B. 40.
3566. By., D.R.P. 131,538.
» B.A.S.F.. D.R.P. 215,006.
3 Ullmann and Conzetti, B. 53, 832. Afga. D.R.P. 290,879.
•" B.A.S.F.. D.R.P. 12S.845, 252,578, 254,450.
* M.L.B., D.R.P. 267.544, 271.681, 284,976.
« Ullmann, A. 381. 2. Wolbling. B. 36, 3941. Heller, B. 46, 2703,
By., D.R.P. 205,195, 205,913, 214,150. M.L.E., D.R.P. 77,179, 78,^2,
97.287.
174 ANTHRACENE AND ANTHRAQUINONE
be generated by allowing sodium hypochlorite solution, or
sodium chlorate solution, to run slowly into a boiling
solution of the sulphonic acid in dilute hydrochloric acid,
and the author has found that the use of sodium chlorate
gives particularly good results. The reaction proceeds
quite readily and the chloro compound usually separates
out in the crystalline condition, but it is "advisable to use
rather dilute solutions. There is no necessity to isolate
the sulphonic acids, it being sufficient to pour the crude
sulphonation melt into water and then treat the resulting
solution with molecular or nascent chlorine or bromine. In
the case of polysulphonic acids either one or more sulphonic
acid groups can be replaced by halogen, and if nitro groups
are present these remain unaffected. Sulphonic acids when
treated with halogens in concentrated stdphuric acid are
halogenated without the stdphonic acid group being affected,
so that by halogenating an anthraquinone sulphonic acid
in concentrated sulphuric acid solution and then running
the melt into water and again treating with halogen, a very
large number of halogen anthraquinones can be obtained
with very little trouble, i Another very fruitful method is
to sulphonate, with or without the addition of mercury-, a
halogen anthraquinone and then to dilute the melt and treat
it with a halogen. 2
If an anthracene sulphonic acid is treated with sodium
chlorate in boiling dilute hydrochloric acid solution, simulta-
neous replacement of the sulphonic acid group and oxidation
take place, the product being a chlorinated anthraquinone. 3
Properties. — Halogen atoms when situated in a side
chain seem to be rather less reactive than would be expected,
and as a rule the ctj-dLhalogenmeth)^ anthraquinones are
unaffected by dilute alkali and can only be converted into
the corresponding aldehyde by heating to 130° with con-
centrated sulphuric acid.* Eckert,^ however, states that
/3-tribrommethyl anthraquinone gives the carboxylic acid
1 B.A.S.F., D.R.P. 214,714, 216,071.
2 Hepp, Uhlenhuth, and Romer, B. 46, 709. Schilling, B. 46, 1066.
3 B.A.S.F., D.R.P. 228,876.
* See p. 159. 5 M. 35, 299.
THE HALOGEN COMPOUNDS 175
when heated to 180° with milk of Hme. In some wa^^s the
a>-dibrommethyl compounds, however, are very reactive,
and jS-dibrommethj^anthraquinone when heated to 240-
250° evolves torrents of hydrobromic acid and passes into
dianthraquinonyldibromethylene,Ci4H702CBr : CBrCi4H702,
from which diauthraquinonyl acetylene can be obtained by
the action of diethylaniline or sodium phenolate.^
Halogen atoms when directly attached to the nucleus
are somewhat less firml}^ bomid than is usually the case with
aromatic halogen compomids. When in the a-position they
are decidedly more reactive than when in the j3-position.
Halogen atoms in the a-position direct the entering
nitro group to the /(-position, so that a-chloranthraquinone
gives i-chIor-4-nitroanthraquinone, and 1.5- and i.8-dichlor-
anthraquinones give corresponding compounds.^ From 1.4-
dichloranthraquinone Walsch and Weizmami ^ obtained a
mononitro compound (m.p. 238°), but did not determine
the position of the nitro group. From i.4-dichlor-5.8-
dimethyl anthraquinone Harrop, Norris, and Weizmann ^
obtained a dinitro compound, but offer no information as
to the position of the nitro group. Heller ^ by nitrating
3-chloralizarin obtained a mononitro compound which must
be 3-chlor-4-nitroalizarin, as it gives phthalic acid when
oxidised.
^ UUmann and Klingenberg, B. 46, 712.
* Eckert and Steiner, M. 35, 1138. By., D.R.P. 137,782, 249,721.
3 Soc. 97, 687. ■» Soc. 95, 1318. * B. 46, 2703.
CHAPTER X
THE SULPHONIC ACIDS, MERCAPTANS,
AND SULPHIDES
I. The Sul,phonic Acids
Anthraquinone is not very easily sulphonated, but treat-
ment with oleum leads first to the ^-monosulphonic acid and
then to a mixture of disulphonic acids in which the 2.6- and
the 2. 7-disulphonic acids predominate.! If it is desired to
prepare anthraquinone monosulphonic acid reasonably free
from disulphonic acid it is absolutely essential to interrupt
the reaction while some 20 per cent, of the anthraquinone is
still unchanged, as if the process is carried on until the whole
of the anthraquinone has been attacked the product will
be foimd to contain considerable quantities of disulphonic
acid. In an}- case the sulphonation of anthraquinone is
always accompanied by a certain amount of simultaneous
hydroxylation, and consequentl}^ a deep purple colour is
developed when a portion of the melt is made alkaline.
Under suitable conditions, however, the loss by hydrox3da-
tion is only slight.
Both the j3-sulphonic acid and the two disulphonic acids
are manufactured on the technical scale and are used in the
manufacture of alizarin dj-es. The monosulphonic acid is
isolated by diluting the stdphonation melt, filtering off the
unchanged anthraquinone and then saturating the solution
with sodium chloride. Under these conditions the sodium
^ Perkin, A. 158, 323. Graebe and Liebermann, A. 160, 130. Caro,
Graebe, and Liebermann, B. 3, 359. Liebermann and Bollert, A. 212, 56;
B. 15, 229. Schunck and Romer, B. 9, 679. Liebermann and Dehnst, B.
12, 1288. Perger, B. 12, 156O. Romer, B. 15, 224. Crossley,Am. Soc,
37, 2178.
176
THE SULPHONIC ACIDS 177
salt of the monosulphonic acid separates out in silvery-
scales, the silvety appearance having given rise to the technical
name " silver salt." The disulphonic acids are more soluble,
and to isolate them it is best to neutralise the solution and
then remove the sodium sulphate by fractional crystal-
lisation.
It should be noticed that when anthraquinone is
sulphonated without the use of a catalyst only two sulphonic
acid groups can be introduced into the molecule, and that
the products formed are almost exclusively /3-sulphonic
acids although verj^ small quantities of a-sulphonic acids are
also formed. 1
If the sulphonation of anthraquinone is carried out in
the presence of a small quantity of mercuric sulphate a
totall}' different result is obtained, the sulphonic acid
groups under these circumstances exclusively entering the
a-positions.2 The first product formed is anthraquinone-
a-sulphonic acid, further sulphonation leading to a mixture
of the 1.5- and i.8-disulphonic acids. All these are easily
salted out as their potassium salts by adding potassium
chloride to their solutions in dilute sulphuric acid. The two
disulphonic acids are readily separated by taking advantage
of the fact that the 1.5-disulphonic acid is insoluble in con-
centrated sulphuric acid, whereas the i.8-disulphonic acid
is soluble. If, therefore, the sulphonation melt is diluted
with concentrated sulphuric acid the former acid crystallises
out and can be filtered off and washed with concentrated
sulphuric acid and finally dissolved in water and salted out
by the addition of potassium chloride. The concentrated
sulphuric acid mother liquors contain the i.8-disulphonic
acid, and when they are diluted and treated with potassium
chloride the potassium salt of this acid separates.
By sulphonating anthraquinone itself in the presence of
mercury only two sulphonic acid groups can be introduced
into the molecule, but trisulphonic acids, presumably the
1.3.6- and the 1.3.7-tTisulphonic acids, can be obtained
^ Diinschmann, B. 37, 331. Liebermann and Pleus, B. 37, 64G.
» Iljinsky, B. 36, 4194. R. E. Schmidt, B. 37. 66. By., D.K.P.
149,801.
12
178 ANTHRACENE AND ANTHRAQUINONE
either by snlphonating an a-sulphonic acid without the
addition of mercuty, or by snlphonating a j3-sulphonic acid
in the presence of mercury. i
By sulphonating anthraquinone itself in the presence of
mercuric sulphate which is only coarsely powdered, it has
been claimed that anthraquinone-i.6- and 1.7-disulphonic
acids can be obtained in one operation. 2 •'
The directing influence of mercury is not confined to
anthraquinone itself, but also extends to anthraquinone
derivations, and Ullmann ^ has foimd that when halogen
anthraquinones are sulphonated in the presence of mercury
the sulphonic acid group enters the a- position.
It has been claimed that the sulphonation of anthra-
quinone is facilitated by the catalytic action of vanadium,
but experiments w^hich have been made by the author fail
to support this claim. *
Although direct sulphonation is by far the most im-
portant method of preparing anthraquinone sulphonic
acids, sulphonic acid groups can also sometimes be intro-
duced into the molecule by other means. Thus halogen
atoms are sometimes replaced by sulphonic acid groups by
treatment with sulphiiric acid,^ although the reaction is by
no means a general one, and many halogen compoimds can
be sulphonated in a normal manner. ^ In the case of
i-amino-4-ar>damino-2-halogen anthraquinones the halogen
atom can be replaced by the sulphonic acid group by heating
with aqueous sodium sulphite solution.'^
Boihng with aqueous sodium sulphite solution in many
cases leads to the production of sulphonic acids by replace-
ment of the nitro group, i-nitroanthraquinone, 1.5- and
i.8-dinitroanthraquinone and some hydrox>'nitroanthra-
quinones reacting in this way .» In the case of i .4-dihydroxy-
1 Wed.. D.R.P. 170,329; 202,398.
2 Wed., D.R.P. 202,398.
3 D.R.P. 223,642.
* Thiimmler, D.R.P. 214,156.
* Perkin, A. 158, 319. Graebe and Liebermann, A. 160, 137.
« E.g. Walsh and Weizmann, Soc. 97, 688. By., D.R.P. 217,552.
Ullmann, D.R.P. 223,642.
' By., D.R.P. 288,878.
8 R. E. Schmidt, B. 36, 39. By., D.R.P. 164,292, 167,169.
THE SULPHONIC ACIDS 179
anthraquinones, i.4-aminohydrox>'antliraquinones and 1.4-
diaminoanthraquinones, treatment with aqueous sodium
sulphite solution will bring about sulphonation without
replacement. 1 Here the reaction is no doubt due to the
formation of a true quinonoid compound, ^-quinone,
quinone-imide or quinone di-imide, and then addition to this
of sodium bisulphite. This view of the reaction is supported
by the fact that sulphonation takes place most readily in
the presence of an oxidising agent such as manganese
dioxide. In the absence of an oxidising agent the formation
of the quinonoid compound is no doubt brought about at the
expense of part of the ox>'gen of the cyclic carbonyl groups.
The anthraquinone sulphonic acids are usually fairly
easily dcsulphonated by hydrolysis, although the ease with
which the sulphonic acid group is split off varies to a great
extent in different mdividual substances. As a rule, the
hydrolysis can be effected by heating to 170-190° with
sulphuric acid of 80 per cent, strength,^ but sulphonic acid
groups in the a-position are somewhat less firmly held than
similar groups in the jS-position and are usually readil}- split
off by treatment with sulphuric acid of 50-80 per cent,
strength. 3 The addition of boric acid sometimes has a
favourable effect, and in man}- cases the addition of a
reducing agent such as a phenol, amine, sugar, metal, or
stannous chloride greatly assists the reaction. The effect of
the reducing agent is largely catalytic, as only relatively
small amounts are required. ^ The presence of other groups
in the molecule also renders hydrolysis more easy, a notable
example being that of i.3.5.7-tetrahydroxy-4.8-dinitro-
anthraquinone-2.6-disulphonic acid, which is dcsulphonated
when boiled with sulphuric acid of 20 per cent, strength. ^
It should be remembered that during hydrolysis bromine
atoms if present are apt to wander. ^
» B}'., D.R.P. 287,867 ; 288,474; 289,112.
» By., D.R.P. 56,951 ; 172,688. Wed., D.R.P. 210,863.
» By., D.R.P. 160,104.
* By., D.R.P. 190,476.
* M.L.B., D.R.P. 71,964 ; 77,720.
« B.A.S.F., D.R.P. 263,395 ; 265,727 ; 266,563. M.L.B.. D.R.P.
253.683. G.E., D.R P. 277.393
i8o ANTHRACENE AND ANTHRAQUINONE
Desiilpiionatioii of sulphonic acids can also sometimes
be brought about by reduction. Thus hexahydroxy anthra-
quinone is obtained when its disulphonic acid is reduced in
acid solution by zinc, iron, or aluminium, the sulphonic acid
group being split off in the form of sulphuretted hydrogen. ^
The anthraquinone sulphonic acids are converted into
the sulphochlorides by treatment with pHbsphorus penta-
chloride and phosphorus oxy chloride, 2 sulphochlorides also
being obtained in many cases by the action of chlorsulphonic
acid on the anthraquinone sulphonic acids. ^
These sulphochlorides behave like other sulphochlorides.
On reduction with sodium sulphide they give the corre-
sponding sulphinic acids.*
The nitration of anthraquinoue-a-sulphonic acid leads
to a mixture of 1.5- and i.8-nitroanthraquinone sulphonic
acids, the isomers being very easily separated owing to the
insolubility of the former in the nitrating acid.^ The
nitration of anthraquinone-/3-sulphonic also leads to two
isomeric raononitro compounds, one of which, according to
Claus 6 and lyifschtitz,'^ can be converted into alizarin.
R. E. Schmidt,^ however, has found that the two nitro
compounds formed are really i-nitroanthraquinone-6-
sulphonic acid and i-nitroanthraquinone-7-sulphonic acid,
and Frobenius and Hepp ^ have severely criticised Claus'
work and have shown that what Claus described as erythro-
hydroxyanthraquinone sulphonic acid is really the diazo
sulphonic acid, Claus having overlooked the presence of
nitrogen.
II. The Sulphinic Acids
The anthraquinone sulphinic acids are of no particular
interest and can be obtained either by reducing the sulpho-
chlorides with sodium sulphide, 10 or by the oxidation of the
sulphenic acids (sulphoxylic acids). They behave very
much like other aromatic sulphinic acids. Thus anthra-
1 Bv-.D.R.P. 103,898. * Ullmann, B.52, 545. ^ m.L.B.. D.R.P. 266,521.
« M.L.B., D.R.P. 26^,340. Cf. M.L.B.. D.R.P. 224,019.
8 R. E. Schmidt, B. 37, 71. « B. 15, 1521.
» B. 17, 899. » B. 37, 69. » B. 40, 1048.
»» M.L.B., D.R.P. 263,340. Cf. M.L.B., D.R.P. 224,019.
THE SULPHENIC (SULPHOXYLIC) ACIDS i8i
quinone-j3-sulphinic acid very readily condenses with
tetramethyldiaminobenzhydrol (Miscliler's hydrol) to form
an ester, i Ci4H702.SOOCH(C6H4NMe2)2, and also readily
adds on to quinonoid compounds, 2 e.g. with benzoquinone
it gives Ci4H702.S02.C6H3(OH)2.
III. The Sulphenic (vSulphoxylic) Acids
When an anthraquinone mercaptan or disulphide is
treated with chlorine or bromine in chloroform solution an
anthraquinone sulphur halide, Ci4H702.SHlg, is often obtained,
although the reaction is by no means a general one and
several exceptions are known. ^ The bromides are also often
obtained by reducing the sulphinic acids in glacial acetic
acid solution by means of hydrobromic acid.*
The sulphur halides of the anthraquinone series usually
show reactions ver}^ similar to those of other aromatic
sulphur halides, s although the}- are much more stable than
is usually the case with compounds of this class. Thus
anthraquinone-j3-sulphur chloride reacts with acetone to
form an acetyl compound, and with water to give the
anhydride of the sulphenic acid (Ci4H702S)20. With
alcohol it gives a mixture of disulphide, disulphoxide, and
sulphinic acid.^
Anthraquinone-a-sulphur chloride is not nearly so
reactive as the j8-compound and will not react with acetone,
phenyl benzyl ketone, acetophenone, or acetoacetic ester,
although it behaves normally towards ammonia with the
production of a sulphamide which under the influence of
mineral acids readily passes into a thiazole :
* Hinsberg, B. 50, 472. ^ Hinsberg, B. 50, 953.
^ Friess, B. 45, 2965. Friess and Schurmann, B. 52, 2182.
•• Friess and Schiirmann, B. 47, 1192. M.L.B., D.R.P. 277,439.
* Cf. Zincke, A. 391, 55 ; 400, i ; 416, 86.
* Friess, B. 47, 2965. Friess and Schurmann, B. 52, 2170.
i82 ANTHRACENE AND ANTHRAQUINONE
The a-sulphur chloride is quite stable towards water and
only reacts with alcohol after prolonged boiling, and then
gives the ester of the sulphenic acid, from which the free
acid can be obtained by hydrolysis although it cannot be
obtained from the chloride directly by the action of water.
The alkali salts of the acid when treated with dimethyl
sulphate give the methyl ester of the acid, -but the free acid
itself gives methyl anthraquinonyl sulphoxide, so that salt
formation is probably accompanied by a change in structure :^
/O
CuHvOa.Sf ^ CuH^O^.S-OH
Normal form. Pseudo form.
Alkaline solutions of the acid are readily oxidised by
th-e air with the production of the sulphinic acid. When
the acid itself is boiled in glacial acetic acid solution simulta-
neous oxidation and reduction takes place with the pro-
duction of a mixture of sulphinic acid and disulphide.
As stated above anthraquinone-a-sulphur chloride will
not react with acetoacetic ester. It will react, however,
with sodioacetoacetic ester, the product on hydrolysis
giving an acetyl thiopheneanthrone :
COQLi
^S CH,COCr
ch,ccch:^
CO
CO
IV. The Mercaptans
The anthraquinone diazonium salts do not give the
mercaptan when treated with potassium sulphydrate,
although, as will be seen later, they readily give mixed
sulphides when treated with aromatic alkali mercaptides.
The mercaptans can, however, be prepared from the diazo-
nium salts b}^ indirect methods. The diazonium salts react
^ Friess, B. 45, 29G5. Friess and Schiirmann, B. 52, 2170.
THE MERCAPTANS 183
only very slowly with copper thiocyanate, but react readily
with potassium thiocyanate, and this is especially true when
the diazonium group occupies an a-position. The resulting
thiocyanate cannot be hydrolysed by acids but can be
hydrolysed by alcoholic caustic potash, and then yields the
mercaptan.i A second method of obtaining the mercaptan
is to treat the diazonium salt with potassium xanthate and
then to hydrolyse the resulting anthraquinone xanthate by
boiling with aqueous alcoholic alkali. 2 Another alternative
method is to treat the diazonium salt with thiourea, no
catalyst being necessary, and then to hydrolyse the carbamyl
derivative thus formed. ^ In this case, however, there is
some tendency when dealing with a-derivatives of a side
reaction taking place with the formation of a heterocyclic
compound in which one of the cyclic carbonyl groups is
involved :
Both a-cliloranthraquinone and iS-cliloranthraquinone
give the corresponding mercaptan when heated with alkali
sulphide, sulp hydrate, or poly sulphide, * and anthraquinone-
i-mercaptan and anthraquinone-i.5-dimercaptan can be
obtained in the same way from anthraquinone- i-sulphonic
acid and from anthraquinone-i.5-disulphonic acid.^ Mer-
captans can also be obtained by reducing the corresponding
sulphochlorides ^ or disulphides,'^ and in the case of a-
hydrox>'anthraquinones and j6-hydroxyanthraquinones a
mercaptan group can be directly inserted into the molecule
in the ortho- position by fusing with sodium sulphide at 150°.
» Gattermann, A. 393, 113. By., D.R.P. 206,054 ; 208,640.
* M.L.B.. D.R.P. 241,985.
3 M.L.B., D.R.P. 239.762.
♦ By., D.R.P. 204,772 ; 206,536.
« By.. D.R.P. 212.857. ■
« M.L.B., D.R.P. 292.457. By., D.R.P. 281.102.
» Gattermann, A. 393, 113. UUmann, B. 49, 739. Friess and Schiir-
mann, B. 52, 2176, 2186.
t84 anthracene AND ANTHRAQUINONE
When two hydroxyl or amino groups are present in a-
positions, if these two groups are attached to different
benzene nuclei, two mercaptan groups can be inserted ; but
if the amino or hydrox}4 groups are attached to the same
nucleus, e.g. as in quinizarin, only one mercaptan group
enters the molecule. ^ Finally, anthraquinone mercaptans
have been obtained by inserting the mercaptan group into
the benzoyl benzoic acid and then closing the anthraquinone
ring. 2
The anthraquinone mercaptans are rather troublesome
substances to handle as they are very readily oxidised to
the corresponding disulphide, in the absence of an external
oxidising agent the oxidation often being brought about
at the expense of the cj-clic carbonyl groups. Those
mercaptans in which the mercaptan group is in the
a-position are much more easily oxidised than those
compounds in which the mercaptan group occupies a
^-position.
The mercaptans have great affinity for the fibre but
are scarcely to be regarded as dyes, as the shade obtained is
that of the corresponding disulphide owing to oxidation
taking place in the dye bath. Thus, if a dyeing is carried
out with anthraquinone-a-mercaptan at a temperature of
over 50° the shade obtained is fast, but is that of the disul-
phide owing to oxidation taking place. Even if the dyeing
is carried out in an atmosphere of carbon dioxide the
disulphide is formed owing to intermolecular oxidation
and reduction. If the dyeing is carried out at a temperature
below 50° the shade obtained is that due to the mercaptau
but is very loose to soap. Owing to their greater stability
it is somewhat easier to apply the j3-mercaptans to the fibre,
but the shades obtained are very poor. The benzoyl
derivative of anthraquinone-a-mercaptan has been prepared ^
but was found to have no tinctorial properties.
The mercaptans are, as would be expected, much more
highly coloured than the corresponding oxygen compounds,
1 G.E,, D.R.P. 290,084. - B.A.S.F , D.R.P. 247.412.
' Seer and Weitzenbock, M. 31, 371.
THE MERC APT ANS
185
and this is particularly true of the alkali salts. This will be
clearly seen by comparing the following substances, the
colours given being in all cases those of the solutions in
caustic soda : —
OH
Red.
SH
Violet.
OH
Yellowish- Red.
SH
Bluish-Red.
OH
OH
Violet.
OH
SH
Blue.
OH
SH
SH
Green.
SH
HO
Yellowish- Red.
HS
Violet.
V. The SeIvEnophenols
Selenophenols of the anthraquinone series have been
obtained by treating anthraquinone diazonium salts with
potassium selenocyanide and then hydrolysing the seleno-
cyanide,* and also from negatively substituted anthra-
quinones, such as a-chloranthraquinone and ^-chloranthra-
quinone, by heating with alkali selenides.2 They are of no
particular interest.
^ By., D.R.P. 264,940, 2 By., D.R.P. 264,941.
i86 ANTHRACENE AND ANTHRAQUINONE
VI. The vSui^phtdes
Sulphides of the anthraquinone series can be obtained
by condensing anthraquinone mercaptans with alkyl, arv^l,
or anthraquinonyl halides,i but when an anthraquinone-
a-mercaptan is condensed with an alykl hahde there is often
a great tendency for loss of water to take place with forma-
tion of a thiophene anthrone.2 When preparing dianthra-
quinonyl sulphides it is often imnecessary to isolate the
mercaptan, dianthraquinonyl sulphides, for example, being
obtained in one operation when either a- or /3-chloranthra-
quinone is boiled with potassium xanthate in some suitable
solvent such as amyl alcohol or nitrobenzene. 3 The dianthra-
quinonyl sulphides are also obtained from the mercaptans
when these latter are heated to about 320°, either alone or
with some substance such as an alkali or a metal which is
capable of combining with sulphuretted hydrogen.*
The sulphur chlorides of the anthraquinone series also
condense qiiite readily with aromatic substances such as
benzene under the influence of aluminium chloride, and in
the case of dimethyl aniline and phenols, especiall}- resorcinol
and ^-naphthol, the sulphide is formed without the use of
any condensing agent. ^ Very similar to this is the formation
of sulphides ^ by condensing anthraquinone mercaptans
with aromatic compounds such as benzene, toluene, naphtha-
lene, phenol, etc., by treatment with concentrated sulphuric
acid at about 30°. Here no doubt the sulphuric acid first
oxidises the mercaptan to the sulphenic acid, sulphide
formation then taking place by loss of water. ^ All the
above methods involve the preparation of anthraquinone
mercaptans, but sulphides can also be obtained from
anthraquinone compounds containing negative substituents,
^ Gattermann, A. 393, 113. Friess and Schiirmann, B. 52, 2194. By.,
D.R.P. 213,960; 272,300; 274,357. M.L.B., D.R.P. 249,225 ; 253,507.
- See p. 370.
3 UUmann and Goldberg, D.R.P. 255,591. By., D.R.P. 272,298.
* By., D.R.P. 254,561.
5 Friess and Schiirmann, B. 52, 2179, 2194. M.L.B., D.R.P. 277,439.
« M.L.B., D.R.P. 262,^77.
' Cf. Davis and Smiles, Soc. 97, 1220. Prescott, Hutchison, and
Smiles, Soc. 99, 640.
THE BISULPHIDES
187
such as sulphonic acid groups, 1 nitro groups,^ or halogen
atoms, 3 by condensing them with an alkali salt of an
aromatic mercaptan.
The sulphides are usually yellow vat dyes, although of
no technical importance. The presence of a hydroxyl or
an amino group in the para- position to the sulphur atom
changes the shade to violet or blue.
VII. The Bisulphides
The anthraquinone disulphides are easily obtained from
the halogen anthraquinones by the action of alkali di-
suljDliides,'* and as already stated are VQTy readily produced
by the oxidation of the mercaptans either by atmospheric
cxj'gen or by potassium ferricyanide.s Ullmann ^ has
found that a-chloranthraquinone will condense with thiol-
benzoic acid, and that the product on hydrolysis yields a
disulphide. Here probably the mercaptan combines with
the thiolbenzoic acid to form 5-benzoylanthraquinone-
I -mercaptan, hydrolysis of this leading to the mercaptan,
which under the experimental condition undergoes intra-
molecular oxidation with the formation of a disulphide :
SCOCeHg
SH
/3-Chloranthraquinone does not condense with thiolbenzoic
acid, but from ^-bromanthraquinone 2.2'-dianthraquinonyl
disulphide can be obtained.
The sulphonic acids of the disulphides have very great
1 Decker and Wursch, A. 348, 238. By., D.R.P. 224,589.
2 By., D.R.P. 116.951 ; 224,589.
* Harrop, Norris, and Weizmann, Soc. 95, 1316. Schaarschmidt, A.
409, 59- B.A.S.F., D.R.P. 250,273; 251,115; 251,709. By., D.R.P.
224,589.
* Friess, B. 45, 2967 ; 52, 2176, 218G. Ullmann, B. 49, 739. By.,
D.R.P. 204,772 ; 206,530.
* Gattermann. A. 393, 113. "A. 399. 352.
i88 ANTHRACENE AND ANTHRAQUINONE
affinity for animal fibre, the dyestuff being taken up quanti-
tatively and the dyebath left completely colourless.
A large number of sulphur containing dyes have been
described as being obtained by heating anthraquinone
derivatives with sulphur chloride or sodium sidphide and/or
sulphur. 1 The constitution of these compounds is quite
imknown, but they are probably sulphides, 'disulphides, or
mercaptans. In a number of cases it is claimed that a brighter
shade and improved fastness is obtained by treating the
dye with a mild oxidising agent such as a hypochlorite, 2 and
this improvement in the tinctorial properties is probably
due to the oxidation of a mercaptan to a disulphide.
Yellow and brown vat dyes have also been claimed as
being obtained when anthraquinone diazonium salts are
treated with sulphur chloride 3 or with a thioarsenate,
thiostannate, or thioantimonate ; ^ nothing whatsoever is
known of the constitution of these bodies. The same remark
also applies to the dyes obtained by treating anthraquinone
derivatives with sodium thiosulphate.s
VIII. The Diselenides
The diselenides are of very little interest, but have been
obtained by the action of alkali diselenides on a-chloranthra-
quinone and on jS-chloranthraquinone.^
IX. The Thianthrenes
From thianthrene itself by the phthalic acid synthesis
Scholl ' obtained a compound which was probably lin.-
^ The following are the chief patents relating to this class of compound :
Agfa, D.R.P. 240,792 ; 246,867. B.A.S.F., D.R.P. 91,508 ; 186,990 ;
242,621. By., D.R.P. 172,575 ; 175,629; 176,641; 176,955; 178.840;
179,608; 179,671; 180,016; 226,879; 226,957. Cassella, D.R.P.
242,029; 247,416. G.C.I. B., D.R.P. 204,958; 205,212; 205,217-8;
208,559; 209,231; 209,232-3; 209,351; 211,967; 213,506; 223,176; 243,751 ;
254,098 ; 261.557 ; 265,194- M.L.B., D.R.P. 251,234-5 ; 311,906. Wed..
D.R.P. 237,946; 293,970; 311,906.
* E.g. G.C. I.E., D.R.P. 209,231-2-3 ; 211,967; 213,506; 265,194.
3 Agfa, D.R P. 229,465. * Agfa, D.R.P. 229,110.
6 Wed., D.R.P. 296,207 ; 297,079 ; 297,080 ; 297,567 ; 298,182-3 ;
290. "iio,
» By., D.R.P. 264,941. ' B. 44, 1233.
THE THIANTHRENES 189
diplithaloylthiauthrene (I.), whereas from methylthianthreiie
he obtained what was most probably trans, bisang.-^.^'-
dimethyldiphthaloylthianthrene (II.) :
CO CHj
CO s CO
CO S CO
trans. ^tsan^g-Diphthaloylthiauthrene itself can be obtained
by condensing 1.2-dichloranthraquinone with anthraquinone-
1 .2-dimercaptan. ^
All three of these substances are red in colour, but only
the two trans, bisang. compounds are capable of being used
as dyes, as the /zw.- compound has no tinctorial properties.
> B.A.S.F., D.R.P. 248,171.
CHAPTER XI
THE AMINOANTHRAQUINONES AND
DIANTHRAQUINONYLAMINES
The aminoanthraquinones are of great importance, as they
form the starting-out point in the synthesis of a very large
number of important anthraquinone derivatives. The
simple primary aminoanthraquinones as a rule have nc
tinctorial properties, although some of the amino-hydroxy
compounds are valuable dyes, e.g. Alizarin Saphirol.i The
sulphonated aryl aminoanthraquinones are used as acid
wool dyes to a considerable extent, the best known being
Alizarin Cyanine Green ^ : ,
/CH3
NHC6H3/
^SOsH
CH.
I
NC«H.NH
SO3H'
'6-^-^3
This dyes in yellowish-green shades which become faster
when after-chromed.
The dianthraquinonylamines are vat dyes, but as a rule
the tinctorial properties are feeble unless three anthra-
quinon5'l groups are present, these dianthraquinon3^1amino
anthraquinones actmg as a rule as vat dyes giving bordeaux
shades, e.g. Indanthrene Bordeaux B :
1 Solway Blue (Scottish Dyes, Ltd.).
* Kymric Green (Scottish Dyes, Ltd.).
iqo
THE A MI NO A NTHRA Q U I NONES
-NH—
IQI
I
I
— NH-
I
Although neither the primary aminoanthraquinones nor
their acetyl derivatives have any tinctorial properties, the
acylamino anthraquinones, in which the acyl group is
derived from a dibasic fatty acid, or from a mono- or di-basic
aromatic acid, are powerful vat dyes, and by selecting a
suitable aminoanthraquinone all shades from yellow to blue
and violet can be obtained. Two of the simplest dyes of
this class which have found technical application are Algol
Yellow W.G (a-benzoyl aminoanthraquinone) and Algol
Yellow 3G (a-succinyl aminoanthraquinone) :
NHCOCgHg NH.CO.CH2.CH2.CO.NH
Algol Yellow W.G.
Algol Yellow 3G.
The anthraquinonyl ureas also belong to this class and are
vat dyes.
The two chief methods which are utilised for introducing
the amino group into the anthraquinone molecule are the
reduction of nitro groups, and the replacement of negative
atoms or groups such as halogen atoms or nitro, hydroxyl,
or sulphonic acid groups. In addition amino and hydroxyl
groups can often be introduced simultaneously by reducing
the nitro compomid to the hydroxydamine derivative and
then treating this with an acid in order to cause the hydroxyl
group to wander to the para- position. This last type of
reaction will be discussed in the section dealing with the
aminohydroxy anthraquinones.
The reduction of the nitro group leads, of course, only
to piimar>' amino compounds ; but the second method, viz.
192 ANTHRAC3NE AND ANTHRAQUINONE
the repiacemeut oi negative groups, can be used for the
production of primarx-, secondary, or tertiary amino com-
pounds, and as the reaction usually takes place very easily
it has been widely applied.
The primary aminoanthraquinones are extremely weak
bases, but the basicity increases with the entrance of
alkyl groups, the alkylaminoanthraquinones being more
strongly basic than the primary compounds, and the di-
alkylamino anthraquinones being sufficiently basic to form
salts which are not hydrolysed.
Reduction of Nitro Groups
Although nitro groups when attached to the anthra-
quinone nucleus can be reduced by tin and hydrochloric or
acetic acid,i it is much better to carr>^ out the reduction in
alkaline solution by means of sodium stannite,^ glucose and
caustic soda, 3 zinc dust and caustic soda or ammonia,* or
sodium sulphide or sulphydrate.^ Of these sodium sulphide
gives by far the best results, and is to be regarded as the
standard reagent for the reduction of nitroanthraquinones.
As a rule, the reaction is carried out by making the nitro
compound into a thin paste with cold aqueous sodium
sulphide solution and then pouring this into boiling water
and boiling the whole for a few minutes. The action of the
cold sodium sulphide on the nitro compound usually pro-
duces a highly coloiired solution owing to reduction to the
hydroxylamine derivative, reduction to the amino compound
only taking place on the application of heat. As a rule, the
yield of amino compound obtained by the above method is
almost quantitative, but in some cases the production of
substances containing sulphur has been recorded. Thus
^ Bottger and Petersen, A. 160, 149. Walsh and Weizmann, Soc. 97,
687. Lifschutz, B. 17, 899.
* Bottger and Petersen, A. 160, 149. R6mer, B. 15, 1790 ; 16. 366.
" Wacker, B. 34, 3922.
4 Claus, B. 15, 1517. Przibram, D.R.P. 6,526.
* Bottger and Petersen, A. 160, 149 ; 166, 149. UUmann, A. 388, 203.
Schaarschmidt, A. 407, 184. Claus. B. 15, 1517. R. E. Schmidt, B. 37.
171. SchoU and Kacer, B. 37. 4531. Noelting and Wortmann, B. 39,
637. Scholl, B. 40, 1696 ; 43, 354. Schaarschmidt and Stahlschmidt, B.
45. 3454. Seer, M. 32. 160. Eckert, M. 35, 298. Bv.. D.R.P. 100,138;
119,228. Lauth, C. r. 137. 662.
THE AMINOANTHRAQUINONES 193
Terres ^ states that when i-nitro-2-ammoanthraquinone is
reduced with sodium sulphide side reactions take place
with the production of compounds containing sulphur, but
that this is not the case if ammonium sulphide is used in
place of the sodium salt. 2 Schaarschmidt/'^ on the other
hand, reduced both 2-nitro-3-aminoanthraquinone and
i-nitro-2-aminoanthraqmnone with sodium sulphide and
does not seem to have noticed any marked tendency to
produce sulphur compounds. In the case of the former sub-
stance he states that the 3deld of the diamino compound was
almost theoretical, but that in the preparation of 1.2-dianiino-
anthraquinone the yield was not quite so good. He gives
the melting point as 301° as compared with 297-298°
found by Terres.
Although the use of sodium sulphide may in some cases
lead to an impure amino compomid, the results as a rule
are excellent, the preparation of a-aminoanthraquinone
from a-nitroanthraquinone being particularly easy.'* In
this case there is no need to purify the nitroanthraquinone
before reduction, as the author has found that reduction of
a crude nitro compound melting fifteen or twenty degrees
below the correct temperature will give an amino compound,
which without recrystallising will melt within three degrees
of the correct melting point.
In some cases the reduction of nitroanthraquinone
sulphonic acids is accompanied by simultaneous loss of the
sulphonic acid group, although this can usually be avoided
by carr3'ing out the reduction under carefiilly controlled
conditions. Claus ^ for example, finds that i-nitro-anthra-
quinone-2-sulphonic acid is best reduced to the amino acid
by means of sodium amalgam.
The partial reduction of dinitroanthraquinones can in
some cases be effected by heating under pressure with
sodium sulphite, 6 although there is considerable danger
1 B. 46, 1641. C/. Schaarschmidt. A. 407, 84. M.L.B., D.R.P.
72,552; 73.6S4; 77.720; 81,741; 145. 237-
- Cf. Romer, B. 15, 1790. ' A. 407, 1S4.
* Lauth, C.r. 137, G62. Ullmann, A. 388, 203.
fi B. 15, 1517. " M.L.B., D.R P. 78,772-
13
104 ANTHRACENE AND ANTHRAQUINONE
that the reaction will take a different course, the nitro
groups being replaced by sulplionic acid groups. ^ In the
case of 1.5-dinitroanthraquinone and i.8-dinitroanthra-
quinone reduction of one nitro group is easily and quanti-
tativel)' brought about by heating with secondary or tertiar\^
aromatic amines, especially dimethyl aniline. 2 This is a
rather remarkable reaction and merits gfeater attention
than it seems to have received.
The simultaneous reduction and sulphonation of nitro-
anthraquinones is sometimes brought about by the use of
sodium bisulphite. This is particularly the case with
dinitrodiaminoanthraquinone,3 dinitroanthrarufin, and di-
nitroanthrachrysazin,^ although not confined to these
substances.^ The simultaneous reduction and sulphonation
of nitro compounds by the action of sulphites is, of course,
a well-known reaction in the aromatic series, one of the
best known examples being the formation of ?;?-nitraniline
sulplionic acid from w-dinitrobenzene.o
The simultaneous reduction and bromination of nitro-
anthraquinones can be effected by heating under pressure with
h3'drobromic acid with or without the addition of bromine.''
Instead of preparing aminoanthraquinones by nitrating
and then reducing an anthraquinone compound, a benzoyl
benzoic acid can be nitrated and reduced, ^ and the amino-
benzo}^ benzoic acid then converted into the aminoanthra-
quinone by closing the anthraquinone ring in the usual
way, viz. b}^ heating with sulphuric acid.^ In many cases
the aminobenzo3'l benzoic acid can be readily purified by
converting it into its well-cr^^stallised. and sparingly soluble
lactam. 10
When crude dinitroanthraquinone, obtained b}' the
nitration of anthraquinone, is reduced with sodium sulphide
a mixture of diaminoanthraquinones is obtained. This has
been examined by Noelting and Wortmann,ii who found that
1 By., D.R.P. 164,292; 167,169. 2 By., D.R.P. 147,851.
3 M.L.B.. D.R.P. 126,804. « Bv., D.R.P. 103,395 ; 152,013.
6 See p. 283. 6 Nietzki, B. 29, 2448. D.R.P. 86,097.
' B.A.S.F., D.R.P. 128,845. 8 Agfa, D.R.P. 248,838.
» Agfa, D.R.P. 260,899. See also p. 140. '» Agfa, D.R.P. 258,343.
1' B. 39, 637.
THE AMINO ANTHRAQUINONES 195
if the crude bases are recrj^stallised from aqueous sulphuric
acid (1:1 by volume) the dilHcultly soluble sulphate of
1.5-dianiinoanthraquinoiie separated. The free bases could
then be precipitated from the mother liquor and boiled in
equal volumes of glacial acetic acid and acetic anhydride.
On cooling the acetyl derivative of i.8-diaminoanthraquinone
separated. Fritzsche ' obtained a dinitroanthraquinone by
boiling anthracene with dilute nitric acid, and this on reduc-
tion gives a diaminoanthraquinone, which Noelting and
Wortmann2 have identified as 2.7-diaminoanthraquinone, as
they find that it gives isoanthraflavic acid when diazotised
and boiled with water.
vScholl has found that i-nitro-2-methylanthraquinone
is reduced to i-amino-2-methylanthraquinone when boiled
with methyl alcoholic caustic potash of 30 per cent, strength.
In relation to this he discusses the mechanism of the change
of o-nitrotoluene to anthranilic acid when heated with
aqueous or alcoholic alkali, or even with water at 500-
1000° C, and concludes that the first step is the formation
of the quinonoid o-meth5dene nitrolic acid, which then passes
into the nitrosobenzyl alcohol by the wandering of the
hydroxyl group ; but for details the reader is referred to the
original literature. ^
RepIvAcement of Negative Groups
Negative atoms and groups, especially when m the
a-position, are very readil}- replaced by primary' amino
groups by heating with ammonia, and if a primary- or
secondar}- amine is used in place of ammonia, secondary' and
tertiar}' amino compounds can be obtained. Piperidine
behaves like a secondan.- amine and leads to N-anthra-
quinonyl piperidines.
Owing to the importance of the reaction the number of
patents which have been taken out is extremely large, and
1 Z. 1869, 114, Cf. E. Schmidt, J. pr. [2] 9. 26O.
- B. 39, 637.
» SchoU, M. 34, loii.
196 ANTHRACENE AND ANTHRAQUINONE
only the more important of these will receive individual
notice in the text.i
The dianthraquinonylamines will receive separate treat-
ment, as they are somewhat less readily obtained than the
other amino and alkyl- and aryl-aminoanthraquinones,
although of considerable importance as vat dyes.
In addition to their preparation directly from negatively
substituted anthraquinones, the secondary and tertiary
compounds can, of course, also be obtained by the alkylation
and arylation of the primary compounds, and reactions of
this nature will be discussed after the description of the
direct method.
REPI.ACEMENT OF HALOGEN ATOMS. — Halogen atoms are
usually fairly easily replaced by amino groups when the
halogen compound is heated with aqueous ammonia, 2 the
reaction in many cases being facilitated by the use of metallic
copper as a catalyst. ^ In preparing i-aminoanthraquinone-
2-carboxylic acid from the corresponding chloro acid,
UUmann * found that the best results were obtained by
using an ester instead of the free acid, and according to the
Badische Anilin u. Soda Fabrik,^ esters with aromatic
alcohols such as benzyl alcohol are the most suitable.
Halogen anthraquinones will not usually react with
secondary aromatic amines, but will react with primary
aromatic amines and with primary and secondary aliphatic
amines, including piperidine, and here again the reaction is
facilitated by the use of a copper catatyst.^ The ease with
1 In addition to those mentioned in the sequel, the following are the
more important patents and for the most part deal with alkyl and arylamino
anthraquinone sulphonic acids. Agfa, D.R.P. 261,885, B.A.S.F., D.R.P.
106,227; 108,274; 108,873; 111,866; 113,011; 113,934; 121,155;
206,645. By., D.R.P. 101,805-6; 103,396; 107,730; 116,867; 125,578:
125.666 ; 126,542 ; 127,458-9 ; 127,532 ; 137.078 ; 142,052 ; 145.239 ;
148,767; 151,511; 159,129; 163,646; 165,140; 166,433; 216,773;
263,424. M.L.B., D.R.P. 99,078 ; 108,420; 144,111; 149,780; 158,257;
183. .395; 185,546; 191. 731 ; 209,321; 265.725; 268,454; 269.749;
272.614 ; 282,672 ; 286,092.
- Frey, B. 45, 1360. UUmann, P.. 47, 561. Schaarschmidt, A. 405,
95. M.L.B., D.R.P. 231,091. By., D.R.P. 295,624.
3 UUmann. B. 49. 747. By., D.R.P. 195,139 ; 295,624.
" B. 49, 747. Cf. B. 47, 561. 6 D.R.P. 247,411 ; 256,344.
6 UUmann, B. 52, 2109. B.A.S.F.. D.R.P. 247,411. Agfa, D.R.P,
280,646; 288,665. By., D.R.P. 195.139; 295,624. M.L.B., D.R.P.
270,790.
. THE AMINOANTHRAQUINONES 197
which, the reaction takes place depends also on what other
groups are present in the molecule. Thus Schaarschmidt ^
finds that the bromine atom in i-nitrilo-2-bromanthraquinone
is very reactive and is very easily replaced by an amino or
alkyl or arylamino group. With ammonia, however, the
condensation is accompanied by the hydrolysis of the nitrile
group, the product being the amide of 2-aminoanthraquinone-
i-carboxylic acid. With methylamine the tendency to
hydrolyse the nitrile group was not so great, and fair yields
of the N-methylamino nitrile could be obtained. The
bromine atoms in 4.8-dibromanthrarufin-2.6-disulphonic acid
are also extremely reactive and are readily replaced by
amino groups by heating to 30-40° with aqueous ammonia
of 20 per cent, strength in the presence of copper.
In some cases the use of boric acid has been recommended
as facilitating the replacement of halogen atoms by arylamino
groups, and Harrop, Norris, and Weizmann 2 have applied
this method to various derivatives of 1.4-dichloranthra-
quinone.
In the great majority of cases alkylamines will only
react with chloroanthraquinones when heated with them
under pressure, 3 and in order to prepare alkylamino anthra-
quinones from chloroanthraquinones without the necessity
of using an autoclave Ullmann * introduced what is usually
known as the sulphonamide process. This elegant method is
based on the fact that sulphonamides will condense with
chloroanthraquinone at the ordinary pressure, and that the
sulphonic acid group is then readily split off by hydrolysis.
The sulphonamide generally employed is that of the easily
accessible _^-toluene sulphonic acid. If ^-toluene sulphon-
amide itself is used the condensation product with a chloro-
anthraquinone on hydrolysis gives a primary aminoanthra-
quinone. If, however, ^-toluene sulphochloride is first con-
densed with a primary amine, a N-alkyl sulphonamide is
1 A. 405. 95-
2 Soc. 95, 1313.
3 By., D.R.P. 136,777-8.
* A. 380, 317 : 381, 17. B. 49, 741, 2158 ; 52, 2112 ; 53, 834. D.R.P.
224.982 ; 227,324. Cf. B.A.S.F., D.R.P. 293,100.
igS ANTHRACENE AND ANTHRAQUINONE
obtained, and this can then be condensed with a chloro-
anthraquinone to a product which on hydrolysis gives an
N-alkylaminoanthraquinone :
CI n/ NHR
CHsCeHiSOoNHR
^S02C6H4CH3
An exactly similar reaction takes place with N-aryl
sulphonamides, the final product in this case being, of course,
an N-ar\4 aminoanthraquinone. The sulphonamide process
has proved to be of the utmost use in the study of the second-
ary^ aminoanthraquinones, and vSchaarschmidt i attempted
to apply it to the preparation of i-nitrilo-2-aminoanthra-
quinone. In this case, however, it was not successful, as
the hydrolysis of the anthraquinonyl sulphonamide was
always accompanied b}' the h3-droh'sis of the nitrile group.
The replacement of halogen atoms b}' heating halogen
anthraquinones with amines has been applied to the manu-
facture of one or two d3^estiiff s. Thus Alizarin Pure Blue B
is obtained from 2.4-dibrom-i-aminoanthraquinone b}' heat-
ing it with _/)-toluidine and then sulphonating the product,
and Anthraquinone Blue SR Extra is obtained by heating
tetrabromdiaminoanthraquinone with aniline and then
sulphonating^
Replacement of Nitro Groups. — Nitro groups can be
replaced b}^ amino groups b}^ heating the nitro compound
with ammonia, 3 or with primary 4 or secondary- aliphatic
amines, 5 or primar^^ aromatic amines. ^ An amino compomid
is not formed, however, when a nitroanthraquinone is heated
with a secondary' aromatic amine. The reaction in the case
of i-nitroanthraquinone-2-carboxylic acid is particularly
1 A. 405, 95-
2 B.A.S.F.. D.R.P. 121,684.
3 Przibram, D.R.P. 6,52b.
* By.. D.R.P. 139,581 ; 144.634-
* By.. D.R.P. 136.777-8. Cf. D.R.P. 151,512-3.
« Heller. B. 46, 2702. By.. D.R.P. 125,578 ;
M.L.B., D.R.P. 150.332.
126,803 ; 148,767.
THE AMINOANTHRAQVINONES
199
easy and can be brought about simply b}- boiling this
substance in aqueous solution with the amine. ^
It is vety doubtful if a nitro group in the ^-position is
sufficiently reactive to be replaced by an amino or an alkyl
or ar\lamino group. All the examples of the replacement
of the nitro group by heating with a base seem to be confined
to compounds in which the nitro group occupies an a-
position,- and Kauffler 3 states that ^-nitroanthraquinone is
unaffected by boiling with aniline or toluidine, although
similar treatment of a-nitroanthraquinone leads to the
production of phenyl and tolyl aminoanthraquinone. In
this connection it is notable that the nitro group of ^-nitro-
anthraquinone is very readily replaced by the methox>'
group by boiling with methyl alcoholic caustic potash.
The most important application of replacement of nitro
groups by arylamino groups is the preparation of Anthra-
quinone Violet, which is obtained by heating 1.5-dinitro-
anthraquinone with _/'-toluidine and then sulphonating the
product. 4 It is used as an acid dye for wool and silk, and
gives fast shades of violet. The fastness of the dye is
increased by chroming, although the shades are scared}-
altered. The difference in colour between Anthraquinonc
Violet and the isomeric 1.4-compound (Alizarin C}-anine
Green, p. 203) should be noted.
I
Anthraquinone Violet.
I
Hoi
CcHgNH
ISO3H
Erweco Acid Alizarin Blue R.
Erweco Acid Alizarin Blue R is obtained by heating
dmitroanthraflavic acid disulphonic acid with aniline. 5 It
» B.A.S.F., D.R.P. ^47,411.
» Cf. Wed., D.R.P. 235,776 ; 244,372 ; 245,014 ; 247,245.
^ B. 36, 65. * B.A.S.F., D.R.P. 108,274.
' Wed., D.R.P. 235,776.
200 ANTHRACENE AND ANTHRAQUINONE
dyes wool from an acid bath in violet-red tones which
change to deep blue on chroming. The shades are very
fast.
RepIvACEment of Hydroxyi. Groups. — The replacement
of hydroxyl groups by amino groups by heating hydroxyl-
anthraquinones with ammonia or primary or secondary
aliphatic amines or primary aromatic amines is a reaction of
very considerable importance in view of the ease with which
hydroxyl groups can be introduced into the anthraquinone
molecule by direct oxidation. The replacement of a hydroxyl
group by an amino group appears to take place with rather
greater difficulty than does the replacement of a nitro
group or a halogen atom. Thus Heller ^ was able to replace
the nitro group in 3-chlor-4-nitroalizarin without affecting
the hydroxyl groups or the halogen atoms, and Ullmann ^
found that when i-chlor-2-methyl-4-hydroxy anthraquinone
was heated with ^-toluidine and copper only the chlorine
atom was affected. The production of 2-phenylamino-
quinizarin from 2-bromquinizarin and aniline, 3 and the
conversion of 4-nitroalizarin monoalkyl ethers into the
4-arylamino compounds * also supports this view, and other
instances could be cited. The data available, however, do
not justify any definite conclusions being drawn, and in the
above cases the increased reactivity of the nitro groups or
halogen atoms may be due to their orientation and to the
effect of other groups present in the molecule.
The replacement of hydroxyl groups can be brought
about simply by heating the hydroxy compound with the
base, but in many cases the reaction is facilitated by the
presence of acids, ^ such as hydrochloric, sulphuric, phos-
phoric, and, in particular, boric acids. The sulphite esteis
of the hydroxy compounds react much more readily than the
hydroxy compounds themselves, and it is claimed that amino
compounds can be obtained from sulphite esters by the
action of ammonia at the ordinary temperature. ^
Replacement of hydroxyl by amino groups is also
1 B. 46, 2702. 2 B 52, 2109.
3 By., D.R.P. 114,199. * M.L.B., D.R.P. 150,322.
■' By., D.R.P. 86,150. 6 By., D.R.P. 61,919 ; 65.650 ; 66,917.
THE AMINOANTHRAQUINONES 201
greatly facilitated by first reducing the hydroxyl anthra-
quiuoiie to its leiico- compound, and then treating this with
ammonia or an amine, the product being finally converted
into the aminoanthraquinone by oxidation. 1 The increase
in reactivity of nuclear hydroxyl groups which takes place
on the reduction of one or both of the cyclic carbonyl groups
is remarkable, condensation with ammonia and aliphatic
amines often taking place at or about the ordinar^^ tempera-
ture, and condensation with primary aromatic amines being
rapidly effected at or below 100°.
In some cases it is not necessary to reduce the whole of
the hydroxy compound in order to take advantage of the
increased reactivity of the reduction product. Thus it has
been claimed 2 that if a mixture of quinizarin and leuco-
quinizarin is heated with _/>-toluidine, the /^wco-quinizarin
reacts with the toluidine to produce /ewco-ditolylamino
anthraquinone, which then reduces an equivalent amount of
quinizarin to /ewco-quinizarin. being itself thereb}^ oxidised
to 1.4-ditolylamino anthraquinone. The /<?zfco-quinizarin
thus produced then reacts with ^-toluidine and the process
is repeated until the whole of the quinizarin has been
converted into ditolylamino anthraquinone. It wiU be
seen that the action of the /^wco-quinizarin is purely
catalytic.
When the /ewco-hydroxyanthraquinones are heated with
ammonia or an amine the h5^drox5d groups attached to the
wts-carbon atoms remain unaffected, although under more
drastic conditions it is probable that the}- would be involved in
the reaction, as it has been found that such compounds can be
obtained from the reduction products of anthraquinone and
anthraquinone sulphonic acid by heating with ^-toluidine. 3
Even without reduction there is danger of the cyclic carbonyl
groups becoming involved if too drastic conditions are
employed. Thus von Perger,^ by heating alizarin with
1 Schrobsdorf, B. 35, 2930. By., D.R.P. 91. MQ- M.L.B., D.R.P.
205,096; 205,149; 205,551;
2 By., D.R.P. 91,150-
3 By.. D.R.P. 136,872 ; i.|7.277 '. 148.079.
4 J. pr. [2] 18, 133-
202 ANTHRACENE AND ANTHRAQUINONE
aqueous ammonia, obtained a substance which he considered
to be i.2-diaminoanthraquinone, and lyiebermann and
Troschke i by the same method obtain a substance which
they considered to be an ammonium salt of an imide of
aHzarin. More recently Scholl and Parthey - have shown
that the substances obtained by von Perger and by lyieber-
mann and Troschke are really identical. They state that
it is not i.2-diaminoanthraquinone, and as it is soluble in
alkali it apparently contains a hydroxyl group. As on
hydrolysis it loses a molecule of ammonia and passes into
i-hydrox>^-2-aminoanthraquinone Scholl and Parthey con-
sider that it must be :
f^ OH CO OM
or I A A /
CO L
Prudliomme,3 by the action of ammonia on /^wco-alizarin,
claims to have isolated both of these isomers, and states
that he has obtained similar compounds from anthrapurpurin.
In the case of hydroxy^anthraquinones in vvhich two or more
hydroxyl groups are present, it is often possible to replace
onl}' one group by heating with an amine.* The remaining
hydroxjd groups can then be replaced by treatment with
a different base if desired, and by this means a great variety
of amino compounds can be prepared. ^
Alkoxy groups and ar3doxy groups can also be replaced
by amino groups b}^ heating with primary or secondary-
amines, and in mau}^ cases the reaction takes place more
readily than when the free hydroxyl compound is used.^
The replacement of hydroxyl groups by ainino or alkyl
or arylamino groups has been used for the preparation of a
number of dyestuffs of which the following are the more
important.
1 A. 183, 209.
2 B. 39, 1201.
3 Bl [3] 35, 71.
* Schrobsdorf, B. 35, 2930.
5 By.. D.R.P. 86,539.
« By., D.R.P. 165,728 ; 205,881.
M.L.B., D.R.P. 201,905.
THE AMINOANTHRAQUINONES
20'
Alizarin Irisol 1). ' — This is obtained by heating quinizarin
with one molecule of /)-toluidine and then sulphonating the
product. 2 It dj^es silk and wool from an acid bath in
bluish-violet vShades which are fast to light, and which
become greenish-blue when after-chromed. Alizarin Direct
Violet R and Alizarin Cyanol Violet R are very similar and
differ only from Alizarin Irisol D in the position of the
sulphonic acid group. They are obtained by condensing
leuco-qmnizann with ^-toluidine-2-sulplionic acid.
^«W^^"'[3]s5h
I
NH[4]C„H3WCH^
OH
Alizarin Irisol D.
OH
Alizarin Direct Violet R.
Alizarin Cyanol Violet R.
By replacing both the hydroxyl groups in quinizarin
several important dyestuffs have been obtained. B}^ far
the most important of these is Alizarin Cyanine Green or
Quinizarin Green, ^ which is obtained by heating quini-
zarin * or much better /cwco-quinizarin ^' with /)-toluidiue
and then sulphonating the product, ^ but 1.4-dichloranthra-
quinone or i-chlor-4-nitroanthraquinone can be used in
place of quinizarin.'^ The product dyes wool green from
an acid bath, the shades being very fast and becoming even
more so by chroming.
Alizarin Direct Green G and Alizarin Brilliant Green G
are isomeric with Alizarin Cyanine Green and are obtained
by condensmg /^wco-quinizarin with ^-toluidine-2-sulphonic
acid : ^
1 Solwav Purple (Scottish Dyes, Ltd.).
^ By., D.R.P. 86,150 ; 91,149.
' Kymric Green (Scottish Dyes, Ltd.).
« By., D.R.P. 86,150; 86,539.
5 By., D.R.P. 91,149 ; 91,150; 91.152;
» By.. D.R.P. 84, 509 : 89,862 ; 93.3io-
' By., D.R.P. 125,698 ; 126,803.
8 B.A.S.F., D.R.P. 128,753 : 137.566 ;
92,591 ; 93.223 ; 94.396.
155.572. C/. M.L.B., D.R.P. 172,464; 181,879; 201,905.
148,306; 151.018; 151,384;
204 ANTHRACENE AND ANTHRAQUINONE
NHWCeH^WgHs^
NHMCgHg
[i]CH3
[3]S03H
NH[4]CeH3[^]^^H3^
Alizarin Cyanine Green.
Quinizarin Green.
NHMCeHsWCH.^
Alizarin Direct Green G.
Alizarin Brilliant Green G.
Isomeric green dyes in which the snlphonic acid groups
are in the anthraquinone nucleus are obtained by condensing
/^wco-quinizarin sulphonic acid with ^-toluidine.i They are
said to give purer shades of green than either of the above
but do not seem to have come into technical use. In this
connection it is interesting to notice that it has been claimed
that 1. 4-ditoluido-8-hydroxy anthraquinone is sulphonated
in the anthraquinone nucleus when the sulphonation is
carried out in the presence of boric acid. 2 If this is the case
it is no doubt due to the directing influence of the hydrox>'l
group, or rather of its boric ester.
As stated on p. 202, the two hydrox}^ groups in quini-
zarin and other polyhydroxy anthraquinones can be replaced
by different aryl or alkj'lamino groups. This has been done
in the case of Alizarin Astrol, in which one hydroxyl group
has been replaced by a meth3^1amino group and the other by
a tolylamino group, the sulphonated product being a
greenish-blue wool dye. It is interesting to notice the
transition in colour from Alizarin Pure Blue through Alizarin
Astrol to Alizarin Cyanine Green :
/CH3 /CH3 /CH3
NHC6H3<' NHCgHa^ NHCeHg^
'SO.H
Br
NH2
I
^SOgH
NHCHo
I
.CH,
Alizarin Pure Blue. Alizarin Astrol.
1 By., D.R.P. 95.625 ; 101,919.
NHC6H3<
Alizarin Cj-anine Green.
« By., D.R.P. 170,113.
THE AMINOANTHRAQUINONES
205
Of the various other dyes which have been obtained by
heating hydroxyanthraquinones with bases only two call
for special notice. Alizarin Viridine is 5.6-dihydroxy-
quinizarin green and is obtained by heating Alizarin Bordeaux
with ^-toluidine and then sulphonating the product. It is
a mordant dye and is used for producing green shades on
chrome mordanted cotton. Alizarin Blue-Black 1 is
obtained by heating purpurin with aniline and then
sulphonating the product. As it is also obtained by
sulphonating the condensation product of 2-bromquinizarin
and aniline it must have the formula 2 :
NHCcHiSOsH
— NHC6H4SO3H
I
or
OH
NHC6H4SO3H
I
OH
NHC6H4SO3H
and cannot be a sulphonation product of 2-hydrox5'-i.4-
diphenylaminoanthraquinone as originally thought.
Replacement of Sulphonic Acid Groups. — The re-
placement of sulphonic acid groups by amino groups is of
ver}^ considerable importance, as a very large number of
sulphonic acids can be readily obtained by sulphonating
with or without the addition of a mercury catalyst (p. 176).
As stdphonic acid groups enter the anthraquinone nucleus
in the j3-position when the sulphonation is carried out in the
absence of mercur>^ the replacement of the sulphonic acid
group renders ^-amino compounds easil)^ accessible, although
they are often troublesome to obtain by other methods.
Thus jS-aminoanthraquinone, the mother substance of many
of the valuable Indanthrene colours, is easily obtained from
sodium anthraquinone-j8-sulphonate (the "silver salt" of
commerce) by heating with aqueous ammonia, although it is
expensive and troublesome to produce by other methods.
The conversion of the sulphonic acids into the amine is also
the best method of characterising the sulphonic acids, the
» Solway Blue-Black (Scottish Dyes, Ltd.). • By., D.R.P. 114,199-
2o6 ANTHRACENE AND ANTHRAQUINONE
methylamiuo compounds, obtained by the use of meth^'l-
amine, being specially suitable for this purpose.
The sulphonic acid group can be replaced by the primary
amino group by heating the sodium salt with sodamide,^
but it is much simpler and better to use aqueous ammonia ; 2
and primary and secondary alkylamines and primarj'-
arylamines react in the same way. It is Usual to employ
aqueous solutions, and to obtain a sufficiently high tempera-
ture it is necessary to work under increased pressure.
In all these reactions sodium sulphite is formed, and at
the high temperatures used (about 180-220°) this attacks
the anthraquinone nucleus unless it is destroyed or rendered
inactive as rapidly as formed. This can be done by the
addition of barium chloride, 4 as this reacts with the sulphite
to form the barium sulphite, which being almost insoluble is
more or less harmless. Much better results are obtained,
however, by adding an oxidising agent, & such as manganese
dioxide (preferably in the form of Weld on mud), which is
capable of oxidising the sulphite to sulphate. Attempts
have also been made to utilise the reducing power of the
sulphite. Thus it has been stated ^ that satisfactorj^ yields
of j8-aminoanthraquinone are obtained by heating sodium
anthraquinone j8-sulphonate with aqueous ammonia and
nitrobenzene. In this case the nitrobenzene acts as an
oxidising agent and is thereby reduced to anilme, so that the
manufacture of aniline and of /3-aminoanthraquinone is
combined in one process. As the aminoanthraquinones are
not volatile with steam there is no difficult}^ in separating
the j8-aminoanthraquinone from the aniline and imchanged
nitrobenzene.
Hofmann's Reaction. — Aminoanthraquinones can be
prepared from the amides of the anthraquinone carboxj-Uc
acids by Hofmann's method (treatment with hypochlorite or
hypobromite) , but the method has not been extensivel}- used
1 Sachs. B. 39, 3019.
2 R. E. Schmidt, B. 37. 70.
3 By., D.R.P. 135,634 ; 142,154 ; 175,024 ; 181.722. B.A.S.F.,
D.R.P. 288,464. Cf. D.R.P. 77,721 ; 90,720.
* M.L.B., D.R.P. 267,212. Cf. Geigy, E.P. I27,223i».
' B.A.S.F., D.R.P. 256,515, fi G.C.I. B., A.P. 1,255.719.
THE AMINOANTHRAQUINONES 207
as the amides are not particularly accessible and the amino-
authraquinones are usually more easily obtained by other
methods. Hofmann's method, however, has been employed
by Eckert 1 and b}' Willgcrodt and Maffelzzoli,2 who prepared
2-aminoanthraquinone-3-carbox3dic acid from the amide of
anthraquinone-2.3-dicarboxylic acid. Other investigators
have also made use of the method ^ although to no consider-
able extent.
Alkylation and Arylation.
So far the methods which have been discussed have been
those by which an amino group is introduced into the
anthraquinone molecule. The primary amino anthra-
quinones can, however, be converted into secondary' and
tertiary- compounds b)' the usual methods of alkylation
and arylation, and attention will now be directed to some
of the more interesting results which have been obtained.
The description of compounds in which two anthraquinone
residues are attached to the same nitrogen atom (the di-
anthraquinonylamines) will, however, be reserved for a
separate section (p. 231) as the}- merit special treatment.
The alkylation of the aminoanthraquinones can be
brought about in the usual wa}- by means of alkyl halides,
but in some cases abnormal results are obtained. Eckert,"*
for example, endeavoured to prepare the glycine of 2-aniino-
anthraquinone-3-carbox3-lic acid by treating it with chlor-
acetic ester, but instead of the glycine the chloracetyl
compound Ci6H60.(COOH)(NHCOCH2Cl) was obtained.
Seer and Weitzenbock ^ succeeded in preparing glycines
from monamino and 1.5-diamino anthraquinone and found
that the diglycine of the latter compound had tinctorial
properties and was capable of dyeing wool m red shades.
They also prepared some benz}^ derivatives and found
that 1.5- and i.8-dibenzylaminoanthraquinone could not be
reduced in alkahne solution.
1 M. 35, 290. 2 J. pr. [2] 82, 205.
' Scholl, B. 40, 1691. Schaarschmidt, B. 50, 294 ; 51, 1074. Terres,
B. 46, 1640. Graebe and Blumenfeld, B. 30, iini.
« M. 35, 290. - M. 31 379.
2o8 ANTHRACENE AND ANTHRAQUINONE
Methylation with dimethyl sulphate sometimes leads to
abnormal results as i-amino-4-ar}damino anthraquinones
are simultaneously sulphonated, i the product being a
i-methylamino-4-ar>4aminoanthraquinone sulphonic acid,
although it is doubtful whether the sulphonic acid group is
attached to the anthraquinone nucleus or to the aryl group.
The sulphonation can hardly be a side reaction due to
liberation of srdphuric acid from the dime thy Isulphate, as it
takes place even in the presence of excess of sodium carbonate.
Other amino anthraquinones are conveniently meth^^lated
by heating to 180-200° with methyl alcohol or dimethyl
sulphate in the presence of concentrated sulphuric acid or
oleum, this procedure rendering possible the use of open
vessels. 2
Alkylene oxides will combine with primary aminoanthra-
quinones, a-aminoanthraquinone and ethjdene oxide ^ giving
C14H7O2NHCH2CH2OH, and epichlorhydrin * giving a com-
pound which contains chlorine and probably has the formula
C14H7O2NHCH2CHOHCH2CI. On sulphonation this yields
a yellow acid dye.^
Glyoxylic acid combines with a- and /i-aminoanthra-
quinol to form the glycine of a- and jS-aminoanthraquinone.^
Here probably the azomethine compoimd of anthraqumo]
is first formed, the azomethine group then being reduced
at the expense of the quinol group :
OH
I
C CO
CeH^^nCcHgN : CHCOOH -> C6H4<>C6H.3NHCH2COOH
C CO
1
OH
In some cases primary aminoanthraquinones can be
converted into secondary- and tertiary^ compounds by
diazotising and then treating the diazonium salts with a
1 M.L.B., D.R.P. 174. 131. 2 By., D.R.P. 288,825.
3 By., D.R.P. 235,312. * By., D.R.P. 218,571.
5 Bv., D.R.P. 220,627. 6 M.L.B., D.R.P. 232,127.
THE AMINOANTHRAQUINONES
209
primary or secondary amine, and this process has been
investigated b}- WackerJ He found that i-aminoanthra-
quinone-2-sulphonic acid when diazotized gave an internal
anhydride which reverted to the original amino compound
when treated with ammonium carbonate, but which gave
the methylammo and diethj-lamino sulphonic acid when
treated with methylamine carbonate or diethylamine :
NHCHa
SO3H
CHjNHj
<
3 (C.HJaNH
N(C2H5),
SO3H
HNO.f |(NH4)X03
HNo
When treated with aniline, however, the diazo anhydride
gave lirst the diazoamino compoimd, which under the
influence of acids broke down into the original amino-
sulphonic acid, phenol and nitrogen.
The above reactions are by no means general, as 1.5-
and i.8-diaminoanthraquinone when tetrazotized gave with
ammonia a mixture of the original diamino compound and
an aminohydrox>'- compound, with methylamine the original
diamino compound only, and with diethylamine only the
dih3-drox5' compound, whereas the diazonium salt of i-amino-
4-hydrox}-anthraquinone when treated with methylamine
gave quinizarin.
Primar3^ aminoanthraquinones combine with aldeli}dcs
and compounds of the type Ci4H70oNHCH2[i]C6H4[4]NRo
are obtained by condensing a-aminoanthraquinone with
formaldehyde and tertiary' aromatic amines such as di-
methyl aniline. 2 Kauffler ^ has studied the benzylidene
1 B. 34, 2593, 3922. 2 xM.L.B., D.R.P. 236.769. ' F.T. 2. 471.
14
210 ANTHRACENE AND ANTHRAQUINONE
aminoanthraquinones but without obtaining results of any
particular interest.
The arylation of the aminoanthraquinones can be carried
out in the usual way by heating the amino compound with
the aryl halide in the presence of a copper catalyst such as
copper powder, copper acetate or cuprous chloride, and a
substance such as sodium acetate which is'capable of com-
bining with the halogen acid split out during the reaction.^
The same compounds can, of course, also be obtained by
condensing the halogen anthraquinone with a primary or
secondary arylamine.2 When the condensation is being
carried out with a primary amine either the chlor- or the
brom-anthraquinone can usually be used, but when a
secondary amine is employed it is usuallj- necessar}- to
make use of the iodo- compound. Thus carbazol and
diphenylamine will condense with a-iodoanthraquinone,3
but if chlor- or brom-anthraquinone is used little or no
reaction takes place. Aminoanthraquinones also condense
with benzoquinone and a-naphthoquinone to give compounds
of the type (HO)2[i.4]C6H3[2]NHCi4H602NH2, from which
vat dj^es giving fast shades of bordeaux can be obtained
by condensation with halogen anthraquinones so as to form
a dianthraquinonylamine derivative. -^
Tinctorial Properties.
Although the primar}- aminoanthraquinones are liiglily
coloured substances, the}- have little or no afEnit}^ and con-
sequentl}' are useless as dyestuffs. To a certain extent
the same is true of the secondary and tertiar>^ compounds,
but in some cases these show very considerable affinity,
and as has already been shoM^n (p. 203), valuable acid dyes
are formed by sulphonating the secondary 1.4-diamino-
anthraquinones.
1 Laube, B. 40, 3564. By., D.R.P. 175,069. B.A.S.F., D.R.P. 280,881.
For further references see p. 211.
2 Laube and Konig, B. 41, 3874. Agfa, D.R.P. 243,489. M.L.B.,
D.R.P. 255.821.
3 Laube, B. 40, 3564. * Cas., D.R.P. 267,414-5-6 ; 269.801.
THE AMINOANTHRAQUINONES 211
When the uitrogen atoms of two molecules of an amino-
anthraquinone are jomed by a carbon cham so as to produce
a compound of the type C14H7O2NH— X— NHC14H7O2,
tmctorial properties are often developed and some of the
products thus formed are said to act as very fast vat dyes,
although they do not seem to have been placed on the market.
One of the simplest of these is sym-dianthraquinonyl-
ethylenediamine, which Ullmann and Medenwald ^ prepared
from j3-aminoantliraquinone and ethylene dibromide by the
sulphonamide process. When used as a vat dye it gives
orange shades, but the affinity is very poor. Cuiiously
enough, the corresponding compound derived from a-amino-
anthraquinone does not seem to have been described,
although it should be of considerable interest, as it would no
doubt readil}' pass into a complex heterocyclic com[)oimd.
In the above type of compound much greater aflinity is
obtained when X represents an aryl residue, and at the same
time the colour is shifted towards the violet end of the
spectrum. Such compounds can be obtained by condensing
two molecules of a halogen anthraquinone with one molecide
of an aromatic diamine such as /^-phen^'lene diamine, benzi-
dine, 2 etc., or by condensing two molecules of an amino-
anthraquinone with one molecule of an aromatic dihalogcn
compound such as ^-dichlorbenzene ^ (violet shades), po-
dichlorbenzil * (red shades), /Jo'^iclilordiphem-lmethanc ^
(bordeaux shades), diclilorphenanthraquinone 6 (red shades),
diclilorbenzophenone " ' ' (red shades) , or />2-dichlordiphen\-i ^
(violet shades). The condensation product from amino-
anthraquinone and ^2"<iiclil^r^^iph^^i3'l ^^^^ ^^^^ ^^ obtained
from cliloranthraquinone and benzidine, and Brass ^ has
obtained it and similar compounds b}' oxidising diaryl-
amhioanthraquinones with manganese dioxide and sulphuric
acid.
Vat dyes have also been obtained ^^ by condensing
I B. 46, 1798. - Agfa, D.R.P. 24^,489.
* By., D.R. p. 215,294. « B.A.S.F., D.R. P. 222,205; 230,400.
• B A.S.F., D.R.P. 230,411. « B.A.S.F., D.R.P. 222,206; 230,40c.
' n.A S.F., D.R.P. 220,579; 2:50,399. « Bv., D.R.P. 230,409.
' B. 46, 2907. W.T.M., D.R.P. 251,845. " By.. D.R.P. 248,655
212 ANTHRACENE AND ANTHRAQUINONE
two molecules of a primary aminoantliraqmnone with
one molecule of a compound of the general formula
CL'^.r — X — ArCl, where Ar represents an aryl residue and
X is O, S, or NH, and may or may not form part of a ring,
e.g. a carbazol ring.
Of somewhat different structure are the vat dyes which
are obtained by condensing two molecules of an ammo-
anthraquinone with one molecule of a sym-dihalogen diaryl
urea.i or with compounds of the type 2 HlgRNHC0(CH2)n-
CONHRHlg, where w is 0, i, 2, 3, etc. Somewhat similar
dyes are obtained by condensing dihalogen sulphones with
aminoanthraquinones. ^
The shades produced by the diar>daminoanthraquinones
depend to a considerable extent on the position of the
arylamino groups. As already shown (p. 203) the 1-4-
diarjdaminoanthraquinones give rise to green dyes, e.g.
Alizarin Cj-anine Green. When the ar^damino groups are
in the 1.5 positions, the shades are usually violet, e.g. Anthra-
quinone Violet (p. 199), whereas when in the 1.8- positions
they are red.
ACYLAMINOANTHRAQUINONES
Converting an aminoanthraquinone into an ac5damino
compound is alwa3-s accompanied by a marked increase in
tinctorial properties, powerful vat dyes being obtained when
the acyl group is derived from an aromatic acid like benzoic
acid, or from a dibasic fatty acid such as malonic or succinic
acid. The acyl groups derived from the monobasic fatty
acids, such as formic and acetic acid, also confer tinctorial
properties, although to a much lesser degree, the afiinit}^
of the resulting acyl aminoanthraquinones being too slight
for them to be of an}^ value as technical d3'es. Although
the ac5d aminoanthraquinones derived from monobasic
aromatic carboxylic acids have great affinity, this is not
the case with the derivatives of aromatic sulphonic acids,
1 M.L.B.. D.R.P. 241,837. 2 M.L.B., D.R.P. 241,838.
" By.. D.R.P. 234,518.
THE AMINOANTHRAQUINONES 213
the N-anthraquiuon}-! sulphonamides as a rule having no
tmctorial properties.^
The ac)4aminoanthraquinones are very readily obtained
from the amino compound by heating it with the acid
chloride 2 or with the free acid ^ in some inert solvent of high
boiling point such as nitrobenzene or naphthalene. The
acid chloride, of course, reacts most readily, sodium acetate
being added in order to neutralise the hydrochloric acid
liberated. When preparing acetyl derivatives it is often
advantageous to dissolve the amino compound in concentrated
sulphuric acid or oleum containing 10-25 P^r cent, of sulphur
trioxide and then to add acetic anhydride, glacial acetic acid
or anhydrous sodium acetate. By this means both primary
and secondary compounds, including dianthraquinonyl-
amines, can be acetylated, although in some cases acetylation
only takes place with diihculty when less drastic methods
are employed.'*
In some cases an ester or an amide of the acid can be used
for inserting the acyl group, -^ but in other cases the reaction
takes a different course. ^ Thus the aminoanthraquinones,
when heated with alkaline alcoholic solutions of ethyl
oxalate, do not give the oxalyl derivatives, but yield yellow
or red vat dyes which probably have the constitution
A — N=C — C=N— A, where A is an anthraquinone residue.
I 1
OEt OEt
Ac3daminoanthraquinones can also be obtained by
condensing a halogen anthraquinone with an acid amide,*^
although this method has not been employed to any great
extent. The condensation is carried out in the presence of
a copper catalyst, sodium acetate being added to neutralise
the hydrochloric acid liberated.
As stated on p. 212, the acj^laminoanthraquinones
1 Seer and Weitzenbock, M. 31, 371.
- By., D.R.P. 223,069 ; 225,232; 227,104; 227,398; 248,289.
» By.. D.R.P. 210,019; 212,436; 216,980; 223,069; 223,510;
224.808 ; 226,940.
* B.A.S.F., D.R.P. 211.958.
* By., D.R.P. 210,019 ; 212.436 ; 216.980.
6 By.. D.R.P. 270,579. ' By., 216.772.
214 ANTHRACENE AND ANTHRAQUINONE
derived from the monobasic fatty acids are of but minor
interest owing to their feeble tinctorial properties. Greater
affinity is obtained by condensing one molecule of chlor-
acetyl chloride with two molecules of aminoanthraquinone,
the resulting N-anthraquinonylglycylaminoanthraquinones
being brown or bordeaux dyes.i The shades, however, are
rather weak, and not particularly fast to ligtt, so that the
substances have but little technical interest.
Of the acylaminoanthraquinones derived from dibasic
fatt}' acids, compounds derived from oxalic, malonic, suc-
cinic, adipic, maleic, malic, tartaric, and camphoric acids
have been described. 2 These are all vat dj-es, and are
fairl}^ readily obtained by boiling an aminoanthraquinone
with the acid in nitrobenzene solution, with or without the
addition of a condensing agent such as phosphorus penta-
chloride, zinc chloride, boric acid, etc. The reaction takes
place in two steps, and if desired one molecule of the acid
can be made to condense with two different aminoanthra-
quinones.3 The only technical dyestuff derived from a
dibasic fatty acid appears to be Algol Yellow 3G (succinyl-
a-aminoanthraquinone) , although it is probable that Algol
Brilliant Violet R is succin}^ diaminoanthrarufin,
Of the aromatic acids which have been used for pre-
paring acylaminoanthraquinones, benzoic, phthalic, tere-
phthalic, salicylic and cinnamic have all been used,* and
5'ellow and orange vat dyes have also been obtained b}-
condensing the chloride of anthraquinone carboxjdic acid
with diamines such as benzidine, ^ and also with amino-
anthraquinone. ^ They are, however, of no technical im-
portance. Only the benzoyl derivatives have met with an)-
wide technical application, and these are almost invariably
prepared b}' means of the readily accessible benzo}'! chloride.
a-vSalicylaminoanthraquinone has, however, been used to a
' B.A.S.F., D.R.P. 248.997.
- By., D.R.P. 210,019; 212,436; 216,980; 223,069; 226,940. For
ureas, thioureas, urea chlorides and iirethanes, see p. 219.
^ By., D.R P. 223,510; 224,808.
* For references see p. 213.
^ li.A.S.F., D.R.P. 215,182; 236.442.
* Seer and Weitzenbock, M. 31, 371.
THE AMINOANTHRAQUINONES
215
certain extent as a pigment colour under the name Helio
Fast Yellow.
Of the technical dyes which are benzoylaminoanthra-
quinones the following are the most important : —
NHCOCeHs NHCOCcHs NHCOC0H5
I
I
I
OH
OCH3
Algol Yellow WG. Algol Pink R.
Algol Scarlet G.
NHCOC0H-,
NHCOCoH^
NHCOCfiHr, CeHgCONH
Algol Red 5G.1 Algol Yellow R.
HO NHCOCoHg HO NHCOCoHq
CeH^CONH
Algol Red FF.
CfiHgCONH OH
Algol Brilliant Violet 2B.
HO NHCOCoHg
HO OH
Algol Violet B.
The position and nature of substituent groups has a
considerable effect on tlie colour of the benzoylaminoanthra-
quinones. Thus when there is a benzoylamino group at 1 :
1 Caledon Red 5G (Scottish Dyes LM.).
2i6 ANTHRACENE AND ANTHRAQUINONE
(a) Substituents at 2 have comparatively little effect.
(b) Substituents at 4, other than halogen atoms, have a
great effect and shift the shade towards the violet end of the
spectrum.
The effect of the h5^drox}^ and methoxy group is seen by
comparing Algol Pink R and Algol Scarlet G with Algol
Yellow WG. As would be expected, the effect of the hydroxy
group is greater than that of the methoxy group, Algol
Pink R giving bluish shades of pink, whereas Algol Scarlet G
gives slightly yellowish shades of scarlet. The effect of
an amino group is very pronounced, as will be seen b}^ com-
paring the shades obtained from the following compounds :
NHCOC6H5 NHCOCeHg NHCOCsHg
I
I
NH2
Corinth.
NHCHc
Blue.
I
NHCOCgHg
Yellowish-red.
It will be seen that benzoylating the second amino group
lessens its effect. The influence of a nitro group in the
para- position to the benzoylamino group is, as would be
expected, ver}- great, i-benzoylamino-4-nitroanthraquinone
dyeing in violet shades. The presence of a nitro group,
however, is objectionable in a vat dye owing to its liabilitj^
to become reduced in the dyebath.
Although the above remarks refer to the benzoyl amiuo-
anthraquinones, they are equally applicable to other acyl-
aminoanthraquinones, as will be seen b}'- comparing the
following succinyl derivatives :
NHCOCHoCH.,CONH NHCOCHoCH.CONH
YeUow.
OH HO
Scarlet.
THE AMINOANTHRAQUINONES 217
NHCOCH2CH2CONH NHCOCH,CH<.CONH
I
OCH,
I
CH,0
I
NO.
I
NO5
Orange.
Violet- red.
(c) Substituents at 5 have, as a rule, comparatively little
effect on the colour, amino groups producing red shades.
The effect of the nitro group is extraordinarily small and
merely changes the colour from yellow to orange or led.
The very slight infliience of groups at 5 will be clearly seen
by comparing the shades produced by the following com-
pounds with those obtained from the isomers mentioned
above :
NHCOCfiHs
NHCOCr.H,
NHCOCr.H-
CH3NH
HO
NO2
Orange-red.
Red. Yellow.
NHCOCH2CH2CONH NHCOCH2CH2CONH
I
NHo
I
I
NH., NO.,
I
NO.
Orange.
Red.
(c) But little information is available as regards the
influence of substituents at 8, but the effect is probably
decidedly less than that of substituents at 4, as the succinyl
derivative of i.8-diaminoanthraquinone dyes only in yellow
shades.
(d) When several substituents are present the case
becomes somewhat complicated, as they often modify or
2i8 ANTHRACENE AND ANTHRAQUINONE
reinforce one another. In connection with this it will be
sufficient to give five examples :
NHCOCgHg NHCOCgHs
NHCOCgHg
I
NHCOCgH,,
Orange.
(Algol Brilliant Orange FR.)
CfiHsCONH NHCOC^Hg
I
CeHgCONH NHCOCeHg
Bordeaux.
HO NHCOCcH^
CeHgCONH NHCOCaHg
Red -violet.
CfiHgCONH OH
Blue-violet.
(Algol Brilliant Violet 2B.)
HO NHCOCfiHs
HO OH
Red-violet.
(Algol Violet B.)
One or two acylamino dianthraqmnon54s have been
studied, e.g. 4.4'-dibenzoylamino-i.i'-dianthraquinonyl has
been found to be a yellow vat d^^e, 1 but compounds of this
nature have not been found to be of any technical value.
It should be noted that the shades obtained from amino-
benzoylaminoanthraquinones are usually rather loose to
acids and chlorine, although this can be remedied to a large
extent by acetylating the amino group. 2
The presence of a sulphonic acid group attached to the
anthraquinone nucleus has the effect of reducing the colour
slightly. The products, however, are readily soluble in
» By., D.R.P., 227,104. 2 M.L.B., D.R.P. 240,079.
THE AMINOANTHRAQUINONES 219
water and are not hydrolysed by boiling dilnte acids, and
can, therefore, be used as acid wool dyes.i
Ureas and Thioureas
A considerable amount of work has been carried out in the
study of the carbonic acid derivatives of the aminoanthra-
quinones, but the whole of the work published so far has been
in the form of patent specifications, and consequently the
information available at present is far from complete.
Ureas are formed by the action of carbonyl chloride on
the aminoanthraquinones at about 170° in solution or
suspension in some indifferent solvent such as nitrobenzene. 2
In the case of j8-aminoanthraquinone the reaction takes
place without the use of any condensing agent, but a urea
can only be obtained from a-aminoanthraqmnone in the
presence of anhydrous sodium acetate or other substance
capable of neutralising the hydrochloric acid set free. The
urea is not the only product obtained by the action of phosgene
on aminoanthraquinones, as at the ordinary temperature
a mixture of the urea chloride and the hydrochloride of the
base is formed. 3 This latter substance by the prolonged
action of excess of phosgene passes into the urea chloride,
although the change is more rapid if the calctdated amount
of phosgene is allowed to react with it at 40-120°. Anthra-
quinone iso-cyanates do not seem to be formed directly by
the action of phosgene on the amino compounds, although
they are obtained in good yield by heating the urea chloride
in nitrobenzene solution.*
Instead of treating the aminoanthraquinone with phos-
gene the urea can be prepared by means of chlorcarbonic
ester, ^-aminoanthraquinone", for example, giving the urea
when boiled in naphthalene .solution with ethylchlor-
carbonate.s although under less drastic conditions the
urethane is produced.^' The urea is also formed when
» Bv., D.R.P. 22^.o6q. 2 M.L.B., D.R.P. 232,739.
3 M.L.B., D.R.P. 238,550 ; 241.822. " M.L.B., D.R.P. 224,490.
« M.L.B., D.R.P. 242,292. <; By., D.R.P. 167,410; 171,588.
220 ANTHRACENE AND ANTHRAQUINONE
/S-aminoanthraquinone is heated to 70° with urea in nitro-
benzene solution.!
Mixed ureas containing either two different anthra-
quinone residues, or one anthraquinone residue and one
aromatic residue, can be obtained by condensing the anthra-
quinone urea chloride or the urethane 2 with a molecule of
an aminoanthraquinone or an alk3damine or arylamine.
By using ammonia a monoanthraquinonyl urea is obtained. ^
The procedure can, of course, be inverted and the urethane
condensed with j8-aminoanthraquinone. In this case ure-
thane itself gives dianthraquinonyl urea,^ whereas mixed
aryl anthraquinonyl ureas are obtained from ar}d urethanes.^
Mixed ureas can also be obtained by condensing an amino-
anthraquinone with an ar>4 iso-cyanate,^ or by condensing
an anthraquinone-iso-cyanate with a primary or secondarj^
aliphatic amine or a primary- aromatic amine, "^ Finally, it
may be pointed out that an aminobenzoyl benzoic acid can
be converted into a urea derivative by any of the usual
means, e.g. by treatment with phosgene, and the anthra-
quinone ring then closed by treatment with a dehydrating
agent, such as concentrated sulphuric acid at 90°. As a
rule, the closing of the ring takes place ver^^ easil}^ and to
avoid hydrolysis should be brought about at as low a tempe-
rature as possible. 8
Sulphonated anthraquinonyl ureas can be obtained by
converting an anthraquinone sulphonic acid into its urea
derivative,^ or by sulphonating the anthraquinonyl urea, 10
but are of but little interest. The ureas can also be halo-
genated. ^ ^
Very few of the anthraquinonyl ureas have been found
to be of sufficient value to justify their use as commercial
dyes, but 2. 2 '-dianthraquinonyl urea has been placed on
the market as Helindon Yellow 3GN, and a more complex
1 M L.B., D.R.P. 238,551 ; 238,553. Cf. Sonn, B. 47, 2437.
2 M.L.B., D.R.P. 236,375 ; 236,978-9; 236.980; 236,983-4; 238.550.
3 M.L.B.. D.R.P. 236.978. * M.L.B.. D.R.P. 238,552.
5 M.L.B., D.R.P. 236,981. « M.L.B., D.R.P. 229,111.
- M.L.B.. D.R.P. 231,853. 8 Agfa, D.R.P. 281.010.
9 M.L.B., D.R.P. 236.984. i« M.L.B.. D.R.P. 229,408.
" M.L.B., D.R.P. 240.192.
THE AMINOANTHRAQUINONES
221
dye, Helindon Brown 2GN, is obtained by condensing two
molecules of anthraquinone-^-urea chloride with various
diaminoanthraquinones :
-NHCONH-
Helindon Yellow 3GN.
I-NHCONHC14H6O2NHCONH-
I
Helindon Brown 3GN.
The urea chlorides condense readily with phenols and
naphthols when boiled with these in some indifferent solvent
such as xylene J The products are yellow vat dyes, but
are of no particular interest. They have the structure
C14H7O.NHC— OAr.
II
O
Of greater interest are the yellow vat dyes which are
obtained when the urea chloride is treated with a tertiary
base such as dimethyl aniline or pyridine. 2 The reaction
takes place at the ordinary temperature with the evolution
of heat, but the constitution of the products obtained is
not known. They are yellow, but become red or violet in
the presence of strong alkali, the colour being discharged,
however, on dilution. The urea chlorides also imdergo a
little-understood condensation when boiled with sodium
acetate or sodium carbonate and some indifferent solvent,
such as nitrobenzene.'^ The products are vat dyes, Helindou
Orange GRN being obtained from anthraquinone-^-urea
chloride by this reaction. The same products are obtained
from the /so-cyanates and from the dianthraquinonyl
ureas themselves. *
The thioureas of the anthraquinone series have been
much less studied than the ureas, and the information in
the patent literature is often contradictory- . Thus, the
Hochst colour works state that the thiourea is formed when
an aminoanthraquinone is treated with thiocarbonyl cliloride,^
1 M.L.B , D.R.P. 242,291.
3 M.L.B.. D.R.P. 232,135.
' Loc. cil.
2 M.L.B., D.R.P. 236,982.
^ M.L.B., D.R.P. 232,791-2.
222 ANTHRACENE AND ANTHRAQUINONE
whereas the Badische Anilin u. Soda Fabrik state that the
action of thiocarbon^d chloride on jS-aminoanthraquinone
gives a substance which is useless as a vat dye and is certainly
not the thiourea. 1 According to their patent the product
consists of at least two substances, and can be separated
into two parts b}' the action of alkali, the portion which is
insoluble in alkali being converted into a fast orange-yellow
vat dye when heated alone or with an indifferent solvent.
It is probable that the action of thiocarbonyl chloride on
aminoanthraquinone leads to a mixture of the thiourea and
thiourea chloride, and this view receives some conj&rmation
from the fact that Bayer & Co. claim the production of
orange-yellow vat dyes b}- the prolonged heating of jS-amino-
anthraquinone with excess of thiocarbon5'l chloride. 2
The anthraquinonyl thioureas can also be obtained b)^
heating the aminoanthraquinones with carbon bisulphide,
best by using pyridine as a solvent, 3 or with sodium xanthate,^
and in addition also seem to be formed when ammoanthra-
quinones are heated with perchlormeth}^ mercaptan in an
indifferent solvent, such as nitrobenzene, with or without
the addition of copper or copper salts ana basic substances. ^
They can also be built up from the thioureas of the amino-
benzo^-l benzoic acids b}' closing the anthraquinone ring by
means of sulphuric acid.^
As in the case of the formation of anthraquinonyl ureas
by this method the ring closes ver}' easily, and as the
thioureas are not very readily hydrolysed a higher tempera-
ture can be used than is permissible in the case of the ureas
themselves.
Mixed alkyl and ar^-l anthraquinonyl thioureas can be
obtained b}' condensing the anthraquinonyl /so-thiocyanates
with primary or secondary aliphatic amines or primary
aromatic amines. '^ The reaction is lacilitated and a much
purer product obtained if a condensing agent such as
aluminium chloride is used.^
1 B.A.S.F., D.R.P. 246,086.
' By.. D.R.P. 271.475.
5 B.A.S.F., D.R.P. 234,922.
'' M.L.B., D.R.P. 229,111.
2 Bv., D.R.P. 256,900.
* G.E.. D.R.P. 291,984.
« Agfa, D.R.P. 282,920.
8 M.L.B.. D.R.P. 254.744.
THE AMINO ANTHRAQUINONES 223
If an authraquiuoue aldehyde or an cu-dibronimethyl
anthraquinone is heated to 120-130° with thiourea in a
suitable solvent such as pyridine or quinoline, a compound
which contains both the thiourea and the azo-methine
group is obtained.! These are red vat dyes, the correspond-
ing oxygen compounds, obtained in the same way from
urea, being yellow :
CmH,0.,.C : N.C.N : CCi^H^O. CMH7O2.C : N.C.N : C.CHH7O.,
II II
s o
Addendum
At this point brief mention may conveniently be made
of compounds which appear to be derived from the amidines
of the aromatic acids. These can be obtained by con-
densuig one molecule of benzotrichloride with two molecules
j8-aminoanthraquinone :
^NC,4H70.,
C6H5CCI3+2CHH7O2NH0 ^ CoH^C^
^NHCuH702
or by condensing j8-ammoanthraquinone simultaneously with
carbon tetrachloride or other derivative of carbonic acid,
such as chlorcarbonic ester, and an aromatic h5-drocarbon
such as naphthalene, diphenyl, etc., the condensation taking
place in the presence of copper. 2 The reaction is an mterest-
ing one and is worthy of further investigation.
Nitration
The nitration of the aminoanthraquinones is complicated
by the fact that the position taken by the entering nitro
group is influenced not only b\' the position of the amino
group, but is also dependent to a considerable extent on
the means, if any, which have been taken to protect this
group, and further complications arise from the fact that in
the anthraquinone series there is a considerable tendency
towards the formation of nitramines. These latter, however,
1 B.A.S.F., D.K.P. 241.805. 2 B.A.S.F., D.R.P. 246.477 ; 248.656.
224 ANTHRACENE AND ANTHRAQUINONE
are only formed in nitration reactions after all the easily
available ring positions have been occupied b}' nitro
groups. They are briefly discussed on p. 226.
Primary aminoanthraquinones are much more stable
than the majorit}- of primary- aromatic amines, and can often
be nitrated without previousl}^ protecting the amino group.
Thus, j3-aminoanthraquinone when treated 'with the calcu-
lated amount of nitric acid in concentrated sulphuric acid
at —5° is converted into 2-amino-3-nitroanthraquinone.^
Here the o-^ position is the only one readily available for
nitration, and the further action of nitric acid leads to the
formation of a nitramine.^ When the amino group is in
the a- position, however, both the ortho- and para- positions
are readily nitrated. Thus, 1.5-diaminoanthraquinone gives
a tetranitro compound, the further nitration of this leading
to nitr amine formation. ^
If the amino groups are protected by conversion into
acyl amino groups, then the products obtained on nitration
seem to depend ver37^ largely on the experimental conditions.
By nitrating i-acetylaminoanthraquinone, and 1.5 and 1.8-
diacetylamino anthraquinone, Eckert and Steiner * obtained
nitro compoimds in which the nitro groups were in the para-
position to the amino groups, but the nitration of i-acyl-
alkylamino anthraquinones leads to a heteronuclear nitro
compounds, the nitration product, after hydrolysis, being
5-nitro-i-alkylamino anthraquinone. 3 The nitration of the
unacylated a-monalkyl aminoanthraquinones and of the
a-dialkylamino anthraquinones, however, leads to homo-
nuclear nitro compounds, the nitro group taking the ^im-
position. ^ The nitration of 2-acet3'laminoanthraquinone
leads to 2-aniino-i-nitroanthraquinone.'^
The products obtained by the nitration of 1.4-diacyl-
aminoanthraquinone depend very largely on experimental
» M. 32, 1037. G.E., D.R.P. 290,814.
2 Scholl and Eberle, B. 37, 4434. M. 32, 1037.
3 B.A.S.F., D.R.P. 146,848.
* M. 35, 1 137. Cf. M.L.B., D.R.P, 158,076. Noelting and Wortmann,
B. 39, 643.
5 M.L.B., D.R.P. 292,395.
6 By., D.R.P. 156,759. ■ Ullmann and Medenwald. B. 46, 1798.
THE AMINOANTHRAQVINONES 223
conditions, the action of mixtures of nitric and sulphuric
acids leading to the heteronuclear nitration with the pro-
duction of both i.4-diacylaniino-5- and 8-nitroanthra-
quinone,^ whereas the action of nitric acid and an indifferent
solvent such as nitrobenzene leads to homonuclear nitration,
the product being i.4-diac3^1amino-2-nitroanthraquinone.2
If 1.4-dianiinoanthraquinone is heated to 50-60° with
oleum containing 45 per cent, of free sulphur trioxide a
sulphonamide, Ci4H602(N:S02)2, is formed. This is a
perfectly stable compound which is insoluble in water, and
its formation provides a convenient means of protecting the
amino groups. On nitration and subsequent hydrolysis it
yields i .4-diamino-5-nitroanthraquinone.
Amino groups can also be protected during nitration by
converting the aminoanthraquinone into the urethane,
either by treatment with clilorcarbonic ester or by the action
of carbonyl chloride followed by treatment of the result-
ing urea chloride ^ with alcohol. When nitrated the ure-
thane of a-aminoanthraquinone gives a mixture i-amino-
2-nitroanthraquinone and i-amino-4-nitroanthraquinone,
further nitration of both isomers leading to i-amino-2.4-
dinitroanthraquinone. The diurethanes of both 1.5- and
i.8-diaminoanthraquinone behave in the same way, the
nitro groups takmg the ortho- and para- positions to the
amino groups. The urethane of /5-aminoanthraquinone
when nitrated gives first a mixture of 2-amino-i-nitro-
anthraquinone and 2-amino-3-nitroanthraquinone. Both of
these on further nitration yield the same dinitroamino
compound which must, therefore, be i.3-dinitro-2-amino-
anthraquinone.4 From this it is clear that the behaviour
of the urethanes on nitration differs from that of other
acj-lamino compounds. The diurethanes of the hetero-
nuclear j8jS-diaminoanthraquinones behave in the same way.
Ullmann and Medenwald ^ have also studied the nitration
of the urethane of 2-aminoanthraquinone and find that the
1 By., D.R.P. 268,984.
* By., D.R.P. 267.445. Cf. M.L.E.. D.R.P. 254,185.
^ See p. 219.
« By.. D.R.P. 167.410; 171.58S. 6 B. 46, 1798.
15
226 ANTHRACENE AND ANTHRAQUINONE
chief product is 2-amino-i-nitroanthraquinone, but that
about 20 per cent, of 2-amino-3-mtroanthraquinone is also
formed. As the separation of the isomers is easy the nitra-
tion of the urethane provides a ready means of obtaining
this latter substance.
Amongst other methods which have been proposed for
protecting amino groups during nitration m^y be mentioned
the formation of the azomethine compound, obtained by
warming the amino compound with formaldehyde or tri-
oxymethylene and concentrated sulphuric acid, and the
conversion of the aminoanthraquinone into the oxaminic
acid by heating to 150° with oxalic acid. The nitration of
a-methyleneaminoanthraquinone yields a mixture of the
ortho and para nitro compound. ^ The oxaminic acids are
said to be particiilarly suited for nitration purposes as they
are readily obtained, and although the free acids are almost
insoluble their salts are often readily soluble and well crystal-
lised. On nitration the nitro group enters the para- position
to the amino group. ^
The Nitramines. — When a primary or secondar>^ amino-
anthraquinone is nitrated, the nitro groups first enter the
easily attacked ring positions, but when these positions are
all occupied the nitro group enters the amino group. ^ Thus,
if j3-aminoanthraquinone is nitrated first 2-amino-3-nitro-
anthraquinone is formed.'* In this there is no readily nitrated
ring position vacant, so that the further action of nitric
acid leads to 2-nitramino-3-nitroanthraquinone. In the
case of a-aminoanthraquinone there are two easily nitrated
ring positions available so that first i-aniino-2.4-dinitro-
anthraquinone is formed, and then i-nitramino-2.4-dinitro-
anthraquinone. The behaviour of 1.5-dianiinoanthra-
quinone is exactly similar, first diaminotetranitroanthra-
quinone being formed and then the dinitramine. In 1.5-
diamino-2.4.6.8-tetrabromanthraquinone, on the other hand,
1 B.A.S.F., D.R.P. 279,866.
2 M.L.B., D.R.P. 158,076.
3 B.A.S.F., D.R.P. 111,866; 121. 155; 146,848.
* Scholl and Eberle, B. 37, 4434. M. 32, 1037. Ullmann and Meden-
wald. B. 46. 1798.
THE AMINO ANTHRAQVINONES
227
no readily nitrated ring position is available so that nitration
leads at once to the diuitraniine.
The sodium salts of the uitramines can be obtained by the
action of sodium hypochlorite on the anthraquinonediazonium
sulphates, and the free uitramines can be liberated from
these salts b}' the action of weak acids such as carbonic or
acetic acid J This reaction, however, seems to be confined
to the anthraquinone-a-diazonium sulphates, as in another
patent 2 it is stated that under similar conditions the
j3-diazonium sulphates give only unstable substances which
smell of and contain chlorine. The authraquinone jS-nitra-
mines can be obtained, however, by oxidising the iso-
diazotates with hj-pochlorites.^
The uitramines are rather unstable compounds which are
more or less explosive but can, as a rule, be nitrated, "* e.g. by
the action of fuming nitric acid at 0°. Owing to their
instabilit}' they act as nitrating agents towards easily
nitratable substances,^ such as phenol, benzene, etc., and
frequentl}^ undergo self-nitration when treated with con-
centrated sulphuric acid.^ During this self-nitration the
nitro group takes the ortho- position to the amino group,
i-uitraminoanthraquinone passing into i-amino-2-nitro-
anthraquiuone, whereas when the nitramine is treated with
nitric acid the entering nitro group takes the para- position,
i-nitraminoanthraquinone forming i-nitramino-4-nitro-
anthraquinone.'^
The uitramines on reduction lose the nitro group and
pass into the primary- amine, whereas when heated with
water slightly soluble substances of unknown composition are
formed which dve mordanted or unmordanted wool brown. ^
Halogenation
A considerable amount of work has been recorded dealing
with the behaviour of the aminoanthraquinones when
1 M.L.B., D.R.P. 156,803.
3 G.E., D.R.P. 259.432.
5 B.A.S.F., D.R.P. 148,109.
' G.E., D.R.P. 156.803.
2 G.E., D.R.P. 262,076.
* M.L.B., D.R.P. 156.803.
6 G.E., D.R.P. 259,432.
» By., D.R.P. 220.032.
228 ANTHRACENE AND ANTHRAQUINONE
halogenated under various conditions, the subject being com-
plicated by the great ease with which halogen atoms under
ceitain conditions wander from one position to another.
It should also be noted that aminoanthraquinones, at all
events the a-amino compounds, can under certain con-
ditions form N-halogen derivatives quite readity.^ Thus
a-aminoanthraquinone when brominated under stdtable con-
ditions yields N-brom-a-aminoanthraquinone, Ci4H702NHBr,
and 1,5-diaminoanthraquinone gives an octachlor com-
pound in which some of the chlorine atoms are attached
to the nitrogen atoms. 2 SchoU and Berblinger 3 have also
found that the bromination of 1.5-diaminoanthraquinone
by molecular bromine without a solvent leads to a product
which loses the whole of its bromine when kept in a vacuum.
This ma}^ be merely a solid solution, although Scholl and
Berblinger incline to the belief that it is a perbromide, although
they were unable to obtain it in a pure state. Against the
belief that the substance in question was a perbromide it
must be pointed out that tertiary a-dialkylaminoanthra-
quinones when treated with bromine are brominated in the
para- position to the amino group, and at the same time
add on two atoms of bromine to form a perbromide. * These
perbromides are well crystallised substances and are stable
towards water, although they readily lose bromine when
treated with bases. The substance obtained by Scholl and
Berblinger, on the other hand, was decomposed by water
with the production of tetrabromaminoanthraquinone.
N-Chlor- compovmds can also sometimes be obtained by
the action of hypochlorous acid, i-acet5daminoanthraquinone
giving by this means N-chlor-i-acetaminoanthraquinone,
In all these compounds the halogen is very easily removed
by reduction.
The majority of investigators who have studied the
halogen ation of the aminoanthraquinones have used molecular
chlorine, although it has been claimed ^ that aminoanthra-
quinones are ver^- smooth!}^ chlorinated b}' sulphury!
1 By., D.R.P. 104,901 ; 115,048; 126,392-3.
- B.A.S.F., D.R.P. 125,09.1. » B. 37. 4180.
« By.. D.R.P. 146,691. ' B.A.S.F., D.R.P. 158,951.
THE AMINOANTHRAQUINONES 229
chloride, either at the ordinary temperature or on the water
bath.
When a-aminoanthraquinonc is brominated in glacial
acetic acid solution the first bromine atoms enter the ortho-
position,^ further bromination (or chlorination) leading to
i-amino-2.4-dihalogenanthraquinone.2 The alkyl and acyl
a-aminoanthraquinones, however, differ from the primary
compound as the para- position is first attacked, ^ this
difference in behaviour probably being due to the primary
compound first forming an N-halogen derivative, the halogen
atom then wandering to the ortho- position.-* The exhaustive
chlorination of a-aminoanthraquinone has recently been
studied by Friess and Auffenberg,^ who find that the amino
group is split out and then the anthraquinone ring opened,
the products being 2.3.4.5.6-pentachlorbenzophenone and
finally phthalic acid and pentachlorphenol.
The behaviour of 1.5-diaminoanthraquinone w'hen bromi-
nated is analogous to that of a-aminoanthraquinone, the
2.4.6.8-tetrabrom derivative being formed. ^ On chlorination
an octachlor compound is formed as mentioned on p. 228,
and also a hexachlordihydrox}^anthraquinone and octachlor-
anthraquinone."^ It is curious to notice that both dibrom-
and tetrabrom-i-s-diaminoanthraquinone give tetra-acetyl
derivatives, although the imbrominated product will give
onl}' a diacetyl compound. ^
Probably owing to the instability of the N-halogen
compounds the presence of a primar}^ amino group in the
/3- position greatly facilitates the entrance of halogen atoms
into the anthraquinone ring. The halogenation of /S-amino-
anthraquinone has been studied in some detail by several
investigators, and it has been found that its reactivity is
so great that it is almost impossible to obtain a m^onohalogen
1 By.. D.R.P. 160,169.
2 Ullmann, B. 49. 2165. B.A.S.F.. D.R.P. 199,758.
3 By., D.R.P. 164,791.
* Compare the behaviour of the nitramines (p. 227).
6 B. 53, 23.
« SchoU and Berbhnger, B. 37. 4180. B.A.S.F., D.R.P. 137,783.
' B.A.S.F.. D.R.P. 125.094 ; 137.074.
8 Scholl and Berbhnger, B. 37, 4180. Romer, B. 16, 36G.
230 ANTHRACENE AND ANTHRAQUINONE
compound, the result of using only the calculated amount
of the halogen being usually to produce a mixture of 2-amino-
1.3-dihalogenanthraquinone and unchanged 2-aminoanthra-
quinone.i If, however, 2-aminoanthraquinone is treated
with bromine dissolved in an organic solvent, such as glacial
acetic acid or nitrobenzene, it is possible, tmder carefully
controlled conditions, to obtain 2-amino-3-bromanthra-
quinone, the position of the bromine atom being proved by
the fact that the substance gives 2-bromanthraquinone
when the amino group is eliminated b}' the diazo reaction. 2
As stated above, the usual product obtained by bromi-
nating 2-aminoanthraquinone is 2-amino-i.3-dibromanthra-
quinone. In this compound the bromine atom in the a-
position exhibits remarkable reactivity, and is readily split
off when boiled with compounds like acetic acid or aniline,
these substances being brominated in the process and the
aminodibromanthraquinone being simultaneously degraded
to 2-amino-3-bromanthraquinone. The same reaction takes
place when the aminodibrom compound is heated with
2-aminoanthraquinone, one molecule of 2-amino-i.3-dibrom-
anthraquinone reacting with one molecule of 2-aminoanthra-
quinone to produce two molecules of 2-amino-3-bromanthra-
quinone, a reaction which has been made use of in the pre-
paration of the last-named substance. ^
The acetyl derivative of 2-aminoanthraquinone is much
less readity halogenated than the primary compound itself,
and by chlorinating 2-acetaminoanthraquinone a monochlor
compound can be obtained.* In this, however, the halogen
atom is in the a-position, as Jimghaus has found that it
gives i.2-diaminoanthraquinone when the chlorine atom is
replaced by an amino group by the sulphonamide process. ^
It is interesting to observe that whereas a primar\- amino
group in the ^- position directs the entering halogen atom
first to the contiguous j8- position, the acetylamino group
directs the halogen to the contiguous a- position, although
1 SchoU, B. 40. 1701. Junghaus, A. 399, 316. D.R.P. 273,809. M.L.B.,
D.R.P. 253,683.
- Junghaus, loc. cit. ^ B.A.S.F., D.R.P. 261,270-1.
« B.A.S.F.. D.R.P. 199.758. * A. 399, 316.
THE ANIMOANTHRAQUINONES 231
the 8-lialogen compound must be regarded as the more
stable, as the halogen atom in all homonuclear halogen
derivatives of both a- and j3- aminoanthraquinone wanders
to the j8- position which is contiguous to the amino group if
this position is unoccupied. ^ This wandering of the halogen
atom is brought about by heating the substance alone or
with sulphuric or phosphoric acids. If the ^- position con-
tiguous to the amino group is occupied by a sulphonio acid
group this latter is split off by heating with acids, and as a
rule a simultaneous wandering of the halogen atom takes
place, 2-amhio-i-bromanthraquinone-3-sulplionic acid, for
example, passing into 2-aniino-3-bromantliraquinone when
boiled with sulphuric acid of 80 per cent, strength. 2 This
wandering of the halogen atom can often be avoided by
carr5ang out the hydrol3^sis of the sulphonic acid at as low
a temperature as possible, by avoiding prolonged heating or
by carrying out the hydrolysis by means of concentrated
sulphuric acid, monohydrate or dilute oleum, preferably in
the presence of mercur\\3
When an aminoanthraquinone sulphonic acid is haloge-
nated the halogen can enter the molecule either by the
replacement of hydrogen or b}- the replacement of the
sulphonic acid groups. Which reaction takes place depends
ver>'' largely on the position of the groups present, and on
the experimental conditions under which the halogenation
is carried out, but for further information the reader is
referred to the original literature. ^
The Dianthraquinonyi^amines
Although dianthraquinonylamines can be obtained b}'
heating a-aminoanthraquinone or jS-aminoanthraquinone
with a-nitroanthraquinone ^ or with an anthraquinone-a- or
-j3-sulphonic acid,^ preferably in the presence of sodium
1 By., D.R.P. 275,299.
2 M.L.B., D.R.P. 253,683. B.A.S.F., D.R.P. 263,395.
» B.A.S.F., D.R.P. 265,727; 266,563.
« Ullmann and Medenwald, B. 46, 1798. B.A.S.F., D.R.P. 113,292 ;
114.840; 128,196; 138,134; 138,166.
* M.L.B.. D.R.P. 201, 327. 8 M.L.B., D.R.P. 216,083.
232 ANTHRACENE AND ANTHRAQUINONE
carbonate, the reaction only takes place with some difficulty,
so that they are always made by condensing a primary-
aminoanthraquinone with a halogen anthraquinone. The
condensation is usually brought about by heating the amine
and the halogen compound together in some indifferent
solvent of high boiling point, such as naphthalene or nitro-
benzene, copper powder or cuprous chloride being used as
a catalyst, and anhydrous sodium carbonate or acetate
being added to neutralise the halogen acid liberated. ^ B}^
condensing two molecules of a halogen anthraquinone with
one molecule of a diaminoanthraquinone,or, mutatis mutandis,
by condensing two molecules of an aminoanthraquinone
with one molecule of a dihalogen anthraquinone, dianthra-
quinonylaminoanthraquinones * are obtained, several of
which have found application as vat dyes. jS^-Dianthra-
quinonylamines can also be obtained by condensing anthra-
quinone-jS-diazonium salts with ammonia and then heating
the resulting product with a solvent of high boiling point,
with or without a condensing agent. ^
The ease with which dianthraquinonylamines are formed
depends on the orientation of the amino group and of the
halogen atom in the reacting substances. If both are in
the a- position the reaction takes place easily, e.g. a-chlor-
anthraquinone reacts readily with a-aminoanthraquinone to
form 1 .1 '-dianthraquinonylamine.
If one group is in the ^- position the reaction takes place
with rather greater difficulty, and in this case it is best to
condense the /S-halogen compound with the a-amine.^ Thus,
)8-chloranthraquinone and a-aminoanthraquinone yield 1.2'
dianthraquinonylamine rather more readily than do a-chlor-
anthraquinone and j3-aminoanthraquinone. When both
1 Seer, M. 32, 162. Eckert, M. 35, 762. Eckert and Steiner, M. 35,
1129. UUmann, B. 47, 564: 49. 2162. Frey. B. 49, 1363. B.A.S.F..
D.R.P. 184,905; 197,554; 206,717; 212,470; 216,280; 217,395-6;
218,161; 279,867; cf. also 176,956. By., D.R.P. 162,824; 174.699;
194,253; 208,162; 216,668; 220,581; 230,052; 240,276. M.L.B..
D.R.P.' 257,811.
* In the literature these are frequently described as trianthraquinonyl-
amines, a nomenclature which would suggest that three anthraquinonyl
groups are attached to the same nitrogen atom {cf. triphenylamine).
2 M.L.B., D.R.P. 308,666. ' By., D.R.P. 174,699.
THE DIANTHRAQUINONYLAMINES 233
the halogen atom and the ammo group are in the j3- position,
e.g. j8-chloranthraquinone and iS-aminoanthraquinone, the re-
action onl}^ takes place with great difficulty, ^ and under these
circumstances it is advisable to use the iodo compound.
Hydroxydianthraquinonylamines can be obtained by
condensing an aminohydroxyanthraquinone with a halogen
anthraquinone, or a hydroxy halogen anthraquinone with
an amino anthraquinone, but hydroxy 1 groups can also be
introduced into the dianthraquinonylamine molecule by
the usual methods, e.g. by direct oxidation with nitrosyl
sulphuric acid in the presence of boric acid,^ or by the
replacement of halogen atoms or nitro groups b}' heating
with alcoholic caustic potash. ^
On nitration i.i '-dianthraquinonylamine gives a dinitro
compound in which the nitro groups must be in the paya-
positions to the imino group, as the same compound is obtained
by condensing i-chlor-4-nitroanthraquinone with i-amiiio-
4-nitroanthraquinone. Further nitration leads to a tetra-
nitro, and possibly also to a pentanitro, compound.*
The nitration of 1.2 '-dianthraquinonylamine gives first
4.i'-dinitro-i.2'-dianthraquinon3'lamine ^ and then 2.4.1'-
trinit ro- 1 . 2 '-dianthraquinony lamine . 6
Reduction of 4. 4'-dinitro-i,i '-dianthraquinonylamine
with sodium sulphide gives the corresponding diamino
compound,"^ but reduction with boiling sodium stannite
leads to replacement of the nitro groups by hydroxyl groups,
the product being 4. 4'-dihydrox3^-i.i '-dianthraquinonyl-
amine. ^ The tetranitro compound on reduction with alkaline
stannite also loses two nitro groups and forms 2.2'-diamino-
4.4' - dihydroxy - i.i' - dianthraquinonylamine. ^ Reduction
with sodium sulphide, however, appears to lead first to the
^ Eckert and Steiner, M. 35, 1129.
- M.L.B., D.R.P. 249,938. See also p. 251 et seq.
' By., D.R.P. 232,262. Cf. Eckert and Steiner, M. 35, 1129.
< Eckert and Steiner. loc. cit. By., D.R.P. 213,501. M.L.B., D.R.P.
254,186.
* Eckert and Steiner, loc. cit. B.A.S.F., D.R.P. 186,465.
* Eckert and Steiner, loc.xit. By., D.R.P. 178,129.
' M.L.B., D.R.P. 255,822.
» Eckert and Steiner, M. 35, 1129. Cf. By., D.R.P. 178,129.
* Eckert and Steiner, loc. cit.
234 ANTHRACENE AND ANTHRAQUINONE
tetramino compound, which at once loses a molecule of
ammonia and passes into diaminoindantbrone : i
,NHx
/^'^\
NH. H2N
1
1
I
NHo
HoN
NH,
I
HoN
The reduction of 4.i'-diniLro-i.2'-dianthraquinon3damine
by sodium stannite also leads to the replacement of the nitro
groups by hydroxyl groups (4.i'-dihydroxy-i.2'-dianthra-
quinonylamine), although the diamine compound is obtained
when the reduction is carried out in acid solution. 2 As
would be expected, the trinitro compound on alkaline reduc-
tion yields 2-amino-4.i'-dihydroxy-i.2'-dianthraquinonyl-
amine, it being only nitro groups in the a- positions which
are replaced. ^
Although the aminodianthraquinonylamines can be
obtained in some cases by the reduction of the nitro com-
pounds it is usually best to obtain them by condensing
halogen anthraquinones with polyaminoanthraquinones, one
or more amino groups being protected during the reaction by
previous acylation.^
The dianthraquinonylamines when treated with con-
densing agents such as caustic alkaH,^ aluminium chloride, 6 or
zinc chloride,'^ give rather indefinite products, many of which
have tinctorial properties. The constitution of these pro-
ducts is unknown although some at least of them seem to be
carbazol derivatives. ^ For further information the reader
is referred to the original literature.
The tinctorial properties of the simple dianthraquinonyl-
amines are, as a rule, somewhat feeble, although 1.2'-
dianthraquinonylamine has been placed on the market under
^ Eckert and Steiner, loc. cit.
« Ibid. * Ibid.
5 M.L.B., D.R.P. 208,969 ; 251,021.
« M.L.B., D.R.P. 240,080 ; 262,788.
' M.L.B., D.R.P. 251,350. 8 M.L.B., D.R.P. 267,522 ; 267,833.
« By., D.R.P. 220,581.
By., D.R.P. 230,407.
THE DIANTHRAQUINONYLAMINES 235
the name Algol Orange R, and Algol Red B is also a diantlira-
quinon3^1amine although containing also a pyridone ring.i
The introduction of a benzojdamino group, however, confers
tinctorial properties,^ although the unbenzoylated amino-
dianthraquinonylamines have little or no affinity, so that in
this respect there is a close analogy between the aminodi-
anthraquinonylamines and the aminoanthraquinones. The
anthraquinonylaniinodianthraquinonylamines are usually
powerful d3'es and, when other substituents are absent,
produce red or bordeaux shades. Several dyes of this class
have been placed on the market, of which the two following
are typical :
1
__NH
1
-NH
1
1
— NH
1
_NH
1
Indanthrene Bordeaux B.
Indanthrene Red G.
Indanthrene Bordeaux R Extra is a dichlor compound
somewhat similar to the above, and is derived from i-amino-
6-chloranthraquinone (2 molecules) and 2.7-dichloranthra-
quinone (one molecule) . It would be interestmg to trace the
relation between the colour and the constitution of the
dianthraquinonylamines and the anthraquinonylamino-
dianthraquinonylamines, but the data available at present
are insufficient to render possible any generalisation.
The introduction of amino, hydroxy or alkoxy groups
into the molecule often has a considerable effect on the
shade of the resulting dye, and in many cases shifts the
colour right into the violet end of the spectrum. A fair
number of derivatives of this nature have been described, ^
but the subject is a ver}- complicated one and no inferences
of the relationship between colour and constitution can be
drawn profitably from the facts so far available.
1 By., D.R.P. 194.253. * By., D.R.P. 220,581 ; 238,488.
3 B.A.S.F.. D.R.P. 206,717 ; 212,470 ; 216,280. By., D.R.P. 208,162 ;
216, 668.
CHAPTER XII
THE HYDROXY- AND AMINOJIYDROX Y-
ANTHRAQUINONES AND ETHERS
I. The Hydroxy Compounds
The hydroxy anthraquinones constitute a very important class
of substances, partly on account of the valuable tinctorial pro-
perties exhibited by many of them, and partly owing to their
forming convenient starting-out substances in the synthesis of
other anthraquinone derivatives, e.g. Alizarin C5'anine Green.
The actual constitution of man}^ of the hydrox5'l com-
pounds is open to some doubt, as although h3^drox>d groups
in any position can be readily acylated, hydroxyl groups when
in the ortko- position to a carbonyl group cannot be alk3dated,
or can only be alkylated with the utmost difficult}-, by
the usual means, e.g. b}^ treatment with dimeth}^ sulphate
or methyl iodide and caustic potash. Hydroxj-l groups in
the P- position, however, behave in a perfectly normal
manner towards alkylating agents. The abnormal behaviour
of hydrox}^ groups in the a- position is obviously due in
some way to the influence of the carbonyl group, as the
difficulty of alkylation disappears when the anthraquinone
compound is reduced to the corresponding anthrone, and
the corresponding hydroxy anthracenes, the a-anthrols, can
be alkylated without an}- trouble. It has been suggested
that the a-hj-droxyanthraquinones really have the tautomeric
o-quinonoid structure :
CO OH OH P
CO CO
and this would explain the difficulty in alkylation.
Although, as stated above, hj-drox^-l groups both in the
236
THE HYDROXY COMPOUNDS 237
a- and /3- position can be acylated with ease, groups in the
j3- position are more easily attacked than those in the a-
position, so that by moderating the conditions of experiment
it is often possible to acylate groups in the j3- position
without affecting those in the a- position. In the case of
acetyl derivatives Dimroth, Friedemann and Kammerer ^
have found that this is most readily effected by dissolving
the hydroxy compound in pyridine and then, without heating,
adding the calculated amount of acetic anhydride necessar}^ to
acetylate the /S-hydroxyl groups. Only the calculated amount
of acetic anhydride must be used, as otherwise all the hydroxy 1
groups will be attacked, although those in the a-position react
only slowh" with acetic anliydride in cold pyridine solution.
In addition to methods based on the replacement of
other groups such as amino groups, sulphonic acid groups,
nitro groups, etc., the hydroxyd group can be inserted into
the anthraquinone molecule with great ease by direct oxida-
tion, and it is possible by this means to obtain a vers' large
number of different hydroxys compounds according to the
conditions employed. As has been already stated, hydrox}--
anthraquinones can often be built up from phenolic ethers
by the phthalic acid S5-nthesis, and in many cases the reduc-
tion of the higher hydroxylated anthraquinones leads to
the loss of h^'droxyl groups. The oxidation of the h^-droxy
anthracenes, or rather of their acetyl derivatives or meth}!
ethers, also leads to hydroxyanthraquinones, although the
method is of little importance except as a means of identify-
ing the anthrols.-
A great many of the hydroxyanthraquinones have
received special names, and for ease of reference these have
been tabulated together with the melting ]:>oint of the
hydroxy compound and its acetyl derivative. The prepara-
tion of the acetyl derivatives is usually very easily effected
by boiling the hydroxy' compound with acetic anhydride
and anhydrous sodium acetate, and they often provide a
ready means of characterising the hydroxy- compound.
» B. 53, 481.
* Lieberraann and Boeck, B. 11, 1616 ; 12, 185. Liebcrmann and
Hormann, B. 12, 250. Dienel, B. 38, 2862.
238 ANTHRACENE AND ANTHRAQUINONE
HYDROXYANTHRAQUINONES.
Position
of Hydroxyl.
Usual name.
M.p.
Acetyl deriva-
tive m.p.
I-
Erythrohydroxyanthraquinone
190°
176-179°
2-
—
302"
159°
1.2-
Alizarin
289-890°
184°
1-3-
j Piirpuroxanthin. Xantho- 1
( purpurin J
262-263°
184°
1.4-
Quinizarin
194°
200°
1-5-
Anthrarufin
280°
244-245°
1.6-
1
276°
205-206°
1-7-
—
291-293°
199°
1.8-
Chrysazin
191°
227-232°
2.3-
Hystazarin
( Decomp. )
\ above 260°/
206-207°
2.6-
Anthraflavic acid
Above 330°
228°
2.7-
iso- Anthraflavic acid
Above 330°
About 195°
1.2.3-
( Anthragallol, |
\ Anthragallic acid 1
310°
181-182°
1.2.4-
Purpurin
256°
192-193°
1.2.5-
Hydroxyanthrarufin -
278°
228°
1.2.6-
Flavopurpurin
Above 330°
195-196°
1.2.7-
Anthrapurpurin. iso-Purpurin
369°
224°
1.2.8-
Hydroxychrysazin ^
239-240°
219°
I-4-5-
3
—
—
1.4.6-
4
256°
1.4.8-
5
—
—
1.2.3.4-
—
—
205°
1.2.4.6-
Hydroxyflavopurpurin
202°
—
1.2.4.7-
Hydroxyanthrapurpurin
—
214°
1.2.4.8-
— •
—
—
1.2.5.6-
Rufiopin *
—
—
1.2.5.8-
Quinalizarin. Alizarin Bordeaux
Above 275°
201°
1.2.7.8-
7
—
—
I-3-5-7-
Anthrachrysazin
Above 360'
253*
1.4.5.8-
246°
j Decomp.
1 about 250°
i.?.?.8-
8
217°
195"
i.?.?.8-
9
292°
238-240°
1.2.4.?-
Hydroxypurpurin ^°
Above 290°
Above 240°
1 Frobenius and Hepp, B. 40, 1048.
2 Wed., D.R.P. 205,965 ; 210,863.
2 By., D.R.P. 161,026; 163,041.
* Dimroth and Pick, A. 411, 315.
Wed., D.R.P. 202,398.
Crossley, Am. Soc. 40, 404, states
that the substance does not melt below 300°.
5 R. E. Schmidt, Bull. Soc. Ind. Mull. 84, 409.
^ Liebermann and Chojnacki, A. 162, 323 (from hemipinic or opianic
acid and cone. H-,S04). By., D.R.P. 103,988 (from anthrarufin).
' By., D.R.P. 103,988. See also note 9.
8 Schrobsdorf. B. 36. 2936.
9 Wolbling, B. 36, 2941. Probably identical with 1.2.7.8-tetrahydroxy-
anthraquinone.
10 Diehl, B. 11, 185. Gattermann, J. pr. [2] 43, 251.
THE HYDROXY COMPOUNDS
239
HYDROXYANTHRAQUINONES— co«/JHuecf.
Position
of Hydroxy!.
Usual name.
M.p.
Acetyl deriva-
tive m.p.
1.2.3.5 or 7-
1.2.3.5 or7-
1.2.3.5.7-
1.2.3.6.7-
1.2.4.5.8-
1.2.5. ?.8-
1.2.3.5.6.7-
1.2.4.5.6.8-
1.2.4.5.7.8-
1.2.3.4.5.6.7.8-
a-Hydroxyanthragallol ^
^-Hydroxyanthragallol ^
Dihydroxyanthragallol
Alizarin Cyanine R
3
Rufigallic acid
Anthracene Blue WR
4
5
Above 350**
Above 380*
Above 360"
207-209"
189°
229°
282-283*
( Decomp.
1. at 330°
Replacement of Groups
Replacement of Sulphonic Acid Groups. — The con-
version of an anthraquinone sulphonic acid into a hydroxy-
anthraquinone by fusion with caustic alkaH is complicated
by the fact that during the alkali melt simultaneous oxida-
tion takes place, so that the product usually contains more
hydroxyl groups than there were sulphonic acid groups in
the original acid, anthraquinone-2-sulphonic acid when
fused with caustic soda giving alizarin, purpurin, and other
polyhydroxyanthraquinones. Here it will be seen that
replacement of the sulphonic acid group is accompanied by
hydroxy-lation by oxidation, and this type of reaction is
discussed in greater detail on p. 252.
By moderating the conditions under which the caustic
melt is carried out, it is often possible to replace sulphonic
acid groups in the /3- position without simultaneous oxidation
taking place, although the yields are usually poor. Thus,
Graebe and Liebermann ^ fomid jS-hj'droxj-anthraquinone
in crude alizarin, and Liebermann and Simon ' were able to
obtain the same substance from anthraquinone-^-sulphonic
1 From gallic acid and w-hydroxybenzoic acid. Noah, A. 241, 270.
' Bentley and Weizmannr Soc. 93, 438. (Tetramethyl ether.)
* R. E. Schmidt, J. pr. [2] 43, 242. Gattermann, ibid. 250.
* By., D.R.P. 103,988. 5 Georgie\ncs, M. 32, 347.
6 A. 160, 143. ' B. 14, 464 ; A. 212. 25. 53.
240 ANTHRACENE AND ANTHRAQUINONE
acid by fusion with caustic alkali. The anthraflavic acid and
iso-anthraflavic acid which Romer and Schunck i found in
commercial alizarin no doubt originated in the anthraqui-
none disulphonic acids present in the crude monosulphonate
from which the alizarin was made, and a few years later
Romer and Schwazer 2 succeeded in making eso-anthraflavic
acid from anthraquinone-2.7-disulphonic acfd. Since then
many other cases have been discovered in which replacement
of sulphouic acid groups takes place in the alkali melt
without simultaneous oxidation, ^ but as a rule it is difficult
to avoid oxidation taking place unless one of the modified
methods described below is emploj^ed. It should be noted
that the above remarks apply chiefly to anthraquinone sul-
phonic acids in which the sulphonic acid group is in the j3-
position. When the sulphonic acid group is in the a- position
fusion with caustic alkali usually leads to rupture of the
benzene ring, so that in these cases it is essential to use
special methods in order to obtain a hj'drox}' anthraquinone.
Sulphonic acid groups in the a- position are somewhat
more reactive than similar groups in the ^- position, and are
usually replaced by hydroxyl groups when the compound
is heated to about 200° with aqueous sodium carbonate,
anthraquinone-i -sulphonic acid, for example, giving erv'thro-
hydroxyanthraquinone . when treated in this way.^ They
can also often be replaced by the use of caustic alkali, for
although fused caustic alkali or highly concentrated solu-
tions almost always cause rupture of the ring when there is
a sulphonic acid group in the a- position, this is not the case
when more dilute solutions are used at a comparativeh- low
temperature, 5 and anthraquinone-a-sulphonic acids are
often fairl}- readil}'^ converted into a-hydroxyanthraquinones
when heated with ten per cent, caustic soda solution at
about 150°.
Sulphonic acid groups in any position in the anthra-
1 B. 8. 1628 ; 9, 379- " B. 15, 1040.
3 Wolbling, B. 36, 3941- By., 103,686 ; 103,988; 178,631. C/. also
Lifschiitz, B. 17, 901. Frobenius and Hepp, B. 40, 1048.
4 By., D.R.P. 197.649. M.L.B., D.R.P. 149,781.
* By., D.R.P. 172,642.
THE HYDROXY COMPOUNDS 241
quinoiie molecule can be replaced by hydroxyl groups by the
use of aqueous solutions of calcium or barium li5^droxide at
temperatures of 150-180°. This method has the great
advantage that in the case of anthraquinone-a-sulphonic
acids rupture of the ring does not take place, and that in
the case of anthraquinone-j8-sulphonic acids replacement
of the sulphonic acid group by h^'droxyl can be effected
without simultaneous oxidation taking place. 1 In many
cases the sulphonic acid groups in aminoanthraquinone
sulphonic acids can be replaced by hydroxyl groups by this
means without afTecting the amino group, e.g. i-amino-
anthraquinone 5- and -8- sulphonic acids give respectively
i-amino-5- and -8- hydroxy" anthraquinone.^ As the sodium
or potassium salt of the sulphonic acid is almost invariably
used, hydrox^'lation by means of alkali earth hydroxide
leads to the liberation of sodium or potassium sulphite :
2Ci4H702S03Na+Ca{OH)2=2Ci4H702.0H+CaS03+Na2S03
and it is advisable to destroy this or to render it harmless
as rapidh- as formed by carrying out the reaction in the
presence of an oxidising agent such as a chlorate or nitrate,
or in the presence of calcium or barium chloride. ^
The alkali earth hydroxide method has been used to a
considerable extent, and in the case of anthraquinone
disulphonic acids it has been found possible to replace one
group at a time,* e.g. in the cases of anthraquinone-2.6-
and -2.7-disulphonic acids. From alizarin-5-sulphonic acid,
hydroxy^anthrarufin has been obtained, alizarin-8-sulphonic
acid giving hydroxy chrysazin.^ Sulphonic acid groups can
also be replaced by heating the sulphonic acid with methyl
alcoholic caustic potash, but in this case a methox\- and not
a hydrox}- group is inserted. This type of reaction is treated
in greater detail on p. 287, in connection with the ethers.
Replacement of Nitro- Groups. — Nitro groups can, of
1 R. E. Schmidt, B. 37, 69. Bv., D.R.P. 172,642 ; 197.607. M.L.B.,
D.R.P. 106,505 ; 145.188.
2 xM.L.B., D.R.P. 14S.S75.
3 Wed., D.R.P. 195.874.
* M.L.B.. D.R.P. 106.505.
5 Wed.. 170.329; 202,398 ; 210.863. Cf. Frobeaius and Hepp. B. 40, 1048.
16
242 ANTHRACENE AND ANTHRAQUINONE
course, be replaced by hydroxyl groups indirectly by first
reducing the nitro compound to the amino compound and
then treating this by any of the methods discussed on p. 249.
The direct replacement of nitro groups can, however, often
be effected. If the nitro groups are in a- positions heating
with aqueous alkali or alkali earth hydroxide sometimes
leads to their replacement by hydroxyl gfoups, e.g. 1.5-
and i.8-dinitroanthraquinone give respectively anthrarulin
and chrysazin, but the yields are usually very poor.* Alco-
holic alkali reacts more readily, but unless water is carefully
excluded simultaneous reduction is apt to take place and
impure products are obtained. 2 When absolute alcoholic
alkali is employed it is the alkyl ether of the hydroxy
compound which is formed, the free hydroxy compound
being liberated by subsequent hydrolysis. 2 The method,
however, often gives excellent results and is applicable to
the replacement of nitro groups in either the a- or the jS-
position.3 Nitro groups can also be replaced by hydroxyl
groups with great ease by heating the nitro compound in
open or closed vessels with crude pyridine or quinoline,
a-nitroanthraquinone giving er^^throhydroxyanthraquinone
and 1.5- and i.8-dinitroanthraquinone giving respectively
anthrarufin and chrysazin. * The reaction is an interesting
one and deserves further investigation. The patent does
not state if the method is also applicable to the replacement
of nitro groups when in the )8- position, but in all the examples
given the nitro groups occupy a- positions.
Much more important than the above is the replacement
of nitro groups by hydroxyl groups by heating with concen-
trated sulphuric acid or oleum. The reactions which take
place are extremely complicated and are rendered more so
by the fact that the nitrous acid liberated may react with
the hydroxyanthraquinone, either reducing hydrox^-l groups
present, 5 or inserting more hydroxyl groups into the molecule
by oxidation. Sulphonation, of course, also often takes
1 By., D.R.P. 158,891. M.L.B.. D.R.P. 75,054.
* Kaufler, B. 37. 63. Eckert, M. 35, 290. M.L.B., D.R.P. 73.860;
75.054; 77.818; 167,699.
3 See p. 287. « By., D.R.P. 145, 238. " Nienhaus, B. 8, 778,
I
THE HYDROXY COMPOUNDS 243
place, aud insoluble products are then only obtained by
subsequently boiling the hydroxyanthraquinone sulphonic
acids with dilute sulphuric acid, although in many cases the
sulphonic acid groups can be split off by heating with
hydrochloric or phosphoric acid or even alone with water. ^
Work on the replacement of nitro groups has chiefly been
published in patent specifications, and in many cases the
nature of the product is not stated and no information is
given as to whether it is nitrogenous or not. Also many
specifications describe the reaction as being carried out by
heating " nitroanthraquinones or partially reduced nitro-
anthraquinones with concentrated sulphuric acid or oleum,
with or without the addition of a reducing agent such as
sulphur." As the mechanism of the reaction seems to
depend very largely on whether a nitroanthraquinone or
a partially reduced compound is used, and on whether a
reducing agent such as sulphur is or is not added to the
melt, it is difhcult to co-ordinate the various claims.
It appears that the nitro group is particularly easily
replaced when it is in the para- position to a hydroxyl
group, and under these circumstances the reaction is best
carried out by heating with concentrated sulphuric acid in
the presence of boric acid. 2 The action of the boric acid
in this case seems to be specific and not to be limited to
protecting hydroxyl groups, as dinitroanthrarufin is stable
towards concentrated sulphuric acid at 100° in the absence
of boric acid, but in the presence of boric acid one nitio
group is replaced by a hydroxyl group at this temperature,
and at higher temperatures both are replaced. Dinitro-
anthrarufin disulphonic acid exhibits the same behaviour, as
it is unaffected when heated for four hours at 150° with
concentrated sulphuric acid in the absence ot boric acid,
but in the presence of boric acid one nitro group is easily
replaced at 80-90°, and both are replaced at 120°.
The action of concentrated sulphuric acid on nitroanthra-
quinones was first studied by Graebe and Liebermann.^
1 B.A.S.F.. D.R.P. 76,941. 2 By., D.R.P. 125,570.
3 B. 3, 905 ; 4, 231.
244 ANTHRACENE AND ANTHRAQUINONE
Bottger and Petersen, i and Liebermann and Hagen.^ These
last treated the product with nitrous acid and obtained
erythrohydroxyanthraquinone and a dihydroxyanthra-
quinone which thej^ regarded as xanthopurpurin. Their
analyses agreed with the figures required by the formula
C28H18O7N2, and they concluded that the substance in
question was probably an amide of erythrohydroxyanthra-
quinone and xanthopurpurin.
Claus 3 examined the action of concentrated sulphuric
acid on nitroanthraquinone sulphonic acid and obtained
two products to which he gave the formulas :
C14H5O,
OS03H
r 'SO3H-1
OH
and
C14H4O2 OH
INO2
INO2 .
,0
but he was unable to obtain them in a state of purity ; and
Lifschiitz,^ on repeating Claus' experiments, was unable to
obtain either.
Lifschiitz ^ studied the action on concentrated stdphuric
acidoni.5-dinitroanthraquinone and isolated four substances.
All these when diazotised and reduced gave dihydroxy-
anthraquinones, such as anthrarufin, and lifschiitz regarded
them as anh3-drides (ethers) of aminohydroxyanthraquinones,
^•g- [Ci4H402(OH)(NH2)2]20- His analyses, however, do
not agree sufficiently well either among themselves or with
the figures calculated for the proposed formulae to allow
these results to be accepted without further confirmation.
More definitive information concerning the action of
sulphuric acid on dinitroanthraquinone is to be found in
two patents. 6 In these it is stated that when 1.5-dinitro-
anthraquinone is treated with oleum containing 30 per cent,
of free anh^-dride at 50° a molecular rearrangement takes
place and i -hydroxy -4-nitroso-8-nitroanthraquinone is formed,
i.8-dinitroanthraquinone and also, apparently, 1,8-dinitro-
naphthalene reacting in the same way. These ^-nitroso-
phenols are, of course, tautomeric with the quinone mon-
1 A. 160, 155 ; 166, 152. B. 4, 229, 301. " B. 15, 1801.
» B. 15, 1521. « B. 17, 902. » B. 17, 891.
« By., D.R.P. 104,282 ; 105,567.
THE HYDROXY COMPOUNDS
245
oximes so that hydroxj^lation can take place by the addition
of the elements of water, subsequent loss of water leading
to the formation of a qiiinoneimide :
O
NO.,
HO NO,
O NOo HO NO.
NO.
1
->
1
-^
1
->
HO
1
— >
HO
1
^2
NC
)
HON
HONH
NH
Presumably the other nitro group reacts in exactly the
same way, so that the final product is a bisquinoneimide, or
its sulphonic acid :
O NH
I
OH
HO
HN O
In support of this view of the reaction the patentees
point out that although the final product of the action of
oleum on 1.5-dinitroanthraquinone is 1.2.4.5.6.8-hexa-
hydrox}' anthraquinone disulphonic acid, the absorption
spectrum of the finished melt is quite different from the
absorption spectrum of a solution of hexahydroxyanthra-
quinone sulphonic acid in concentrated sulphuric acid.
Also the solution at first obtained by running the melt into
water is bluish-violet in colour although it changes almost
at once to red. Finally, they claim that by running the melt
into a saturated solution of sodium chloride or potassium
chloride at —10° the disulphonic acid of the bisquinoneimide
can be isolated.
The quinoneimide is unstable towards water and is very
readily hydrolysed with loss of ammonia and production of
the hexahydroxyanthraquinone, but if the solution in con-
centrated sulphuric acid or oleum is run direct into a reducing
246 ANTHRACENE AND ANTHRAQUINONE
solution (e.g. sulphurous acid) reduction takes place, and
diaminoanthrachrysazin disulphonic acid is obtained,^
which by oxidation with oleum or manganese dioxide and
sulphuric acid is converted back into the quinone imide.
The above facts render it fairly certain that the con-
version of dinitroanthraquinone into hexah3'drox>^anthra-
quinone by concentrated sulphuric acid or oldum is preceded
b}' the formation of a quinoneimide. This is also the case
when the reaction is brought about by means of oleum and
a reducing agent such as sulphur. 2 Here, however, it is
probable that the formation of the quinoneimide is not due
so much to the preliminary formation of a ^-nitrosophenol
as to partial reduction of the nitro groups to hydroxy^lamine
groups, and then immediate rearrangement of these hydrox^'l-
amine compounds to ^-hydroxy^amines : ^
NO, HONH NHo OH NH O
H
NO,
o
HNOH HO NH2 o NH
The rearrangement of hydroxylamine derivatives into
^-aminophenols under the influence of acids is, of course,
a well-known reaction which is common to the aromatic series.
That the anthraquinonyl hydroxylamines react normally in
this respect has been shown by several investigators. *
From the above it will be seen that the final product of
the action of sulphuric acid or oleum, with or without the
addition of sulphur, on 1.5 -dinitroanthraquinone is 1.2.4.5.6.8-
hexahydroxyanthraquinone disulphonic acid, a water-
soluble product used to some extent as a mordant dye imder
various trade names such as Acid Alizarin Blue BB, Alizarin
Cyanine WRS, BBS, 3RS and Anthracene Blue SWX.
1 By., D.R.P. 115,002.
=» B.A.S.F.. D.R.P. 76,262 ; 87,729 ; 88,083 ; 89.144 ; 92,800 ;
92,998; 109,613; 121,315. By., D.R.P. 96,197; 105,567; 108,362;
113.724; 116,746; 119,229.
* R. E. Schmidt and Gattermann, B. 29, 2934. By.. D.R.P. 81,694.
* R, E. Schmidt and Gattermann, B. 29, 2934. ^y.. D.R.P. 119,229.
THE HYDROXY COMPOUNDS 247
Hydrolysis, e.g. b}' heating with concentrated sulphuric
acid, has the effect of removing the sulphonic groups and
rendering the product insoluble (Anthracene Blue WR, WG,
WB). The commercial dyes as a rule consist of mixtures
of isomeric hexahydroxy and pentahydroxy compounds.
The production of polyhydroxj-anthraquinones by the
action of sulphuric acid or oleum, with or without the addition
of sulphur, on nitro compounds has been extended to sub-
stances such as nitromethylanthraquinone, dinitroanthra-
rulin, tetranitrochrysazin, nitroalizarin, nitroflavopurpurin,
nitroanthrapurpurin, etc., but without results of any
particidar interest. ^
Replacement of Halogen Atoms. — Halogen atoms
when attached to the anthraquinone nucleus are not easil}-
replaced by hydroxyl groups by the action of alkali, although
the first synthesis of alizarin was effected by Graebe and
Liebermann by fusing dibromanthraquinone with caustic
potash. 2 Alcoholic alkali is much more effective than
aqueous solutions and will attack halogen atoms when these
are situated in a- positions, but as a rule the ether and not
the free hydroxy- 1 compound is obtained, ^ although, of
course, the alkyl group can be removed by subsequent
hydroh'sis, and according to O. Fischer and Sapper ^ this
is generally the most satisfactory method of replacing halogen
atoms by hydrox^d groups. In some cases, however,
alcoholic alkali can be emploj-ed for replacing halogen atoms
directly by hydroxr\d groups, and Decker and Laube ^ have
found that when i-chlor-2-methox5-anthraquinone is heated
with methyl alcoholic caustic potash a mixture of alizarin
dimeth>-l ether and alizarin j8-monomethyl ether is obtained.
The use of solutions of caustic potash in ethyl alcohol gave
ver>' similar results, viz. a mixture of alizarin methyl ethyl
ether and alizarin /3-monomethyl ether. Schrobsdorf ^
has obtained a tetrahydroxy- compound from dibromchrj-s-
azin by fusing it with caustic potash, and this tetrahydroxy
» By.. D.R.P. ior,^86; 119,229.
* B. 2, 14, 332. 505. Mon. Sci. 1869, 384.
» See p. 287. 4 J. pr. [2] 83. 206.
» B. 39. 112. • B. 36,2936.
248 ANTHRACENE AND ANTHRAQUINONE
compound is not identical with that obtained b}' Wolbling ^
from chtysazin disulphonic acid, as it melts at 217° and its
acet^'l derivative at 195°, whereas Wolbling's product melts
at 292° and gives a tetraacetyl derivative melting at 238-240°.
Halogen atoms can also sometimes be readily replaced by
hydroxy^l groups by heating to 150-160° with concentrated
sulphuric acid and boric acid, and in this way Ullmann and
Conzetti 2 prepared quinizarin from i -hydroxy -4-chloranthra-
quinone. Only halogen atoms which occupy a- positions
are affected, so that i-hydrox)^-2.4-dichloranthraquinone
gives 2-chlorquinizarin.
Although halogen atoms are only replaced by hydrox>-l
groups with difficulty imder the influence of caustic alkali,
it seems that in some cases solutions of the alkali earth
hydroxides in the presence of a copper catalyst are effective,
as Hovermann 3 obtained a dichlortetrahydroxy compoimd
(probably 2.3-dichlor-i.4.5.8-tetrahydroxyanthraquinone) by
heating tetrachlorquinizarin with lime-water and a trace of
copper under pressure. It is probable in this case that the
replacement was chiefly due to the catalytic action of the
copper, as Frey ■* had previously obtained 1.4.5.8-tetra-
h3'drox5^anthraquinone by heating 4.8-dichlorquinizarin with
water and a trace of copper at 250°.
Halogen atoms w^hen in the a- position can sometimes be
replaced b}* hydroxyd groups by heating with concentrated
sulphuric acid or oleum, with or without the addition of
boric acid. By this means quinizarin is readily obtained
from 1.4-dichloranthraquinone or i-h3'drox>'-4-chlor anthra-
quinone,5 and Ullmann ^ has found that 2-methyl-i-hydroxy'-
4-chloranthraquinone passes into 2-methyl quinizarin when
heated to 150-160° with concentrated sulphuric acid and
boric acid. Fuming nitric acid, with or without the addition
of boric acid, can also in some cases cause the replacement of
halogen atoms by hydrox>'l groups, O. Fischer and Rebsa-
men "' having found that i-methyl-4-chloranthraquinone is
' B. 36, 2941. « B. 53. 833. Cf. By., D.R.P. 203,083.
3 B. 47, 1210. * B. 45, 1361. * By., D.R.P. 203,083.
• B. 52, 21 10. » B. 47, 461.
THE HYDROXY COMPOUNDS 249
converted into i-methyl-4-hydroxynitroantliraquinone under
the influence of nitric acid and boric acid, whereas without
boric acid a methyl dih3'droxynitroanthraquinone was
obtained. The exact positions of the groups in these two
compounds is uncertain, but they must all be attached to the
same benzene ring, as both give phthalic acid when oxidised.
The behaviour of the nitro compound, however, is peculiar, as
it is slowly decomposed by alkali at the ordinary temperature
and rapidly on heating, and decomposes with the evolution
of nitrous fumes when boiled with acetic anhydride and
sodium acetate. It is not tmlikely that the nitro group is
situated in the side chain.
In the case of the phthalic acid s}-nthesis, when halogen
atoms are present in the benzoyl benzoic acid there is a
possibility of their being replaced by hydrox>-l groups during
the closing of the anthraquinone ring, e.g. dichlordihydrox^--
benzoyl-benzoic acid when heated with oleum and boric acid
gives chlorpurpurin.i
Replacement of Amino Groups. — Amino groups can
be replaced by hydroxyl groups in the usual way by diazo-
tising and then boiling the diazonium sulphates with water
or dilute sulphuric acid, 2 but as a rule it is best to diazotise
the amine in concentrated sulphuric acid solution, and then
to heat to 90-100° without first diluting. ^ A large number
of hydroxyanthraquinones have been obtained by this
method, which has proved of considerable value as a means
of determining the position of amino groups.
Amino groups can in some cases be replaced by hydroxyl
groups by boiling with caustic alkali,* but the reaction takes
place much more readily if the cyclic carbonyl groups are first
partly reduced, the amino compounds in this way resembling
other substituted anthraquinones. Advantage has been
taken of this to combine the preparation of the amino
compoimd and the replacement of the amino group in one
1 Mettler, B. 45, 8oi.
* Bottger and Petersen, A. 166, 151. Romer, B. 15, 1793 ; 16, 369 ;
Lifschutz, B. 17, 900.
3 Eckert, M. 35, 290. Ullmann and Conzetti, B. 53, 828. M.L.B.,
D.R.P. 97.688. B.A.S.F.. D.R.P. 108,459.
* M.L.B.. D.R.P. 75,490 ; 81,742 ; 104,367.
250 ANTHRACENE AND ANTHRAQUINONE
operation, this result being achieved by reducing the
corresponding nitro compound in boiling alkaline solution. ^
The majority of the cases recorded in which the above
reaction has been applied refer to compounds in which the
nitro (or amino) group occupies an a- position, but it appears
also to be applicable to j8-nitro (or amino) compounds, as
Simon 2 has found that 2-hydroxy-i.3-dinitJ'oanthraquinone
gives anthragallol when reduced in boiling alkaline solution.
Amino groups can also often be replaced by h^^drox}-!
groups by reduction in acid solution, a good example of
this type of reaction being the production of quinizarin by
the reduction of i.4-aminoh3'drox3'anthraquinone, 1.4-
hydroxynitroanthraquinone or 1.4-diamino anthraquinone
by stannous chloride and hydrochloric acid.^
It must be borne in mind, however, that the reduction
of the cyclic carbon3'l group also loosens other groups
attached to the anthraquinone ring and these may be
simultaneously split off. Thus, in the above reactions
1. 4-aminoalkoxy anthraquinone and i ,4-alkox}^nitroanthra-
quinone are dealk5'lated on reduction and yield quinizarin
and not quinizarin monoalkyl ether. Alkox\' groups if
present at 2 or 3 are also dealkylated, and halogen atoms
or nitro, amino or sulphonic acid groups if present in these
positions, are replaced by hydrogen.* The production of
h3'drox3^anthraquinones by the reduction of nitroanthra-
quinones in concentrated sulphuric acid or oleum is usualh'
accompanied b}' simultaneous h3"drox>4ation, the reaction
being due to the production of hydrox\'lamine compounds
and quinoneimides, and this reaction is discussed at greater
length elsewhere. 5
Exhaustive chlorination of primary aminoanthraquinones
in glacial acetic acid, chloroform, or other suitable solvent
sometimes leads to the replacement of the amino group by
hydroxyl, but in these cases replacement of amino b}' halogen
also takes place, e.g. 1.5- and i.8-diamino anthraquinone
1 M.L.B.. D.R.P. 75,490. a D.R.P. 119,755.
» M.L.B., D.R.P. 148.792 ; 207.668. * M.L.B., D.R.P. 183,332.
' See p. 244,
THE HYDROXY COMPOUNDS 251
give a mixture of hexachloranthraruliii, hexachlorchtysazin,
and octachlorantliraquinone.i In some cases the action of
the halogen depends on the solvent used. Thus, 3-amino-
alizarin when treated with bromine in a mixture of glacial
acetic acid and concentrated sulphuric acid is brominated,
3-amino-4-bromalizarin being formed ; but if treated with
bromine in aqueous solution the amino group is replaced by
hydrox3'l, the product being anthragallol ; and other j8-amino-
hydroxyanthraquinones behave in the same way. 2
Direct Oxidation
Anthraqumone differs from other aromatic compounds
in the great ease with which hydrox>4 groups can be inserted
into the molecule by direct oxidation, and use has been made
of this reaction very widely both in the laboratory and on
the large scale. In spite of the large amount of work which
has been recorded on the preparation of hydrox>'anthra-
quinones by direct oxidation, investigators seem to have
paid little or no attention to the mechanism of the reaction,
a fact which may be due to the ver}- great majority of the
work having only been pubhshed in the form of patent
specifications. Consequently there is little or no data on
which any theor}' of the actual mechanism of the change can
be based, and, mdeed, it is probable that the actual mechanism
depends in some degree on the oxidising agent used.^
If the peroxide formula is adopted as representing one
of the phases in the vibration of the anthraquinone molecule,
then when the molecule is in this state one of the benzene
rings will have an ortho- quinonoid structure. All quinonoid
bodies show enhanced reactivity, and in this case addition of
the elements of water would lead to a body which, by tauto-
meric change, would pass into a hydrox3'anthraquinol.
The anthraquinols are well-known compounds and are
extremely readily oxidised to the correspondmg anthra-
quinone, in this case the hydrox^-anthraquinone. On this
» B.A.S.F., D.R.P. 125.094; 137.074.
- By., D.R.P. 126,015. B.A.S.F.. D.R.P. 126.603.
9 Cf. Bucherer, " Lehrbuch der Farbeachemie " (1914). pp. 327-328.
252 ANTHRACENE AND ANTHRAQUINONE
basis the formation of a hydroxy anthraqtdnone would take
place in successive stages thus :
H OH
H;0
OH OH
CO *H
OH
CO
Further h3^drox34ation might then take place in exactly
the same way, or through the production of a compound of
quinonoid structure by the wandering of the hydrox^l
hydrogen atom :
H OH.
0
OH II
HjO
\.
CO
CO OH
OH
CO
It should be noted that when hydroxylation is brought
about without the use of an oxidising agent, e.g. when
anthraquinone-jS-sulphonic acid is fused v/ith caustic soda
without the addition of a nitrate or chlorate, the hydroxyl
compoimd is obtained as its reduction product.
Hydrox}'! groups can be introduced into the anthra-
quinone molecule b3' direct oxidation in either alkaline or
acid solution, the most interesting results being obtained
by the latter means, although oxidation in alkaline solution
is of great technical importance, as it is b}' this means that
alizarin is manufactured.
Alkaline Solution. — As stated on p. '239, when an
anthraquinone-^-sulphonic acid is fused with caustic alkali,
not only are the sulphonic acid groups replaced by hydroxyl
groups, but at the same time oxidation takes place and
further hydroxyl groups enter the molecule. If no oxidising
agent is present in the melt the hydrox}^ compotmd is ob-
tained in the form of its reduction product, this being due
either to the reaction having taken the course outlined
THE HYDROXY COMPOUNDS 253
above, or to the oxidation of one molecule having taken
place at the expense of the ketonic oxygen atoms of another
molecule, or to a combination of these causes. In order to
obtain a more satisfactor\' jdeld of the hydrox}'anthra-
quinone it is usual to carr>' out the alkali melt in the presence
of an oxidising agent such as air or an alkali nitrate or clilorate,
chlorates usually giving the most satisfactory^ results. The
reaction obviously takes place in at least two steps, viz.
replacement of the sulphonic acid groups followed by further
hydrox}4ation, as further hydroxyl groups can be introduced
into the hj-drox^-anthraquinones themselves by fusion with
caustic alkali and an oxidising agent. Thus, Schunck and
Romer ^ obtained fiavopurpurin and anthrapurpurin by
fusing anthraflavic acid and zso-anthraflavic acid with
caustic potash, and more recently several patents have been
granted for improved methods of carr3-ing out these re-
actions. 2 Anthraruiin and chrysazm are also readily con-
verted into trihydroxy compomids (hydroxrs-anthrarulin and
hydroxychrj'sazin) by heating with caustic alkali ^ and
alkali nitrate, and many other examples of this type of
reaction are known.
The most important product obtained by the fusion of
an anthraquinone sulphonic acid with caustic alkali is,
of course, alizarin, this d3'estuff being obtained almost
universally by fusing the sodium salt of anthraquinone-)S-sul-
plionic acid with caustic soda and sodium chlorate* As
a rule the alkali melt is carried out with caustic soda solution
of 30 to 40 per cent, strength, the heating being effected in
an autoclave. 5 The alizarin obtained by this method is not
pure and contains also higher hydroxylated anthraquinones
such as fiavopurpurin and anthrapurpurin, derived from the
disulphonic acid present as an impurity in the technical
1 B. 9, 678.
- Wed., D.R.P. 194.955- By., D.R.P. 205,097 ; 223,103.
3 M.L.B., D.R.P. 195,02s ; 196,980.
* For references to the literature dealing with the earlier history of
alizarin, see Schultz, " Chenxie des Steinkohlenteers," vol. ii. pp. 250-J02,
and Auerbach, "Das Anthracen."
* For technical details see UUmann, " Enzyklopadie der technischen
Chemie."
254 ANTHRACENE AND ANTHRAQUINONE
mouosulphonic acid, and purpurin, derived from alizarin
b}' oxidation. The presence of the flavopurpurin and anthra-
purpurin causes the alizarin to dye in rather yellowish
shades, and various mixtures of alizarin with flavopurpurin
and anthrapurpurin are sold as Alizarin RA, RR, etc., the
letters referring to the shades obtained from the difi'erent
brands, i
Another method ^ of carrjang out the manufacture of
alizarin is to mix intimately six parts of finely powdered
caustic potash with six parts of sodium anthraquinone-
j3-sulphonate and one part of alcohol. The mixing must be
very intimate and must be carried out with the total exclusion
of air. When the mixture is exposed to the air in thin
layers it immediately warms up and alizarin is formed.
This method of carrying out an " alkali melt " is not confined
to the preparation of alizarin but seems to be fairly general,
e.g. indanthrone can be made from j3-aminoanthraquinone,
and pyranthrone can be obtained from 2.2'-dimethyl-i.i'-
dianthraquinonyl by a similar procedure. The method is
a rapid one and is well adapted for continuous working.
As stated above, anthraquinone-2.6- and -2.7-disulphonic
acids when fused with caustic alkali 3'ield flavopurpurin
(Alizarin RG, GI, SDG, etc.) and anthrapurpurin (Alizarin
SX, GD, RX, etc.), but if the fusion is carried out in the
presence of air under suitable conditions it is possible
to replace only one sulphonic acid group, the products
being alizarin - 6 - sulphonic acid and alizarin-7-sulphonic
acid. 3
The insertion of hydrox>4 groups into the anthraquinone
molecule by alkaline media is not confined to the hydroxy-
anthraquinones, as anthraquinone itself can be hydroxylated
under suitable conditions by fusion with caustic soda and
a chlorate. The product in this case is alizarin of exceptional
purity and free from anthrapurpurin and flavopurpurin.
Such alizarine dyes in slightly bluish shades of red (Alizarin
No. I, Alizarin V, Alizarin mit Blaustich), and the process
1 Schultz, " Farbstofftabellen." ^ B.A.S.F., D.R.P. 287,270.
» By., D.R.P. 50,164 ; 50,708.
THE HYDROXY COMPOUNDS 255
seems well adapted to its manufacture.! The alkaline oxida-
tion of anthraquinone under other conditions can lead to
various hydrox>'anthraquinones, and it is claimed that when
the oxidation is brought about by heating to 200° for 3-4
days with caustic soda of 30 per cent, strength together
with a sulphite, or compound capable of yielding a sulphite,
and an oxidising agent such as potassium nitrate, the
product is j3-hydroxyanthraquhione, alizarin, anthrapurpurin,
flavopurpurin or anthraflavic acid or a mixture of these. 2
In connection with the preparation of hydroxyanthra-
quinones by the alakli melt method it is interesting to
notice that if lime, strontia, baryta., or magnesia is added to
the alkali melt before heating, the hydrox}' anthraquinone is
left as an insoluble lake which can be filtered off, and it is
claimed that this procedure greatly facilitates the recovery
of the excess of alkali. 3
Acid Soi^ution. — The preparation of hydroxy anthra-
quinones by the direct oxidation in acid solution of anthra-
quinone or lower hydroxylated derivatives is a reaction of
the greatest importance and has been very widely applied.
Here again, however, nearl}- all the work published has
only been recorded in the form of patent specifications,
with the usual result that the information available is in-
sufficient to permit any general rules to be detected. Also
the directions given in the specifications are often unsuitable
for laboratory experiments, and in the majority of cases any
statements as regards yield are conspicuous by their absence.
The writer, however, has prepared several hydroxj^anthra-
quinones by direct oxidation in acid solution and has found
that the yields obtained are usually quite satisfactor}-.
Oxidation in acid solution is always brought about in
concentrated sulphuric acid, and ma}^ be effected with
concentrated sidphuric acid or monohydrate alone, ^^■ith
oleum, with nitrosyl sulphiiric acid or with sulphuric acid
and an oxidising agent such as nitric acid, manganese
1 B.A.S.F., D.R.P. 186,526.
2 By.. D.R.P. 241,806; 245,987; 249,368; 251,236.
» M.L.B., D.R.P. 17.627.
256 ANTHRACENE AND ANTHRAQUINONE
dioxide, arsenic acid, amnioniuiii persulphate, etc. The
introduction of hydrox>4 groups, of course, weakens the
benzene ring, and to prevent further oxidation with rupture
of the ring taking place it is usually necessary- to carry out
the oxidation under such conditions that the hydroxy 1
group becomes protected. This is best done by carr^-ing
out the oxidation in the presence of excess 'of boric acid, as
under these conditions a boric ester is formed which is much
more stable towards oxidising agents than the free hydroxy
compounds. These boric esters, however, are easily hydro-
lysed by dilute acids, so that when the oxidation is com-
plete it is only necessary to dilute the solution and then
boil for a few minutes in order to liberate the free hydroxy
compound.
Concentrated Sulphuric Acid or Oleum. — Oleum of
high concentration, viz. an acid containing about 80 per
cent, of free anhydride, readily hydroxy lates anthraquinone
and its derivatives, the reaction usually being carried out at
35°-40°, and never at a temperature exceeding 100°. With
oleum of lower strength a higher temperature is necessar3^
and, of course, the same is true if the oxidation is brought
about by means of ordinary concentrated sulphuric acid or
sulphuric acid monohydrate,* in these cases temperatures
of 260-280° usually being the most suitable.
When sulphuric acid acts as an oxidising agent it is, of
course, reduced to sulphurous acid and this combines with
the hydroxy- compound produced to form a sulphite ester,
this ester formation to some extent protecting the hydroxy-l-
ated anthraquinone from destruction by further oxidation.
Much more satisfactory results are obtained, however, by
carr^'ing out the oxidation in the presence of boric acid so
that the boric ester is formed, and the same method is used
when the oxidation is carried out with sulphuric acid and
an oxidising agent. In any case when oxidation is complete
the melt must be diluted and then boiled in order to hydrolyse
* The term " monohydrate " denotes an acid containing 100 per cent, of
H0SO4, i.e. the monohydrate of sulphur tri oxide. This explanation appears
necessary as in the abstracts published by the Chemical Society, e.g. Soc.
100, 548, it is sometimes quite wrongly taken to mean HjSOi.HoO.
THE HYDROXY COMPOUNDS 257
tlie ester present. When the boric acid method is employed
it is usual to add one part of crystallised boric acid to
twenty parts of concentrated sulphuric acid, monohydrate,
or oleum, and then to add the anthraquinone compound
(one part) which it is desired to oxidise. The temperature
is then maintained at a suitable point until examination of
a sample shows that oxidation has gone as far as desired,
when the whole is cooled, diluted with water, boiled to
hydrolyse the ester, and the hydroxy compound then
liltered off.
The addition of boric acid also slows down the reaction
and, if sufficient is added, may even in some cases inhibit it
altogether. This retarding action of boric acid is often
very useful in preventing the reaction going too far. Thus
the oxidation of alizarin with oleum of high concentration
leads to quinalizarin in the absence of boric acid, but with
the addition of a suitable amount of boric acid the reaction
is so retarded that an almost quantitative yield of hydroxy-
anthrarufin can be obtained. In the same way the addition
of boric acid renders it possible to oxidise chrysazin to
1 . 4. 8- trihydroxy anthraquinone.
It is impossible to detect with certainty any regularities
in the positions taken by entering hydrox\'l groups, but it
seems to be a fairly general rule that the a-position is pre-
ferred, and that the ^-position is never taken unless there is
a hydroxyd group in the contiguous a- position. Even when
there is such a group present the entering hydroxyd group
often prefers the a- position. The ease with which hydrox}d-
ation takes place varies very much with the different
compounds used as starting -out substances. Thus oleum
of high concentration rapidly converts erythrohydroxy*-
anthraquinone into anthrarufin, but the conversion of
anthrarufin or quinizarin into 1.2. 4.5.6. 8-hexahydroxy-
anthraquinone only takes place extremely slowly. On the
other hand, this hexahydroxy compound is rapidh^ and
quantitatively formed from chrs'sazin, and from anthra-
chrj'sazin its formation is almost instantaneous.
Oxidation by means of sulphuric acid is a catalytic
17
258 ANTHRACENE AND ANTHRAQUINONE
reaction aud does not take place if chemically pure acids
are used. When ordinar>^ commercial acids are employed
the small quantities of selenium present act as the catalyst :
Se02=Se+02
Se +2SO3 =Se02 +2SO2
Oxidation by means of sulphuric acid is ajso facilitated by
the presence of mercury compounds, ^ and bromine is stated
to facilitate attack by oleum, although this can hardly
be regarded as a catalytic effect as bromination and
hj^droxy^ation take place simultaneously. 2 Hydrox>4ation
by oxidation with sulphuric acid or oleum often leads to
the production of polyhydroxy^anthraquinone sulphonic acids,
but in mau}^ cases the sulphonic acid groups are readily
removed by hydrolysis by heating the product with sulphuric
acid of about 70 per cent, strength. ^
Hydroxylation by means of sulphuric acid or oleum
often leads to the simultaneous replacement of other groups
such as halogen atoms ^ and amino and nitro groups ^ when
these are present in the molecule, and it is possible to obtain
hydroxyanthraquinones from halogen derivatives of anthra-
cene in which both ws-hydrogen atoms have been replaced by
halogen atoms. ^ The behaviour of the nitroanthraquinones
towards oleum is particularly interesting but has already
been discussed."^ Amino groups in aminoanthraquinones,
although often replaced by hydroxyl groups under the
influence of oleum, b}^ no means always behave in this way,
both a-amino and a-alkylaminoanthraquinones being often
converted into ^ara-hydroxyaminoanthraquinones by treat-
ment with 80 per cent, oleum at 30-40°, or with 20 per cent,
oleum, monohydrate or concentrated sulphuric acid ^ in
the presence of boric acid at 200°.
1 Georgievics, M. 32, 347. By., D.R.P. 162,035 ; 172,688.
a By., D.R.P. 97,674 ; 99,314-
3 By., D.R.P. 172,688. Cf. M.L.B., D.R.P. 71,964.
* By., D.R.P. 81,962 ; 83,055.
5 M.L.B., D.R.P. 75-490. By., D.R.P. 79,768 ; 81,244 ! 83,055 ;
83,085.
6 By., D.R.P. 68,775 ; 69.835.
Page 242.
By., D.R.P. T54,353 ; I55.440-
7
THE HYDROXY COMPOUNDS 259
Sulphonic acid groups when present in the molecule
have a tendency to protect the benzene ring to which they
are attached, and when there is only one sulphonic group
present the hydrox}^ groups enter the other ring. Thus
anthraquinone-a-stdphonic acid when treated with oleum
gives alizarin-5-sulphonic acid ^ and purpurin-8-sulphonic
acid,- the use of boric acid and mercury apparently not
influencing the positions taken by the hydroxyd groups.
The influence of sulphonic acid groups in the jS- position is
micertain.
The data available as regards the product obtained
when fresh hydrox>d groups are introduced into a molecule
in which such groups are alread}- present are confusing and
insufficient to allow any reliable deductions to be made.
IMany of the hydroxyl compounds described in the patent
literature are not characterised, and probably a large pro-
portion of them are mixtures of isomers. It appears, how-
ever, that when two hydrox>d groups are present in the
para- position to one another, the tendency of the entering
hydrox}d group is to attach itself to the same ring, e.g.
quinizarin gives purpurin,^ and quinizarin-8-sidphonic
acid gives purpurin-3.8-disulphonic acid.-* This is the
behaviour that would be expected on the assumption that
direct hydrox^dation is primarily the addition of the elements
of water to a compound with a quinonoid structure, as
quinizarin is fairly easily oxidised to anthradiquinone, a
compound which is a true quinone in its chemical re-
actions. Gattermann,5 however, finds that quinizarin
when oxidised with oleum mider certain conditions gives
quinalizariu.
Anthraquinone itself when oxidised with oleum containing
about 80 per cent, of free anhydride and boric acid gives
anthrarufin,^ whereas with more dilute oleum or with
ordinary concentrated sulphuric acid it is first rapidly
converted into quinizaiin and then more slowly into
1 By.. D.R.P. I72,68g. M.L.B., D.R.P. 158,413.
'- R. E. Schmidt. B. 37, 71. By., D.R.P. 155,045.
3 By., D.R.P. 81.481. * By., D.R.P. 172.688.
5 J. pr. [2] 43, 246. « By., D.R.P. 101,220.
26o ANTHRACENE AND ANTHRAQUINONE
purpuriii.i Oleum of high concentration also seems capable
of oxidising anthraquinone to a hexahydroxy compound, ^
probably Anthracene Blue WR.
Erythroltydrox3^anthraquinone on oxidation with oleum
of high concentration gives anthrarufin,^ but the effect of
more dilute acids does not seem to have been studied, and
there appears to be no record of the hyflroxylation of j3-
hydroxyanthraquinone bj^ acids.
Alizarin when oxidised by oleum of high concentration
gives quinalizarin '^ (Alizarin Bordeaux B, Alizarin Cj^anine
3R) and hydroxyanthrarufin,^ chrysazin gives 1.4,5-tri-
hydroxy anthraquinone, 6 and anthragallol when oxidised
with dilute oleum or concentrated sulphuric acid in the
presence of boric acid gives 1.2.3.4-tetrahydroxyanthra-
quinone.'^
Oxidation with monohydrate in the presence of mercuric
sulphate and boric acid has resulted in the preparation of
octah3^droxyanthraquinone, Georgievics ^ having prepared
this substance from rufigallic acid by this method.
Polyhydrox>'anthraquinones have also been obtained by
the action of oleum or sulphuric acid upon purpurin,^
anthrapurpurin,io flavopurpuiin,^^ h5^droxyanthrarufin,^2
hydroxyclirysazin,i3 rufigallic acid,^* and manj- other similar
compounds. 1^
NiTROSYi. Sui<PHURic AciD. — Nitrosyl sulphuric acid is
a valuable reagent for inserting hydroxyl groups into the
anthraquinone molecule and can be used either as chamber
crystals or, more conveniently, simply as the solution
obtained by slowly adding solid sodium nitrite to about
15 parts of cold concentrated sulphuric acid. Oxidation is
usually carried out at a temperature of 180-230°, and
1 By., D.R.P. 81,960. " By., D.R.P. 65,182.
3 By., D.R.P. 97,674. * Bv., D.R.P. 6o,8^s5-
5 By., D.R.P. 156,960. 6 By., D.R.P. 161,026.
' By., D.R.P. 86,968. Cf. By., D.R.P. 60,855.
8 M. 32, 347- ° By., D.R.P. 60,855.
10 By., D.R.P. 60,855 ; 67,061. i' By., D.R.P. 60,855 ; 67,061.
1- By., D.R.P. 67,06^. 13 By., D.R.P. 67,063.
'■« By., D.R.P. 62, 531.
15 By., D.R.P. 63,693 ; 64,418; 65,375; 65,453; C9.013 ; 81,481;
S1.959; 172.688.
THE HYDROXY COMPOUNDS 261
boric, arseuic, or phosphoric acid ^ is added to protect the
hydrox}^! compound as formed by converting it into an ester.
Boric acid is certainly the most efficient of these, and is
usually added in the proportion of one part of crystallised
acid to one part of substance to be oxidised, but it is probable
that in many cases better results would be obtained b}^
using different proportions. Thus Dimroth and Fick 2
foimd that the oxidation of flavopurpurin and anthrapurpurin
to the tetrahydroxy compounds by means of nitros3'l
sulphuric acid was best effected when only one-tenth of the
above proportion of boric acid was used, as if larger quantities
were employed it was necessarj^ to carry out the oxidation
at a higher temperature and the ^-ields obtained were much
poorer.
Hydroxylation with nitrosyl sulphuric acid is a catalytic
reaction and depends on the presence of mercurs'. If the
nitros3-l sulphuric acid is made from pure sulphuric acid no
h}'drox\^]ation takes place, but as a rule commercial sulphuric
acid which has been made from pyrites contains sufficient
mercur>'. In most cases, however, the addition of a mercury
salt is advantageous, 3 and the study of the reaction under
these conditions has thrown some light on its mechanism.
Thus it has been found that the action of nitrosyl sulphiuric
acid at 120° in the presence of boric acid and mercuric sul-
phate converts anthraquinone into i-hydroxj^anthraquinoue-
4-diazonium sulphate,'* this being converted into quinizarin
when heated with concentrated sulphuric acid at i70°-i8o°.
This direct insertion of the diazonium group is rather
remarkable, and the reaction is one which merits further
investigation.
Other groups when present in the molecule are often
affected during the process of h3'droxylation, ^-methyl-
anthraquinone, for example, being converted into quinizarin
carboxylic acid,^ and 1.5-dinitroanthraquinone 3aelding
5-nitroquinizarin.*^
» B.A.S.F.. D.R.P. 153,129 ; 154,337. * A. 411, 326.
3 B.A.S.F.. D.R.P. 153.129; 154.337- * By.. D.R.P. i6i.954-
* By.. D.R.P. 84,505. « By., D.R.P. 90,041.
I
262 ANTHRACENE AND ANTHRAQUINONE
Oxidation with nitrosyl sulphuric acid seems speciall}^
adapted to the preparation of hydroxj-anthraquinones in
which two h3^droxyl groups are in the para- position to one
another, and it appears that a hydroxyl group does not
enter a j8- position unless both a- positions in that ring are
already occupied b}^ hydrox}-!. Too great reliance, however,
must not be placed on this rule, as the d^a available are
insufficient to establish it beyond doubt.
Anthraquinone on oxidation with nitrosyl sulphuric
acid gives quinizarin,i reference having already been made
to the production of i -hydroxy anthraquinone-4-diazonium
sulphate as an intermediate product. The production of
quinizarin by this method takes place very readily, and as
the yields obtained are quite satisfactory it forms the
easiest means of obtaining quinizarin in the laboratory.
Erythrohydroxyanthraquinone also gives quinizarin 2
and, curiously enough, so does jS-hydroxy anthraquinone. 3
In this latter case it is probable that the nitrous acid first
reduces the hydroxyl group and then oxidises the resulting
anthraquinone, and this behaviour explains why hydroxyl
groups so rarely take the j8-position.
Quinizarin on oxidation gives purpurin,.* although in
poor yield, and this is one of the very few cases in which a
hydroxyl group enters the jS-position.
Chrysazin gives 1.4.5-trihydroxyanthraquinone very
readily and in a state of purity, as, curiously enough, no
1.4.5.8-tetrahydroxyanthraquinone is formed.^
Flavopurpurin on oxidation yields hydroxyflavopurpurin
(1.2.4.6.), and anthrapurpurin yields hydroxyanthrapurpurin
(1.2.4.7), the position of the h3'droxyl groups being proved
by the fact that both hydroxyflavopurpurin and hydroxy-
anthrapurpurin on reduction and subsequent oxidation of
the leuco- compound give 1.4.6-trihydroxyanthraquinone,
the orientation of the h3^droxyl groups in this compoimd
1 By., D.R.P. 81,245 ; i6i,954- B.A.S.F., D.R.P. 154.337-
- By., D.R.P. 162,792.
=* By., D.R.P. 86,630.
^ By., D.R.P. 86,630. B.A.S.F., D.R.P. 153,129.
* By.. D.R.P. 163,041.
THE HYDROXY COMPOUNDS 263
being known by its formation from 4-hyd.roxyphtlialic acid
and hj'droquinone.i
Anthraquinone-j3-sulphonic acid when heated with
nitrosjd sulphuric acid gives a purpurin sulphonic acid which
is different from that obtained by the sulphonation of
purpurin, as the sulphonic acid group is not removed by
hydrolysis when the acid is heated with hydrochloric
acid.2
Various Oxidising Agents. — Hydroxy^ groups have
been introduced into the anthraquinone nucleus by the use
of numerous oxidising agents in conjunction with con-
centrated sulphuric acid, and in all of these cases it has been
found that boric acid exerts a verj- beneficial influence by
protecting the h3'droxy compounds formed from further
attack. 3
Nitric acid in the presence of concentrated sulphuric
acid can act on hydroxyanthraquinones either as a nitrating
agent or as an oxidising agent or as both. Thus alizarin
stdphonic acid when dissolved in concentrated stdphuric
acid at 10° and then treated with nitric acid gives purpurin
sulphonic acid, ^ alizarin itself when nitrated giving a mixture
of nitroalizarin, purpurin, and nitropurpurin.^ Flavo-
purpurin and anthrapurpurin are also oxidised by nitric
acid when dissolved in concentrated sulphuric acid and give
tetranitro compounds. ^ The action of nitric acid on the
polyhydrox}^anthraquinones is often complicated by the
formation of diquinones,"^ although to some extent this can
be avoided by the protectmg influence of boiic acid. Highly
hydroxylated derivatives often undergo complete decom-
position, rufigallic acid giving only oxalic acid,^ and amino
groups when present are often replaced b}' nitro groups.^
The action of nitric and sulphuric acids at a high tempera-
ture on anthraquinone derivatives is in many cases similar
to the action of sulphuric acid on the nitroanthraquinones,
1 Diraroth and Pick, A. 411, 326. - B.A.S.F., D.R.P. 154,337-
3 By., D.R.P. 102,638. * M.L.B., D.R.P. 84,774.
- M.L.B., D.R.P. 150,322. , '■■ M.L.B., D.R.P. 84,774.
' By., D.R.P. 70,782. * Klobukowski, B. 8, 931 i 9. 125O.
'' M.L.B., D.R.P. 104,244 ; 107,238; 111,919.
264 ANTHRACENE AND ANTHRAQUINONE
a somewhat important reaction which is treated in greater
detail elsewhere. 1
Manganese dioxide in the presence of concentrated
sulphuric acid oxidises hydrox5^anthraquinones to higher
hydrox34ated compounds, the product usually being obtained
in the form of an anthradiquinone, which can be reduced
to the corresponding hydroxy anthraquinone by sulphur
dioxide. 2 The most important application of this reaction
is the oxidation of quinalizarin to i.2.4.5.8-pentah3^droxy-
anthraquinone (Alizarin Cyanine R, 2R, RA Extra, etc.), the
diquinone at first obtained being subsequently reduced. 3
The pentah5^droxy compound is a powerful mordant dye
giving violet shades on alumina and blue shades on chrome.
Anthragallol is readily oxidised to i.2.3.4-tetrahydrox3--
anthraquinone by manganese dioxide and sulphuric acid in
the presence of boric acid at or about the ordinar}- tempera-
ture. The presence of boric acid is absolutely essential, as
otherwise the anthragallol is completely destro3^ed.*
Alizarin-3-carboxylic acid is also oxidised b}" manganese
dioxide and sulphuric acid at or about the ordinary tempera-
ture and passes into purpurin-3-carbox3dic acid, a substance
which has proved to be identical with the " ^sew^o-purpurin "
present in madder.^
In addition to the oxidising agents mentioned above
hydrox>4 groups can be introduced into the anthraqumone
ring by means of lead dioxide, bleaching powder, arsenic
acid, ferric salts, chromates, persulphates, and perchlorates,^
but for further details the reader is referred to the original
literature. Electrolytic oxidation has also been described.'
Reduction of Polyhydroxy Compounds
Hydroxy anthraquinones can sometimes be obtained
from the higher hydrox}4ated compounds by removing one
^ See pp. 242-247. 2 -Qy ^ D.R.P. 66,153 ; 68,113 ; 68,114.
3 By., D.R.P. 62.018. « By., D.R.P. 102,638.
^ By., D.R.P. 260,765 ; 272,301.
« By., D.R.P. 62,018 ; 62,504-5-6; 66,153; 68,123; 68,113; 68,114;
69,842; 69,933-4; 73.942; 102,638; 104,244; 107,238; 111,919-
' By.. D.R.P. 74,353.
THE HYDROXY COMPOUNDS 265
or more liydroxyl groups by reduction, although the method
is not one of great importance. The cycHc carbonyl groups
are, of course, simultaneously reduced, but if the reduction
is carried out under suitable conditions it is usually possible
to avoid their reduction being carried beyond the quinol
stage, so that the product is readib,- converted into the
anthraquinone derivative by air oxidation.
Exhaustive reduction of hydroxyanthraquinones by
means of hydriodic acid and red phosphorus leads to
hydrogenated anthracenes, ^ but imder less drastic conditions
it is often possible to split off one ltydrox}4 group without
reducing the carbonyl groups beyond the anthraquinol
stage. Thus lyiebermann ^ and Pleus 3 by reducing qmni-
zarin obtained i-hydroxy-anthraquinol from which er>'thro-
hydroxyanthraquinone was obtained by mild oxidation.
H3-driodic acid, however, is not a particularl}^ suitable
reducing agent for removing h3^droxyl groups while avoiding
complete reduction of the C3xlic carbonyl groups.
The reduction of purpurin with alkaline stannite solution
leads to xanthopurpurin,'^ and the same substance is said to
be obtained in quantitative 3'ield when the reduction is
carried out by sodium hydrosulphite and ammonia, ^ In
acid solution it seems, however, that a different hydroxyl
group is split off, the product being quinizarin. According
to one patent ^ the reduction of purpurin with zinc and
glacial acetic acid leads to two products which are designated
as leuco-qmnizann I and /cwco-quinizarin II. Of these the
analytical figures and the melting point (150°) quoted in the
specification for leuco-quimzann II agree closel)- with those
of i.4-dihydrox5^anthraquinol.' The analytical figures
quoted for /cz^co-quinizarin I, however, agree with those
required for a trihydroxyanthraquinol,* so that the so-called
" /e^^co-quinizarin I " would appear to be nothing but
^ Liebermann, A. 212, 26. ^ ^ 212, 14. B. 10, G07 ; 11, 1610.
» B. 35, 2923. 4 Plath, B. 9, 1204.
« M.L.B., D.R.P. 212,697 6 By.. D.R.P. 89,027.
' Liebermann, A. 212, 14. B. 10, G08. Grandmougin, J. pr. [2] 76,
138.
* Found 0 = 65-11, 6508; H=3'95, 3-90. Calculated forCuHioOj,
0=6512; H=3-88.
266 ANTHRACENE AND ANTHRAQUINONE
leuco-pnrpurin, tlie reduction not having been taken far
enough to remove the hydrox^d group. In spite of this,
however, the specification states emphatically in two places
that " /^Mco-quinizarin I" is more readily oxidised to
quinizarin than is /ewco-quinizarin II. This is rather difficult
to understand if the analytical figures given were really
obtained experimentally.* In a later patent ^ the same
firm claims that the best yields of /ewco-quinizarin are
obtained by reducing purpurin with aluminium bronze and
concentrated sulphuric acid in the presence of boric acid.
Elimination of hydrox}^ groups can also be brought about
by reducing other polyhydroxyanthraquinones with zinc
and glacial acetic acid, Dimroth and Fick,2 for example,
obtaining 1.4.6-trihydroxyanthraquinone from both hydroxy-
flavopurpurin and hydroxyanthrapurpurin by this method.
In some cases nitrous acid appears capable of removing
hydroxyl groups from hydroxyanthraquinones, Nienhaus 3
having reduced both alizarin and purpurin by treating them
with nitrous acid in concentrated sulphuric acid solution.
The reaction is, however, not one that is likely to find an}'
extensive use owing to the tendency of nitros}^ sulphuric
acid to introduce fresh hydroxyl groups.'^
Hj^droxyl groups can in some cases be removed by an
indirect method. Thus Schrobsdorf,^ by heating chrj^sazin
with ammonia, replaced one hydroxjd group by an amino
group, and by then diazotising and reducing the i.8-amino-
hydroxyanthraquhione obtained erythrohydrox3^anthraqui-
none.
M1SCE1.1.ANEOUS Methods
The hydroxyanthracenes can be converted into the
corresponding hydroxyanthraquinones by first protecting
the hydroxyl groups by acetylation and then oxidising. In
this way erythrohydroxyanthraquinone,^ ^-hydrox3'anthra-
quinone,' chrysazin,^ and other hydroxy^anthraquinones
* For explanation of this reaction see "Addenda."
1 By., D.R.P. 246,079. "- A. 411, 330.
3 B. 8, 778. 4 See p. 260.
5 B. 35, 2930. G Dienel, B. 38, 2862.
" Liebermann and Hormann, B. 12, 259.
8 Liebermann and Boeck, B. 11, 1616; 12, 185.
THE HYDROXY COMPOUNDS 267
have been obtained, but the method is chiefly valuable for
determining the positions of the hydroxy^l groups in the
hydroxy anthracenes. The ms-nitro derivatives of anthra-
cene, such as dihydrotrinitroanthracene and Meisenheimer's
nitroanthrone,! pass into alizarin when heated with alkali to
temperatures exceeding 100°. The yield is said to be
improved by adding lime, sodium nitrate, and sodium
sulphite to the melt.^
Properties and Reactions
The h3-drox>-anthraquinones show the ordinary reactions
of the phenols and dissolve in caustic alkali to form higlily
coloured solutions. Hydroxyl groups when in the a-
position are influenced by the cyclic carbonyl groups and
are then only alkj-lated with the utmost difficulty, and are
rather more difficult to acetjdate than when in the j3-
position. Whether the influence of the carbon3'l group upon
a hydrox}'! group in the ortho- position to it is due to the
formation of a quinonoid compound or whether it is due to
other causes cannot be decided with certainty from the
data available at present.
The absorption spectra ^ of erythroltydroxyanthraquuione
and anthrarufin in alkaline solution are almost identical,
each showing one and only one broad band with its head at
^oofj-fx. In concentrated sulphuric acid solution erythro-
hydroxj'anthraquinone shows a broad band with its head
at 475/^/i and also two narrow bands with their heads at
305^^ and 260^/^/, and closely resembles that of anthraqiii-
none in sulphuric acid solution. Anthrarufin, on the other
hand, when in concentrated sulphuric acid solution has an
absoq:)tion spectrum almost identical with that of quinizarin
although the bands are slightly nearer the red end of the
spectrum, whereas although the sodium salts of anthrarufin
and quinizarin have absorption spectra which are somewhat
1 See p. 54. 2 G.E., D.R.P. 292,247.
» K. Meyer and O. Fischer, B. 46, 85. Meek and Watson, Soc. 109,
557-
268 ANTHRACENE AND ANTHRAQUINONE
similar, the addition of excess of alkali affects that of quiiii-
zarin to a considerable extent.
The absorption spectrum of jS-li^-drox^'anthraquinone in
alkaline solution differs from that of er}-throhydrox}'anthra-
quinone by showing two narrow bands with heads at 305jU,u
and 235^/^, whereas in concentrated sulphuric acid solution
it shows very shallow bands at 410/^/^ and 325^fji, and a
slightly deeper band at 290^/x, these in addition to the broad
band with its head at 500^/x.
The spectrum of the sodium salt of alizaiin in the
absence of excess of alkali resembles that of /3-hydroxy-
anthraquinone, whereas when excess of alkali is present
the absorption spectrum is ver)^ similar to that of purpurin,
although the bands in the visible region are nearer the red
end of the spectrum. The spectra of anthraflavic acid and
iso-anthrafiavic acid in alkaline solution are, as would be
expected, somewhat similar, although the bands differ in
breadth and persistence. They both show absorption in
the idtraviolet, and so far as alkaline solutions are concerned
this type of absorption seems to be confined to hydroxy-
anthraquinones in which there is at least one hj^droxyl
group in the ^- position. In concentrated sulphuric acid
solution, however, ultraviolet absorption seems to be
exhibited by all hydrox3-anthraquinones including anthra-
quinone itself. 1
A comparison of the absorption spectra of the h}- droxy-
anthraquinones and their ethers would be interesting and
might throw light on the constitution of the a-hydroxy
compounds, but at present data are not available.
The presence of hydrox>d groups in the anthraquinone
nucleus weakens the ring to which they are attached,
although not to the same extent as is usually the case in the
aromatic series. The weakening influence is especiall}^
marked when two groups are present in the p- positions to
one another, this being no doubt due to the ease with which
compounds pass into anthradiquinones on oxidation. Thus
1 R. Meyer and O. Fischer, B. 46, 90. Cf. Baly and Stewart, Soc. 89,
511-
THE HYDROXY COMPOUNDS 260
both purpurin and qiiinizarin are readilj' oxidised to phthalic
acid by the action of atmospheric oxygen on their alkaUne
solutions, whereas alizarin is not destroyed under similar
conditions. 1
The further Itydroxylation of hydroxy- anthraquinones
by direct oxidation has already been discussed,^ and so also
has the fomiation of anthradiquinones,^ and but little
information is available as to what products are obtained
under different conditions.
SchoU ^ has found that when alizarin is oxidised in
alkaline solution with a Iwpochlorite i.i'.2.2'-tetrahydroxy-
3.3'-dianthraquinonyl is formed, and that the same product is
also formed to some extent when alizarin is fused with caustic
soda under suitable conditions. Oxidation witli ferric3'anide
in alkaline solution, on the other hand, leads to rupture
of the benzene ring, the product obtained at the ordinary
temperature being 2-hydroxy-(i.4)-naphthoquinonyl-3-acr}--
lic acid.''
Naphthoquinonyl derivatives have also been obtained
by Dimroth and Schulze ^ by the degradation of carminic
acid and other naturally occurring hydroxyanthraquinone
derivatives, and Bamberger and Praetorius "^ have obtained
3-hydrox3^-(i.4)-naphthoquinonyl-2-acetic acid by the auto-
oxidation of anthiagallol in alkaline solution. They explain
the degradation as follows, anthragallol being assumed to
be ^-qninonoid when in alkaline solution :
0
^^ ,CO-COOH
IcOH
The same investigators have also fomid that the oxidation
1 Dralle, B. 17, 376. - Pp. 251-264. ^ pp t)2-<,4.
« B. 52, 1829 ; 2254. C/. By., D.R.P. 146.223 ; 167,461.
^ Scholl, B. 51, 1419. « A. 411, 339. ' M. 23, 688.
270 ANTHRACENE AND ANTHRAQUINONE
of piirpurin in alkaline solution by li5^drogen peroxide in
the presence of a cobalt catalyst leads to 2-liydroxy-3-acet3-l-
1.4-naplithoquinone, a change which they explain by a
similar series of reactions to those just given.
Wolft'enstein and Paar 1 have studied the action of
boiling nitric acid on anthraflavic acid, 1.7-dihydroxy-
anthraquinone and anthrarufin. The first action of the
nitric acid is to nitrate the hydrox3^anthraquinone, but
further action leads to the rupture of the central ring and
formation of 3.5-dih3^drox3^-2.4.6-trinitrobenzoic acid.
The hydroxyanthraquinones in many cases combine
with formaldehyde to yield h5^droxyanthraquiaonyl carbinols,
and in this way resemble the ordinary phenols. Thus
anthrachrj'sazin 2 combines very readily with formaldehyde
to form a dicarbinol (I), which in turn will combine with
tertiary aromatic amines, ^ such as dimethyl aniline, to
produce compounds such as II, or with ammonia or with a
primary or secondar^^ aliphatic amine ^ or a primary
aromatic amine ^ to produce such compounds as III :
OH OH
HO CH5OH HO CHoCeH^NRa
HOCH
HO
OH
R2NC6H4CH2
HO
OH
I.
II.
OH
HO CHoNHAr
I
ArNHCH^
HO
III.
OH
Attention has already been drawn to the acet5^1ation of
hydroxyanthraquinones by means of acetic anhj'dride and
1 B. 46, 586. ■ B.A.S.F., D.R.P. 192,484. M.L.B.. D.R.P. 184,768.
3 M.L.B., D.R.P. 184,807; 188,597. * M.L.B., D.R.P. 188,189.
•■* M.L.B., D.R.P. 184,808; 188,596.
THE HYDROXY COMPOUNDS 271
pyridine, I but it ma}^ here be remarked that benzoylation
can often be effected by heating at atmospheric pressure
with 10-15 parts of benzoic acid with or without the addition
of concentrated sulphuric acid, thus avoiding the use of
benzo}'! chloride. 2 It is claimed that /3-hydroxy-anthra-
quinone, anthraflavic acid, flavopurjnirin and anthra-
purpurin are especially easily benzoylated by this method.
The reduction of the hydroxj^anthraquinones to the
corresponding anthranols can be brought about in the usual
way, although, as pointed out on p. 264, there is always a
danger of partial dehydrox^-lation taking place simulta-
neously. Reduction can also be effected by means of zinc
dust and acid,^ and some of the hydroxy- anthranols have
been recommended as valuable remedies for psoriasis and
other skin diseases.
TiNCTORiAi, Properties
The absorption spectra of the h^'droxj-anthraquinones
in alkaline and in concentrated sidphuric acid has been
already discussed, and it need only be added that Meek and
Watson 4 have measured the coefficient of absorption of
light of various wave-lengths when reflected from fabric
dyed with several of the more important hydrox^^anthra-
quinones on various mordants. Georgievics » has discussed
the position of hydrox}l groups in relation to the shade of
the dye and has come to the general conclusion that hydroxyl
groups in the a- position tend to produce red or blue shades,
whereas hydroxyl groups in j3- positions favour the pro-
duction of 3-ellows and browns, although too much reliance
must not be placed on these conclusions, as one group may
mask the effect of another. These conclusions have been
criticised by Meek and Watson, ^ who consider that they have
sufficient evidence to support the following conclusions : —
(a) Two homonuclear hydrox\'l groups in the ofiJio- or
1 Page 237. a Wed., D.R.P. 297,261.
3 By.. D.R.P. 296,091 ; 301,452 ; 305.886. ♦ Soc. 109, 545.
^ M. 32, 329. « Soc. 109, 545.
272 ANTHRACENE AND ANTHRAQUINONE
para- positions to one another are necessary in order to
deepen the colour, i.e. to produce reds, violets, or blues,
[h) If both rings contain such pairs of hydroxyl groups,
each pair reinforces the effect of the other.
(c) Three hydroxyl groups at i, 2, and 4 produce a greater
effect than a pair in the ortho- or para- positions to one
another. •
Id) Three hydroxyl groups at i, 2, and 3 produce a
brown.
The connection between the position of the hj^droxj^l
groups and the capacity of a h3'drox3'anthraquinone to form
a lake is quite obscure, and is likel}- to remain so until some
satisfactory^ definition as to the meaning of " mordant d^-e "
is evolved. The old rule (Rule of Kostanecki and Lieber-
mann) that two hydroxyl groups in the " alizarin position,"
i.e. at I and 2, are necessary in order to produce a mordant
dye is certainly not a law of nature, although for a matter
of fact aU the hydrox5'anthraquinones which have proved
to be of commercial value have such hydrox}^ groups.
Alizarin itself is a powerful mordant dye, but quinizarin,
hystazarin and xanthopurpurin all have marked tinctorial
properties, and the other dihydroxyanthraquinones, and
even the monoh5'droxy compounds, have slight capacity for
forming lakes. 1
Increase in the number of hydrox>-l groups does not
necessaril}^ increase tinctorial properties, as although quini-
zarin is a comparatively powerful mordant dye, 1.4.5.8-
tetrahydroxj^anthraquinone has no capacity for formmg
lakes 2 except, curiously enough, on a beryllium mordant, ^
and octah3^drox>'-anthraquinone has very feeble tinctorial
properties. The presence of other groups or atoms in the
molecule also affects the capacity for forming lakes, as
although rufigaUol itself is a VQ.ry feeble mordant dye its
affinity is very greatly enhanced by halogenating.*
1 Georgievics, F.T. 1, 623. 2 Georgievics, F.T. 4, 185.
3 Georgievics; Grand mougin, " Lelirbuch der Farbenchemie," fourth
edition, p. 257.
«|By., D.R.P. 114,263. Cf. also L. B. Hollidav & Co., Ltd., and
H. D. Law. E.P. 126,52818.
THE HYDROXY COMPOUNDS 273
The constitution of the lakes formed by the hydroxy-
anthraquinones and, for example, the exact fmiction of the
lime and Turkey red oil used in alizarin dyeing, has never
been properly cleared up, although there is no doubt that
the usual alumina lake is a complex aluminium calcium
salt.i
For further information as to theories of lake formation
the reader is referred to the original literature, 2 a good
review of the subject having been recently published by
Scholl and Zinke.^
Halogenation
A considerable amount of work on the halogenation of
the hydrox}'anthraquinones has been recorded, but as in a
great mam- cases the positions of the halogen atoms in the
product have not been determined, it is difficult to detect
with certainty an}^ rules relating to the directmg influence
exerted by the hydroxjd groups, although from the data
available one or two conclusions can be drawn.
When h3^droxyl groups are present only in a- positions
the entering halogen atom is first directed to the para-
position, the second atom entering taking the ortho- position.
Thus er\' throh3'drox3-anthraquinone when treated with mole-
cular or nascent halogen {e.g. NaBr04+HBr) gives first
4-brom-i -hydroxy anthraquinone and then 2.4-dibrom-i-
hydroxj-anthraquinone,"* and anthrarufin and chrysazin
behave in the same wa}'.^ The bromination can be carried
out in boiling glacial acetic acid solution, but unless sodium
acetate is added the reaction is ver}^ slow. In the presence
of sodium acetate, however, the reaction is rapid and the
bromo- compound cr^'stallizes out on cooling. ^ The reaction
can also be convenient!}- carried out by suspending the
1 Mohlau, B. 46, 443. Wieland and Binder, B. 47, 977.
- Soc. 75, 433 ; 83, 129. J.S.C.I. 22, 600. A. 398, 151. B. 41, 1002,
3469 ; 44, 2653 ; 45, 148, III6; 47, 738, 977. F.T. 1. 624 ; 3, 366 ; 4. 186.
3 B. 51. 1419-1428.
' By., D.R.P, 127,532 ; 1^1,403. Wed., D.R.P, 202,770, Cf. Eckert
and Steincr, M. 35, 1144.
^ Schrobsdorf, B. 35, 2930. By., D.R.P. 127,699 ; 197,082.
* Friess and Schiirmaun. B. 52, 2182.
18
274 ANTHRACENE AND ANTHRAQUINONE
hydroxy compound in boiling dilute sulphuric acid (45-50
per cent, strength) at 140° and then treating with molecular
chlorine or bromine,! and in many cases molecular halogen
can be used in aqueous solution 2 at the ordinar}^ temperature
or at 100°. Krythrohydroxyanthraquinone, anthrarufin, and
chr^^sazin have all been chlorinated and brominated by
these methods, but the claim that chrj^sazin is chlorinated in
aqueous suspension has been contradicted, ^ although it is
said to yield a dichlor compound with great ease if sufficient
sulphuric acid is added to raise the boiling point to 120-
140°.
Chlorination can also be effected convenient^ by heating
with sulphuryl chloride in nitrobenzene solution, er^^thro-
hydroxyanthraquinone being readily converted by this means
into I -hydroxy -4-chloranthraquinone and i-hydroxy-2.4-
dichloranthr aquinone . *
In the case of quinizarin, in which there is no vacant
para- position, chlorination in glacial acetic acid ^ leads to
3-chlorquinizarin, the same product being obtained by the
action of hydrochloric acid on i.4.9.io-anthradiqumone.6
Comparatively little work has been done on the chlorina-
tion and bromination of hydroxyanthraquinones in which
hydroxyl groups are only present in the j8- positions. It is
claimed that j3-hydroxyanthraquinone and anthraflavic acid
are readily brominated by the action of molecular bromine
on their aqueous suspensions, and that the bromme atoms
hrst attack those j3- positions which are contiguous to the
hydroxyl groups, no a- position being entered until all
such j3- positions have been occupied.' Anthraflavic acid
is not chlorinated in aqueous suspension at 100°, but if
sulphuric acid is added so as to raise the boHing point a
dichlor compound is formed. ^ The melting point of this
compoimd and also the melting points of its acet}'l and
benzoyl derivatives agree with those of the dichlor compound
1 By., D.R.P. 197,082. Wed., D.R.P. 167,743 ; 172,300.
2 By., D.R.P. 127,699. 3 Wed., D.R.P. 172,300.
* Ullmann and Conzetti, B. 53, 829. ^ Bv., D.R.P. 114,199.
« Diraroth and Schiilze. A. 411, 348. ' Wed., D.R.P. 175,663.
8 Wed., D.R.P. 187,685.
THE HYDROXY COMPOUNDS 275
obtained by the action of sodium hypoclilorite on anthra-
flavic acid, but their sohibilities are different and their
identity is questionable. If the chlorination of anthraflavic
acid is carried out in suspension in calcium chloride solution
a totally different reaction takes place, as under these
conditions a hexachlor addition product is obtained. ^
This is resiniiied by treatment with alkali, but when heated
with an inert solvent of high boiling point a trichlor-
anthraflavic acid is obtained. 2
But little work has been recorded concerning the be-
haviour of hystazarin when halogenated, but Schrobsdorff,-"^
by heating it to 140° with bromine in a sealed tube, obtained
a dibromo compound, but did not determine the positions
of the bromine atoms.
Although a-hydroxyanthraquinones are usually com-
pletely destroyed by hypochlorites, the j8-hydroxy compoimds
are often easily and smoothly chlorinated by the action of
sodium hypochlorite on their alkaline solutions. B}^ this
means Decker and Laube ^ obtained 2-hydrox3'-i-chlor-
anthraquinone from j3-hydrox3'anthraquinone, and it has
been claimed that the action of hypochlorite often leads to
the entrance of one, two, or three chlorine atoms into the
molecule. 5 The reaction seems to be restrained by alkali,
and in the presence of excess of alkali as a rule only one
chlorine atom is taken up.
In the case of h^-drox^-anthraquinones, in which hydroxyl
groups are present both in a- positions and in j3- positions,
the behaviour on halogenation becomes complicated and
seems to depend on which hydrox}d groups have the pre-
dominathig influence in the molecule, but the data available
are too scanty to permit the detection of regularities.
Flavopurpurin and anthrapurpurin are readily brominated
in aqueous suspension, ^ the bromine entering the vacant
/3- positions, and aqueous suspensions of flavopurpurin
when treated with sodium chlorate and hydrochloric acid
give a monoclilor derivative, the position of the chlorine
1 Wed., D.R.P, 179,916. - Wed., D.R.P. 181,659.
3 B. 36, 29:58. * B. 39, 112.
^ Wed.. D.R.P. 152.175 ; 153.194. ' Wed., D.R.P. 175.663.
276 ANTHRACENE AND ANTHRAQUINONE
being unknown, i Xanthopurpurin when brominated also
gives a dibromo compound which is probably i.3-dihydrox3-
2.4-dibronianthraquinone.2 The chlorination of 1.7- di-
hydroxyanthraquinone can be effected b}' sodium hypo-
chlorite, but the reaction proceeds with difficult}^ and onty
one chlorine atom is taken up.^ The chlorination of aUzarin
in aqueous suspension b}^ sodium chlorate and hydrochloric
acid leads to 3-chloralizarin/i
The bromination of hydrox5"anthraquinones such as
alizarin, anthrapurpurin and flavopurpurin is often very
greatly facilitated by first reducing to the corresponding
anthranol and then treating this with bromine. Under these
conditions the bromine both enters the nucleus and also
becomes attached to the ^;?s-carbon atoms ; but subsequent
oxidation leads to the brominated hydroxyanthraquinone,
e.g. monobromalizarin.^
One of the most convenient methods of chlorinating the
hydrox^^anthraquinones is to treat them with sulphur^-l
chloride. The reaction takes place quite readily by heating
the h3^drox}^anthraquinone on the water bath with sulphured
chloride in nitrobenzene solution, and is facilitated by the
presence of a trace of iodine. The method was first described
by Ullmann,6 who by this means obtained 4-chlorerythro-
hydrox>'^anthraquinone and 5.8-dichloranthrarufin, and has
been extended b}^ L. B. Hollida}^ and Co., Ltd., to various
polyhydroxj^anthraquinones such as alizarin, anthraflavic
acid, iso- anthraflavic acid. Alizarin Bordeaux, etc. Ap-
parently under some conditions one or more of the hydroxj-l
groups is simultaneously replaced by chlorine.'^
SUI^PHONATION
Comparative!}^ little reliable information is available
concerning the sulphonation products of the hydroxy-
anthraquinones, but it has been claimed that a-hj-droxy
1 Wed., D.R.P. 189,937. ' Plath, B. 9, 1204.
3 Wed., D.R.P. 152,175 ; 153,194. * Wed., D.R.P. 189,937.
5 B)'., D.R.P. 117,923. « D.R.P. 282,494.
" L. B. HolUday and Co., Ltd., and H. D. Law. E.P. 126,727-8".
THE HYDROXY COMPOUNDS 277
compounds sulphonate in the j3- position, and that further
sulphonation then leads to aj3-polyhydrox}'authraquinones.i
Anthraruiin, for example, gives anthrarufin-2.6-disulphouic
acid 2 and chr>^sazin gives chrysazin-2.7-disulphonic acid.^
Wolbling,-* on the other hand, by sulphonating chr}-sazin
obtained a disulphonic acid from which a tetrahydroxy-
authraquinone was obtained, which may or may not be
identical with the i.2.7.8-tetrah3-drox>'anthraquinone de-
scribed in the patent literature.^ They are both stated to
give blue solutions in caustic soda, but whereas Wdlblmg
characterises his product by its melting point and that of its
acetyl derivative, the patentees confine themselves to
describing the colour of its solutions in various solvents and
its tinctorial properties, points concerning which Wolblmg
gives no information except in so far as the blue solution in
caustic soda is concerned. In connection with this it should
be noted that simultaneously with Wolbling, Schrobsdorf <*
described a dibromchr>'sazin which yielded a tetrahydrox>--
anthraquinone which one would expect to be 1.4.5.8-tetra-
hydrox)'anthraquinone, but which differs widely from this
substance in its properties,'^ and also cannot be 1.2.7.8-
tetrahydrox^-anthraquinone ^ or i.2.5.8-tetrah3'drox3'anthra-
quinone (quinalizarin),^ although it is conceivable that
either of these might have been formed. As Schrobsdorf
and Wolbling both carried out their work in the same
laboratory at the same period, it is fair to assume that they
both used the same sample of chr^'sazin, so that any error
arising from their starting-out substance would vitiate both
their results.
The sulphonation of anthraflavic acid ^^ and iso-anthra-
flavic acid ^^ and their methyl ethers 12 also appears to lead
to the entrance of sulphonic acid groups into the j3- positions.
1 By., D.R.P. 141,296. 2 Bv., D.R.P. 96,364.
3 By., D.R.P. 100,136. * B' 36, 2941.
s By., D.R.P. 103,988. « B. 36, 2936.
' B., D.R.P. 125,579 ; 143.804. 8 By.. D.R.P. 103,988.
» Bv., D.R.P. 60,855. 10 M.L.B., D.R.P. 99,6ii ; 99.874-
11 bV., D.R.P. 104,317. M.L.B., D.R.P. 99,612.
12 M.L.B., D.R.P. 143,858. Cf. also M.L.B., D.R.P. 139.425 (sulphona-
tion of anthrachrj'sazin dimethylether).
278 ANTHRACENE AND ANTHRAQUINONE
In the case of 1.4.5- and i.4.6-trih3''droxyanthraqumone
sulphonation under ordinary conditions leads to impure
mixtures, but in each case if the sulphonation is carried out
in the presence of boric acid a single stilphonic acid group
enters at 7.1
On account of its technical importance the sulphonation
of alizarin has attracted considerable attentioti, sulphonation
with oleum leading to alizarin-3-sulphonic acid 2 (Alizarin
Red vS), alizarin-6- and -7-sulphonic acids being only obtain-
able from antliraquinone disulphonic acids by fusion with
caustic potash under suitable conditions. ^ Further sulpho-
nation of alizarin-3-sulphonic acid leads to disiilphonic
acids, 4 from which, however, one sulphonic acid group can
be split off by subsequent hydrolysis at 190° with sulphuric
acid of 80 per cent, strength. ^
When alizarin is sulphonated in the presence of mercur\'
the products obtained are not the same as those which are
formed in the absence of mercury. Both alizarin and alizarin-
3-sulphonic acid when sidphonated in the presence of mercury
give a mixture of alizarin-3.5- and alizarin-3.8-disulphonic
acid, and as purpurin behaves in a similar way it must be
concluded that as a rule a hydroxyl group in a ring directs
to the j8- position more powerfully than the mercur>' directs
to the a- position ; but in the ring free from hydroxyl groups
the mercury exerts its usual influence. ^ Both these di-
sulphonic acids also lose one sulphonic acid group when
heated to 180-190° with sulphuric acid of about 80 per
cent, strength,*^ alizarin thus yielding alizarin-5- and alizarin
8-sulphonic acids, and purpurin yielding purpurin-8-sulphonic
acid.
Dihydroxyanthraquinones such as quinizarin in which
the hydroxyl groups are in the para- position to one another
1 By., D.R.P. 165,860.
2 Graebe and Liebermann. A. 160, 144. Graebe, B. 12, 571. Perger,
J. pr. [2] 18, 173. Pryzbram and Co., D.R.P. 3,565-
^ See p. 241.
^ By., D.R.P. 56,952.
5 By.. D.R.P. 56.951-
6 Wed.. D.R.P. 205.965 ; 210,863.
• By.. D.R.P. 172,688. Wed., D.R.P. 210.863. Cf. By., D.R.P.
160,104.
THE HYDROXY COMPOUNDS 279
can also be siilphonated by heating with solutions of
sulphites. 1 In this case the reaction is no doubt due to
oxidation to the anthradiquinone, followed by the addition
of sodium sulphite, and as would be expected takes place
most rapidly in the presence of an oxidising agent such as
manganese dioxide. In the absence of an oxidising agent
the necessary'- oxidation is brought about by the partial
reduction of the cyclic carbonyl groups. The 1.4-hydroxy-
aminoanthraquinones and the 1.4-diaminoanthraquinones
are sulphonated in the same way, the intermediate product
in these cases being the quinone imidc or di-imide.
Only a few hydroxj-anthraquinone sulphonic acids have
found application as dyes, as the presence of the sulphonic
acid group tends to decrease the fastness of the shades to
washing. The best known are Alizarin Red vS (alizarin-3-
sulphonic acid), which gives scarlet shades on an alumina
mordant and is also used to a certain extent in the laboratory
as an indicator, and Erweco Alizarin Acid Red BS, which is a
mixture of alizarin-5- and alizarin-8-sulphonic acids and
gives bordeaux shade on both chrome and alumina. Flavo-
purpurin-3-sulphonic acid is used to a small extent under the
names Alizarin Red 3WS or SSS, and gives brownish-red
shades on alumina. The disulphonic acid of 1.2.4.5.6.8-
hexahj'-droxyanthraquinone (Anthracene Blue WR) is ob-
tained by the action of oleum on 1.5-dinitroanthraquinone,
the subsequent hydrolysis being omitted. It has received
several trade names, such as Acid Alizarin Blue BB, Alizarin
Cyanme WRS, BBS, and 3RS, and Anthracene Blue SWX.
Nitration
The liydrox3'anthraquinones being much more stable
than the phenols can often be fairly easily nitrated without
protecting the hydroxyl groups, but under these conditions
there is always considerable chance of simultaneous
hydroxylation taking place, e.g. both alizarin and quini-
zarin give 3-nitropurpurin. Protection of the hydrox^-l
» By.. D.R.P. 287,867 ; 288,474; 289,112.
28o ANTHRACENE AND ANTHRAQUINONE
group greatly lessens the danger of simultaneous li3^drox}'la-
tion ; but, on the other hand, the directing influence of a
protected group is often quite different from that of a free
h3''drox34 group, and to some extent depends on how the
protection is effected.
When h^'^drox}^ groups are present only^ in a- positions
the}^ direct entering nitro groups to the para- position, but
the oHho- position is also readil}- taken, so that there is
usually no difficult}^ in inserting two nitro groups for each
h3'droxyl group present. Er^^throhydrox^-anthraquinone,
anthrarufin, and chr>'sazin i are fairly easily nitrated in the
free state, although much purer products are obtained b}-
nitrating the boric esters, 2 and the nitration and subsequent
demethylation of chr>^sazin dimeth^^l ether has been recom-
mended as the best method of obtaining mononitrochr3-sazin.3
In the case of quinizarin the nitration is somewhat more
troublesome owing to the tendenc}' to form nitropurpurin,
and in this case the boric ester method fails. B}^ nitrating
in an organic solvent, however, such as glacial acetic acid or
nitrobenzene, quinizarin can be converted into 2-nitroquini-
zarm.4
When h3'drox3'l groups are present only in the ^- position
the entering nitro groups take the ortho- positions to them, a-
positions usualty being preferred to j3- positions. ^-TLydio-xy-
anthraquinone itself readil)^ gives a dinitro compound, ^ the
position of the nitro groups being proved by its conversion
into anthragallol. Anthraflavic acid ^ and jso-anthraflavic
acid '^ give both dinitro and tetranitro compoimds, and
h3^stazarin gives a mono and a dinitro compound, ^ both of
these latter giving phthalic acid when oxidised.
As would be expected from its technical importance, the
nitration of alizarin has received most attention. If alizarin
1 By., D.R.P. 98,639.
^ Eckert and Steiner, M. 35, 1144. Bv., D.R.P. 163,042.
3 M.L.B., D.R.P. 193,104.
« By., D.R.P. 272,299.
^ Liebermann and Simon, A. 212, 25, 53. B. 14, 464 ; 15, 692. Simon,
D.R.P. 119,755.
« Schardinger, B. 8, 1487. M.L.B., D.R.P. 112,179.
' Romer and Sclnvazer, B. 15, 1040.
8 Schrobsdorf, B. 36, 2938.
THE HYDROXY COMPOUNDS 281
itself is nitrated in ordinary concentrated sulphuric acid
solution a mixture of 3-nitroalizarin, purpuriu, and 3-nitro-
purpurin is obtained owing to simultaneous liydrox^-lation
taking place. ^ If, however, the boric ester of alizarin is
nitrated, i.e. if nitric acid is added to a solution of alizarin
in concentrated sulphuric acid containing an excess of
boric acid, the side reactions are to a large extent avoided
and almost pure 3-nitroalizarin results. 2 The same com-
pound is also obtained by nitrating alizarin when dissolved
or suspended in some suitable solvent such as ligroin,
toluene, nitrobenzene, or, best of all, glacial acetic acid,
and also b}' the action of nitrous acid on alizarin, 3 although
the action of nitrous acid in concentrated sulphuric acid
solution leads to 7-nitroalizarin.^
If the diacetyl derivative of alizarin is nitrated the nitro
group enters a different position, and 4-nitroalizarin is
obtained,^ but the nitration is rather troublesome to carry
out, as the acetyl groups are readUy lost by hydrolysis
during the nitration, and for this reason it is better to use
the dibenzoyl derivative,^ the subsequent hydrolysis being
ven- readily effected b}' cold caustic soda. This method
has also been extended to the nitration of other hydroxy-
anthraquinones such as anthrapurpurin, flavopurpurin,''
etc. Instead of protecting the hj^droxyl groups by forming
an ester with an organic acid, the sulphate ^ or arsenate ^
can be used, i.e. the alizarin can be nitrated when dissolved
in oleum of 20 per cent, strength at —5° to —10°, or when
dissolved in concentrated sulphuric acid in the presence of
arsenic acid below 0°. It is ver}^ remarkable that whereas
the nitration ot the sulphate or arsenate gives 4-nitroalizarin,
1 Schunck and Romer, B. 12, 583. M.L.B., D.R.P. 150.322. Cf. also
By., D.R.P. 50,164 ; 50,708.
■ "- By., D.R.P. 74.562.
3 Caro, B. 10, 1760; 12, 1008. Rosenthiel, C. r. 82, 1455 ; 83, 73.
Ann. [5] 12, 519. B. 9, 1036. Cf. also Strobel, Mon. Sci. 1878, 1337.
B. 12. 584.
* Grawitz, B. 10, 1165. Xaro, Mon. Sci. 1879, 424. Girard and Pabst,
C. r. 91, 570.
* Perkin, Soc. 2, 578 ; B. 8, 780. Caro, A. 201, ^=53.
« M.L.B., D.R.P. 66,Sii. ' xM.L.B., D.i^.P. 70,515 ; 74,212.
« M.L.B.. D.R.P. 74,431. » By., D.R.P. 74,598.
282 ANTHRACENE AND ANTHRAQUINONE
the nitration of the borate gives the isomeric j3-nitroaHzarin,
but other hydrox^^aiithraquinones such as flavopurpurin,
anthrapurpurin, and AHzarin Bordeaux exhibit the same
peculiarity. The a-nitro compound is also formed when
alizarin monomethjd ether is nitrated, i although as already
stated alizarin itself yields the ^-isomer.
Xanthopurpurin is fairly easily nitrated to a dinitro
compoimd,2 and anthrachrj'sazin is easil}- and quantitatively
converted into a tetranitro compound. ^
It is worth observing that methyl ethers are often de-
methylated during nitration, especially when the methoxy
group is in the a- position. Thus O. Fischer and Ziegier ^
found that i-methyl-4-niethox5'anthraquinone when gently
warmed with excess of nitric acid of 70 per cent, strength
gave a mononitro methyl hydroxy anthraquinone, although
they did not determine the position of the nitro- group.
The chief technical interest in the nitroalizarins lies in
the fact that they are intermediate products for the pro-
duction of the important h3^drox3^antliraquinone quinolines
(hydroxy pyridino anthraquinones) , but 3-nitroalizarm is
used to a considerable extent as a d5^e under the name
Alizarin Orange A, W, SW, Cy, etc. It gives orange shades
in both chrome and alumina mordants.
II. Aminohydroxy Compounds
When 1.5-dinitroanthraquinone is reduced in alkaline
solution a bishydroxylamine derivative is formed, which
under the influence of acids is at once rearranged into
4.8-diaminoanthrarulin,5 the same product being obtained
by oxidising 1.5-diaminoanthraqumone with manganese
dioxide, etc., in concentrated sulphuric acid solution.^
This diaminoanthrarufin has scarcely any tinctorial pro-
perties, but these are very greatly increased by the entrance
of negative groups or atoms such as sulphonic acid groups
1 M.L.B., D.R.P. 150,322. 2 Plath, B. 9, 1204.
» M.L.B., D.R.P. 73,605, * J. pr. [2] 86, 292.
^ By., D.R.P. 81,694. 0 By., D.R.P. 106,034.
THE AMINOHYDROXY COMPOUNDS 283
or bromine atoms. ^ The bromo compounds are of but little
importance, although it is worth remarking that the entrance
of bromine into the molecule is accompanied by an increase
in solubilit}^ a phenomenon not infrequently met with in
the anthraquinone series. The diaminoanthrarufin sulphonic
acids, especially 4.8-diaminoanthrarufin-2.6-disulphonic acid,
have met with wide application as acid wool dyes under the
name Alizarin Saphirol 2 and give reddish-blue shades which
become greener and duller when chromed.
If anthraruhn is sulphonated by treatment with oleum
the 2.6-disulphonic acid is obtained. This on nitration
gives the 4.8-dinitro compound from which the dj-e is formed
b}^ reduction, 3 but if the reduction is pushed too far one
sulphonic acid group is split off.4 Alizarin Saphirol is also
obtained direct from dinitroanthrarufin by heating on the
water bath with aqueous solutions of alkali sulphites or
bisulphites. 5 Here simultaneous reduction and sulphona-
tion takes place, a reaction which is very common in the
aromatic series, and this is probably the most convenient
method of obtaining the dye. Of lesser interest is its forma-
tion by the action of a sulphite on dibromdinitroanthrarufin,
the sulphite reducing the nitro group and at the same time
replacing the bromine atoms by sulphonic acid groups, ^
and from dibromanthrarufindisulphonic acid by heating
with ammonia and a copper catatyst.'^ The dye can also
be obtained by oxidising diaminoanthrarufin disulphonic
acid with manganese dioxide and concentrated sulphuric
acid, 8 and by the reduction of the quinoneimide sulphonic
acid obtained by the action of oleum and sulphur on 1.5-
dinitroanthraquinone.9
An isomer of Alizarin Saphirol is obtained from chrysaziu
either by sulphonation, nitration, and reduction, ^o or by
heating dinitrochrysazin with sulphites or bisulphites, ^ 1 or
> By., D.R.P. 102,532. 2 Solway Blue (Scottish Dyes, Ltd.).
' By., D.R.P. 96,364 ; 100,137; 105,501; 108,362; 119,228.
* By., D.R.P. 108.578. 6 By., D.R.P. 103,395.
« By., D.R.P. 163,647. " By., D.R.P. 195.139.
« By., D.R.P. 106,034.
» By.. D.R.P. 113,724; 116,746. See also p. 245.
»» By., D.R.P. 100,136. " By.. D.R.P. 103,395.
284 ANTHRACENE AND ANTHRAQUINONE
by heating dinitrodibromchrysazin witli a sulphite. ^ It
dyes in rather greener shades than Alizarin Saphirol itself.
Isomers are also obtained by successive sulphonation, nitra-
tion and reduction of anthraflavic acid 2 and «so-anthraflavic
acid, 3 that from anthraflavic acid giving fiery red shades and
that from ^'so-anthraflavic acid giving 3^ellowish-red shades.
The formulae of the various dyes are * :—
NH2 OH
HO OH
NH2
NH. NHo
s
S
s
s
OH
HO
OH
!
1
1
1
S
HO
S
S
S
OH NH2
NH2 NH2
NH2
Alizar
From
Red
s]
in Sa
anth
Idish
tiade
Lphirol.
irarufin.
-blue
s.
From
Gre
Alizai
chr
ener
inS;
^'sazin.
than
iphirol.
From anthraflavic
acid.
Fiery red shades,
bordeaux on
chrome.
From Mo-anthra
flavic acid.
Yellowish-red
shades.
Bordeaux on
chrome.
In addition to Alizarin Saphirol one or two hj'drox}--
aminoanthraquinones have found technical application as
dyes. Of these may be mentioned 4-aminoalizarin
(Alizarin Garnet R, Alizarin Cardinal) which is obtained by
the reduction of 4-nitroalizarin,4 and gives bluish-red
tones on an alumina mordant. The corresponding 3-amino-
alizarin (Alizarin Maroon W) is used to a small extent in
printing, but is of very minor importance. It gives rather
loose shades of red on an alumina mordant. Alizarin
Cyanine G and New Anthracene Blue WR may possibly be
hydroxyimino compounds, although they are more probably
imides. The former is obtained b}^ heating Alizarin C^^anine
R with ammonia,^ the latter by heating Anthracene Blue
with ammonia and caustic soda.^ Both give blue shades
on alumina.
The other hydroxj^aminoanthraquinones which are of
1 By., D.R.P. 163,647. 2 M.L.B., D.R.P. 99,611 ; 99,874.
' M.L.B., D.R.P. 99,612. * S = SO,H.
* By.. D.R.P. 66,8x1. ^ gy^ D.R.P. 62,019,
« B.A.S.F., D.R.P. 119,959.
THE ETHERS 285
technical importance are chiefly secondary amino compounds
and are mentioned in Chapter XI.
III. The Ethers
As already stated hydroxjl groups when in the /3- position
are readily alkylated by heating with the alkyl iodide or
dimethyl sulphate and caustic potash in alcoholic or aqueous
alcoholic solution. ^ In the case of a-h3'drox3d compounds,
however, this method fails, and although Plath 2 claimed to
have obtained dimethyl and diethyl ethers of xanthopuqourin
it is fairly certain that he really obtained only the mono-
methjd and monoetltyl ethers. Methylation of a-hydroxy
compomids, however, can be effected by heating the dry
potassium salts with dimethyl sulphate, ^ and in many cases
the alk>dation can be brought about without difficulty by
first reducing the hydrox}-anthraquuione to the anthrone.^
These are usually easil}- alk3dated and the restdting ether
can then be oxidised to the anthraquinone. The method
fails, however, when there are h3'drox3d groups m the
ortho- position to both C5-c]ic carbonyl groups. In spite of
the weU-known difficult}- in alkylating hydrox}'l groups
when in the a- position, it has been claimed that a cyclic
ether is formed when alizarin is heated with ethylene
dichloride or ethylene dibromide and sodium acetate, with
or without the addition of a catalyst such as copper.^ This
compotmd has been assigned the structure :
CHz
Oi^CHt
0
but this can only be accepted with reserve pending further
conlirmation.
1 Graebe, A. 349, 201. Graebe and Aders, A. 318, 369. M.L.B.,
D.R.P. 158,277.
2 B. 9, 1205.
' O. Fischer and Gross, J. pr. [2] 84, 372. O. Fischer and Ziegler,
J. pr. [2] 86, 297- M.L.B., D.R.P. 242,379.
* Graebe. A. 349, 201 ; B. 38. 152. ^ M.L.B.. D.R.P. 280,975.
286 ANTHRACENE AND ANTHRAQUINONE
But little work has been done on the direct arylation of
hydrox>^anthraquinones, although it has been claimed ^
that hydrox>4 groups in the a- position are readily arylated
when the alkali salt is heated with an alkyl ester of an
aryl sulphonic acid, with or without the addition of a basic
substance.
Dianthraquinonyl ethers are obtained by condensing a
halogen anthraquinone with a hydroxy anthraquinone by
heating in an inert solvent such as nitrobenzene with sodium
acetate and a copper catalyst. 2 The patent does not
state whether the reaction is confined to /3-hydroxy com-
pounds, although this is probably the case. From i-chlor-
2-hydroxyanthraquinone and similar compounds cyclic
ethers are said to be obtained. 3 These have the structure —
/0\
and are yellow vat dyes although apparently of no technical
value. In their formation an a-halogen atom reacts with
a jS-hydroxyl group so that aj8-dianthraquinonyl ethers
would seem obtainable by this method. It is very improb-
able, however, that an a-halogen atom would react with
an a-hydrox}d group to produce an aa-dianthraquinonyl
ether.
Cyclic dianthraquinonyl ethers are also formed from
02-dihydrox>"dianthraquinonyl compounds by heating with
condensing agents such as zinc chloride.* Here loss of water
takes place between two hydroxyl groups with the formation
of a furfurane ring :
i M.L.B.. D.R.P. 243,649.
2 M.L.B. 216,268.
^ Wed., D.R.P. 257,832 ; 263,621; 265,647; 269,215.
^ Scholl, D.R.P. 274,783.
THE ETHERS
287
OH HO
^0\
According to one patent specification ^ when qiiinizarin
is heated to about 120° with a salt of a weak acid such as
a carbonate, borate, phosphate, or acetate, it is converted
into two compounds. These are present in the melt more or
less as reduction products, and the patent suggests that they
are formed by the union of two molecules by self -oxidation
at the expense of the cyclic carbonyl groups. If this is the
case they ma}- or may not be ethers. The analytical figures
given agree with the formulae C28H14O8 and C28H13O8.
Both substances give blue alkali salts.
Both alkyl and aryl ethers can be obtained directly by
the replacement of halogen atoms, 2 or svdphonic acid
groups, 3 or nitro- groups. ^ The alkyl ethers are obtained
by heating with a solution of caustic potash in the alcohol
or with an alcoholic solution of the alkali alcoholate, and in
the case of nitro- compounds it is very desirable to exclude
all moisture, as otherwise simultaneous reduction takes place.
The ar3'l ethers are formed by heating with the alkali pheno-
late in alcohol or in some indifferent solvent of high boiling
point, such as the phenol. The addition of a catalyst such
as copper or copper acetate is often advantageous. In the
case of halogen atoms and sulphonic acid groups the replace-
ment takes place most readily when the atom or group is
in the a- position, but in the case of nitro groups replacement
when in the j8- position is most easy.^ The reaction with
nitro compounds, however, although quite common, is by
no means a general one. 6
' By., D.R.P. 146.223.
2 Frey, B. 45, 1359. UUmann, B. 49, 2162 ; 21G8. By., D.R.P.
158,531 ; 229,316; 263,423.
3 R. E. Schmidt, B. 37, 10. Laube, B. 39, 2245. By.. D.R.P. 156,762 ;
158.531 ; 166,748.
« By., 75,054; 77.818; 145,188; 158,531- M.L.B., D.R.P. 15S.278 ;
167,699.
6 M.L.B., D.R.P. 167.699- « M.L.B., D.R.P. 158,278.
288 ANTHRACENE AND ANTHRAQUINONE
In some cases heating a nitroantliraqvdnone witli potas-
sium carbonate in nitrobenzene solution leads to a dianthra-
quinonyl ether. ^
No great interest attaches to the ethers as a class. They
are a great deal more easily hydrolysed than the phenolic
ethers of the benzene or naphthalene series, and hence their
formation is often a useful means of protecting hydrox)^
groups during nitration. On sulphonation the alkyl ethers
are dealkylated, but the ar>^l ethers are more stable and can
be sulphonated in the aryl group. ^
The methyl ethers of the a-hydroxyanthraquinones show
considerable tendency to form oxonium salts such as hydro-
bromides, zincibromides, and perchlorates.^ The hydro-
bromides, however, are unstable and readily imdergo
spontaneous demethylation.
1 Agfa, D.R.P. 283,482. 2 By., D.R.P. 164,129.
' O. Fischer and Ziegler, J. pr. [2] 86, 297.
CHAPTER XIII
PYRIDINE AND QUINOLINE
DERIVATIVES
Compounds containing both an anthracene or anthraquinone
residue and a pyridine ring can be conveniently divided
into two classes, viz. compounds in which the ms-carhon
atom of the anthracene residue forms part of the pyridine
ring, and compounds in which the pj-ridine ring is fused
into one of the benzene rings of the anthracene nucleus,
both w7s-carbon atoms remaining intact. Compounds of
the former class are very similar in structure to the
benzanthrenes and benzanthrones and are known as
pyridanthrenes and pyridanthrones —
CO
I (N).9-Pyridanthrene. i (N).9-Pryidanthrone.
Compounds of the latter class are similar in structure to the
benzanthracenes and benzanthraquinones and are known as
anthraquinolines (pyridinoanthracenes) and anthraquinone
quinolines (pyridinoanthraquinones) :
CO
CO
Anthraquinoline Anthraquinonequinoline
i(N).2-Pryidinoanthracene. i.2(N)-Pyridinoanthraquinone.
289
19
290 ANTHRACENE AND ANTHRAQUINONE
A third class of compound is also known in which two
anthracene residues are united by one or two pyridine rings.
In these each pyridine ring is present as a pyridanthrene
with reference to one anthracene nucleus, and as an anthra-
quinoline with reference to the other anthracene nucleus.
The most important compounds of this nature are the
pyranthridones and flavanthrones * :
CO
Pyranthridone.
CO
Flavanthrone.
I. The Pyridanthrones
When an a-acetylaminoanthraquinone is heated alone
at 200-280°, or when it is boiled with aqueous caustic
alkali, loss of water takes place with the formation of a
pyridanthrone : ^
or
A similar reaction is also brought about when the a-acetyl
amino compoimd is heated with a formate or acetate, 2 or
with an acid chloride such as sulphur>''l chloride or phos-
* Intheliteraturethetermusually employed is "flavanthrene." Owing
to the ketonic nature of the body the name should terminate in -one, and
consequently the word " flavanthrone " has been adopted in the sequel.
The term " flavanthrene " is reserved to denote the oxygen free reduction
product. Flavanthrone itself was originally known commercially as
Flavanthrene, spelt with a capital, but as the name has been altered to
Indanthrene Yellow G confusion will not arise on this score. See also
footnote on p. 342.
1 By., D.R.P. 185,548; 192,201; 199,713; 203,752. B.A.S.F., D.R.P.
212,204; 216,597. M.L.B., D.R.P. 280,190.
» B.A.S.F., D.R.P. 191,111 ; 192,970. By., D.R.P, 209,033.
PYRIDINE AND QUINOLINE DERIVATIVES 2qi
phorus oxycliloride.i lu a great many cases it is not
necessaty to isolate the acetyl derivative as pyridone
formation takes place simultaneously with acetylation
when an a-aminoanthraquinone is boiled with acetic anhy-
dride, 2 or is heated with acetic anhjdride and concentrated
sulphuric acid or oleum. ^
Several variations of the above method of forming
pyridanthrones have been described. Thus the a-amino-
anthraquinone can be condensed with one molecule of
diethyl malonate and the product then boiled with caustic
alkali.^ Under these conditions the pyridoneanthrone
carboxylic acid is first formed, but this readily passes into
the pyridanthrone itself by loss of carbon dioxide :
CO
Another variation consists in condensing an aryl sulphone
acetyl chloride of the type ArS02.CH2COCl with a primary
or secondary a-aminoanthraquinone and then boiling the
product with aqueous alcoholic alkali. f* Under these con-
ditions the ar\'lsulphone group is split off, and at the same
time the pyridine ring is closed, the product being a hyrlroxy-
pyridone anthrone :
ArSOjCHiCO
CO
NH
CO
Pyridoneanthronepyridinium chlorides are obtained when
a-chloracetylaminoanthraquinones are treated with pyridine,
formation of the pyridinium cHoride and of the pyridone
ring taking place simultaneously ^ ;
' B.A.S.F., D.R.P. 198.048. 2 By., D.R.P. 209,033.
3 B..\.S.F., D.R.P. 198,025 ; 200,015. * M.L.B., D.R.P. 250,885.
* M.L.B., D.R.P. 284,209. « By., D.R.P. 290,984.
292 ANTHRACENE AND ANTHRAQUINONE
9 '\
PhNCHz ^NH
CO
CO
Other tertiary bases behave in the same way..
The C-alkyl and aryl p^-ridanthrones can be obtainea by
condensing a primary a-aminoanthraquinone with a ketone
which has at least one methyl group directly attached to
the carbonyl group, ^ such as acetone, acetoacetic ester,
acetophenone, etc. When acetone itself is used the product
is Py.a-methyl-i(N).9-pyridanthrone :
The above methods of preparing the pyridanthrones
are of very general application and have been extended to
a-aminoindanthrones, a-aminodianthraquinonylamines 2 and
1.4-diaminoanthraquinone, although in this last case it is
not certain whether pyridanthrone formation takes place
with both amino groups. 3
It will be observed that the compoimds prepared from
primary aminoanthraquinones by all the above methods
except the last can be regarded either as pyridoneanth rones
or as hydroxypyridanthrones (see formulae on p. 290),
although those prepared from secondar}^ aminoanthra-
quinones must have the pyridone structure. Those prepared
from the primary aminoanthraquinones are probabty tauto-
meric, and react in the enolic form when treated with phos-
phorus pentachloride, passing under these conditions in
Py.a-chlor-i(N)-9-pyridanthrones.4 The Py-chlorpyrid-
anthrones are also readily obtained by chlorinating the
p3'ridanthrones.5 In them the chlorine atom is ver}'-
1 By., D.R.P. 185,548. 2 B.A.S.F., D.R.P., 198,025; 200 015.
» By., D.R.P. 185,548. « M.L.B., D.R.P. 256,297.
5 By., D.F.P. 264,010.
i
PYRIDINE AND QUINOLINE DERIVATIVES 293
reactive and is readily replaced b}' a hydrox>d group by
boiling with 10 per cent, alcoholic alkali, 1 and by an aryl-
aniino group by boiling with a primary aromatic amine. 2
The Bz-amino, alkylamino and arylaminopyridanthrones
and the Bz-anthraquinonylaminopyridanthrones are easily
obtained by the usual methods, e.g. by replacing negative
groups attached to the benzene rings by heating with
ammonia or with a primar}^ secondary amine, 3 or by
condensing a Bz. -halogen or Bz.-aminopyridanthrone with
halogen compounds or amino compounds. ^ Some of the
products thus obtained have been described as vat dyes
and their sulphonic acids as acid wool dyes,^ but they do
not seem to have found any technical application.
II. The Anthraouinone Quinounes
There are three possible anthraquinone quinolines
(pyridinoanthraquinones) viz. :
CO
CO N
N
i(N).2-Pyridinoanthra- 2.3-Pyridinoanthra- 2(N).i-Pyridinoanthra-
quiaone, m.p. 169°. quinone, m.p. 322°. quinone, m.p. 185°.
and all three have been prepared although they have been
comparatively little studied, the chief interest centring
round the technically valuable hydroxy compounds.
The preparation of quinolines from aminoanthraquinones
by Skraup's method often gives very satisfactory- results,
but in other cases the quinoline is only obtained imder
special conditions. Mejert ^ claimed to have obtained a
quinoline from aminoanthraquinone b}^ Skraup's method,
but his specification contains no details and his claims must
1 By., D.R.P. 268,793. 2 M.L.B., D.R.P. 256,297.
• By., D.R.P. 201,904. B.A.S.F. 205,095.
B.A.S.F./D.R. P. 217,395-6; 218,161. By., D.R.P. 194,252.
By., D.R.P. 194.253; 233,126. <= D.R.P. 26,197.
294 ANTHRACENE AND ANTHRAQUINONE
be accepted with considerable resen'e. Bally i was unable
to obtain a quinoline from a-aminoanthraqninone b}-
carr\-ing out Skraup's synthesis under the usual conditions,
but a quinoline is readily obtained if sulphuric acid of
78 per cent, strength is used in place of concentrated sulphmic
acid, and if nitrobenzene sulphonic acid is used as an
oxidising agent. 2 By this means i(N).2-jA'ridinoanthra-
quinone has been obtained from a-aminoanthraquinone and
i(N).2.5(N).6-dipyridinoanthraquinone has been obtained
from 1.5-diaminoanthraquinone. In the case of jS-amino-
anthraquinone the tendenc}- to form a benzanthrone com-
pound 3 is so great that it is almost impossible to obtain
the pyridinoanthraquinone. A small amomit of a substance
which melts at 322°, and which has the formula C17H9O2N,
is obtained, however, and this is probably 2.3-pyridino-
anthraquinone * although it has never been properly investi-
gated. The third isomer, 2 (N) .i-pyridmoanthraquinone is best
obtained from the corresponding 2(N).i-p3-ridmoanthracene
(anthraquinoline) by oxidation by chromic acid.^ The pyridi-
noathracene can be ODtained by distilling Alizarin Blue with
zinc dust, 6 or from ^-authramine b}- Skraup's method."^
The p3-ridinoanthraquinones have been but little in-
vestigated, although a certain amount of work has been
recorded in connection ■v\-ith the technicall}- important
hydroxy- derivatives. All three isomers are smoothly
nitrated, the nitro group entering the benzene ring to which
the quinoline group is not attached. ^ Dinitro compounds
do not appear to have been described.
The hydroxyanthraqiii}ione qiiinolines can be obtained
from the corresponding aminohydrox\-anthraquinones by
Skraup's method, and by this means quinolmes have been
prepared from 3-aminoalizarin,9 4-aminoalizarin,io amino-
1 B. 38, 194. - M.L.B., D.R.P. 189,234.
3 See p. 332. * B.A.S.F.. D.R.P. 171,939-
5 Graebe, A. 201, 349- ® Graebe. A. 201, 344.
• Graebe, B. 17, 170. Kniippel, B. 29, 70S.
8 B.A.S.F.. D.R.P. 218,476.
9 Pnid'homme, Bl. 28, 62. Graebe, B. 11, 522, 1646; 12. 1416; 15,
17S3 ; A. 201. r, V Kauppel, B. 29. 70S. Auerbach, Chem. Ztg. 3, 5-5.
682. C/. Ort, M.L.B.. D.R.P. 62,703.
10
M.L.B., D.R.P. 67,470.
PYRIDINE AND QUINOLINE DERIVATIVES 295
flavopurpurin, aminoanthrapurpiirin,^ aminoquinalizarin,^
and other similar compounds. 3 They are nearly all mordant
dyes and several of them have found technical application,
e.g.
OH OH OH
OH
,N— ^CH
^CH-CH
Alizarin Blue.
OH
.CH=CH
\
HO
N=CH
OH
/N=-CH
I
^CH-CH
Alizarin Black P.
Alizarin Green.
Of these Alizarin Blue is by far the most important and
numerous brands are placed on the market, viz. Alizarin
Blue ABi, X, R, RR, A, F, GW, WA, etc. It is manu-
factured from ^-aminoalizarin by Skraup's method. The
isomeric dye, Alizarin Green, is obtained from a-amino-
alizarin, but is of much less importance, although it finds
some little application in printing, being then used in con-
nection with a nickel-magnesium mordant. Alizarin Black
P is only very little used.
Another method of synthesising hydroxyanthraquinone
quinolines has been described by Niementowski,^ who
states that 3.7-dihydroxy-i.2(N).4.5(N)-dipyridinoanthra-
quinone is obtained when 8-hydroxyquinoline-6-carbox}dic
acid is heated with concentrated sulphuric acid and phos-
phorus pent oxide. He describes it as an orange vat dye.
Other dipyridinoanthraquinones have also been described.^
COOH
HOCO
Hydrox>l groups can be introduced into the anthra-
quinoline molecule by sulphonating and then heating the
1 M.L.B., D.R.P. 54,624 ; 70,665. " B.A.S.F., D.R.P. 58,480.
8 Schaarschmidt and Stahlschmidt, B. 45, 3452. By., D.R.P. 50,164;
50,708. M.L.B., D.R.P. 149,781.
* B. 49. 23. » M.L.B., D.R.P. 189.234.
296 ANTHRACENE AND ANTHRAQUINONE
sulphonic acid with milk of lime at 180°, but more important
results are obtained by direct hydrox5'lation by oxidation.
If Alizarin Blue is oxidised under carefully controlled
conditions, e.g. b}^ treatment with bromine, nitric acid, or
manganese dioxide, it is converted into the corresponding
diquinone 1 (3(N).4-pyridino-i.2.9.io-anthradiquinone) ; but
if the oxidation is brought about by heating with oleum a
tetrahydroxy compound (Alizarin Green X) and a penta-
hydroxy compoimd (Alizarin Indigo Blue) are obtained ^ :
HO OH HO OH
OH HO OH
I
/
N=CH
I
HO V^_,
HO
.N=CH
^CH=CH
Alizarin Indigo Blue.
^CH=:CH
Alizarin Green X.
This last on oxidation with nitric acid very readily yields
quinolinic acid.
When Alizarin Blue and similarly constituted dyestuffs
are allowed to remain in contact with concentrated aqueous
solutions of sodium bisulphite for several days they combine
with two molecules of the bisulphite and pass into water-
soluble products which are very largely used in printing 3
(Alizarin Blue S, Alizarin Green S, etc.). In text-books on
tinctorial chemistry these soluble products are usually
represented as being formed by union of the bisulphite with
the cyclic carbonyl groups, but such a structure is very
improbable as neither anthraquinone itself nor the hydroxy-
anthraquinones combine with bisulphite. Quinoline itself,
however, forms an addition product with sodium bisulphite,
and this resembles Alizarin Blue S by being decomposed by
water at 60°. It is therefore probable that in the soluble
dyes the bisulphite is imited to the quinoline ring and not to
the cyclic carbonyl groups. ^
1 By., D.R.P. 171,836.
2 Graebe and PhiUps, A. 276, 21. B.A.S.F., D.R.P. 46,654 ; 47,252.
3 B.A S.F., D.P.P. 17,695 ; 23,008.
* Brunck and Graebe, B. 15, 17S3.
PYRIDINE AND QUINOLINE DERIVATIVES 297
III. Anthraquinone Phenanthridones
The anthraquinone phenanthridones are of no particular
interest but are quite readily obtained from those benzoyl-
aminoanthraquinones in which there is a halogen atom in the
o-position to the nitrogen atom, either in the anthraquinone
nucleus or in the benzene ring :
The reaction is brought about by boiling with sodium
carbonate or sodium acetate, preferably in naphthalene
solution. It is not necessary to isolate the benzoylamino
anthraquinone as the phenanthridone is formed by the
prolonged boiling of an aminoanthraquinone with o-chlor-
benzoyl chloride in nitrobenzene solution in the presence of
sodium carbonate. 1
IV. The Pyranthridones
The pyranthridones are intennediate in structure between
the pyranthrones (p. 335) and the flavanthrones (p. 300),
and were studied by Scholl during liis investigations on these
substances. Scholl 2 found that when a mixture of 2-methyl-
i-chloranthraquinone and 2-benzylideneamino-i-chloranthra-
quinone is heated with copper powder, a mixture of three
different dianthraquinonyl derivatives is formed, although
1 B.A.S.F., D.R.P. 236,857 ; 238,158.
= B.51,441. D.R.P. 307,399. C/. Ullmann, A. 399, 332 ; D.R.P. 248,999.
298 ANTHRACENE AND ANTHRAQUINONE
he was unable to separate them. When the mixture was
heated with sulphuric acidi however, the benzylidene
group was split off and simultaneous loss of water took place,
and from the product he was able to isolate flavanthrone
and 2'-meth3'l-i.2.a.j3-pyridanthrone anthraquinone. These
two compounds had obviously been formed from two of the
dianthraquinonyls thus : ••
CO CO
Flavanihrone
CO
^-f^eiby\-\■^.<ji-pyndanihrone
The third dianthraquinonyl derivative was unaffected by
the sulphuric acid under the conditions of the experiment,
and was, of course, 2.2'-dimethyl-i.i'-dianthraquinonyl.
The pyridanthrone anthraquinone was found to be a
3'ellow vat dye although the tinctorial properties were ven.-
feeble. When reduced with sodium hydrosulphite in alkaline
solution it gives first a comparatively stable red vat and then
a very easily oxidised blue vat. As each of these gives a
di-brombenzoyl derivative they probably have the structures :
OH
Red product.
OH
Blue product.
PYRIDINE AND QUINOUNE DERIVATIVES 299
The chief interest attached to methylpyridanthrone-
anthraquinone Hes in its behaviour when heated alone or
with concentrated sulphuric acid or with alcoholic caustic
potash, as under these conditions another molecule of water
is lost and pyranthridone is formed :
This is a powerfrd vat dye which d3'es in orange-red shades
which are somewhat yellower than those obtained from
pyranthrone itself, but much redder than those obtamed from
flavanthrone. Its bromo derivatives are also orange-red dyes.
Pyranthridone when reduced by sodium h5'drosulphite
in alkaline solution gives a violet-coloured vat, and since
this gives a di-brombenzoyl derivative it probably has the
formula :
Reduction with hydriodic acid and phosphorus leads to
dihydropyranthridene, which when heated with copper
powder loses two atoms of hydrogen and passes into
P3'ranthridene itself :
H H
H H
Dihydropyranthridene.
Pyranthridene.
300 ANTHRACENE AND ANTHRAQUINONE
V. The Flavanthrones *
When /3-aminoanthraquinone is fused with caustic alkali
a mixture of the reduction products of indanthrone and
flavanthrone is obtained, ^ although when the fusion is
carried out in the presence of a reducing agent, or more
particularly when alcoholic solutions of caustic potash are
used, the reduction product of flavanthrone becomes almost
the sole product. 2 Flavanthrone, mixed with indanthrone,
can also be made by oxidising j3-aminoanthraquinone,3
and when /3-aminoanthraquinone is heated with aluminium
chloride without a solvent at 250-280° considerable
quantities of flavanthrone are obtained. ^ Curiously enough
the use of an indifferent solvent such as nitrobenzene leads
to quite a different result, as under these conditions little
or no flavanthrone is formed, the chief product consisting
of a reddish-brown vat dye of unknown constitution. ^ The
best method, both for laboratory and for manufacturing
purposes, of obtaining flavanthrone is to boil /3-aminoanthra-
quinone with antimony pentachloride in nitrobenzene
solution.*^
None of the above methods of preparing flavanthrone
throw any light on the constitution of the dyestuff, and the
first direct proof of its structure was given by Scholl."^ He
started with 2.2'-dimethyl-i.i'-dianthraquinonyl and first
oxidised this to the corresponding dicarbox34ic acid. This
he then converted into its amide and then endeavoured to
obtain diaminodianthraqmnonyl from this by Hofmann's
method. In this he was not successful as the diamino-
dianthraqmnonyl proved to be unstable under the experi-
mental conditions and at once lost two molecules of water
and passed into flavanthrone :
* See footnote on p. 290,
^ See p. 343.
2 B.A.S.F., D.R.P. 133,686; 135,408.
3 B.A.S.F., D.R.P. 139,633 ; 141.355; 211,383.
4 B.A.S.F., D.R.P. 136,015.
B B.A.S.F., D.R.P. 138,119; 206,464.
« Scholl, B. 40, 1691. B.A.S.F.. D.R.P. 138.119
7 B. 41, 1691.
PYRIDINE AND QUINOLINE DERIVATIVES 301
CO
CO
CO
At a later date SchoU ^ showed that i.i'-dianthraqiiinonyl
when nitrated gave a mixture of nitro compounds from
which small quantities of flavanthrone could be obtained
by reduction with sodium sulphide, the production of
flavanthrone being no doubt due to the instability of 2.2'-
diamino-i.i'-dianthraquinonyl. Behesh 2 also found that
diaminodianthraquinonyl was unstable, as he obtained only
flavanthrone by heating 2.2'-dimethoxy-i.i'-dianthra-
quinonyl with ammonia.
To establish the structure of flavanthrone beyond all
possible doubt it was desirable if possible to isolate the
diaminodianthraquinonyl and prove that it did readily
pass into flavanthrone. If 2-amino-i-bromanthraquinone
is heated with copper powder this last acts as a catal5'St and
splits out two molecules of hydrobromic acid, the product
being indanthrone (see p. 345). If this catal3'tic eft'ect
could be prevented it should be possible to split out the two
atoms of bromine and thus obtain diaminodianthraquinonyl.
Scholl 3 first tried to achieve this result by using the acetyl
derivative of the aminobromanthraquinone, but was not
successful. By using the benzylidene derivative, * however,
he succeeded in preparing the dibenzylideneaminodianthra-
quinonyl and was then able to hydrolyse this in alcoholic
solution at the ordinary temperature. The resulting
2.2'-dianiino-i.i'-dianthraquinonyl was found to pass into
flavanthrone when heated alone to 250° or when warmed
to 50° with concentrated sulphuric acid. Boiling with
solvents such as nitrobenzene, pyridine, or glacial acetic
acid also effected flavanthrone formation, and reduction
with sodium hydrosulphite in alkaline solution led at once
» B. 43, 1740. a M. 32, 447.
s B. 40. 1699. * B. 51. 452.
302 ANTHRACENE AND ANTHRAQUINONE
to the blue vat of flavanthrone. This method of preparmg
flavanthrones has been used by Ulltnann ^ for the preparation
of the dibromo derivative.
Flavanthrone is a yellow vat dye which yields extremely
fast shades. It was originally put on the market under the
name Flavanthrene, but this was subseqjiiently altered to
Indanthrene Yellow G.2 The dibrom derivative gives
orange shades. Flavanthrone itself is very stable towards
nitric acid, but by prolonged heating a mixture of substances
is obtained from which Scholl 3 has isolated a dihydroxy-
dinitrosodinitro compound. This on reduction gives the
corresponding tetraminodihydrox}- compoimd, and if boiled
with a primary aromatic amine such as aniline or ^-toluidine
the nitro groups can be replaced by arylamino groups.
The reduction products of flavanthrone have been very
fully investigated by Scholl and his co-workers. Scholl *
finds that reduction in alkaline solution with sodium hydro-
sulphite gives a blue vat which is readily oxidised by the
air. From this solution acetic acid precipitates a greenish-
blue hydrate which loses water slowly at iio° and rapidl}'-
at 150°. It gives a disodium salt but onl}^ a monobenzoyl
derivative, and this monobenzoyl derivative is insoluble in
alkali. Scholl therefore concludes that in the blue vat
there is only one true hydroxy^ group present, and represents
the hydrate by formula I and its disodium salt by formula II :
OH . ONa
CO
I. Flavanthranol hydrate.*
Reduction of flavanthrone with zinc dust and caustic
soda leads to a brown vat which is extremely easily oxidised
1 A. 399, 332. D.R.P. 248,999. Cf. By., D.R.P. 172,733-
2 Caledon Yellow G (Scottish Dyes, Ltd.). » B. 43, 340.
* B. 41. 2304, 2534. Cf. Potschiwauscheg, B. 43, 1748. By., D.R.P.
139.^34- ' Dihydroflavanthrene hydrate (Scholl).
PYRIDINE AND QUI NOLI NE DERIVATIVES 303
by the air. This vat seems to consist of at least four
hydrated substances which lose their water at 160°. In
alkaline solution they are all red, but are blue when pre-
cipitated by acids, so that salt formation is probably ac-
companied by enolisation. SchoU represents them by
formulae III, IV, V, and VI :
OH . OH
ITT. Flavan-ihracujinol Hydrafe WM-Dihydroanihraquinol Hydraie.^
OH H
V Floivanflirenol Hydraie.^ ^ VJ.Flavanihrene Hydrate.'^
When flavanthrone is reduced with hydriodic acid and
phosphorus, non-hydrated products are obtained. When
the reduction is carried out at 170° a product is formed which
is not particularly sensitive to oxidation by the air, and
which is green when in the solid state, but red when in
solution, particularly in the presence of alkali. The red
and green forms are probably due to keto-enol tautomerism
(formulse VII and VIII).
CO CO
Vn Dihydroflavanthranol.5 VIII
* a-Tetrahydroflavanthrene hydrate (Scholl). 2 a-Hexahydroflavan-
threne hydrate (Scholl). ' Flavanthrinol hydrate (Scholl). * Flavan-
thrine hydrate (Scholl). * ^-Tetrahydroflavanthrene (Scholl).
304 ANTHRACENE AND ANTHRAQUINONE
This on alkaline reduction gives a product which is very
sensitive to oxidation by the air, and which is probably
represented by formula IX :
OH
IX. j8-Dihydroflavanthraq\iinol.^
When the reduction of flavanthrone with hydriodic acid
and phosphorus is carried out at 200° flavanthrene hydrate
(formtila VI, p. 303) is obtained, which by loss of water
yields flavanthrene 2 itself. This last is a base and is not
sensitive to oxidation by the air.
Attention may here be directed to a bluish-grey vat
dye which is obtained by converting chlorbenzanthraquinone,
obtained by condensing phthalic anhydride with a-chlor-
naphthalene, into the corresponding amino compound b}^
heating with ammonia, and then boiling this with antimony
pentachloride in nitrobenzene solution. ^ Nothing is known
of its structure, but it is improbable that it is a flavanthrone.
^ /3-Hexahydroflavanthrene (Scholl). ^ Flavanthrine (Scholl).
3 G.C.I.B., D.R.P. 230,455.
CHAPTER XIV
THE ACRIDONES, XANTHONES,
AND THIOXANTHONES
I. The Acrid ones *
The anthraquiiione acridones are almost invariably obtained
by loss of water from ar>^laminoantliraquinones or dianthra-
quinonylamines in which there is a carboxyl group in the
ortho- position to the imino group, although this carbox}!
group may be either in the anthraquinonyl group or in the
ar5'l group. Such carbox3dic acids can be obtained {a) by
condensing an o-aminoanthraquinone carboxylic acid with
an aromatic halogen compound or halogen anthraquinone ;
(6) by condensing an o-halogen anthraquinone carboxy-lic
acid with a primary aromatic amine or aminoanthraquinone ;
(c) by condensing an aminoanthraquinone with an aromatic
o-halogen carboxj^ic acid ; {d) by condensing a halogen
anthraquinone with an aromatic o-amino carboxylic acid.
Of these the last two methods lead only to acridones in
which the heterocyclic ring lies between one anthraquinone
residue and one aromatic ring. Such compounds, however,
are readily obtained owing to the easy accessibility of
o-chlorbenzoic acid and anthranilic acid. When the con-
densation is being carried out with o-chlorbenzoic acid
Ullmann ^ finds that improved 3'ields are obtained by using
the methyl ester in place of the free acid. In cases in which
the carboxj-l group is attached to the anthraquinone nucleus
(methods {a) and (6)) the use of sodium acetate as a
* These can be named either as anthraquinone acridones or as phthaloyl
acridones, and both methods of nomenclature are in use.
1 B. 51, 9. Cf. M.L.B., D.K.P. 254, 475.
305 20
3o6 ANTHRACENE AND ANTHRAQUINONE
condensing agent often leads to very poor jdelds owing to the
tendency- of this substance to cause loss of carbon dioxide.
This, however, can be avoided by replacing the sodium
acetate by the carbonate, acetate, or hydroxide of calcium
or magnesium. 1
The final closing of the acridone ring can usually be
brought about by heating with sulphuric acid,^ but in many
cases it is sufficient to boil the carboxj-lic acid with some
indifferent solvent of high boiling point, such as nitro-
benzene, ^ with or without the addition of acetic anh3'dride
or acet}-! chloride. * The fact that the acridone ring can
sometimes be closed merely by boiling with a solvent has
enabled Eckert and Halla ^ to obtain an acridone by boiling
i-aminoanthraquinoue-2-carboxylic acid with /3-chloranthra-
quinone in nitrobenzene solution in the presence of cuprous
chloride and sodium acetate.
In spite of the ease with which the acridone ring is often
closed by the above methods, Ullmann ^ in many cases
prefers to convert the carbox5'lic acid into its chloride by
treatment with phosphorus pentachloride and then to
obtain the acridone by boiling this with nitrobenzene. It
has also been stated that the ring is closed when an ester of
the acid is reduced by sodium hydrosulphite or by zinc dust
and ammonia. 7
The above methods of preparing the acridones have given
rise to several minor variations. Thus o-methyl dianthra-
quinon34amines when oxidised in alkaline solution pass
into the corresponding carbox>dic acid, from which simulta-
neous loss of water takes place with the immediate pro-
duction of the acridone. 8 In a ver>- similar way o-methyl-
aryl amino anthraquinones, in which the methyl group ma\-
be either in the anthraquinone residue or in the arj^l group,
1 B.A.S.F., D.R.P. 268,219.
2 Ullmann and Billig, A. 381, i ; B. 43, 538. Ullmann, B. 49, 2160.
Ullmann and Dootson, B. 51, 9. Ullmann and Conzetti, B. 53, 836.
Ullmann, D.R.P. 221,853. B.A.S.F., D.R.P. 240,002 ; 269,850 ; 287,614.
M.L.B., D.R.P. 240,327 ; 243,586; 245,875; 254,475; 256,626. Brass,
B. 46, 2907 ; D.R.P. 268,646.
3 B.A.S.F., D.R.P. 248,170. 4 Ullmann, B. 47, 748. » M. 35.. 755.
« A. 381, I. B. 43, 538 ; 47, 553, 562. D.R.P. 221,853.
' B.A.S.F., D.R.P. 246,966. 8 B.A.S.F., D.R.P. 192,436.
THE ACRIDONES 307
pass into the acridone when treated with halogens or with
sulphur}-! chloride. 1 Schaarschniidt,2 on the other hand,
prepares acridones from the o-nitriles of the arylamino-
anthraquinones or dianthraquinonylamines, the nitrile
group being attached either to the anthraquinone nucleus
or to the ar}'l group. Acridone formation takes place on
heating with sulphuric acid, and according to Schaarschmidt
is not preceded by hydrolysis of the nitrile, as he claims that
acridones are formed in excellent yield under conditions
under which little or no hydrolysis takes place. Ullmann,
on the contrary-, is convinced that acridone formation only
takes place subsequent to the hydrolysis of the nitrile to
the carbox3-]ic acid, and a lively and somewhat heated
polemical discussion has taken place between the two
investigators. 3
A further variation consists in condensing an amino-
anthraquinone with i.2-naphthoquinone-3-carboxy'lic acid by
warming on the water-bath in aqueous solution, and then
closing the ring by heating with sulphuric acid ^ :
The yields obtained at both stages are said to be almost
quantitative and the method would appear to deserve more
attention than it has received. A somewhat more compli-
cated variation consists in first preparing an anthraquinonyl
isatin, either by condensing a halogen anthraquinone with
isatin, or by the action of oxalyl chloride on an ar}-lamino-
anthraquinone. The isatin is then converted into the
acridone b}- treatment with aluminium chloride, sulphuric
acid or alkali ^ :
1 B.A.S.F., D.R.P. 272,296 ; 275,671 ; 283,724.
» A. 405. 95. D.R.P. 269,800.
' B. 49. 735 ; 50, 164. 403. 1356. 1360, 1526.
* Cas., D.R.P. 280,712. 5 By., D.R.P. 286,096.
3o8 ANTHRACENE AND ANTHRAQUINONE
coA^kO
A JCO
In all the above methods the acridone ring is closed
through the carbon}^ group. In some cases, however, the
ring can be closed through the imino group, although as a
rule this method is only of minor importance. Thus aryl
anthraquinonyl ketones in which there are amino groups
present in the orlho- position to the ketonic carbonyl group
both in the aryl group and in the anthraquinonyl residue
pass readily into acridones by loss of ammonia, and com-
poimds like 2-0-chlorbenzoyl-i-chloranthraquinone pass
directly into the acridone when treated with toluene-/)-
sulphonamide.i
The purification of the anthraquinone acridones can
often be conveniently effected by taking advantage of the
fact that the majority of them form almost insoluble
salts when treated with sulphuric acid of y8 per cent,
strength. 2
By the above methods a very large number of acridones
have been prepared, some of them of very complex structure.
Starting with 1.5-dichloranthraquinone and condensing this
with anthranilic acid, Ullmann and Billig ^ were able to obtain
a compound containing two acridone groups (formula I.),
but from 1.4-dichloranthraquinone could only obtain a
compound containing one anthraquinone ring, and onl}' a
monoacridone was obtained from i .4-diaminoanthraquinone
and o-chlorbenzoic acid.^ From this it would appear that
two carbonyl groups in the ortho- position hinder one another
(c/- P- 337) ' but Schaarschmidt ^ claims to have obtained
a compound corresponding to formula II by his nitrile
method :
1 B.A.S.F., D.R.P. 272,297. a B.A.S.F., D.R.P. 253,090.
« A. 381, I. * M.L.B., D.R.P, 243,586.
» A. 405, 95.
THE ACRIDONES
309
C6H4
\co/
C6H4
CO
•C0\ ■ /CO
\nh/' " "\nh/
I. II.
An acridone containing two anthraquinonyl residues
(i.2.5.6-diphthalo3-l acridone) is obtained by oxidising
2 - methyl -1.2'- dianthraquinonylamine, ^ and Scliaar-
schmidt 2 has obtained the same substance by his nitrile
method :
CH3
— NH
CN
-NH
Both in the patent and in Schaarschmidt's paper this is
described as an orange-red vat dye. On the other hand,
Eckert and Halla 3 prepared the substance by two methods,
viz. (i) by condensing i-aminoanthraquinone-2-carbox5-Hc
acid with j8-chloranthraquinone and then causing loss of
water, and (2) by condensing 2-brom-3-benzylidene amino-
anthraquinone with i-aminoanthraquinone-2-carboxylic acid
and then removing the amino group by diazotising and
reducing :
1 B.A.S.F., D.R.P. 192,436.
" M. 35. 755.
A. 405, 95-
310 ANTHRACENE AND ANTHRAQUINONE
NH2
COOH CI
1
+
'
->
1
-NH-
-COOH
-NHn
\CO/
NH2
COOH
Br
+
PhCH : n]
I
->
^COOH
PhCH : N
4-
PliCH : Ni
/NHn
^CO-
/NHn
\co/
They describe the substance as a bluish-violet vat dye,
and are therefore at variance with the description of the
substance given by the patentees and by Schaarschmidt. In
Eckert and Halla's first synthesis the ring might close in
two ways, giving either
I
/NH\
\co/
or
\
NH
CO
The second synthesis, however, leaves no doubt that the
THE AC RI DOMES
311
former structure is the correct one. In the patented method
two alternatives are also possible :
1
/NH\
. /NH
\co/
<-
^CH.
1
1
-»
'NH—
but as the product is dijfferent from that obtained by Eckert
and Halla the latter must be the correct one. This con-
clusion is supported by the preparation of an acridone by
Ullmann ^ by condensing i-chloranthraquinone-2-carboxylic
acid with j8-aminoanthraquinone. Here again two alterna-
tives are possible :
I
//NH-
\co-
<-
— NH—
-COOH
/NH\
•CO/
/
but as the product formed is an orange vat dye it must be
concluded that the former structure is correct. It is
difhcult to see how Schaarschmidt's product could have any
structure other than that which he assigns to it ; but the
weight of evidence is against this, and consequently Schaar-
schmidt's claims cannot be accepted.
Substituted acridones of the anthraquinone series are
usually built from the substituted anthraquinones. Halogen
atoms when present in the anthraquinone nucleus are
readily replaced b}" arylamino or anthraquinonyl amino
groups by heating with primar}^ aromatic amines or amino-
anthraquinoues in the usual way, 2 and the same compounds
» B. 47, 553. « UUmann and Billig, A. 381. i. B. 43, 538.
312 ANTHRACENE AND ANTHRAQUINONE
can also be obtained by condensing an aminoacridone with
a halogen compoimd.^ Very few sulphonic acids have been
described, but in some of them the sulphonic acid group
is extremely labile and is easily removed by heating with an
organic solvent or by treatment with an acid, alkali; or
reducing agent. 2
Tinctorial Properties. — The examination of the tinc-
torial properties of the anthraquinone acridones has led to
interesting results. In the case of the monophthaloyl
acridones, i.e. those acridones in which the heterocyclic ring
lies between one anthraquinone ring and one benzene ring,
when the imino group is in the j3- position to one of the cyclic
carbonyl groups of the anthraquinone nucleus the product
is a yellow or orange vat dye, but the shades obtained are
very loose to alkali, and there are no data available to say
whether the fastness is improved by alkylating the cyclic
imino group. When the cyclic imino group is in the a-
position the product dyes in very bluish shades of red and
the dyeings are fast to alkali. That this change in the
tinctorial properties is due to the position of the imino group
and not to the position of the carbonyl group was proved
by Ullmann,^ who prepared all three isomeric monophthalojd
acridones :
I
/NH\
\co/
C6H4
!
Bluish-red.
/CO-
Orange.
C6H4
I
-CO
yC6H4
Brownish-yellow.
Only the first of these (Indanthrene Red BN Extra ^)
is fast to alkali, both the others being extremely loose. The
formation of a second acridone ring with the imino group
in the a- position shifts the colour still more towards the
violet end of the spectrum ^ :
1 M.L.B., D.R.P. 239,543. 2 B.A.S.F.. D.R.P. 287.614-5.
8 A. 381. I ; B. 43, 538 ; 47, 553. 748. Cf. Schaarschmidt. A. 405, 95-
By., D.R.P. 286,095.
* Caledon Red (Scottish Dyes, Ltd.). * B.A.S.F., D.R.P. 234,977.
THE ACRIDONES
313
CO
C«H
\,
6-^M
\co/
I
\nh/
C6H4
Indanthrene Violet RN Extra. ^
The entrance of halogen atoms into the molecule greatly
increases the affinity for the fibre, and at the same time
brightens the shade and shifts it towards the red end of the
spectrum. 2 Amino and methoxy groups when in the para-
position to the cyclic imino group shift the colour towards
the violet end of the spectrum, but when in the para- position
to the acridone carbonyl group they have the opposite
effect, the anthraquinoue acridones thus behaving like the
indigoid and thioindigoid dyes.^ The presence of an aryl-
amino or anthraquinonyl amino group in the para- position
to the cyclic imino group often gives rise to a green or greenish-
grey vat dye, 4 and the same result is frequentty obtained by
the introduction of an aryl mercapto group. ^
In the case of acridones in which the heterocyclic ring
lies between two anthraquinoue ring systems (diphthaloyl
acridones), the colour seems to depend very largely on con-
stitution, as will be seen from the following formvilae :
/COn
Bluish-violet.*
1
\co/
1
1
CO
NH
1
Violet.
Orange.'
' Caledon Violet RN Extra (Scottish Dyes, Ltd.).
■ Schaarschmidt, A. 405, 95- B.A.S.F.', D.R.P. 242,063.
3 UUmann, B, 51, g-" Cf. Ullmann. B. 49, 2168. M.L.B.. D.R.P.
239.543 ; 243,586; 256,626.
« B.A.S.F., D.R.P. 263,078. « B.A.S.F., D.R.P. 248,996. • See p. 309,
' Eckert and Halla, M. 35, 755. * Ullmann, B. 47, 553, 562.
314 ANTHRACENE AND ANTHRAQUINONE
/COx.
CO
/NHs
\co/
/CO\
Reddish- brown, *
Reddish-brown. ^
Blue.i
Very little is known of the a7ithraquinone acridines,
but Ullmann 2 by heating 2.2'-dihydroxy-i.i'-dianthr34-
methane with ammonia obtained a dianthrylacridine which
on oxidation passed into the anthraqninone acridine :
/OH H0\
^H?
\ch/
I
\ch/
I
This was fotmd to be a red vat dye, but the affinity is
very poor.
More complex acridines are said to be obtained when
a halogenated fluorenone or phenanthraquinone is con-
densed with an aminoanthraquinone and the product then
dehydrated. 3
Closelv related to the acridones and acridines are the
^ Schaarschmidt, A. 405, 109. " B. 45, 2259.
3 B.A.S.F., D.R.P. 269,194.
THE XANTHOMES
315
bluish-green vat dyes which are obtained by condensing
two molecules of an aminoanthraquinone with one molecule
of o-chlorbenzaldehyde.i
II. The Xanthones
The anthraquinone xanthones (phthaloylxanthones) are
rather troublesome to prepare, as attempts to condense a
halogen anthraquinone with salic34ic acid generally leads to
loss of the carbox}d group. Salicylic aldehyde, however,
will condense with a-chloranthraquinone and the resulting
aldehyde can then be oxidised to the carboxylic acid, the
xanthone ring being subsequently closed by treatment with
phosphorus pentachloride 2 :
/OCfiH^CHO
O^
HOCO^
/CeHi
/0\
\co/
CfiH^
The method, however, is not a ver^- satisfactory one, as
the aldehyde is extremely stable and ver^^ difficult to oxidise.
In the above case, for example, the aldehj-de could only be
oxidised by boiling it for five hours with chromic acid in
a mixture of glacial acetic acid and sidphuric acid.
A more satisfactory method of preparing the xanthones
is to condense an anthrol with formaldehyde and then to close
the ring by treatment with phosphorus pentachloride. The
xanthone is then obtained by subsequent oxidation : 2
/CH2
OH Hq/
1 Kalischer and F. Mayer, B. 49, 1994. F. Mayer and Stein, B. 50,
1306. F. Mayer and Lever, B. 52, 1641. Cas., D.R.P. 280,711.
2 UUmann and Urmenyi, B. 45, 2259.
3i6
ANTHRACENE AND ANTHRAQUINONE
\o/
I
I
The condensation of the anthrol with formaldeh^^de
takes place quite readily at 70° in aqueous solution, or in
a mixture of acetic acid and alcohol to which a little hydro-
chloric acid has been added. Acetaldehyde can be substituted
for formaldehyde, the condensation then being best effected
in glacial acetic acid solution at 50° in the presence of a little
hydrochloric acid. The methyl group is lost when the
methyl xanthene is oxidised :
H\ /CH3
\o/
->
yCO^
Benzaldehyde also condenses with jS-anthrol, but in
this case subsequent oxidation of the phen^d xanthene leads
only to the anthraquinone phenyl xanthene (diphthaloyl
phenyl xanthene) :
H
\„/c
6^5
H
v/
CeH
/^\ .
\o/
1
1
The xanthones can also be obtained by condensing an
o-chloranthraquinone carbox3-lic acid with a phenol, and then
closing the xanthone ring by treatment with phosphorus
pentachloride ^ :
1 UUmann, B. 47. 566. B.A.S.F., D.R.P. 251.696.
THE THIOXANTHONES
317
I
OCfiHs
COOH
-O
—CO
y^e^H
>C«Ha
The xanthones are of no particular interest. They are
usually yellow substances but are devoid of tinctorial
properties.
III. The Thioxanthones
The anthraquinone thioxanthones (phthaloyl thioxan-
thones) are always obtained from the corresponding sulphide
in which a carbox}-! groujD is present in the ortho- position to
the sulphur atom. This carbox}d group may be in the
anthraquinone ring, in which case the sulphide is prepared
either by condensing an o-mercapto anthraquinone carboxylic
acid with a halogen compound, or by condensing an 0-
halogen anthraquinone carboxylic acid with a mercaptan,i
or the carbox}d group may be present in the ar>^l group.
In this case the sulphide can be prepared by condensing an
anthraquinone mercaptan with an o-halogen carboxylic
acid ; but as a rule it is more convenient to condense the halo-
gen anthraquinone with thiosalicylic acid. 2
The closing of the thioxanthone ring can usually be
effected by heating with concentrated sulphuric acid, but
as a rule much better results are obtained by the use of
phosphorus pentachloride or toluene sulphochloride.3 Schaar-
schmidt ^ has also prepared a number of thioxanthones
from the corresponding nitrile by the action of sulphuric
acid, and claims that the formation of the thioxan-
thone is not preceded by the formation of the carboxylic
acid. 5
1 B.A.S.F.. D.R.P. 243,750. Sanders, D.R.P. 253,983.
» UUmann. B. 43, 539; 44, 3125. Frey, B. 45. 1361. By., D.R.P,
216,480. B.A.S.F., 234, g";. M.L.B,, D.R.P. 243,587.
3 Ullmann, B. 43, 539; 44, 3125. D.R.P. 238,983. B.A.S.F., D.R.P
243.750-
« A. 409, 59. D.R.P. 269,800.
5 Cf. p. 307.
3i8 ANTHRACENE AND ANTHRAQUINONE
Halogenated thioxanthones are usually best prepared by
direct halogenation either before or after closing the thi-
oxanthone ring.^ They can be converted into arylamino-
and anthraquinonylamino-anthraquinone thioxanthones b}-
treatment with a primar}^ aromatic amine or aminoanthra-
qmnone.2 Primary amino compounds can be obtained
by the nitration and subsequent reduction of the thio-
xanthones themselves. 3
Tinctorial Properties. — The thioxanthones of the
anthraquinone series are all vat dyes, but it is only those in
which the cyclic sulphur atom is attached to the anthra-
quinone ring system in the a- position which are of any
value.
The relationship between the shades obtained and the
constitution of the dye is of interest. It is well known that
in the indigoid d5^es the replacement of the C5^clic imino
group by a sulphur atom is accompanied b}^ a shifting of
the colour towards the red end of the spectrum, and a
preciseh^ similar effect is noticeable when the anthraquinone
acridones are compared with the corresponding thioxan-
thones. The thioxanthones are decidedly less highly
coloured than the corresponding acridones and, as a rule,
dye in yellow, orange, or red shades. Those compounds in
which the siilphur atom is in the a- position are more highly
coloured than the isomeric substances in which the sulphur
atom is in the j8- position :
/C0\
•CoHj
Yellow.
N:o/
CoHj
Orange.
C.H,:
Vq/
\co/
C6H4
Red.
1 Ullmann, D.R.P. 242,386. B.A.S.F., 258,561.
> Ullmann, D.R.P. 242,386. Cf. M.L.B., D.R.P. 231,854 ; 248,996.
3 Schaarschmidt, D.R.P. 250,271-2. Cf. M.L.B.. D.R.P. 243,587 ;
248,469.
THE THIOXANTHONES
319
/
CeHjx^
/COn
CO
/C«H4
\co^
.CO\
\co/
I
Red.
Yellowish-orange.
Reddish-orange.
The entrance of halogen atoms into the molecule renders
the shades lighter :
Indanthrene Yellow GN.
Indanthrene Orange GN.
CHAPTER XV
THE BENZANTHRONES
Benzanthrones are anthraquinone derivatives in which
one carbonyl group has remained intact, whereas the carbon
atom of the other carbonyl group forms part of a new
benzene ring in which is also involved one of the a-carbon
atoms :
CO
9 . 1 o-Benzanthrone.
The chemistry of the benzanthrones has become ex-
tremely important during recent years, owing to the ver}-
valuable tinctorial properties exhibited by some of the more
complex members.
I. Simple Benzanthrones
The discovery of the benzanthrones originated in the
observation ^ that only ver>' little anthraquinonequinoline
(p3^ridinoanthraquinone) is obtained when j8-aminoanthra-
quinone is treated with gtycerine, sulphuric acid and an
oxidising agent (Skraup's quinoline synthesis), the main
product of the reaction being a compoimd which melts at
251°, and which has the formula CooHnON. The same
compound is obtained by treating anthraquinone quinoline
with sulphuric acid and glycerine,^ and Bally and Scholl 3
1 B.A.S.F., D.R.P. 171,939- * BaUy, B. 38. 194-
» B. 44, 1656.
320
THE BENZANTHRONES 321
found that anthraquinone itself condenses readily with
glycerine in the presence of sulphuric acid to produce a
compound (benzanthrone) with the formula C17H10O. In
all these cases it is obvious that one of the cyclic carbonyl
groups has become involved in the condensation, and as
benzanthrone itself on oxidation yields anthraquinone a-
carboxy^lic acid, it follows that one of the a-carbon atoms
has also become involved in the reaction. The formula
given above is the only one which explains these facts.
The formation of benzanthrones by treating an anthra-
quinone derivative with glycerine and a dehydrating agent
is a very general one, and in addition to anthraquinone
itself 1 is also shown by anthraquinone homologues,^ 1.2-
benzanthraquinone,3 hydroxyanthraquinones,^ halogen
anthraquinones,^ and other anthraquinone derivatives,
provided alwa3's that there is a free a- position available.
The best yields, however, are usually obtained by reducing
the anthraquinone to the corresponding anthraquinol or
anthranol.6 Anthracene itself will undergo benzanthrone
formation, but in this case it is almost certain that con-
densation is preceded by oxidation.' Benzanthrone forma-
tion is not limited to the anthraquinone series as a similar
type of compound, naphthindenon, is obtained when a-
naphthol is treated with glycerine and an oxidising agent. ^
The mechanism of benzanthrone formation has been discussed
b}' Bally and Scholl,^ who conclude that the first reaction
consists in the formation of an aldol-like condensation
product from one molecule of anthranol and one molecule
of acrolein, that this then loses a molecule of water, and that
the final closing of the ring is brought about by the loss
of two atoms of hydrogen. This hydrogen is not, of course,
evolved as such, but is utilised in reducing a further quantity
of the anthraquinone to the anthranol. This view of the
1 Bally, B. 38. 194. Bally and SchoU, B. 44, 1656. B.A.S.F., D.R.P.
176,018.
2 B.A.S.F., D.R.P. 200.335. 3 B.A.S.F., D.R.P. 181,176.
^ B.A.S.F., D.R.P. 187,495. A. G. Perkin, See. 117, 697.
* B.A.S.F.. D.R.P. 205,294. « B.A.S.F., D.R.P. 176.018. etc.
' B.A.S.F., D.R.P. 176.01^. 8 B.A.S.F., D.R.P. 283.066.
B. 44. 1656.
21
322 ANTHRACENE AND ANTHRAQUINONE
reaction is supported by the fact that it has been found
impossible to induce benzanthrone formation to take place
with both carbonyl groups.
yCH ; Cxi2
HOCH— CH : CH2 HC^
C,H,
CH C
C«H
6-^M
COH COH
In place of glycerine it is, of course, possible to use
mono- or di-chlorh^'drin, epichlorhj-drin, triacetin,i etc.,
and Jacob Meyer 2 has prepared benzanthrones by
condensing anthraquinone with ketones of the type
R.COCHg.^
In the above method the benzanthrone is formed by
building the benzene ring on to the anthraquinone nucleus.
Benzanthrones, however, can also be formed by building up
the anthraquinone residue, and extremely important results
have been obtained by reactions of this type. The methods
used for achieving this result fall broadly into two classes,
viz. methods in which the anthraquinone ring system is
completed through the cyclic carbonyl group, and methods
in which the anthraquinone ring system is completed through
the other central carbon atom.
The first method originated in the preparation of a
highl}' condensed benzanthrone, anthranthrone, by loss of
two molecvdes of water from i.i'-dinaphthyl-8.8'-dicarbox>-lic
acid, or from i.i'-dinaphthyl-2.8-dicarbox}-lic acid,^ the
product being an orange-yellow vat dye.
1 B.A.S.F., D.R.P. 204,354. 2 D.R.P. 247,187.
3 Kalb, B. 47, 1724. Cf. Weitzenbock, M. 39, 307.
THE BENZANTHRONES
323
Schaarschmidt ^ extended the method by showing that
allochtysoketone (3.4-benzfluorenone) on fusion with caustic
potash gives two monocarboxj^lic acids, one of these by loss
of water passing back into allochrysoketone, whereas the
other yields benzanthrone :
COOH
COOH
He also found that i-phen3'lnaphthalene-2.3-dicarboxylic
acid b}' loss of water gave both allochr>'Soketone carboxylic
acid 2 and benzanthrone carbox^-lic acid,^ the latter acid
being obtained b}' heating for three hours with sidphuric
acid of 91 per cent, strength. In this case the benzanthrone
could only have been formed by the series of reactions shown
below, i.e. by the opening of the fluorenone ring followed b}-
loss of water in another direction :
COOH
COOH
COOH
COOH
In confirmation of this vSchaarschmidt showed that the
c^'clic imide of i-phenylnaplithalene-2.3-dicarbox}lic acid
can be converted into the amide of allochr^-soketone car-
box^'lic acid, and that this in turn gives the amide of the
benzanthrone carboxylic acid. This method of preparing
1 B. 51, 1082. 2 B. 48. 1827. 3 j3 50, 294 ; 51, 1074.
324 ANTHRACENE AND ANTHRAQUINONE
benzanthrones is not invariabl}^ successful. Thus, starting
with the fluorenone derivative (I) Schaarschmidt i en-
deavoured to prepare the benzanthrone derivatives (II), but
was not successful as the product obtained was the
isomeric fluorenone (III) :
Schaarschmidt established the structure of his product
by synthesising it by the action of copper powder on 2-ben-
zoylanthraquinone-3-diazonium sulphate.
The second method of building up the anthraquinone
ring system so as to produce a benzanthrone is due to Scholl,^
and is generally known as " Scholl's peri-method." It
has proved of the utmost value in the study of the more
complex benzanthrones, as will be seen later. The method
is based on the fact that aromatic ketones in which there is
at least one pair of free positions in the peri- position to
one another evolve hydrogen when heated with anh3^drous
aluminium chloride to about 140°, the two carbon atoms
in the peri- position to one another becoming imited.
Thus, phenyl-i-naphthyl ketone (a-benzoyl naphthalene)
gives benzanthrone itself, 0- and _^-tolyl-i-naphthyl ketone
give the corresponding methyl benzanthrones, the new
bond being shown in the formulae as a dotted line :
CH=
CO CHs CO CO
In the case of m-tolyl-i-naphthyl ketone, two possible
isomeis (A^and B) might be formed :
1 B. 51, 1230. • Scholl, A. 394, in ; B. 44. 1656 ; M. 33, i.
THE BENZANTHRONES
325
As the compound obtained is identical with that obtained
from 2-methylanthrone by the glycerine method,^ formula A
must be the correct one.
Benzanthrone on reduction 2 with sodium hydrosulphite
yields dih3^drobenzanthrone (I), which is ver>^ sensitive to
oxidation by atmospheric oxy-gen. Further reduction leads
to benzanthrene (II or III), and then to dihydrobenzan-
threne (IV or V) :
OH
Hp
H
K
k. Jch
CH\^CH
\A
CH.
A/
\ Jch
CH
CH
CH
I
n
in
This last compoimd is identical with the iso-chrysofluorene
which Graebe ^ obtained by passing benzyl naphthalene over
red-hot pumice.
When benzanthrone is halogenated * by means of molecular
or nascent halogen either in aqueous suspension or in the
presence of an organic solvent such as acetic acid or nitro-
benzene, the halogen atoms first enter the Bz.-ring, the
products giving unsubstituted anthraquinone-a-carboxylic
acid on oxidation. Halogen atoms in this position are
much more reactive than those attached to the anthra-
quinone nucleus.
Bertram Meyer, F.P. 407,593 (G.C.I. B.).
- Ballv and Scholl, B. 44, 1656. ' B, 27 953.
' B.A.S.F.. D.R.P. 193.959-
326 ANTHRACENE AND ANTHRAQUINONE
The majority of the benzanthrone dyes are of compHcated
structure and are treated elsewhere in this chapter, but
orange and brown vat dyes have been claimed as being
obtained b}- condensing halogen benzanthrones with primary
aromatic amines, or by condensing aminobenzanthrones with
halogen compoimds. ^ A black vat dye of uiiknown structure
is said to be obtained when nitrobenzanthrone is fused with
caustic potash. 2 It is probably a violanthrone derivative.
The benzanthrones yield highly coloured solutions when
dissolved in concentrated sulphuric acid, although they
are precipitated unchanged on the addition of water. From
benzanthrone itself, however, a cr^^stalline ferrichloride,
stannichloride and platinichloride can be obtained, and
other benzanthrones form similar compoxmds.^ In these
the metal chloride is probably loosely joined to the carbonyl
ox3'gen atom, and their formation is not surprising as similar
double compounds are formed by other ketones. Thus,
benzophenone and fluorenone both form nitrates b}^ union
with one molecule of nitric acid, and fluorenone also forms
a trichloracetate. Both of them, and also acetophenone,
form salts with metal halides such as stannic chloride and
mercuric chloride, ^ and the union of ketones with aluminium
chloride is well known. ^ Phenanthraquinone, benzil and
other ketones exhibit the same tendency to form addition
compounds with metal chlorides ^ and perchloric acid,"^
but in anthraquinone and its derivatives this tendenc}' is not
so well marked. Thus, neither anthraquinone nor alizarin
forms a perchlorate, although the former unites with two
molecules of antimony pentachloride. It is not known
whether the benzanthrones form perchlorates or not, but it
is extremely probable that they would, and as the ketone
perchlorates are usuallj- well crv^stallised and sparingly
soluble substances, they would probably furnish a useful
means of purifying the benzanthrones.
The hydroxybenzanthrones have been but little studied
1 By., D.R.P. 200,014. 2 G.C.I.B., D.R.P. 262,478.
■• A. G. Perkiu, See. 117, 696. « Kurt Meyer. B. 43, 157-
* See p. 130. « Kurt Meyer, B. 41, 2568.
' K. A. Hofmann and Metzler, B. 43, 178.
THE BENZANTHRONES 327
up to the present. The dihydroxybenzanthrone (beiizalizarin)
obtained from alizarin has been prepared by Perkin.^ who
finds that both hydroxys] groups can easily be methylated
by treatment with methyl iodide and caustic potash. Con-
sequently benzalizariu is probabl}' 7.8-dihydrox>^-i.9-benz-
anthrone :
Curiously enough its tinctorial properties are very similar
to those of alizarin, and a more detailed stud}^ of the hydroxy
benzanthrones would probably lead to valuable information
as regards the constitution of the hydroxy ketone dyestuffs.
II. The C0MPI.EX Benzanthrones
The complex benzanthrones can be broadly divided into
two classes, viz. derivatives of per}dene and derivatives of
pyrene. The former class comprises violanthrones, /so- violan-
thrones, cyanthrones, and helianthrones, whereas the latter
class comprises the p5^ranthrones. * In the following formulae
the characteristic ring system is shown by heavy lines. 2
CO
Violanihrone \y iso-Violanihrone
» Soc. 117. 696.
* In the literature these compounds are almost invariably given names
terminating in -ene, e.g. violanthrene, pyranthrene, etc. In the following
pages the termination -one has been adopted to denote their ketonic structure
the termination -ene being reserved for the parent hydrocarbon which
can usually be obtained by reduction. This nomenclature is merely an
extension of the system proposed by Scholl in connection with the helian-
thrones, and in all cases where confusion seems likely to arise a footnote
has been added. The same system has been adopted when deaHng with
the indanthrones (indanthrenes), the change in this case being particularly
advisable owng to Indanthrene being a registered trade name.
328 ANTHRACENE AND ANTHRAQUINONE
CO co-
co
Heliani-hrone
CO
Pyranihrone^
The hydrocarbons, per34ene and pyrene, themselves have
been studied by SchoU. The former he obtained by heating
naphthalene, or better i.i'-dinaphthyl, with anh5^drous
aluminium chloride, i The latter has, of course, been known
for many j^ears, but has also been investigated b}' Scholl, who
has pointed out that in the case of condensed hydrocarbons
which are readily oxidised to a quinone, the hydrogen
atoms which are attacked during quinone formation are
always those which are split out when the hydrocarbon
undergoes a Friedel-Crafts reaction. On this basis, and
with regard to the structure of the mono-, di-, and tri-benzoyl
derivatives formed by the action of benzoyl chloride in the
presence of aluminium chloride, ^ he concludes that pyrene
quinone must have formula I or II, and not formula III, as
proposed by Bamberger, ^ and as usually given in the
literature :
By oxidising dibenzo3'l pyrene Scholl obtained what
he thought was probably impure pyrene quinone, and there-
fore he gives preference to formula I. Goldschmidt,* on the
other hand, gives preference to formula II.
1 B. 43, 2202.
» A. 240, 158.
2 See p. 337.
* A. 351, 230.
THE BENZANTHRONES 329
Vioi^ANTHRONES. — When benzanthrone is fused with
caustic potash ^ a dark blue vat dye is obtained which was
originally given the trade name of Violanthrene BS, this
being subsequently altered to Indanthrene Dark Blue BO
(Caledou Dark Blue B).2 The constitution of the dye was
definitely proved by Scholl,^ who synthesised it by his
peri- method by heating 4. 4'-dibenzoyl-i.i'-dinaphthyl with
aluminium cliloride, three pairs of peri- positions becoming
united as shown by the dotted lines in the following formula :
The formation of violanthrone by fusing benzanthrone
obviously consists in the linking up of two molecules by
the union of two pairs of carbon atoms as indicated by the
dotted lines (formula I, page 330) . Such reactions are not un-
common, and the appended formulae illustrate cases in which
they have been observed, although several of the substances
obtained have not 3'et been submitted to scientific examina-
tion, so that the structure assigned to them is more or less
guesswork. The substance represented by formula V is
a green dye, whereas that represented by IV gives only
bordeaux shades. From this it is probable that in V union
has taken place at three points, the extra bond being denoted
by the line of crosses. In VI it is probable that imion at
either two or four points can take place, as when the fusion
is carried out at 220-300° a reddish-brown dye (dotted
bonds only) is obtained, whereas the dye obtained at higher
temperatures is greyish-blue (dotted bonds and cross
bonds).
1 B.A.S.F., D.R.P. 185,221; 188,193; 290,079. A. G. Perkin, E.P.
126,765 (1918).
- Scottish Dyes, Ltd. s B. 43, 2208.
330 ANTHRACENE AND ANTHRAQUINONE
BeMzonthrone,
cof\co
n
Naphihinolenon.
m
Naphihindandion.
CO— c
IV
YI
A violantlirone is also obtained when the benzanthrone
prepared from 1.2-beuzanthraquinone is fused with caustic
alkali. It dyes in rather greener shades than violanthrone
itself. Its structure, how^ever, is doubtful, as 1.2-benzanthra-
quinone might form three isomeric benzanthrones.6
Nitration of violanthrone '^ yields a green vat dj-e, which
was formerly known as Viridanthrene B, although the
name was subsequentl}- altered to Indanthrene Green B
(Caledon Green B).^ It is rather remarkable that a nitro
compound should be capable of being used as a vat dye
1 Errera. G. (1911), 190- B.A.S.F., D.R.P. 283,066.
- B.A.S.F., D.R.P. 283,365.
3 Karclos, D.R.P. 276,357-8; 276,956; 286,098. B.A.S.F., D.R.P.
280,880.
* Kardos, D.R.P. 275,220 ; 278,660; 280,8^9; 282,711; 284,210.
3 Kardos, D.R.P. 286,468. Cf. Graebe, A. 276, 17.
« B.A.S.F., D.R.P. 185,223.
' B.A.S.F., D.R.P. 1S5.222 ; 226,215.
« Scottish Dyes, Ltd.
THE BENZANTHRONES 331
without the nitro group being reduced. From nitroviolau-
throne the corresponding amino- compound can be prepared,
and this can be alkylated, arj^lated, or combined with alde-
hydes. These amino compounds dye in rather greener
shades than violanthrone itself, but are of no technical
value. 1
When violanthrone is oxidised, e.g. with sulphuric acid
and boric acid, a product is formed which has very feeble
tinctorial properties. B}^ heating this with a condensing
agent such as boric acid at 160°, however, it is converted
into a powerful green dj^e, the tinctorial properties of which
are improved by bromination, although the shade becomes
somewhat yellower. 2 Violanthrone itself can be halogenated,^
the halogenated product being placed on the market as
Indanthrene Violet RT.
zso-Vioi,ANTHRONES. — z'so- Violauthrouc is isomeric with
violanthrone, and is obtained when brombenzanthrone is
fused with caustic akali.* The patentees assigned to it
formula I, but Scholl regards it as a per^-lene derivative and
prefers formula II.
I II
Scholl 5 endeavoured to confirm his formula by effecting
a synthesis of the dyestuff from dibenzoyl perjlene by his
peri- method, thus :
» B.A.S.F., D.R.P. 267,418 ; 268,224 ; 284,700.
- B.A.S.F., D.R.P. 259,370 ; 260.020 ; 280,710.
=• B.A.S.F., D.R.P. 177.574.
* B.A.S.F.. D.R.P. 194,252.
^ B. 43, 2208.
332 ANTHRACENE AND ANTHRAQUINONE
The synthesis, however, was not successful, and probably
the carbonyl groups in dibenzoyl perylene are not in the
positions in which they are shown in the above formula.
iso-Violanthrone itself is a powerful vat dye, and was
formerly known as Violanthrene R Extra, this being subse-
quently changed to Indanthrene Violet R Extra (Caledon
Brilliant Purple R).i Its dichlor derivative is Indanthrene
Violet RR Extra (Caldeon Brilliant Purple RR) ^ and its
dibrom derivative Indanthrene Violet R Extra. 2 Its nitro
derivative is of no value. ^
Cyanthrones. — These are complex quinoline derivatives
of benzanthrone, and have been but little investigated.
Benzanthrone quinoline itself (3(N).4-pyridino-i.9-benzan-
throne) is obtained from jS-aminoanthraquinone by Skraup's
method, both quinoline and benzanthrone formation taking
place simultaneously. 4 When fused with caustic potash it
gives a vat dye, Indanthrene Dark Blue BT (formerly
Cyanthrene). This has not been scientifically investigated,
but is probably formed by the union of two molecules as shown
by the dotted lines : ^
Its halosfen derivatives have also been described. ^
■'a
1 Scottish Dyes, Ltd. - B.A.S.F.. D.R.P. 217.570.
^ B.A.S.F., D.R.P. 234,749. * B.A.S.F., D.R.P. 171,939-
5 Baely, B. 38, 196. B.A.S.F.. 172,609. « B.A.S.F., D.R.P. 177.574-
THE BEN Z ANT H RONES 333
A much more simple benzanthrone quinoline is obtained
by condensing i?2:.-chlorbenzanthrone with a-aminoanthra-
quinone and then fusing the benzanthronyl-a-aminoanthra-
quinone with caustic potash. Apparently the alkali causes
closing of the quinoline ring as shown by the dotted line.i
The product is a green vat dye, although it is not used
commercially :
Hewanthrones. — When i.i'-dianthraquinonyl is re-
duced, preferably by means of copper bronze and concen-
trated sulphuric acid at 40-50°, ring formation takes place
b}'- union of two ws-carbon atoms. The product is ms-
benzdianthrone or helianthrone, a yellow vat dye, which,
however, has not found technical application : 2
CO
Helianthrone.
By the same method Scholl has prepared dihydrox}- and
tetrahydroxy derivatives. ^
It will be observed that in helianthrone there is a pair
of carbon atoms in the peri- position to one another, so that
a new ring, as indicated b}- the dotted line, should be fonned
by heating with aluminium chloride :
1 B.A.S.F., D.R.P. 2i2,47T[.
2 Scholl. B. 43, 1734. D.R.P. 190,799; 197.933- Q- Eckert and
Tomaschek, M. 39, 839.
' B. 44, io9i.'j'C>. Seer, M. 34, 631.
334 ANTHRACENE AND ANTHRAQUINONE
CO
JMS-Naphthadianthrone.
This Scholl has found to be the case, and he has also prepared
the same compound by distilling dianthraquinonyl with zinc
dust.i Meyer, Bondj^ and Eckert 2 claim that it is more
readil}' obtained by exposing glacial acetic acid solutions of
dianthrone to sunlight or iiltra-violet light, but their observa-
tions require independent confirmation as they deduce the
formula from four analyses in which values obtained for
carbon var}^ from 87*8 to 887 per cent., and those for hydro-
gen from 3*2 to 3*8 per cent. 3 In a later paper, however,
Eckert and Tomaschek ^ describe several halogen derivatives
which the}' have obtained by similar means. ws-Naph-
thadianthrone acts as an orange vat dye, although reduction
to the vat is very difficult.
The reduction products of helianthrone itself have been
investigated b}^ Potschiwauscheg,^ who obtained three
products :
H OH
H OH
H OH
H OH
The first of these he was only able to isolate in the form of
its diacetate. He was unable to obtain the parent hydro-
carbon.
Attention may here be drawn to a series of olive and brown
vat dyes of miknown constitution which are obtained by
B. 52, 1829.
2 M. 33, 1451.
M. 39. 839.
3 C.,,Hi Oj, requires C = 88 -4/11 =
' B. 43, 1746,
=3-16.
THE BEN Z ANT H RONES 335
the action of concentrated sulphuric acid and copper powder
on anthraquinone derivatives. ^ The}- are probably helian-
throne derivatives, although their structure has never been
investigated. The brown and bronze vat dyes which are
obtained from 1.2-benzanthraquinone, dianthrone and di-
anthrol by heating with aluminium chloride are also probably
helianthrones.2
Pyranthrones. — When 2.2'-dimethyl-i.i'-dianthraquin-
onyl is heated alone at 380°, or with zinc chloride at 280°, or,
better, with alcoholic caustic potash at 145°, a very fast
orange vat dye is obtained, ^ which was formerly known as
Pyranthrene, but was later named Indanthrene Golden
Orange G. The dichlor derivative (Indanthrene Golden
Orange R) and the dibrom derivative (Indanthrene Scarlet G)
dye in redder shades and can be obtained either by halogen-
ating pyranthrone, or, syntheticall}-, from the corresponding
halogen dimethyldianthraquinony 1 . '
Pyranthrone formation also takes place when i.i'-
dianthraquinonyl-2.2'-dialdehyde is reduced, e.g. with sodium
h3'drosulpliite and the /gz<co-product thus formed then
oxidised,^ and advantage has been taken of this reaction
in printing, the pattern being printed on to the cloth with
the aldehyde and the colour then developed in a h3-dro-
sulphite bath followed by oxidation. The corresponding
dianthraquinonyl diketones also yield pyranthrones on
reduction, e.g. 2. 2 '-dibenzoyl-i.i '-dianthraquinonyl gives
diphen3'lpyranthrone.6 These diar}-lpyranthrones are yeUow
vat dyes, and Scholl has found that alkyl groups also
decrease the colour.'^ The structure of p3-ranthrone was
definitely established by Scholl b}' sj-nthesis by his peri-
method, but as Scholl used the same methods for preparing
some highly complex pyranthrones it will be best to postpone
the discussion of the synthesis from pyrene, and first consider
1 B.A.S.F.. D.R.P. 190,656. By., D.R.P. 203.436; 205,442.
2 E., D.R.P. 237,751 ; 241,631.
^ SchoU, B. 43, 346, 5t2 ; 44, 1448, 1662 ; M. 32, 687. B.A.S.F..
D.R.P. 174.494; 175.067; 212,019; 287,270.
* Scholl, B. 43, 352; M. 39. 231. B.A.S.F., D.R.P. 186,596 ; 211,927 ;
218,162. ■ ' B.A.S.F.. D.R.P. 238.980.
« B.A.S.F.. D.R.P. 278.424. ^ M. 32, 687.
336 ANTHRACENE AND ANTHRAQUINONE
the mechanism of p^-ranthione formation from2.2'-dimeth3-l-
i.i'-dianthraquinonyl.
At first sight it would seem probable that pyranthrone
formation was preceded by a wandering of hydrogen atoms
to the neighbouring cyclic carbonyl groups with the forma-
tion of an aldol-like product, pyranthrone formation taking
place by subsequent loss of water :
If this were the case, the corresponding diethyl and di-«-
propyl dianthraquinonyls should behave in exactly the
same way, giving rise to dimethyl and diethyl pyranthrone.
In the case of di-zso-propyldianthraquinonyl there is no
reason why the first of the above steps should not take
place, but the aldol-like product could not pass into a pyran-
throne b}" loss of water owing to the necessary hydrogen
being absent. SchoU i has examined the behaviour of all
three substances, and finds that diethyl and di-/so-propyl
dianthraquinonyl both give pyranthrones, although not
nearly so readily as dimethyldianthraquinonyl. In the
case of 2.2'-di-iso-propyl-i.i'-dianthraquinonyl, however,
no reaction whatsoever took place, although it was to be
expected that the aldol-like substance would be obtained.
It is therefore very probable that pyranthrone formation is
a direct loss of water and is not preceded by a migration of
hydrogen atoms. The dimethyl and diethyl pyranthrones
which Scholl obtained are ven^ similar to pyranthrone itself
in their tinctorial properties although they give paler shades.
The synthesis of pyranthrone and of many ver}- complex
pyranthrone derivatives has been achieved by Scholl 2
by means of his peri- method. Starting with pyrene he
first condensed it with benzoyl chloride in the presence of
1 M. 32, 687. = A. 394, III ; M. 33, I. D.R.P. 239,671.
THE BENZANTHRONES
337
aluminium cliloride, and in this wa}- obtained mono-, di-,
and tribenzoyl pyrene. From dibenzoyl pyrene by heating
with aluminium chloride he obtained pyranthrone (I),
whereas the tribenzoyl derivative gave benzoyl pyran-
throne (II) :
In benzoyl pyranthrone it will be noticed that there is
still a pair of carbon atoms in the peri- position to one
another. It was foimd impossible, however, to cause these
to unite, and it seems to be a general rule that in the case of
six-membered rings peri- condensation cannot take place
twice at the same side of the p3'rene nucleus. This is
probably to be attributed to steric influences, for, as will be
seen below, in the case of five-membered rings such double
peri- condensation is possible.
By condensing a-naphthoyl chloride and j3-naphthoyl
chloride with pyrene Scholl obtained dinaphthoyl pyrenes,
which when heated with aluminium chloride passed into
complex pyranthrones (III and IV) :
in IV
In the case of di-a-naphthoyl pyrene, pyranthrone
formation can only take place as indicated by formula III.
In the case of di-/3-uaphtho}l pyrene, however, pyranthrone
22
338 ANTHRACENE AND ANTHRAQUINONE
formation might take place through the a-carbon atoms of
the naphthalene nuclei, as indicated in formula IV, or it
might possibly take place through the j8-carbon atoms. The
a-carbon atoms, however, are always the most reactive, and
it has been shown definitely in the case of phenyl naphthyl
ketone that the a-carbon atom is capable of undergoing peri-
condensation, 1 and also that in the case of jS-anthraquinonyl-
a-naphthyl ketone it is the a-carbon atom which reacts. 2
Hence, in the absence of all evidence to the contrary,
formula IV must be accepted as representing what actually
takes place.
Scholl has also employed his peri- method for building
up complex pyranthrones containing five-membered hetero-
cyclic rings. He first showed that a-thienyl-i -naphthyl
ketone gives a condensation product (V) when heated with
aluminium chloride, and that a-furyl-i -naphthyl ketone
behaves in the same way (VI), although in this latter case
he was unable to isolate the product in the pure condition :
S CO 0 CO
V VJ
By condensing two molecules of a-thienylcarbonyl
chloride with one molecule of pyrene, Scholl obtained two
ketones, both of which when heated with aluminium chloride
underwent condensation (VII and VIII) :
^ See p. 324. * See p. 156.
THE BENZANTHRONES
339
It will thus be seen that in the case of five-membered
rings a double peri- condensation at the same side of the
pyrene nucleus is possible.
As regards the tinctorial properties of these complex
pyranthrones, the pyranthrones derived from both naphthoyl
pyrenes dye in redder shades than pyranthrone itself, this
being particularly noticeable in the case of the j3- compound
(formula IV, page 337). Both thiophene pyranthrones are
brown vat dyes, but the one represented by formtda VII is
the most powerful.
Pyranthrone itself on reduction in alkaline solution gives
onl}' a purple red vat, and in this way differs from many of
the other complex anthraquinonoid vat dyes, such as indan-
throne and flavanthrone, which are capable of giving two
different vats. The pyranthrone vat is verj- unstable towards
atmospheric 0X3'gen, and Scholl 1 was only able to isolate it
in the form of its brombenzoyl derivative, which he found to
correspond to formula IX. Further reduction leads to the
parent h5-drocarbon, pyranthrene, which is represented by
formula X :
X
Brown and green dyes can be obtained b}- the nitration
and reduction of pyranthrone. 2
1 B. 43, 346.
" Scholl, B. 43, 346. By., D.R.P. 220,580. B.A.S.F., D.R.P. 268,504.
CHAPTER XVI
THE CYCLIC AZINES AND-HYDRO-
AZINES
The C}'clic azines and hydroazines of the authraquinone series
can be conveniently divided into two groups, viz. mixed
compounds in which only one authraquinone ring S3^stem
is present, and simple compounds in which the azine ring lies
between two authraquinone residues. Of these two groups
the latter has been studied most fully, as some extremely
important vat dyes have been foimd to be simple authra-
quinone h^'droazines.
I. The Mixed Azines and Hydroazines
Mixed azines are obtained by condensing an o-diamino-
anthraquinone with an a-diketone. The simplest azine
obtainable by this method is the pyrazino- compound (I),
which is formed b}' condensing 1.2-diaminoanthraquinone
with ethyl oxalate. ^ vSomewhat more complicated are the
blue-black vat dyes which are obtained b}" condensing two
molecules of an o-diamino authraquinone with one molecule
of glyoxylic acid by boiling in glacial acetic acid solution,
or in alcoholic solution in the presence of a little stdphuric
acid. 2 Their structure probably corresponds to formula II ;
N N NH '
^COH
N
1 Ertl. M. 35, 1427. Scholl, B, 44. 1729. Terres, B. 46, 1644.
^ G.E., D.R.P. 264.043.
340
THE CYCLIC AZINES AND HYDROAZINES 341
The first of these compounds is of some mterest, as it
is also obtained by the oxidation of indanthrone.
Mixed azines have been obtained by condensing both
i.2-dianiinoanthraquiiione and 2.3-diaminoanthraquinone
with a large number of a-diketonic compounds such as benzil,
phenanthraquinone, ^-naphthaquinone and isatin.^ With
the latter substance under certain conditions 3-enow and
red vat dyes are obtained the structure of which is quite
uncertain, as, unlike other azines, they give almost colourless
vats. 2
The azines obtahied from 1.2-diaminoanthraquinone are,
of course, angular in structure, whereas those obtained from
2.3-diaminoanthraquinone must be linear. The former on
reduction in alkaline solution give blue vats, whereas the
latter give brown solutions. As the azines obtained from
1.2.3-triaminoanthraquinone give brown solutions on alkaline
reduction it is probable that they are linear in structure and
that the free amino group is in the a- position. ^
N-Substituted cyclic hydroazines are said to be obtained
by condensing o-aminoar3'lamino anthraquinones with
aldehydes and ketones, and it has been claimed that their
sulphonic acids are blue wool dyes.^ o-Aminoazo- com-
pounds are also said to yield cyclic azines under certain
conditions. 5
Of greater importance is the cyclic azine sjmthesis devised
by Ullmann.6 He found that when an o-nitrophenyl-i-
amino-anthraquinone is reduced with sodium hydrosulphite
the corresponding primar}- amino- compound is formed,
but that if the reduction is brought about b}^ means of sodium
sulphide an almost quantitative ^-ield of the C3'clic h3-dro-
azine is obtained. The mechanism of this reaction consists,
no doubt, primarily in the production of a hydrox^-lamine
derivative, the azine ring being then closed b}' loss of a mole-
cule of water :
» Scholl, M. 32. 1043. SchoU and Kacer. B. 37, 4531. Terres, B. 46,
1634. By., D.R.P. 170,565.
» Bv., D.R.P. 251,956.
=» Scholl, M. 32, 1043. « By., D.R.P. 184,391 ; 252,529.
* M.L.B., D.R.P. 230,005 ; 232,526. « A. 380, 324.
342 ANTHRACENE AND ANTHRAQUINONE
NH
A somewhat similar synthesis has been devised by Ull-
mann and Medenwald ^ who obtain azines by oxidising o-
aminoatyl aminoanthraquinones with lead dioxide.
The hydroazines are blue substances which are capable
of use as vat dyes although the mixed hydroazines are of
no technical value. The imino hydrogen atoms cannot be
replaced by acet}^ groups, ^ all attempts at acetylation lead-
ing to the diacetate of the anthraquinol derivative owing
to the cyclic carbonyl groups of one molecule becoming
reduced at the expense of the imino hydrogen atoms of
another molecule. On oxidation the hj'droazines pass into
the corresponding azine. These are yellow compounds
and are much more stable than the h3'droazines. As will
be seen later, this is the reverse of what is found to be true
in the case of the simple azines and hydroazines.
II. The Simple Azines and Hydroazines
Simple azines and hydroazines (indanthrones *) can be
obtained by methods ver\^ similar to those employed for
the production of the mixed compounds. Thus simple
cyclic azines or hydroazines are obtained when o-diamino-
1 B. 46, 1809. 2 Ullmann, A. 380, 324.
* The first cyclic azine of the anthraquinone series to be prepared was
trans, iz'sawg.-anthraquinonedihydro azine. This wa's placed on the
market under the name Indanthrene Blue, and the name " indanthrene "
has come into general use in the literature. The word " indanthrene,"
however, is a registered trade name (B.A.S.F.) and is applied to many vat
dyes which are not azines. Indanthrene Blue is an anthraquinone deriva-
tive and ketonic in structure, and in order to denote its ketonic nature
the name should terminate in -one. In the following pages, therefore, the
word " indanthrone" is used to denote the ketonic hydroazine, indanthrene
(without a capital) being used for the parent, oxygen free hydroazine
(trans. bisaiTg. -dihydroa.nthra.zine). Where " Indanthrene " is used as a
registered trade name it is spelt with a capital. This system of nomen-
clature should not lead to any confusion as the dihydroanthrazine is of
very little importance. Where any confusion seems possible a footnote
has been added.
THE CYCLIC AZINES AND HYDROAZINES 343
anthraquinones are condensed with o-dihydroxyanthra-
quinones such as aHzarin, best by heating with boric acid
and a solvent of high boiling point, 1 or with 1.2-anthra-
quinone.2 In the latter case, of course, the product is an
anthracene anthraquinone azine {trans, i^'saw^.-anthroanthra-
quinone azine), but the anthracene residue is readily oxidised
to the quinone. Cyclic azines are also obtained by oxidising
o-aminodianthraquinonylamines by heating alone in the air,
or by heating with a nitro- compound, oleum or sulphuric
acid and manganese dioxide. -"^ The o-nitrodianthraquinonyl-
amines also give C3^c]ic hydroazines on reduction with
sodium sulphide, although in this case it is necessan,- to
csiTTy out the reduction b}- fusion with cr3'Stallised sodium
sulphide, as treatment with aqueous solution leads onl}- to
brown substances of imknown constitution.* Better results
are usually obtained b}' reducing 02-dinitrodianthraquinonyl-
amines with stannous chloride and hydrochloric acid in
acetic acid solution, one nitro group being split out.^ This
method is of very general application for the preparation of
azines and b}' it phenazine itself can be obtained in excellent
yield from 02"dinitrodiphenylamine.<^
From a practical point of view by far the most important
method of obtaining the indanthrones is by fusing the
jS-aminoanthraquinones with caustic alkali, and this method
has been ver>' widel}^ applied not only to ^-aminoanthra-
quinone itself, '^ but also to diaminoanthraquinones ^ and
j3-aminoanthraquinone sulphonic acids, ^ although in the
latter case the sulphonic acid group is often lost. Even
j8-anthramine is said to yield a cyclic hydroazine (anthr azine)
when fused with caustic alkali, ^o The anthraquinonyl-j8-
hydrox^'lamines, however, do not give cyclic azines. '^
1 By., D.R.P. 178,130.
- Terres, B. 46, 1634.
' B.A.S.F., D.R.p! 186,465. By., D.R.P. 239,211.
* By., D.R.P. 178,129; 213,501.
•'• Eckcrt and Steiner, '^\. 35, 1120.
« Eckt-rt, M. 35, 1153. Cf. also B. 38, 2975 ; Soc. 95, 577-
" Scholl, B. 36, 3427. B.A.S.F.. D.R.P. 129,845 ; 135,407-8; 287,270.
» B.A.S.F., D.R.P. 157.685
9 B.A.S.F., D.R.P. 129.846.
«» By., D.R.P. 172,684. Cf. B. 34. 3410. " M. 32. 1035
344 ANTHRACENE AND ANTHRAQUINONE
The mechanism of the conversion of j3-aminoauthra-
quinone into indanthrone is not understood. At one time
it was thought probable that the first product formed was
a h3^drazo compound, and that this then underwent an
ortho-sermdine rearrangement. This, however, can hardly
be the case, as it has been found that no indanthrone is
formed when j8-azox3^anthraquinone is reduced. It is
possible that one molecule of the j3-aminoanthraquinone
reacts in the ^-quinonoid form and then adds on another
molecule reacting in the ordinarj^ form, the azine ring
being completed by a second condensation of a similar
nature :
K OH
H OH
Theories of this nature, however, are merely speculative and
lack experimental verification.
In the alkali melt of jS-aminoanthraquinone the ind-
anthrone is not present as such but as its reduction product
(vat), from which, however, the indanthrone is readrl}-
obtained by blowing air through the aqueous solution.
Also in addition to indanthrone, flavanthrone (pages 300-
304) is formed, and when the melt is carried out with caustic
alkali alone the reduction products of indanthrone and
flavanthrone are produced in the ratio of about two to one.
If a reducing agent is added to the alkali, indanthrone forma-
THE CYCLIC AZINES AND HYDROAZINES 345
tion is greatly hindered, and the reduction product (vat) of
flavanthrone is then ahnost exclusively produced.^ If, on
the other hand, the melt is carried out in the presence of
an oxidising agent such as potassium nitrate or chlorate, 2
flavanthrone formation is prevented and only indanthrone
is obtained. In this case, of course, it is the dye itself and
not its vat which is produced. On this observation has
been based a series of patents ^ claiming the production
of indanthrone by oxidising ^-aminoanthraquinone with
lead dioxide, manganese dioxide, chromic acid, nitric
acid, etc., although these methods are of no practical
importance.
Indanthrones can also be obtained from a-aminoanthra-
quiuones by treatmg them with halogens,* or bj' fusing
them with caustic alkali in the presence of a phenol or
naphthol,5 or by heating them with acids or metallic salts
such as chromium sulphate or copper sulphate. ^ The
yields, however, are usuall}- ver^- poor although the last
method has been extended to the preparation of complex
indanthrones from aminobenzanthrones and amino-
benzanthrone quinolines.'^
Another method of obtaining indanthrones, and one
which has been of value in proving their structure and in
preparing N-substituted indanthrones, consists in splitting
out two molecules of halogen acid from two molecules of an
o-amino halogen anthraquinone. Thus indanthrone itself
is obtained when i-amino-2-bromanthraquinone is heated
in some indifferent solvent of high boiling point with
anhydrous sodium acetate and either cuprous chloride or
copper powder ^ :
1 B.A.S.F., D.R.P. 135,408.
- Morton, Dandridgc, and Morton Sundour Fabrics, Ltd., E.P. 126,112
(1918). In spite of this A. G. Perkin claims in E.P. 126,764 (1918) that the
\-ield and purity of the indanthrone is improved by carrying out the alkali
hision in the presence of sucrose, glucose, lactose, or the like.
3 B.A.S.F., D.R.P. 139.633 ; 141.355 : 238,979.
* By., D.R.P. 161,923.
^ By.. D.R.P. 175,626.
« B.A.S.F., D.R.P. 186,636-7; 238,979.
' B.A.S.F., D.R.P. 198,507; 204,905; 210,565.
» By., D.R.P. I5«.287; 193.121.
346 ANTHRACENE AND ANTHRAQUINONE
CO CO
For the extension of this method to the preparation of
indanthrone derivatives the reader is referred to the original
literature.!
The cyclic hydroazines or indanthrones are blue com-
pounds which act as powerful vat dyes. They are fairly
easily oxidised to the yellow azines, but these are verj^
stable substances and strongh^ resist further oxidation
although the}^ are readily reduced to the cyclic hydroazine.
The most important member of the series is indanthrone
itself (Indanthrene Blue R) , and as this has been uivestigated
in detail it wUl be described at some length, as it serves as a
general type.
In spite of the numerous methods which have been
proposed for the manufacture of indanthrone, the onl}' one
which is of any practical importance consists in fusing
j3-aminoanthraquinone with caustic alkah.2 The dye itself
forms an insoluble blue powder which usuallj' occurs in
commerce in the form of a 20 per cent, paste.
Indanthrone is rather easily oxidised to the yellow azine,
so that material dyed with Indanthrene Blue R is apt to
become slightly 3^ellow on washing, although the original
blue shade can be restored by treatment with a mild reducing
agent. The oxidation to the azme is best carried out in the
laborator^^ b}' means of nitric acid, a bimolecular product
in which the two molecules are joined through the nitrogen
atoms being formed as an intermediate product. ^ The
azine itself is yellow and is much more stable than the
hydroazine, the simple anthraquinone azines in this respect
1 Ullmann, A. 399, 341. By., D.R.P. 158,287; 158,474; 167,255;
193. 121.
" For laboratory details see SchoU, B. 36, 3427.
3 Scholl, B. 36. 3431 ; 40. 320.
THE CYCLIC AZINES AND HYDROAZINES 347
differing from the mixed azines. So stable in fact is the
azine obtained from indanthrone that Scholl 1 was only-
able to oxidise it by boiling it for forty hours with chromic
acid in glacial acetic acid solution. Under these conditions
it passes into the pyrazinoanthraquinone mentioned on
P- 340.
Indanthrone itself is a very feeble base and its salts
even with strong acids are very readily decomposed. For
a long time it was believed that the imino-hydrogen atoms
could not be replaced by acyl groups, as treatment with
acyl chlorides alwa3-s lead to the entrance of halogen atoms
into the molecule with simultaneous reduction and ac^dation
of the cyclic carbonyl groups. 2 In this way indanthrone
resembles indigo,-^ benzoquinone,^ chloranil,^ and the
oxazines and thiazines,^ but Scholl ^ succeeded in preparing
a dibenzoyl indanthrone by boiling indanthrone for a few
minutes with a great excess (70 parts) of benzoyl chloride.
This derivative must have been N-dibenzoyl indanthrone,
as on h3^drolysis indanthrone itself and not its reduction
product was obtained. It was found to be a stable red
substance, so that indanthrone, like indigo, changes from blue
to red on acylation, both diacetyl indigo ^ and dibenzoyl
indigo being red.
The behaviour of indanthrone on reduction has been
carefully investigated by Scholl and his students. When
the reduction is carried out b}^ means of sodium hydro-
sulphite in alkaline solution, first a blue vat and then a brown
vat is obtained, both being ver}- readil}' oxidised by the
air and thereby being changed back to indanthrone. The
blue vat consists of the sodium salt of anthraquinolanthra-
quinone dihydroazine (formula I) and tmder the name
Indanthrone Blue RS ^ has been used in printing. ^^ Scholl.
* B. 44, 1727.
- Scholl and Berblinger, B. 40, 395. B.A.S.F., D.R.P. 229,166.
^ Heller, B. 36, 2762.
* Buchka, B. 14, 1327. - Sarauw, A. 209, 129.
' Graebe, A. 146, 12.
* Scholl, B. 40, 399. Private communication from Bernthsen.
" B. 44, 1732. '^ Liebermann and Dickhuth, B. 24, 4133.
» Caledon Blue R (Scottish Dyes, Ltd.). i" B.A.S.F., D.R.P. 129,848.
348 ANTHRACENE AND ANTHRAQUINONE
Steinkopf and Kabacznik i have prepared the dibenzoyl
derivative, and Scholl and Stegmuller 2 have shown that if
the sodium salt is heated to 220°-230° with concentrated
caustic soda, or if it is heated alone at 250° in an indifferent
atmosphere, auto-oxidation and reduction takes place with
the production of a mixture of anthraquinoneanthranol-
dihj^droazine (formula II) and indanthrone :
OH
I
CO NH C
2C6H4X /C6H2X xCgHoN^
CO NH C
CgH4
OH
OH
CO NH C
CcH4\ /CoH2< ^CgHoC I/C6H4
CO NH C
1
H
CO NH CO
+ C6H4<^C6H2<(^C6H2<0)C6H4+HoO
CO NH CO
II
The former compound, however, is much more readily
obtained b}' reducing indanthrone with boiling alkaline
sodium hydrosulphite solution and then oxidising the
anthraquinol anthranol dihydroazine thus formed by
exposure to the air. On oxidation with sodium hypo-
chlorite it passes into the azine.
The brown vat obtained by the alkaline reduction of
indanthrone consists of the sodium salt of anthraquinol-
dihydroazine ^ and Scholl, Steinkopf, and Kabacznik * have
prepared a tetrabenzoyl derivative.
1 B. 40, 390, ' B. 40, 924-
3 Scholl, B. 36, 3410. ^ B. 40, 390.
THE CYCLIC AZINES AND HYDROAZINES 349
Exhaustive reduction of iiidantlirone by means of zinc
and caustic soda gives N-dihydroantlirazine. The dihydro-
azine group in this is less stable than in indanthrone, so that
heating alone suffices to split off two atoms of hydrogen,
the product left being anthrazine. Both anthrazine and
dihydroanthrazine on oxidation with chromic acid give
anthraquinone azine. Anthrazine when boiled with nitric
acid (D=i40o) gives a compound which is probably penta-
nitrotetrahydrox}- anthrazine, although it has not been
obtained in a state of purit}-.!
The reduction of indanthrone by hydriodic acid has
been studied by SchoU ^ and by Kaufier,^ who find that three
products are formed, viz, C28H16O2N2, CogHigOaNo and
CO NH CO CO N CO
:,K,<: )CoH2< >C6H2<^>C6H, -4" C6H4<^))C6H2^)>C6H2^\C6H,
yC\ NH CO , ^^.--^ CHo N CO
W ^OH
H\ /OH
CO NH ^C-^ CO N CH2
:,H,<0>C6H2<^^C6H2<3>C6H4 ^-$ C6H4<^))C6H20C6H2<(^C6H4
CHo NH CO ^-^ CH2 N CO
0^ -' Anthronazine, CogHigOjN
CO NH CH2 CH N CH2
:eH,(()>C6H20C6H2<()>C6H4 '--^ Cen,(pC,li^^yCeli2(yCell,
CHo NH CO ^^^ CH N CO
N-Dihydroanthronazine, CjjHjgOjNj *
CH NH CH2 CH N CH
CeH^v I /C6H2\ /C6H2\yC6H4 > CeH4\^j^C6H2\^^C6H2N^ y^6^4
CH NH CO CH N CH
Anthrazine, C^gHnNj
» Scholl. B. 40, 933. Cf. SchoU, B. 86, 3442. Bv.. D.R.P. 172,684.
* B. 36, 3410. ' B. 36, 930.
350 ANTHRACENE AND ANTHRAQUINONE
C28H16N2. The last of these is anthrazine, and of the two
former, the second is readily oxidised to the first either by
loss of hydrogen when heated alone to 340°, or by boiling
with nitrobenzene, and hence is probably a dih^-droazine.
Neither compound is soluble in aqueous caustic alkali, but
both are soluble in alcoholic alkali, and this points to an
anthrone structure. If this be assumed' the reduction of
indanthrone would appear to consist in an alternate adding
on of hj'drogen and splitting off of water.
As stated on p. 346 fabric dyed with Indanthrene Blue R
(indanthrone) tends to become yellow on washing owing to
the oxidation of the dihj'droazine to the azine. Such
oxidation is obviousl}' impossible if the iminohydrogen
atoms are replaced by methyl groups, and N-dimethyl
indanthrone, made from i-meth3-laniino-2-bromanthra-
quinone by heating with sodium acetate and copper powder
or cuprous chloride, 1 has been placed on the market under
the name Algol Blue K. It is much faster to soap than
Indanthrene Blue R, and has the further advantage that
dyeings can be made from a cold vat, 2 whereas Indanthrene
Blue R only gives satisfactory- results if used at a temperature
of at least 50°.
Halogen indanthrones can be obtained from halogenated
aminoanthraquinones,^ or by halogenating indanthrone
itself by treatment with molecular or nascent chlorine, ^ or
with sulphursd chloride, » thionyl chloride, ^ sulphur chloride
or stannous chloride,'' antimon}^ pentachloride,^ or the
chloride of an organic acid.^ The bromination of indan-
throne, however, only takes place with great difficulty, and
chlorindanthrones completely free from bromine are said
1 By., D.R.P. 158,287 ; 193.121 ; 234.294 ; B.A.S.F., D.R.P. 238,979-
- By., D.R.P. 240,265.
3 Ullmann, A. 399, 341. By., D.R.P. 158,474 ; 167,255.
* SchoU and BerbUnger, B. 40, 320. B.A.S.F., D.R.P. 138,167 ; 155,415.
M.L.B., D.R.P. 296,841. G.C.I. B., E.P. 113,783 (1918). G.E., D.R.P.
292,127.
5 B.A.S.F., D.R.P. 157,440. M.L.B., D.R.P. 293.971.
6 M.L.B., D.R.P. 287,590.
' M.L.B., D.R.P. 289,279. G.E., D.R.P. 296,192 ; 271,947. Cf. also
M.L.B., D.R.P. 224,500 ; 240,792; 245,768; 246.867.
8 B.A.S.F., D.R.P. 168,042. » B.A.S.F., D.R.P. 229,166.
THE CYCLIC AZINES AND HYDROAZINES 351
to be obtained when indanthrone is suspended in bromine
and then treated with chlorine. 1 Halogen indanthrones
can also be obtained by boiling the corresponding azines with
halogen acid. 2 The reaction in this case is merely the
usual addition of a molecule of halogen acid to a quinonoid
compoimd. The resulting monohalogen hydroazine can
then be oxidised to the azine and a second atom of halogen
introduced in the same way.
The halogen indanthrones are much less easily oxidised
to the azine than is indanthrone itself, ^ and consequently
the shades obtained by their use are fast to soap. Various
halogenated indanthrones have been introduced as vat
dyes, of which Indanthrene Blue GCD "^ and Indanthrene
Blue GC ^ are the most important. The former consists
chiefly of dichlorindanthrone, whereas the latter seems to
be a mixture of dibromindanthrone and tribromindanthrone.
They are both fast to soap and dye in somewhat greener
shades than indanthrone itself.
Hydroxy indaiithrones can be synthesised from the corre-
sponding aminohydrox}' halogen anthraquinone. Thus i-
amino-4-hydrox>^-2-bromanthraquinone when heated with
sodium acetate and a contact substance such as cuprous
chloride or copper powder gives dihydrox>' indanthrone ^
(Algol Blue 3G). Hydrox}'l groups can also be introduced
into the indanthrone molecule by direct oxidation with a
mixtme of nitric and sulphuric acids, but nitroso and nitro
groups enter at the same time. Thus from indanthrone
SchoU and Mansfield ^ obtained a nitrodinitrosotiihydroxy
derivative and also a tetranitrotetrahydroxy compound.
Both, of course, were azines and on reduction yielded the
corresponding triaminotrihydroxy - N - dihydroazine and
tetraminotetrahydroxy - N - dihydroazine. Sulphonic acid
groups when present in the indanthrone molecule also seem
I G.C.I.B., E.P. 113.783 {1918).
- Scholl, B. 86. 3436. Scholl and Berblinger, B. 40, 320. By., D.R.P.
147.872.
' Scholl and Berblinger, B. 40, 320,
*■ Caledon Blue GCD (Scottish Dyes, Ltd.).
'" Caledon Blue GC (Scottish Dyes, Ltd.).
« Bv., D.R.P. 193,121. ' B. 40, 326.
352 AXTHRACEXE AND AXTHRAQUIXOXE
capable of being replaced by liyd.rox\-l groups. Thus
indanthrone sulphonic acid when heated with concentrated
sulphuric acid gives a vat dye which d^-es in rather greener
shades than indanthrone itself and is probably a h^-drox}*
indanthrone. The same dye is obtained b\' heating indan-
throne with sulphuric acid, with or without the addition of
boric acid, at a temperature insufficient to' cause siilphona-
tion.^
Ami-no indanthroiies can be built up from polyamino-
anthraquinones by the usual methods, or the amino group
can be introduced into the indanthrone molecule by taking
advantage of the quinonoid character of the azine. Thus
Scholl - fotmd that the azine obtained from indanthrone b}*
oxidation reacts with aqueous ammonia at 200° or with
boiling anihne and is converted into amino or phenylamino
indanthrone. These are vat d3-es and dxe cotton in greenish
shades of blue.
A few indanthrone sulphonic acids have been described.
They can be obtained from aminoanthraquinone sulphonic
acids 3 or by sulphonating indanthrone. -^ The}- are soluble
in water and are acid dyes for wool or silk but are of no
importance.
Brief reference may be made to two vat dyes of unknown
constitution which have been obtained from indanthrone.
One is a greenish-blue dye obtained by condensing indan-
throne \^-ith formaldehyde in the presence of sulphiuric
acid.^ The other is a green dye obtained by treating
indanthrone with nitric acid in the presence of nitrobenzene. ^
Neither are of any technical value.
1 B.A.S.F., D.R.P. 227,790. 2 B 36^ .^38,
3 B.A.S.F., D.R.P. 129,846.
* B.A.S.F., D.R.P. 129,847; 216.891; 220,361.
^ By., D.R.P. 159,942. * By., D.R.P. 198,024.
I
CHAPTER XVII
MISCELLANEOUS HETEROCYCLIC
COMPOUNDS
I. The Pyridazineanthrones
Pyridazoneanthrone is prepared by treating the ethyl
ester or the chloride of anthraquinone-a-carboxylic acid
with hydrazine * :
HOCO
CO
CO
and N-phenylpyridazoneanthrone can be obtained by using
phenylhydrazine in place of hydrazine itself. 2 By treating
anthraquinone-a-ketones with hydrazine Schaarschmidt ^
has prepared C-arylpj^ridazineanthrones :
co°^''-
Pyridazineanthrones of more complicated structure are
obtained by a similar reaction from the anthraquinone-
i.2(N)-acridones,4 and the anthraquinone-i.2(S)-thioxan-
thrones,5 the pyridazine ring being formed by bridging the
two carbonyl groups, e.g.
1 Ullmann. A. 388. 211 ; B. 44, 129.
2 Ullmann, D.R.P. 230,454.
3 B. 48. 836.
* Ullmann and Sone. A. 380, 336"; B. 43. 537. B.A.S.F., D.R.P.
248,582.
' B.A.S.F., D.R.P. 254.097.
353 23
354 ANTHRACENE AND ANTHRAQUINONE
Derivatives of pyridazoneanthrone have been prepared
by converting i-chloranthraquinone-4-carboxylic acid into
the pyridazone and then replacing the chlorine atom by
an amino, alkylamino, arylamino, or anthraquinonylamino
group. 1 They are valueless yellow or brown vat dj^es. It
is interesting to notice, however, that whereas the anthra-
quinonylaminopyridazoneanthrone obtained by condensing
the above chloro compound with ^-aminoanthraquinone is
easily reduced to its vat, the isomeric compoimd obtained
by combination with a-aminoanthraquinone is only reduced
with the utmost difficulty.
Ullmann - by condensing pyridazoneanthrone with a-
chloranthraquinone obtained N-a-anthraquinonylpyridazone-
anthrone ; but it proved to be of no interest, and although
a vat dye its tinctorial properties were extremel}^ feeble.
The same remarks apply to the compounds obtained by
condensing N-jfj-bromphenjdpyridazoneanthrone with amino-
anthraquinone.
II. The Pyrimidoneanthrones
These are isomeric with the pyridazoneanthrones and
can be obtained from the a-aminoanthraquinone or o-
alkylamino-anthraquinone b}' treatment with a urethane ^ :
CO
NHg NrrNNH
CO i
EtOCONHj
CO CO
The reaction is a ver}^ general one and can be brought about
1 Ullmann, A. 388, 217 ; D.R.P. 248,998. Agfa, D.R.P. 271,902.
- A. 388, 211. ^ M.L.B., D.R.P. 205,035.
HETEROCYCLIC COMPOUNDS 355
simply by boiling the amine with the urethane, although
the condensation is more rapid in the presence of zinc
chloride or other condensing agent. The method can be
modilied by first converting the a-aminoanthraquinone into
its urea chloride or urethane and then treating this with
ammonia.' A somewhat similar method of preparation
consists in heating the a-aminoanthraquinone with an acid
amide in an indifferent solvent, pyrimidone ring formation
then taking place very readily by loss of two molecules of
water. 2 Urea itself acts as an acid amide, but in this case,
of course, a molecule of ammonia is lost, the reaction taking
place most readily in the presence of copper acetate. 3
A bipyrimidone compound has been obtained from
1.4-diammo anthraquinone. The pyrimidone derivatives
have been ver>' little studied and do not seem to be of any
particular interest.
III. The Oxazines
A few yellow vat dyes of ketomorpholine structure have
been obtained by boiling o-hydroxy chloracetylamino-
anthraquinones with dilute aqueous caustic soda solutions
of 5 per cent, strength.'^ The formation of the morpholine
ring is due to loss of hydrochloric acid, but the resulting
compounds are of no particular interest :
The oxazines themselves are obtained when o-hydrox}--
ar}'lamino anthraquinones are oxidised by means of
manganese dioxide, lead dioxide, chromic acid, oleum, or
an organic nitro compound,-'' and consequently are often
» By., D.R.P. 225,982. 2 By., D.R.P. 220,314.
' M.L.B., D.R.P. 20S.014. •• M.L.B., D.R.P. 290,983.
^ By.. D.R.P. 141,575-
356 ANTHRACENE AND ANTHRAQUINONE
produced when reactions which should lead to o-hydroxy-
arylamino compounds are carried out in the presence of an
oxidising agent. Thus purpurin when boiled with a primary
aromatic amine in the presence of boric acid and an oxidising
agent such as mercuric oxide or nitrobenzene gives an
oxazine.i This method can also be used for preparing
oxazines in which the oxazine ring lies between two anthra-
quinone groups. Thus 2-methoxy-i.i'-dianthraquinonyl-
amine when heated with concentrated sulphuric acid at
170-180° in the presence of boric acid gives an oxazine, the
sulphuric acid in this case acting as the oxidising agent. 2
A somewhat similar reaction also takes place when an
a-amino anthraquinone is heated with a i-amino-2-halogen
anthraquinone in nitrobenzene solution in the presence of
a basic substance such as potassium acetate, and a contact
substance such as copper acetate. ^ In this case the di-
anthraquinonylamine is first formed and is then oxidised
to the oxazine :
0
The oxidation is obviously brought about at the expense of
the nitrobenzene, as the reaction does not take place if amyl
alcohol is used as a solvent. The same oxazine is also
obtained when 2-hydroxy-i-nitroanthraquinone is heated
with copper powder in nitrobenzene solution. *
If the o-hydroxyarylaminoanthraquinone is obtained by
heating an o-hydrox>mitroanthraquinone with a primary
aromatic amine, oxazine formation often takes place without
the use of an oxidising agent, the necessary ox}-gen being
supplied at the expense of the nitrous acid liberated during
the formation of the ar^-laminoanthraquinone. Thus an
oxazine is obtained when 2-hydroxy-i-nitroanthraquinone
^ By., 153.770- - M.L.B., D.R.P. 273,444.
3 M.L.B.. D.R.P. 266,945- " M.L.B., D.R.P. 266,946.
HETEROCYCLIC COMPOUNDS
357
is boiled with a primar}- aromatic amiue, and 2.4-dili3'droxy-
i-nitroanthraquinone undergoes oxazine formation particu-
larly easily under similar conditions. ^
Alizarin might be expected to condense with o-amino-
phenol to give an oxazine, but this is not found to be the
case unless there is an amino or a hydroxyl group present in
the anthraquinone molecule at 4. When such a group is
present, however, oxazine formation takes place extremely
readily, the reaction being brought about by heating under
pressure with o-aminophenol in alcoholic solution in the
presence of boric acid, or in aqueous solution when the
aminoanthraquinone contains a sulphonic acid group.
According to the patent - in which this reaction is described,
purpurin gives a hydrox}'Oxazine which has one of the
following formulae :
This statement, however, must be accepted with some
reserve pending further confirmation, as it seems more
probable that a dihydroxy^oxazine would be produced.
A ver>' curious case of oxazine formation has been
described as taking place when i-ar3damino-2-hydroxy-3-
halogen anthraqumones are heated alone or with basic
substances. 3 The resulting oxazines contain no halogen,
so that oxazine formation seems to be brought about by
oxidation at the expense of the halogen atom :
ci 0
' By., D.R.P. 141.575.
By., D.R.P. 153.517-
M.L.B., D.R.P. 156,477.
358 ANTHRACENE AND ANTHRAQUINONE
There is no need to isolate the arylamino compound, as
oxazine formation takes place when 3-halogenalizarin is
boiled with a primary aromatic amine.
lyittle or nothing is known of the substituted anthra-
quinone oxazines, but sulphonic acids can be obtained by
sulphonation.i •
IV. The Thiazines
Very little is known of the thiazines of the anthraquinone
series although a few such compoimds have been described.
SchoU 2 obtained what was probably /w-thiodianthra-
quinonylamine
1
I
\s/
from thiazine (thiodiphenylamine) itself by the phthalic
acid synthesis. He found that it was a greenish-blue dye,
but that the affinity for the fibre was extremel)^ poor. The
same was also found to be the case with the N-methyl
derivative. Ullmann ^ found that a thiazine was formed
when 2-amino-i.3-dibromanthraquinone was boiled with
anthraquinone-a-mercaptan in nitrobenzene solution :
Br
NH2
I
Br
Br
Br
In this reaction the oxygen necessary for closing the
thiazine ring seems to be obtained from the carbonyl groups.
The product is a violet-blue vat dye. Similar thiazine
dyes have been obtained by condensing o-aminoanthra-
quinone mercaptans with halogen anthraquinones, or by
1 By.. D.R.P. 141,982. 2 B. 44, 1241. =^ B. 45, S32.
HETEROCYCLIC COMPOUNDS
359
condensing o-aminohalogen anthraquinones with anthra-
quinone mercaptans. In either case thiazine formation can
be brought about by self-oxidation (heating alone or with a
solvent of high boilmg point) or by heating with concentrated
sulphuric acid and boric acid.^ Thiazines are also formed
when an o-aminoanthraquinone mercaptan is condensed
with a halogen anthraquinone in which the oytho- position
with reference to the halogen atom is occupied b}^ an amino,
metliox}^ or carbox}^ group, the group being split off during
the condensation. 2
Thiazine formation takes place verj- readily, it merely
being necessarj^ to heat the components together in some
suitable solventsuch as nitrobenzene, pyridine or naphthalene,
no catalj-st or condensing agent being required.
As would be expected a thiazine is also obtained when
i.2-dicliloranthraquinone is condensed with i-aminoanthra-
quinone-2-mercaptan.-'^
A few thiazines containing onl}- one anthraquinone
residue have been prepared. Thus Laube and Libkind •*
obtained a green vat dye by condensing i-chlor-2,4-dinitro-
benzene with a-aminoanthraquinone, reducing the nitro
groups and finally fusing the diaminophenj'lammoanthra-
quinone with sulphur and sodium sulphide at 150° :
NHC6H3(NH2)2
\ S ^
It will be observed that thiazine formation takes place by
loss of an amino group. From ^-aminoanthraquiuone a
thiazine could not be obtained by this method.
Ullmann ^ has also obtained a thiazine containing only
one anthraquinone residue b}'- condensing 2-amino-i.3-di-
bromanthraquinone with thio-_/)-cresol and then treating
» B.A.S.F.. D.R.P. 248,169.
3 B.A.S.F.. D.R.P. 248,171.
■ B.A.S.F., D.R.P. 266,952.
* B. 43, 1730. ' B. 49, 2163, 2165.
360 ANTHRACENE AND ANTHRAQUINONE
the product with formaldehyde and concentrated sulphuric
acid :
S S
^2 ^^HiCH^
I
I
NCH,
V. The Carbazols
Compounds in which a pyrrol ring lies between two
authraquinone rings, or between one anthraquinone ring and
one benzene ring, are best designated as phthaloyl carbazols.
They can be obtained from carbazol by condensation with
phthalic anhydride in the presence of aluminium chloride
(phthalic acid synthesis, pp. 130-141), carbazol itself giving
a diphthaloyl derivative which is probably linear in structure
although this has not yet been definitely proved 1 :
CO
CO
CO
NH
CO
The N-alkyl derivatives of carbazol condense with
phthalic anhydride more readily than carbazole itself, the
condensation in many cases being effected simply by heating
for five to ten hours with sulphuric acid of 80-90 per cent,
strength. 2 The products are usually best purified by wash-
ing with sodium hypochlorite solution.
Phthaloyl carbazols can also be obtained b}' building
up the pyrrol ring. Thus, i.i'-diamino-2.2'-dianthraquin-
onyl when heated with concentrated sulphuric acid loses a
molecule of ammonia and passes into the diphthaloyl
carbazol 3 ;
1 SchoU, B. 44, 1249.
« Ehrenreich, M. 32, 11 13. Cas., D.R.P. 261,495. B.A.S.F., D.R.P.
275,670.
3 M.L.B., D.R.P. 267,833.
HETEROCYCLIC COMPOUNDS
361
and the same compound is also obtained from i.i'
dianthraquinonylamine by fusion with aluminium chloride,
or by oxidation with sodium hypochlorite. ^ This latter
method has also been applied to the preparation of mono-
phthaloyl carbazols, as it has been found that these are
obtained by the oxidation of those a-arylaminoanthraqui-
nones in which the ortho- position in the arj-l group is
unoccupied 2 :
As a rule, the oxidation is effected by means of chromic
acid, ferric chloride, or hydrogen peroxide ; but if an
acylammo group is present in the para- position in the
anthraquinone nucleus the reaction takes place so easily
that the carbazol is formed on heating in the air at
60-70°.
Monophthaloyl carbazols have also been synthesised
by Ullmann ■^ by a somewhat different method. He found
that the diazotisation of 2-amino-i-ar>damino anthra-
quinones led to osotriazoles, similar compounds also being
readily formed by condensing a-chloranthraquinones with
aziminobenzene in the presence of potassium and copper
acetates. These osotriazoles on heating, preferably in
diphenylamine solution, split ojff nitrogen and pass into
monophthalo3-l carbazols :
» M.L.B., D.R.P. 240,080; 251,021; 251,350. C/. also 267,522. These
compounds were formerly ^vrongly regarded as complex indanthrones.
- By., D.R.P. 288,824.
3 B. 47, 380.
362 ANTHRACENE AND ANTHRAQUINONE
iCl JfN 1 J
V
Both the monophthalo}-! carbazols and the diphthaloyl
carbazols are yellow vat dyes, but the affinity is very poor
and the shades are not fast to alkali. The tinctorial pro-
perties of the N-alkyl derivatives, however, are said to be
much more satisf actor3^ ^
VI. The Pyrrol anthrones
If an a-ar}-laminoanthraquinone is condensed with
chloracetic acid, a glycine is obtained which passes into a
pyrrolanthrone when boiled with acetic anhydride - ;
COOHCHt
Nf
CO
NAr
CO CO
In this case the formation of the pyrrol ring is accom-
panied by simultaneous loss of carbon dioxide. If the
glycine is esterified and the ester then heated with an alkali
and an indifferent solvent such as xylene, this loss of carbon
dioxide is avoided and a pyrrolanthrone carboxydic acid
obtained which can be used as an acid wool d^-e.^ If this
carboxylic acid is heated with a dehydrating agent such
as oleum or chlorsulphonic acid a further loss of water takes
place with the formation of a second pyrrol ring :
» Cas.. D.R.P. 261,495. - M.L.B.. D.R.P. 270,789; 272,613.
3 M.L.B., D.R.P. 280,190.
HETEROCYCLIC COMPOUNDS
363
the resulting compound being a red vat dye.'
The C-aryl pyrrolanthrones can be obtained by condens-
ing an atylchloracetic acid with an a-aminoanthraquinone
and then boiling the product with acetic anhydride ^ ;
COOH
CO
CO
An indolanthrone has been obtained by Scholl ^ by
nitrating and reducing 3-methyl-i.2-benzanthraquinone, in
this case reduction being accompanied by loss of water and
formation of a pyrrol ring. The compound thus formed
behaves as a true quinone and is readily reduced by sulphurous
acid, phenylhydrazine and cold hydriodic acid :
CXa>H3 -
CO
The reduction product is soluble in alkali and is readily
oxidised to the indolanthrone by atmospheric ox}-gen. The
indolanthrone can, therefore, be used as a vat dye. It gives
violet-brown shades, but the affinity is very poor.
VII. The Pyrrazols
The a-anthraquinomdhydrazines when boiled with
water or glacial acetic acid readily lose water and pass
into pyrazol compounds,* a monopyrazol being obtained
1 M.L.B.. D.R.P. 284,208.
» B. 44, 2370 ; M. 32, looi.
- M.L.B., D.R.P. 279,198.
* By., D.R.P. 171,293-
364 ANTHRACENE AND ANTHRAQUINONE
from anthraquinone-i -hydrazine and a dipyrazol from
anthraquinone-i.s-dihydrazine :
In the case of i.S-dichloranthraquinone a pyrazol is
formed by boiHng with hydrazine in pyridine solution, one
chlorine atom being unaffected, but it is not certain if this
is a general reaction. 1
Pyrazolanthrone when fused with caustic alkali undergoes
a condensation which is very similar to indanthrone forma-
tion from aminoanthraquinone. The product is a yellow
vat dye which has the structure 2 :
VIII. The Indazols
Anthraquinone indazols having the structure
or
are readily obtained from o-methylanthraquinone diazonium
salts. The formation of the pyrazol ring takes place quite
readily either by boiling the diazonium sulphate with water,
or by heating it to 50° with sodium carbonate, or by treating
^ Mohlau, B. 45, 2233, 2244.
2 G.E.. D.R.P. 255,641 ; 301,554; 302,259; 302,260.
HETEROCYCLIC COMPOUNDS 365
it with cold pyridine. In some cases diazotisation and
indazol formation can be combined in one operation, e.g. an
indazol is formed when 2-methyl-i-aminoanthraquinone is
treated with sodium nitrite in boiling glacial acetic acid
solution. ^
The simple indazols have only extremely feeble tinctorial
properties, but yellow vat dyes are said to be obtained when
they are oxidised by treatment with halogens 2 or ferric
chloride. 3 The structure of these oxidation products is
unknown, but they are probably formed by the union of
two molecules through the carbon atom of the pyrazol ring.
IX. The Imidazols
The imidazols are always obtained from o-diaminoanthra-
quinones and are formed when the acyl derivatives of these
substances are heated with deh3^drating agents such as
sulphuric acid, zinc chloride, or the anhydride or chloride
of an organic acid.* Imidazol formation therefore takes
place when o-diamino anthraquinones are boiled for some
time with acid chlorides or anhydrides, ^ or when the base is
heated with a carboxydic acid in the presence of sulphuric
acid. 6 As would be expected the nitrile can be used in place
of the carboxylic acid, but it is not certain that in this case
imidazol formation is due to the preliminary formation of
the carboxylic acid, as according to Schaarschmidt imidazols
are often formed imder conditions which are insufficient to
bring about the hydrotysis of the nitrile.
A variation of the above method has been introduced
by Ullmann and Medenwald,^ who find that 2-acetamino-
i-nitroanthraquinone passes directly into the imidazol on
reduction with sodium sulphide :
1 By., D.R.P. 269.842.
3 By., D.R.P. 268,505.
' By., D.R.P. 280,840.
' Schaarschmidt, A. 407, 176.
^ By., D.R.P. 238,981. Cf. Ullmann, A. 380, 322.
■^ Schaarschmidt, A. 407, 176. D.R.P. 251,480; 254,033.
" B. 46, 1807.
366 ANTHRACENE AND ANTHRAQUINONE
CCH3
C-Methylanthraquinone-i.2-imidazol.
Another variation consists in heating an o-acylamino
halogen anthraquinone with a primary aromatic amine in
the presence of copper powder. In this case an arylamino
group first replaces the halogen atom, the imidazol being then
formed by loss of water through the ac5damino group reacting
in the enolic form ^ :
>CR
NHCOR
-N^
1
->
1
! ->
1
CI
NH OH
Ar
I
N^
Ar
A somewhat different method of preparing imidazols
consists in condensing o-diaminoanthraquinone with an
aliphatic or aromatic aldehyde or with an a>-dichlor com-
pound such as benzalchloride, or, more particularly, a>-
dichlor-j3-methyl anthraquinone. 2 In this reaction the
primary product formed is a dihydroimidazol, but if sulphuric
acid is used as a condensing agent this is at once oxidised to
the imidazol itself. The dihydroimidazol can, however, be
isolated if pyridine is used as a condensing agent. When
the aldehyde used is chloral a much more complicated reaction
takes place, and blue or black vat d3'es of unknowTi constitu-
tion are obtained.^
If a ketone is substituted for an aldehyde in the above
reaction compounds are obtained which, after sulphonation,
can be used as acid wool dyes. The dyes obtained from
acetone and acetophenone are red, whereas that obtained
1 M.L.B., D.R.P. 298,706.
2 Schaarschmidt, A. 407, 176. Ullmann, A. 399, 332.
238.982 ; 247,246. B.A.S.F., D.R.P. 261,737.
3 M.L.B., D.R.P. 284,207.
By., D.R.P.
HETEROCYCLIC COMPOUNDS
367
from anthrone is violet and that from benzophenone blue.
Nothing is known of the structure of these d.3'es, and it is
doubtful if they contain the imidazol ring system. ^
Schaarschmidt 2 has examined the tinctorial properties of
a number of anthraquinone imidazols and finds that neither
anthraquinone-i.2-imidazol nor anthraquinone-2.3-imidazol
has any affinity for the fibre. Slight affinity, however,
is shown by those imidazols in which a phenyl group is
attached to the carbon atom of the imidazol ring, and the
corresponding anthraquinonyl derivatives, the C-anthra-
quinon}^ anthraquinone imidazols, have good affinity.
The majority of the imidazols are yellow, but Schaar-
schmidt states that C-i3-anthraquinonyl-anthraquinone-i,2-
imidazol :
N
C(i3)CHH;02
which he prepared in three waj-s, viz. from 1.2-diamino-
anthraquinone and anthraquinone-j3-carbox>dic acid, anthra-
quinone-^-nitrile and co-dichlor-jS-methyl anthraquinone, is
red, whereas in a patent specification ^ the same substance is
described as being prepared from 1.2-diaminoanthraquinone
and is stated to be a violet dye.
The onl}' imidazolon of the anthraquinone series which
has been described up to the present was obtained by UU-
mann '^ by treating i.2-diammo-3-bromanthraquinone with
chloroformic ester. It has the formula :
Br
CO
» By., D.R.P. 264,290.
3 B.A.S.F,, D.R.P. 261,737.
= A. 407. 176.
^ A. 399, 332.
368 ANTHRACENE AND ANTHRAQUINONE
and is a yellow vat dye with good affinity although the
shades are vety loose to alkali.
X. The OXAZOI.S
Oxazol formation takes place when o-hydroxyacylamino
anthraquinones are heated with dehydrating agents, j3-amino-
alizarin, for example, giving an oxazol when boiled with
excess of benzoyl chloride i :
OH OH
OH
NHCOCeHg
— Os
— N'
^
CCgHs
Oxazol formation is here obviously due to loss of water
from the enolic form of the benzoylamino compound, and this
view is supported by the formation of an oxazol by loss of
nitrous acid when i-benzoylamino-2-nitroanthraquinone is
boiled with sodium carbonate in naphthalene solution, 2
and also by the production of oxazols by the oxidation of
acylamino-anthraquinones by lead dioxide in glacial acetic
acid solution, or by nitric acid in nitrobenzene solution. ^
A somewhat similar reaction has been described by Ull-
mann,* who finds that when 2-amino-i.3-dibromanthra-
quinone is benzoylated very little of the benzoyl derivative
is produced, the chief product being an oxazol. In this case
it is the bromine atom in the a- position which is lost, the
structure of the oxazol being proved by its decomposition
into 2-amino-i-hydrox3'-3-bromanthraquinone when heated
with sulphuric acid of 80 per cent, strength :
/Ov OH
^N'
^
CCeHg
Br
iNHo
Br
» By., D.R.P. 252.839; 259,037. M.L.B., D.R.P. 284,181 ; 288,842.
2 M.L.B., D.R.P. 286,094. VMI-B., D.R.P. 286.093. * A. 339. 330.
HETEROCYCLIC COMPOUNDS 369
2.6-Diamino-i.3.5.7-tetrabromanthraquinone reacts in
exactly the same way and gives a dibromanthraquinone
dioxazol.
Oxazols and dihydro-oxazols are also formed by condensing
o-aminohydroxyanthraqninones with aldehydes, ketones or
the corresponding w-dichlor compounds. The reaction is
brought about by heating the substances together with or
without an indifferent solvent of high boiling point such as
nitrobenzene. 1
XI. The Isoxazols
Isoxazols of the anthraquinone series in which one or
both of the mcso- carbon atoms form part of an isoxazol ring
have been prepared by Fremid and Achenbach - and by
Schaarschniidt.3 The former investigators found that the
oximes prepared from a-chloranthraquinones existed in
two forms, one of which was unaffected by alkali whereas
the other was converted into an isoxazol. By this means
they prepared both a mono- and a di-isoxazol :
and
0' 'N
The isoxazols prepared by Schaarschmidt were isomeric
with these, and were obtained by boiling anthraquinone-
a-azides with water. B)^ this means one mono-isoxazol and
two di-isoxazols were obtained :
Gattermann ^ also obtained these compounds from the
azides but named them '• semi-azo " compounds, and sug-
gested, with some reserve, that they contained monovalent
J By., D.R.P. 252.839. * B. 43, 3251.
» B. 49, 1632. ^ B. 49,2117.
24
370 ANTHRACENE AND ANTHRAQUINONE
nitrogen, although he has offered no evidence whatsoever in
support of this view :
CO
XII. The Thiophenes
The i(S)-9-thiopheneanthrones have been prepared by
Gattermann,! -^vj^o found that the anthraquinonyl-a-thio-
glycoUic acids, obtained by condensing anthraquinone-
a-mercaptans with chloracetic acid, lose water and carbon
dioxide when boiled with acetic anh3^dride. This tendency
to form a thiophene ring is greatly enhanced by the presence
of a methyl group in the a- position to the mercaptan group,
and in such cases it is usually impossible to isolate the anthra-
quinon5'l thioglj-collic acid owing to the ease with which it
passes into the thiopheneanthrone. In these cases, however,
the loss of carbon dioxide only takes place slowly, so that the
carboxylic acid can usually be isolated, e.g. :
COOH
CO 1
CO
Friess and Schiirmann ^ also prepared thiopheneanthroncs.
Their starting-out substance was anthraquinone-a-sulphur
chloride, which they condensed with sodio-acetoacetic ester,
the thiophene ring being formed on subsequent hj'drotysis :
COOEl
CHjCOCH-S CHjCOCi
CO ^ '
CO CO
They also found that a thiophene anthrone is produced
» A. 393, 122, 190. - B. 52, 2172.
HETEROCYCLIC COMPOUNDS 371
vvheu sodium authraquinone-a-mercaptide is condensed with
/'-liydrox}--w-chloracetophenone :
HOC.H.C
CO
This reaction is by no means a general one, as no thio-
phcne derivative is formed from either o-nitrobenzyl chloride
or ^-nitrobenzylchloride.
XIII. The Thiazols
Anthraquinone thiazols are obtained from o-acylamino
anthraquinone mercaptans by loss of water, the reaction
being brought about by heating with a suitable dehydrating
agent, such as acetic anh^-dride or, in many cases, merely
by heating with an indifferent solvent of high boiling point,
such as nitrobenzene. 1 There is no need to isolate the
acylamino mercaptan, as acylation and thiazol formation
take place simultaneously when the amino mercaptan is
heated with a carboxylic acid or its chloride, anhydride,
amide, ester, or nitrile.2 Even the isolation of the amino
mercaptan can often be avoided, as in many cases thiazols
are formed when o-amino or o-acylamino halogen anthra-
quinones are treated with a sulphide, thiocyanate or other
substance capable of replacing the halogen atom b}' a mer-
captan group, the reaction being usually best carried out in
pyridine solution. ^
In the above reactions carbon disulphide would seem to
act to some extent as an acid anhydride, as it has been
claimed -^ that i-aminoanthraquinone-2-mercaptan when
heated with carbon disulphide m alcoholic solution at 95° is
converted into a thiazol mercaptan in which the mercaptan
group is attached to the carbon atom of the thiazol ring :
. * By., D.R.P. 250,090.
■ B.A.S.F., D.R.P. 260,905.
■' B.A.S.F., D.R.P. 260.905. M.L.B., D.R.P. 311,900.
^ By., D.R.P. 250,090.
372 ANTHRACENE AND ANTHRAQUINONE
/NH2
S : C : vS
^ vS
.N
C:S
or
C.vSH
Thiazol formation also takes place when o-aminoanthra-
quinone mercaptans are condensed with an aldehyde or the
corresponding w-dichlor compound. 1 The reaction is brought
about by heating in a suitable solvent and is exactly analogous
to the formation of oxazols from o-aminohydroxyanthra-
quinones mentioned on p. 369, and to the formation ot imid-
azols from o-diaminoanthraquinones (p. 366). As in the case
of the oxazols, dihydro compounds (thiazolines) are often
formed, this, of course, always being the case when a ketone
is substituted for an aldeh3'de.2
Somewhat similar to the above methods is the formation
of thiazols from o-aminohalogenanthraquinones by means
of thiolbenzoic acid 3 :
NH..
Br
O
%
CPh ~>
HS'
-N
— S
\
CPh
The reaction takes place extremely easily, but the method
has the disadvantage that the thiol acids are troublesome to
prepare and are apt to react with other groups present in
the molecule. Thus, 2-amino-i.3-dibrom anthraquinone
gave the anthraquinone thiazol disulphide :
/^\
^N-
^
CPh PhC
/K
%
w
-s-
1 By., D.R.P. 252,839 ; 259,037.
- M.L.B., D.R.P. 253,089.
3 Ullmann, A. 399, 345. D.R.P.
B.A.S.F., D.R.P. 260,905.
254.743-
HETEROCYCLIC COMPOUNDS
373
Benzyl and benzylidene aminoantliraquinones in wliich
an ortho- position, which is preferably also an a- position, with
reference to the amino group is vacant pass into thiazols
when fused with sulphur. ^ Here again there is no need to
isolate the benzyl or benz^'lidene derivative as the reaction
can be carried out bj- heating the amine with benzalchloride
or benzo-trichloride, preferably in the presence of an in-
different solvent such as naphthalene.-
6?s-Thiazolines in which the two molecules are j oined by
the carbon atoms of the thiazoline rings can be obtained
by fusing the o-acetamino chloranthraquinones with sulphur, ^
or by treating the o-amhioanthraquinone mercaptans with
oxalyl chloride. "i They are vat dyes and have the structure
but have not been studied in detail.
A series of vat dyes giving red, bordeaux or violet shades
has been described -'' as being obtained by heating 2-methyl-
i-aminoanthraquinone with sulphur and an aromatic
monamine or diamine. The patents give no information as
to the structure of these substances, but it is quite possible
that they are complex thiazols.
XIV. The «so-Thiazoi.anthrones
The jso-thiazolanthrones are formed when an anthra-
quinone mercaptan is heated with ammonia and a poh-
sulphide,^ and consequently can be obtained b}- heating
any suitable a-substituted anthraquinone, such as an a-
chloranthraquinone, an anthraquinone-a-sulphonic acid, or
> UUmann, A. 399, 345. Agfa, D.R.P. 229,165 ; 232,711-2 ; 233,072.
■' B.A.S.F., D.R.P. 264,943 ; 267,523.
» B.A.S.F., D.R.P. 280.882. « B.A.S.F., D.R.P. 280,88 s.
* Cas., D.R.P. 283,725 ; 287,005 ; 287,52 i. • By., D.R.P. 216,306.
374 ANTHRACENE AND ANTHRAQUINONE
au a-anthraquinonyl xanthate, with an alkali polysulphide
and ammonia. The a-anthraquinonyl thiocyanates are
particularly suitable as starting-out substances as they pass
into the zso-thiazolanthrone on heating with ammonia at
140°, preferably in alcoholic solution, no polysulphide being
required. 1 By their use Gattermann has prepared one mono
and two isomeric dithiazols :
tso-Thiazolanthrones can also be prepared from the
anthraquinone-a-sulphur chlorides by converting these into
the sulphamide b}^ means of ammonia and then closing the
iso-thiazol ring by treatment with mineral acids. 2 The a-
sulphochlorides behave in a very similar wa}^ as the corre-
sponding sulphonamides yield sulphone zso-thiazolanthrones
by loss of water 3 :
HjN-SOg
CO
The tso-thiazols are pale yellow substances which are
of no particular interest. The iso-selenazolanthrones have
also been described. ^ They are obtained by treating the
anthraquinone-a-selenocyanides ^ with ammonia.
XV. CcEROxENE Derivatives
When p3'rogallol is condensed with phthalic anh3-dride
a pjTonine dye, gallein, is produced which forms a mono-
methyl ester, isomeric colourless and coloured tetramethyl
» Gattermann, A. 393, 123, 192. By., D.R.P, 217,688.
- Friess and Schijrmann, B. 52, 2172.
3 Ullmann, B. 52, 545.
^ By., D.R.P. 264,139.
'■" By., D.R.P. 250,667.
HETEROCYCLIC COMPOUNDS 375
derivatives, a tetra-acetyl derivative, and a compound with
three molecules of phenyl *so-cyanate.i There can be no
doubt that this substance has the ordinary pyronine dye
structure, the coloured tetramethyl compound being derived
from the quinonoid form (I), and the colourless tetra-alkyl
derivative from the lactone form (II) :
OH 0 OH
HOrYV>OH
I II
When gallein is heated with concentrated sulphuric
acid at 190-200° a molecule of water is lost and a new dye,
ccerulei'n (Alizarin Green, Anthracene Green), is obtained. 2
This forms a triacetate, two monometh}^ ethers which are
soluble in caustic alkali, and a trimethyl ether which is
insoluble in caustic alkali. The carbox^d group present in
gallein seems to have disappeared so that the new dye is no
doubt represented by formula III ;
OH 0 OH
■OX"
in
This, it will be seen, contains the anthrone ring system,
and the formation of similar compounds, coeroxenes, from
other pyronine dyes has been recorded. ^
1 Orndorff and Brewer. Am. 23, 425 ; 26, 9G.
- Baeyer, B. 4, 595, 663. Buchka, A. 207, 272 ; B. 14. 1329. Most of
Buchka's work has been contradicted by Orndorff and Brewer. Am. 23, 425 ;
26, 96.
» M.L.B., D.R.P. 86,225. Cf. By., D.R.P. 196,752.
376 ANTHRACENE AND ANTHRAQUINONE
Very similar to the above S3mtliesis is the preparation
of the highly coloured coeroxonium sulphate (IV) by Decker *
by heating fluorane with concentrated sulphuric acid :
OSO4H
In this case better yields are obtained by the use of oleum,
as the reaction then takes place at a much lower temperature
and sulphonation is avoided.
A third method 2 of preparing coeroxonium salts consists
in heating the ar>d ethers of erythrohydroxy^anthraquinone
with sulphuric acid of 70 per cent, strength, or with zinc
chloride'at 160-180° :
o-so^H
Both the a-naphthyl and the jS-naphthyl ethers react in
the same wa3^ as do also the aryl ethers of di-a-h5^droxyan-
thraquinone. The products obtained from these dihydroxy-
anthraquinones do not seem to have been studied in detail,
and Decker does not state whether they contain one or two
pyronine rings, neither is it clear whether he prepared them
from quinizarin or anthrarufin or both.
The coeroxonium salts are highly coloured, but on
neutralisation or when their solutions are sufficiently diluted
^ A.»348, 214, 223.
f2 Laube, B. 39, 2245.
186.882.
Decker, A. 348, 232, 245. By., D.R.P.
HETEROCYCLIC COMPOUNDS
377
with water the colourless carbinol base, cceroxonol, formula
V, is obtained :
These carbiuols are decomposed by light and atmo-
spheric oxygen, but when boiled with alcohol, or when the
coeroxonium sulphate is recrystallised from alcohol, ^ the
corresponding ethyl ether is obtained, and this is much more
stable.
On reduction 2 with zinc dust and acetic acid or am-
monia, stannous chloride or cold h3^driodic acid, the carbinol
base first passes into the coeroxenol, formula VI, These
coeroxenols are soluble in caustic alkali, and do not form
salts with acids. They are rapidly re-oxidised to the
carbinol base by atmospheric ox}-gen, and hence are best
isolated in the form of their stable acetyl derivatives. The}'
can also be obtained direct from the phen}^ xanthene
carboxylic acids by loss of water, the reaction being effected
by concentrated sulphuric acid at the ordinarj' temperature
or, more rapidh-, at 100° :
or
Further reduction of the coeroxenols by boiling with
hydriodic acid and phosphorus leads to the parent com-
pounds, the cceroxenes, formula VII :
1 Laube, B. 39, 2245.
- Laube. B. 39. 2245. Decker, A. 348, 217.
378 ANTHRACENE AND ANTHRAQUINONE
VII
These are yellow fluorescent substances which are readily-
oxidised in acid solution and then pass into coeroxonium
salts. By treating the ethyl-ether of coeroxonol with
magnesium phenylbromide, lo-phenyl cceroxene, formula
VIII, has been obtained, simultaneous reduction taking
place. This is a very stable fluorescent yellow substance.
XVI. The Ccerthiene Derivatives
Coerthionium salts are obtained when a-anthraquinonyl
aryl sulphides are heated for thirty hours at i6o° with sul-
phuric acid of 70 per cent, strength. 1 The dianthraquinonyl
sulphides also undergo a similar reaction although as a rule
more vigorous treatment is required, e.g. heating to 150-180°
with concentrated sulphuric acid. In some cases, however,
the reaction takes place extremeh- easily and may take
place with evolution of heat imder the influence of sulphuric
acid monohydrate at the ordinary temperature, 2
The coerthionium salts are more highly coloured than
the corresponding coeroxonium salts. The}' behave like
the corresponding coeroxonium salts on reduction, but the
parent substances, the coerthienes, have not ^-et been isolated :
S-Ac
NoOH
CO
Coerthionium salt.
CO
Coerthionol.
OH
CcErthienol.
J Decker and Wursch, A. 348, 238. By., D.R.P. 186,882.
- By., D.R.P. 252,530,
HETEROCYCLIC COMPOUNDS
379
XVII. The CacRAMiDiNE Derivatives
Cceramidines can be obtained by treating a-ar>'lamino
anthraquinones with suitable dehydrating agents, such as
sulphuric acid of 60-80 per cent, strength at 150°, crystallised
phosphoric acid at 200° or zinc chloride in glacial acetic acid,
and when a 1.4- or 1.5 -diary lamino anthraquinone is used
compounds can be obtained in which two acridine ring
systems are present ^ :
From i-tolylamino
anthraquinone.
Yellowish-brown.
From 1 .4-ditoly lamino
anthraquinone.
Dark red.
From 1.5-ditolylamino
anthraquinone.
Dark blue.
i.i'-Dianthraquinonylamine and i.2'-dianthraquinonyl-
amine also give cceramidine derivatives when treated with
deh^'drating agents, the products being yeUow or orange vat
dyes, 2 The reaction is a ver}'- general one and has been
applied to the preparation of complex compounds from a-
anthraquinon^^lamino acidrone and from a-anthraquinonyl-
amino thioxanthone.^ It has also led to the preparation
of cceramidine carboxy^lic acids from a-arylamino anthra-
quinone carbox^lic acid, but when the carbox}4 group is
in the oriho-position to the arj-lamino group acridone
formation takes place simtdtaneously and, as would be
expected, the acridone is usually the predominant product.*
The simplest cceramidine can also be prepared by
condensing phthalic acid with diphenylamine in the presence
of zinc chloride, 5 converting the resulting acridyl benzoic
acid into its acid chloride, and linally treating this with
aluminium chloride <* •,
1 By., D.R.P. 126,444. - By.. D.R.P. 239,544. ' Agfa, D.R.P. 258,808.
' By., D.R.P. 262,469. * Bernth.sen, A. 224, 45. " Dammann and
Gattermann, F.T. 1, 325. Cf. Decker and Schenk, A. 348, 242.
38o ANTHRACENE AND ANTHRAQUINONE
When treated with dimethyl sulphate this gives the
quaternary ammonium sulphate from which caustic alkali
liberates the carbinol base, N-methylcoeramidonol i :
NCH,
XVIII. MiscEivLANEOUs Compounds
Anthraquinone-a-sulphochloride when treated with
hydrazine yields a sulphohydrazine 2 :
NH
Anthrone condenses with true ^-quinones such as benzo-
quinone or chloranil to give blue or green vat dyes.^ The
reaction is brought about b}^ boiling in some indifferent
solvent such as nitrobenzene or xylene, but it is doubtful
if the dyes obtained are single substances. For the blue
dye obtained from anthrone and^-benzoquinone the patentees
suggest the formula
0
^ Decker and Shenk, A. 348. 242. 2 Ullmann, B. 52, 545.
=» M.L.B.,D.R.P. 251,020; 267,417.
HETEROCYCLIC COMPOUNDS
381
Oxazoneanthrones are obtained when anthraquinone-
a-carboxylic acids are warmed with hydroxylamine in
aqueous solution ^ : 0
An anthraquinonyl thioglycoUic acid can be obtained
either by condensing i-alkyl (or ar>4) aniino-2-chloranthra-
quinone with thioglycoUic acid or its ester, chloiide or amide,
or by condensing I-alkyl (or aryl) amiuoanthraquinone-2-mer-
captan with chloracetic acid. Such anthraquinonyl thio-
glycoUic acids when heated alone or in an indifferent solvent,
with or without the addition of a condensing agent such as
phosphorus pentachloride, zinc chloride or thionyl chloride,
pass into orange or brownish-red vat dyes 2 :
/NRH /NR— CO
^S.CHg.COOH
-CHs
When an anthraquinone mercaptan is condensed with a
hydroxj-anthraquinone by treatment with concentrated
sulphuric acid at 160°, compovmds are obtained which
probably have the structure :
Instead of the mercaptan the disulphide, thiocyanate or
xanthate can be used. The products are usuall}- red vat
dves.3
1 Ullmann, A. 388, 211 ; 13. 44, 129. - Bv., D.R.P. 232.076.
' By., D.R.P. 235,094.
CHAPTER XVIII
MISCELLANEOUS COMPOUNDS
I. Arsenic Compounds
Very little is known of the arsenic derivatives of anthra-
quinone, although a few compounds have been described
by Benda.i The aminoanthraquinones are not arsinated
when heated with arsenic acid,^ but the anthraquinone
arsinic acids can be readily obtained from the amino com-
pounds b}^ Bart's method, ix. by treating the diaozonium
salts with alkali arsenite. In many cases the ^delds are
almost quantitative although in others the method fails
completely, e.g. aminoalizariu gives no arsinic acid at all.
The arsinic acids are usually fairh- stable, well-crystallised
bodies which are onty decomposed when heated to a high
temperature, and then split off arsenious oxide and form the
h}drox>'anthraquinone. They differ from the arsinic
acids of the benzene series by being precipitated in the cold
both by magnesia mixture and by calcium chloride. They
can be nitrated but with some difficulty, it being necessar}-
to employ a large excess of nitrating acid.
The arsinic acids when reduced show a great tendency to
split off their arsenic, and this is especially true of the anthra-
quinone-a-arsinic acids. It is probably to this tendency
to liberate inorganic arsenic compomids that the anthra-
quinone arsinic acids owe their great toxidit}-. If the
reduction is carried out with sodium hydrosulphite arseno-
anthraquinols are formed. These in caustic alkali solution
are very rapidly reoxidised by the air to the arsinic acids, and
in this way differ from the arseno compounds of the benzene
' J. pr. [2] 95, 74. - Bechamp, C. r. 56, 1172.
382
MISCELLANEOUS COMPOUNDS
383
series which under similar conditions only form arsenoxides,
the use of h^'drogen peroxide or iodine being necessary in
order to convert an arseno benzene into the corresponding
arsinic acid. The anthraquinone arsenoxides can, however,
be obtained by oxidising the arsenoanthraquinols in sodium
carbonate solution by atmospheric oxygen. Oxidation by
hydrogen peroxide converts these into the arsinic acid,
whereas when reduced with sodium hydrosulphite they revert
to the arsenoanthraquinols.
II. ACEANTHRENEQUINONES
By the action of oxalyl chloride on anthracene in the
presence of aluminium chloride lyiebermann and Zsuffa 1
obtained aceanthrenequinone (I), the structure being proved
by the fact that oxidising agents convert it into anthraqui-
none-a-carbox}'lic acid :
CO COOH
CO
At a later date the same investigators described several
substituted aceanthrenequinones,^ and I^iebermann, Kardos
and Miihle ^ by the action of oxalyl-chloride on dianthr}!
obtained similar compounds, the diquinone (II) and the
monoquinone dicarboxjdic acids (III) being the most
interesting compounds obtained, although dianthr3-l tetra-
carboxylic acid was also formed :
COi iCO COOH COOH
CO'-=r-'CO
ct^^co
1 B. 44, 202. » B. 44. 852, 1213 ; 45, 1187, 1213. ' B. 48, 1648.
384 ANTHRACENE AND ANTHRAQUINONE
The action of malonyl chlorine on anthracene ^ is very
similar to that of oxal}-! chloride and leads to anthracene
1.9-indandion, but according to Freund and Fleisher 2 the
reaction in the case of dimethyl malon3'l chloride takes a
different course and leads to either IV or V, from which the
corresponding anthraquinone can be obtained by oxidation :
CO
CO
CO
V
Aceanthrenequinone gives a monoxime 3 which is capable
of dyeing wool 3'ellow from an acid bath. If this monoxime is
treated with concentrated sulphuric acid, or with hydrochloric
acid gas, glacial acetic acid and acetic anhydride, it is con-
verted into anthracene-i.Q-dicarboxjdic acid audits monamide
and cyclic imide.^ The amide and cyclic imide can also be
obtained from anthracene-i.g-dicarboxj'Hc acid b5'the action
of ammonia, and the imide is also formed when the monoxime
of aceanthrene quinone undergoes the Beckmann rearrange-
ment.^ When fused with caustic potash and the solution
subsequently oxidised by exposure to the air a green vat dye
is obtained which has been named aceanthrene green ^ and
probably has the structure represented b}" formula VI :
CO
VI
Hydrolysis of aceanthrenequinone by caustic soda leads
to a mixture of anthracene-i-aldehyde-9-carbox}-lic acid,
' Kardos, B. 46, 2090. D.R.P. 275,248.
- A. 373. 291 ; 399, 193.
3 Kardos, B. 46, 2086. D.R.P. 280,839.
' Kardos, D.R.P. 282,711.
5 Kardos, B. 46. 2086.
" Kardos, B. 46, 2086. D.R.P. 275,220; 278,660; 284,210.
MISCELLANEOUS COMPOUNDS
385
the anhydride of anthracene-i.9-dicarbox>'lic acid and
anthracene hydroxy dion (VII or VIII). This latter gives
a monoxime from which a cyclic imide (IX or X) can be
obtained by the Beckmann rearrangement. The cyclic
iraide on fusion with caustic potash gives a green vat dye
(XI or XII) which has been named zso-aceanthrene green. ^
>coA^c
IX
III. DiAzoNiuM Salts
Primary amino-anthraquinones can usually be diazotised
in suspension in dilute sulphuric acid by dissolving the amine
in concentrated sulphuric acid and then precipitating by the
addition of water. The majority of the acid is then removed
by filtration and the precipitate, without drying or washing,
suspended in water and treated with sodium nitrite. 2 In
most cases, however, it is much better to carry out the
diazotisation in concentrated sulphuric acid solution by
slowly adding a solution of sodium nitrite in the same
solvent. In some cases the reaction takes place rapidly, but
in others it is rather slow, so that as a rule it is best to allow
1 Liebermann and Kardos, B. 47, 1203.
- Lauth, C. r. 137, 662.
25
386 ANTHRACENE AND ANTHRAQUINONE
the solution to stand in the ice chest overnight. Benda *
finds that a large number of primary' aminoanthraquinones
are most easil}- diazotised by dissolving in concentrated
sulphuric acid and then rapidh" adding a large excess of
nitrosyl sulphturic acid, no artificial cooling being used. By
this means he claims that j3-aminoanthraquinone can be
diazotized completely in a few minutes, whereas under other
conditions the reaction requires 12 hours to become complete. 2
As already stated l-h3^drox}^-anthraquinone-4-diazonium
sulphate can be obtained directly from anthraquinone by
heating with nitrosyl sulphuric acid and boric acid in the
presence of mercuric sulphate. ^
The anthraquinone diazonium salts are sometimes soluble
in water, but more usually the}- are only sparingh- soluble, so
that they are often easily isolated. Kacer and Scholl ^ find
that the 6/s-diazonium sulphate derived from i.8-diamino-
anthraquinone is readily soluble, whereas that derived from
1.5-diaminoanthraquinone is only sparingly soluble, and on
this observation they base a method of preparing 1.5- and
1.8- derivatives of anthraquinone in a pure state from a
crude mixture of the corresponding nitro compounds.
The anthraquinone diazonium salts are fairly stable
bodies and are only decomposed by comparatively drastic
treatment. Thus, i-hydrox>'anthraquinone-4-diazonium sul-
phate is only converted into quinizarin when heated to
170-180® with concentrated sulphuric acid.^ Anthraquinone-
I -diazonium sulphate chars if slowlj^ heated, and only explodes
feebly if rapidly heated. ^ Even anthraquinone-i.5-&zs-
diazonium sulphate only explodes when heated to 172°.
The a-diazonium salts are somewhat more' stable than the
corresponding j3- compounds. ^
1 J. pr. [2] 95, 76.
2 Detailed directions for diazotising a large number of aminoanthra-
quinones will be found in the following papers and patents. Benda, J. pr.
[2] 95, 76. Bottger and Petersen, A. 160, 151 ; 166, 149. Gattermann,
A. 393, 132, 149. Kacer and Scholl, B. 37, 4185. Lauth, C. r. 137, 662.
Schaarschmidt, A. 405, 115. B. 49, 2678. Scholl, M. 32, 708. Ullmann
and Conzetti, B. 53, 828. By., D.R.P. 131,538.
3 By., D.R.P. 161,954. See also p. 261.
* B. 87, 4185. » Bv., D.R.P, 161,954.
« Kacer and Scholl, B. 87, 4185. ' Schaarschmidt, B. 49, 2678.
MISCELLANEOUS COMPOUNDS 387
The diazonium group can be replaced by other atoms or
groups by the usual methods, the yields usually being
satisfactory. It should be noted, however, that the action
of cuprous salts sometimes has a tendenc}^ to produce
dianthraquinonyls.i According to Schaarschmidt 2 i-chlor-
anthraquinone-4-diazonium chloride when warmed gives a
nitrogenous, chlorine free product. To this he gives the
formula Ci4H609^ , but further confirmation is necessary
before this can be accepted. When anthraquinone-2-di-
azonium sulphate is heated with ammonia a product is
obtained which contains 6*ii per cent, of nitrogen. Owing
to the meagre information given in the patent 3 it is hardly
possible to hazard a guess at the structure of this body, if
indeed it is a single substance, but nitrogen content corre-
sponds to that required by hydrox>^ azoanthraquinone. The
diazonium sulphates also give nitrogenous condensation
products with primary aromatic diamines * and with
primary aminoanthraquinones.^ In the former case at
least nitrogen is evolved during the condensation, and in
the latter case the products are ^-ellow or orange vat dyes.
IV. AZO, AZIMINO, AND AZOXY COMPOUNDS
Hydroxy and amino azo compounds can be obtained
by coupling anthraquinone diazonium salts with phenols or
aromatic amines in the usual way but are of no interest. ^
Azo compounds are also formed when either a-amino anthra-
quinone or j3-aminoanthraquinone is oxidised with bleaching
powder. 7
The o-amino azo compounds when oxidised, especiall}-
when oxidised with chromic acid, give triazols,^ e.g. :
» B.A.S.F., D.R.P. 215,006.
2 B. 46, 2678. » M.L.B., D.R.P. 253,238.
* M.L.B., D.R.P. 246,085. '^ M.L.B., D.R.P. 255,340.
" Lauth, C. r. 137. 662. Kauffler, F.T. 2. 469. Cf. also G.E., D.R.P.
245.973 I 250,274.
' M.L.B., D.R.P. 247,352.
8 G.E., D.R.P. 238,253 ; 245,191 ; 250,274 ; 253.088. M.L.B., D.R.P.
245,191-
388 ANTHRACENE AND ANTHRAQUINONE
N
N
Some of these have been claimed as vat d3'es, but they are
of no practical importance. They are also fermed when the
o-amino azo compounds are heated with a metallic catalyst,
such as copper or iron, and a suitable solvent such as nitro
benzene,! and when o-diamino anthraquinones are treated
with nitrous acid.^
Azimino compounds (azides) are obtained when diazonium
salts are treated with sodium azide,3 and Gattermann * has
prepared a-aziminoanthraquinone by treating anthraquinone-
a-diazonium sulphate with hydroxylamine and then causing
loss of water from the resulting diazo-hydrox}^amino com-
pound by treatment with acetic anhydride :
C14H7O2N2HSO4 -> C14H7O2N : N.NHOH -> Ci4H702N( j|
The /3-aziminoanthraquinones are more stable than the
a-azimino compounds, these latter when heated losing a
molecule of nitrogen and passing into oxazols,^ although
Gattermann ^ has suggested that the product formed is
a " semiazo " compound containing monovalent nitrogen :
CO N:
" Semiazo " compound.
There seems to be no justification for the " semiazo "
formula which Gattermann has never developed since he
proposed it in a " Preliminary Note."
Very little is known of the azoxy anthraquinones, although
1 G.E., D.R.P. 273.443- "" By.. D.R.P. 254,745.
^ Schaarschmidt, B. 49. 1632. * B. 49,2117.
* Schaarschmidt, B. 49, 1632. See also p. 369.
« B. 49, 2117.
MISCELLANEOUS COMPOUNDS 389
Scholl 1 obtained j8-azoxyanthraquinone by reduciug /3-
nitroanthraquinoue with glucose and caustic soda.
V. Hydroxyi^amines, Hydrazines, and Hydrazo
Compounds
Hydroxylamines can be obtained by the alkaline reduction
of nitroanthraquinones either by sodium stannite 2 or by
glucose and caustic soda, 3 although they are not easy sub-
stances to prepare owing to the tendency of the reduction
to go too far. Hydroxylamines are also formed by reducing
nitro compounds with a solution of siilphur in oleum, but
in this case they are extremely difhcult to isolate owing to
the acid causing a ver}^ rapid rearrangement to the amino
hydroxy compound.-* Phenyl hydrazine can also be used
as a reducing agent, and by this means R. B. Schmidt and
Gattermann ^ were able to confine the reduction to one nitro
group in the case of 1.5-dinitroanthraquinone and 1.8-
dinitroanthraquinone. The hydroxylamines are of very
little interest. They are usually orange or red in colour,
but give intensely green solutions in alkali. On oxida-
tion with ferric}^ anide they give the nitroso- compound,
and on reduction in alkaline solution the primary amine.
Acids rapidly rearrange them into aminohydroxyanthra-
quinones.
Hydrazines can be obtained by the reduction of the
anthraquinone diazonium salts. The diazonium salts them-
selves are not particularly easily reduced, so that it is best
first to prepare the sulphonic acid by treating the diazonium
sulphate with sodium sulphite, and then to reduce this to
the hydrazine sulphonic acid by treatment with stannous
chloride, sodium hydrosulphite or sulphurous acid.^ Use of
sulphurous acid as a reducing agent, however, often leads to
1 M. 32, 1040.
2 R. E. Schmidt and Gattermann. B. 29, 2934. Cf. By., D.R.P. 100,137 ;
M.L.B.. D.R.P. 135.409.
3 SchoU, M. 32, 1033. Wacker, B. 35, 666.
* By., D.R.P. 119,229. See also p. 244.
6 B. 29, 2934-
• Mohlau, B. 45, 2233, 2244. By., D.R.P. 163,^47
390 ANTHRACENE AND ANTHRAQUINONE
the entrance of a second sulplionic acid group, a hydraziue-
a/3-disulphonic acid being produced, Tlie hydrazines them-
selves are readily prepared from the sulphonic acids b}'
hydrolysis with dilute h5'drochloric acid.
Hydrazines can also be prepared by condensing halogen
anthraquinones with hydrazine, the reaction being best
carried out in the presence of pyridine, i* As would be
expected halogen atoms when in a- positions react most easily.
Thus, 1.5-dichloranthraquinone when boiled with hydrazine
in pyridine solution gives i-chloranthraquinone-5 -hydrazine,
and when heated with h3?-drazine in pyridine solution at 145°
it yields anthraquinone-i.5-dihydrazine. 2.6-Dichloranthra-
quinone only reacts with hydrazine in pyridine solution at
170°, and then gives anthraquinone-2.6-dihydrazine. It
should be noted that in the preparation of a-hydrazines
by this method there is always a chance of the cyclic carbonyl
group becoming involved in the reaction. Thus, i.8-dichlor-
anthraquinone when boiled with hydrazine in pyridine
solution gives a pyrazol.
The anthraquinone h3^drazines show much the same
reactions as other aromatic hydrazines, and readily condense
with aldehydes and ketones to form hydrazones. Many of
these hydrazones when derived from aromatic aldehj'des
or ketones have tinctorial properties, but vat dyes are only
produced when there is at least one hydroxyl group present
in the aryl group. 2 When this is the case the hydrazones are
capable of dj-eing cotton either from a hydrosulphite vat or
from their solution in sodium sulphite. The hy drazone formed
from anthraquinone- 1. 5 -dihydrazine with _/)-hydrox>^benz-
aldehyde gives greenish-blue shades, blueish-red shades being
obtained with the hydrazone derived from w-hj^droxy
benzaldehyde, and blue shades with that from 2.4-dihydroxy
acetophenone. The corresponding hydrazones derived from
anthraquinone-2.6-dihydrazine give brown shades.
Both a- and ^-anthraquinone hj'drazines form hydrazones
when treated with acetoacetic ester. When heated with
acetic anhydride the /S-hydrazone loses water and undergoes
I Mohlau, B. 45. 2245. a M.L.B.. D.R.P. 256,761
MISCELLANEOUS COMPOUNDS 391
pyrazalon formation in the normal way. The a- compound,
on the other hand, does not, but when heated with a mixture
of acetic anhydride and sulphuric acid is converted into a
pyrazol, acetoacetic acid being split off.i
The hydrazine sulphonic acids have tinctorial properties
and are capable of being used as acid wool dyes, although these
are of no technical importance. Thus, anthraquinone-i.8-
di-hydrazine-j8-sulphonic acid, Ci4H602[i.8](NH.NHS03H)2,
gives scarlet shades. 2 The introduction of hydroxy 1 groups
into the molecule tends to shift the colour towards the violet
end of the spectrum.
Simple hydrazo- compounds in which the hydrazo group
is joined to two anthraquinone residues, such as
C14H7O2.NHNH.C14H7O2,
do not seem to «have been prepared, although one or two
mixed h5^drazo compounds have been described. Thus,
dichloranthrachpv'sazin disulphonic acid condenses very
readil}^ with phen5dhydrazine to produce a hydrazo com-
pound 3 (di-phenylhydrazo-anthrachr>'sazin disulphonic
acid ?), and a mixed hydrazo- compound is also formed by
condensing phenylhydrazine, or phenylhydrazine sulphonic
acid, with Imico- quinizarin.^
1 Mohlau, B. 45. 2233. See also p. 363. - Bv., D.R.P. 163,447
3 M.L.B., D.R.P. 99.078. * M.L.B., D.R.P. 204,411.
ADDENDA
Page 38. Cf. also pp. 31-32. — Ray 1 has stated that anthra-
cene derivatives are obtained from aromatic hydrocarbons
and chloroform, beuzal chloride, or carbon tetrachloride
by a modification of the Friedel and Crafts reaction in
which the catalyst is prepared from aluminium and mer-
curic chloride by a special process. From benzene and
chloroform or benzal chloride he states that he prepared
g.io-diphenyl-g.io-dihydroanthracene, but gives its melting
point as 159° as compared with i64"2° found by lyinebarger,^
who prepared it from benzal chloride and benzene by means
of aluminium chloride. Haller and Guyot 3 have also
prepared the compound by reducing 9.10-diphenyl anthra-
cene, but give the melting point as 218°. Their product
evolved hydrogen when heated, whereas that obtained by
Linebarger does not appear to have done so. Ray's product
prepared from chloroform appears to have been impure
(found : C=93"2, YL=6j. C26H20 requires C=94'o, H=6-o),
although the analysis of that obtained from benzal chloride
agrees closely with the theoretical. Ray states that his
product on oxidation with chromic acid gave anthraquinone,
whereas Simonis and Remmert ^ found that 9.10-diphenyl-
anthracene itself does not give anthraquinone on oxidation.
Ray also states that his product when treated with acetic an-
hydride and pyridine gave a diacetj-l derivative. It is difficult
to see how a diacetyl derivative could be obtained from a
h^^drocarbon by the method employed, and in any case such
a diacetjd compound would contain thirty carbon atoms and
not twenty-eight as Ray states. (Found: 0=85*3, H =7*4.
^ Soc. 117, 1335- ' Am. 13, 554.
* C. r. 138, 1252. * Page 20.
393
394 ANTHRACENE AND ANTHRAQUINONE
C28H24O2 requires €=857, H=6-8; C30H24O2 requires
C=86-5, H=5-8.)
From benzene and carbon tetrachloride or benzotri-
chloride Ray obtained a hydrocarbon which melted at
159° and which he designates as 9.9.10.10-tetraphenyl-
dihydroanthracene. It should be noted that the melting
point is the same as that of the product obtained from
chloroform or benzal chloride. Ray does not give any
facts serving to differentiate them, and analytical data for
carbon and hydrogen are insufficient. (Found : C=94'0,
94-0; H=6-8, 5-1. CggHgg requires C=94-2, H=5-8 ;
C26H20 requires C==94*o, H=6-o.)
Page 68. — ms-N-Methyl anthramine cannot be obtained
by methylating ws-anthramine either by treatment with
methyl iodide or dimethyl sulphate. It is, however, readily
obtained by heating anthrone with aqueous methylamine
solution at 220°. It forms sulphur-yellow needles which
sinter at 85° and melt at 90°. It is very easily oxidised
and its solutions exhibit an intense green fluorescence.
Page 81. — When anthraquinone is reduced by heating
at 230° with glucose, sucrose, lactose, or other sugar in the
presence of aqueous, caustic soda of 30 per cent, strength,
anthranol is produced. ^
Page 99. — When anthranol is treated with a cold con-
centrated solution of formaldehyde, it passes readily into
methylene anthrone (methylene anthraquinone) 2 :
CO
^6^4^ yC6H4
C
CH2
This forms pale yellow prisms which melt at 148°. It
unites instantaneously with one molecule of bromine to
form brom-methylbromanthrone, also obtained by the
action of bromine on methylanthranol methyl ether. ^
1 A. G. Perkin, E.P. 151,70718. Cf. M.L.B., D.B.P. 249,124.
2 K. Meyer, A. 420, 134. ^ k. Meyer and Schlosser, A. 420, 131.
ADDENDA 395
Page 112. — The alkylation of antliranol has been further
studied by Kurt Meyer and Schlosser.i They find that
alkylation with dimethyl sulphate or diethyl sulphate leads
to the formation of 0-alk3'l compounds (anthranol methyl
and ethyl ethers), whereas alkylation with alkyl iodides leads
to the production of C-alkyl derivatives. From anthranol
and methyl iodide the chief product was methylanthranol
methyl ether (I) together with dimethyl anthrone (II) :
OCH3
I
C CO
c c
I /\
CHg CH3 Crl3
I II
Similar products were obtained by means of ethyl iodide.
Page 118. — Kurt Meyer 2 has extended his investigations
on the tautomerism of the anthraquinone reduction products
to the corresponding compounds obtained from some
hydroxy anthraquinones. The reduction of erythrohydroxy
anthraquinone by sodium hydrosulphite and alkali or by
tin and hydrochloric acid ^ leads to a product which must
be regarded as the anthrone, as the equilibrium mixture in
alcohol (•I--2 gram in 100 c.c.) contains only 3 to 4 per cent.
of the enole (anthranol). Reduction of erythrohydroxy-
anthraquinone with zinc dust and caustic soda leads to
I -hydroxy anthraquinol. The corresponding enole, i(?4).9-
dihydrox}^ anthrone can be obtained by brominating
i-hydrox}' anthrone and then replacing the bromine atom
by the h^'droxjd group by treatment with aqueous acetone.
In alcoholic solution the equilibrium mixture contains only
about 10 per cent, of the enole (anthraquinol). The reduc-
tion products of quinizarin show an even more marked
tendency to become ketonised. Reduction of quinizarin
with tin and hydrochloric acid in glacial acetic acid solution
1 A. 420, 126. « K. Meyer and Sander, A. 420, 113.
» M.L.B., D.R.P. 242,053.
396 ANTHRACENE AND ANTHRAQUINONE
leads to 1.4.9-triiiyd.roxy anthrone, whereas reduction with
zinc and caustic soda leads to the isomeric dihydroxy
anthraquinol. This latter substance, however, is extremely
unstable and is ketonised merely by recrystallisation. The
anthranol obtained by the reduction of jS-hydroxj-anthra-
quinone was also examined, but quantitative results as to
the state of the equilibrium mixtm'e coulH not be obtained,
as even excess of bromine did not cause the disappearance
of the fluorescence. The substance, however, was probably
chiefly enolic, so that the ketonising influence of h^^droxyl
groups would seem to be confined to those occupying a-
positions. In connection with this it is interesting to notice
that Willstatter and Wheeler 1 have found that hydro-
juglone exists in two forms. One of these is probably the
true phenol (1.4.5-trihydroxynaphthalene), whereas the other
is probably i.4-dihydrox^^-5-keto-5.8-dihydronaphthalene :
H H
OH \/ OH
HO OH
O
OH
the presence of the two hydroxyl groups in a- positions
rendering the ketonic form stable.
Page 136. — Phthalic anhydride will condense with
hydrindene 2 to give a ketonic acid which on treatment
with ten parts of 15 per cent, oleum at 60-70° yields a
mixture of two isomeric phthaloyl hydrindenes (I and II) :
CO
CO
CHg
CHg
CHz
n
M.p. 108-110°. M.p. 181°.
^ B. 47, 2796. - Braun, Kirschbaum and Schuhmann, B. 53, 1165.
ADDENDA 397
The second of these substances on reduction with zinc dust
and ammonia passes into the corresponding anthracene
derivative (m.p. 242-243°), whereas the former yields a
product which melts at about 150° but which could not be
obtained pure. It therefore behaves on reduction in the
same way as the a-methyl anthraquinones.
Page 140. — 3-Nitrophthalic acid, 4-nitrophthalic acid,
and the corresponding acetyl aminophthalic acids will
condense with benzene under the influence of aluminium
chloride to form ketonic acids. ^ It is not stated whether or
not dehydrating agents will convert these into anthraquinone
derivatives.
Page 159. — i-Chlor-2-dichlormethyl anthraquinone is
converted into i-chloranthraquinone-2-aldehyde by heating
with concentrated sulphuric acid and boric acid. 2
Page 160. — 2-Methyl-i-aminoanthraquinone when heated
with an aromatic nitro compound and an alkali, with or
without the addition of a primary aromatic amine, gives an
azomethine derivative from which i-aminoanthraquinone-
2-aldehyde can be obtained by hydrolysis with an acid. 3
Page 163. — i-Chloranthraquinone-2-aldehyde is readily
oxidised to the carboxylic acid by chromic acid.*
Page 168. — By nitrating anthraquinone to the dinitro
compound Dhar ^ obtained 1.5-dinitroanthraquinone (m.p.
360°), 1.3-dinitroanthraquinone (m.p. 240°) and two other
isomers w^hich he was unable to identify. For the analysis
of the 1.3-dinitro compoimd he gives the figures : found
N=4'2 ; calculated, N=9-39.
Page 171. — 2-Methyl-i-chloranthiaquinone when chlori-
nated gives 2-dichlormethyl-i-chloranthraquinone.<5
^ Lawrence, Am. Soc. 42, 1871.
- Schaarschmidt and Herzenberg, B. 53, 1809.
=" Cas. E.P. 148,339 (1915).
* Schaarschmidt and Herzenberg, B. 53, 1809.
^ Soc. 117, looi. •
* Schaarschmidt and Herzenberg, B. 53, 1809.
398 ANTHRACENE AND ANTHRAQVINONE
Page 173. — i-Amino-2-meth3-lanthraquinone can be con-
verted, into 2-meth3-l-i-cli]oranthraqmnone by Sandmeyer's
method, but the reaction must be carried out in the cold in
order to avoid the formation of anthraquinone-i.2-indazol.i
Page 208. — Both a-aminoanthraquinone and jS-amino-
anthraquinone can be methylated b}* boiiing with dimethyl
sulphate and a mild alkali such as sodium carbonate, in
the presence of an inert solvent of high boiling point such as
nitrobenzene or tetrachlorethane.2
Pages 265-266. — Kurt Meyer and Sander have examined
leuco-qumizarin. I and /^wco-quinizarin II. The former
can also be obtained from /^wco-purpurin by warming with
glacial acetic acid, but will not give purpurin by oxidation.
Its conversion into quinizarin is not brought about by
oxidation but by loss of water, and can be effected by alkali
even in the absence of atmospheric ox}-gen. In view of
these facts Meyer and vSander consider that leuco-quini-
zarin I must be 2-hydroxy-i.4-diketo-i.2.3.4-tetrahydro-
anthraquinol (I). Loss of a molecule of water from this
substance would give rise to 9.io-dihydrosy--i.4-anthra-
quinone (II), which would pass into the i.4-dih3-drox3'-9.io-
anthraquinone (quinizarin, formula III) b\- ketonisation of the
hydrox\-l groups and simultaneous enoHsation of the qiuno-
noid carbonyl groups :
OH p OH P . CO 5"
'^"iHOH
Hz
OH 5 ^ OH 5 CO 0"
I II . ffl
Page 324. — By condensing the chloride of i-chloranthra-
quinone-2-carbox}-lic acid with /)-x}-lene, Schaarschmidt
and Herzenberg ^ obtained the xylyl chloranthraquinonyl
ketone, from which they were able to prepare the corre-
sponding amino ketone (I) by heating with ammonia.
This when diazotised and then treated with copper powder
^ Loc. cit. * Atack and Haworth, E.P. 147,964.
9 B. 53, 1807. Cf. also B. 53, 1388.
ADDENDA
399
gave four products, viz. {a) traces of xylyl hydroxyanthra-
quinonyl ketone ; (b) about 20 per cent, of X}- lyl anthraquinony 1
ketone itself, also obtained by condensing the chloride of
anthraquinone-2-carbox}'lic acid with _^-xylene ; (c) a fluore-
none derivative (formula II) in about 25 per cent, yield ;
and (d) a benzanthrone derivative (formida III) in about
50 per cent, yield :
The phthaloyl fluorenone (II) passed into the benzanthrone
derivative (III) when heated with zinc chloride. Both
II and III yielded the carbox}-lic acid (IV) when fused with
caustic alkaU, the carboxyl being formed by the opening of
the fluorenone ring.
Page 328. — An investigation of perylene and its aeriva-
tives has been commenced.^
1 Hansgirg and A. Zinke, M. 40. 403. A. Zinke and Unterkreuter, M.
40, 405.
400 ANTHRACENE AND ANTHRAQUINONE
Page 370. — Compotinds wldch are probably isoxazols of
the type :
N
I
CR
are obtained by treating i-nitro-2-alkylantliraqtiinones with
oleum. 1 Compotinds which may or may not be isoxazols
of the above structure are obtained by treating 2-methyl-
i-aminoanthraquinone with alkali alcoholates.^
Phthaloyl acenaphthene.^ — Phthalic anhydride will con-
dense fairly readily with acenaphthene to give a ketonic
acid in which the carbonyl group occupies one of the
a-positicns of the naphthalene ring. This substance, how-
ever, differs from the corresponding naphthalene derivative
in showing great resistance to the action of dehydrating
agents. Neither concentrated sulphuric acid nor phosphorus
pentoxide will convert it into phthaloyl acenaphthene, but
the anthraquinone ring can be closed by heating to 200'' with
phosphorus pentachloride. The yields, however, are poor.
1 M.L.B., E.P. 147.00T (1918). 2 M.L.B., D.R.P. 293,576.
^ Groebe, A. 327, 99-
INDEX TO GERMAN PATENTS
D.R.P.
3.565
6,526
17,627
695
21,178
23,008
26,197
38,417
42.053
46,654
47.252
50.164
50,708
54.624
56,951
56,952
58,480
60,855
61,919
62,018
62,019
62,504
62,505
62,506
62,531
62,703
63,693
64,418
65.182
65,375
65-453
65,650
66,153
65,811
66,917
67,061
67,063
67.470
68,113
68,114
68,123
68,474
68,775
69,013
69.835
Patentee.
Pryzibram
M.L.B.
B.A.S.F.
Agfa
B.A.S.F.
Majert
Reney and
Chem. Fab
B.A.S.F.
By.
MX.B.
By.
Ort and M
By.
M.L.B.
By.
M.L.B.
By.
Erhart
A.G.
.B.
Date.
Page
1S78
278
1878
192, 198
1881^
255
1881^
296
1882
64. 65, 66
1882
296
1883
293
1886
17
1887
17
1888
296
1888
296
1888
254, 281, 295
1888
254, 281, 295
1890
295
1890
179. 278
1890
278
1890
295
1890
260, 277
1890
200
1890
264
1890
284
1890
264
1890
264
1890
264
1890
260
189I
294
1890
260
1890
260
1890
260
1891
260
189I
260
1890
200
1891
92, 264
1892
281, 284
1891
200
1890
260
1891
260
1892
294
189I
92. 264
189I
92, 264
189I
92
1892
17
1890
258
189I
260
189I
258
401
26
402
D.R.P.
69.842
^'9.933
69.934
70.515
7o.«^5
70,78a
7i.9<'4
72,220
72.552
73.605
73.684
73,860
73.942
73.961
74.212
74.353
74.431
74.562
74.508
75.054
75.2SS
74.400
76,262
76,280
76,941
77.179
77.3"
77.720
77.721
77.818
7»."42
78.772
78,861
79,768
80.407
81,244
81.245
81.481
8l.6g4
81.741
81,742
81.959
Ri,o(Hi
81.Q0-'
83.035
8 vo<>8
83.0S5
84. s>' >
84.--
84.774
86.^>97
86.150
86.ii5
80.530
86.6 nO
S7.6JO
87.7?o
IXDEX TO
Pauotee
By.
M.L.B.
By"
Soc. Anon
M.L.B.
By.
Soc. Anon
M.L.B.
By.
M.L.B.
By.
m!l.b.
B.A.S.F.
Soc. Anon
B A.S.F.
M.L.B.
Soc. Anon
M.L.B.
B.A.S.F.
M.L.B.
M.L.B.
By.
m!l.b.
By.
M.L.B.
By.
M.L.B.
Bv.
M.L.B.
Nietxki
Bv.
M.L,B.
B>-.
Bv
K.
B \.SF
GERMAN PATENTS
Dale.
Page.
. 1892
92. :
264
1892
264
1S92
264
1892
281
. 1892
295
1 891
263
. 1893
179.
258
. 1893
62
. 1893
193
. 1892
282
• 1893
193
I ^13
242
l-'ji
264
1893
62
1 8.) 3
281
IS.)2
264
IS02
281
. 1^93
281
. 1893
281
. 1893
242,
287
. 1893
136
1893
249.
250. 25
1892
246
, 1893
62
. 1892
243
• 1893
173
1893
62
. 1894
179.
193
1892
206
. 1893
242.
287
1894
173
1894
193
• 1894
17
• 1893
258
■ 1894
140
1803
258
• 1893
262
. 1893
259.
260
• 1893
246.
282
1895
193
• 1895
249
. i8q^.
260
1893
260
1894
258
1S03
258
1S04
4
1S94
258
. i'>95
261
1894
203
I S03
263
• i>95
194
1S04
200.
203
1895
375
1S05
202,
203
!- -5
262
»^95
s6o
1894
1x6
iSoi
246
I
I
INDEX TO
D.R'.
Patentee
88.03
B.A.S.R ..
89,07
By.
89,14
B.A.S.F. ..
89,82
By.
90,01
it ' '
90,70
B.A.S.F. ..
91.19
By.
91,10
»» • •
91,12
i> • •
91,58
B.A.S.F. ..
92,51
By.
92,80
B.A.S.F. ..
92,98
>» • •
93.23
By.
93.30
>» • *
94.36
»» • •
95.^5
it ' '
96,17
t* • •
96,34
»» ' •
97,27
M.L.B. . .
97.64
Bv.
97,^
m'.l.b. . .
98,69
By.
99,c8
M.L.B. . .
99, ?4
By.
99,ei
M.L.B. . .
99.^
>> • •
99,84
t» • •
100,16
By.
100,17
I> ' •
ioo,i8
>> • •
101,20
By.
ioi,j6
»»
ioi,i>5
»> • •
ioi,>6
f$ • •
101,09
tt ' '
102, =2
i» ' *
102, f.8
ft • •
1 03, .-.5
»» • •
1 03, -.6
»> • *
103,66
i> • "
I03.i28
it • •
I03,c8
tt • •
104,14
M.L.B. . .
I04,d2
By.
io4,'7
>» • •
I04,?7
M.L.B. . .
104,01
By.
105, n
>9 • •
io5,?7
i» ' '
io6,H
»> • '
106,27
B.A.S.F. ..
106,55
M.L.B.
io7,-?8
»> • ■
107,31
By.
i07,;;o
y» • "
108,74
B.A.S.F. ..
108,52
By.
GERMAN PATENTS
Date. Page,
• • •
. 1893 246
. 1895 265
1892 246
. 1895 203
. 1895 261
1892 206
. 1895 201, 203
1896 201, 203
. 1896 203
. 1895 188
1896 203
. 1896 246
1896 246
. 1896 203
. 1896 203
. 1896 203
. 1897 204
1892 246
. 1897 277, 283
. 1897 173
, 1897 258, 260
. 1897 249
. 1897 280
. 1897 196, 391
. 1897 25S
. 1897 277, 2S4
. 1897 277, 2S4
. 1897 277, 284
. 1897 277, 283
. 1897 283, 3S9
. 1899 192
. 1897 259
, 1892 247
. 1897 196
. 1898 196
. 1898 204
. 1898 283
. 189S 263, 264
»
. 1897 194, 283
. 1898 196
i8g8 240
. 1897 180
. 1898 238, 239. 240,
277
. 1897 263, 264
. 1898 169, 244
. 1898 277
. 1898 249
. 1898 228
. 1898 283
. 1897 244, 246
. 1898 282, 283
. 1898 196
. 1898 241
. 1899 263, 264
, 1898 170
, 1898 196
. 1898 196, 199
. 1899 246, 283
403
404
INDEX TO GERMAN PATENTS
D.R.P.
Patentee. Date. Page.
108,420
M.L.B. ..
. 1898 196
108,459
B.A.S.F. ..
. 1897 249
108,578
By. ...
. 1899 283
108,837
Soc. Anon.
. 1898 140
109,613
B.A.S.F. ..
. 1897 246
"1,359
A. G. fur Teer .
. 1899 17
111,866
B.A.S.F.
1899 196, 226
111,919
M.L.B. . .
1898 263, 264
112,179
J» • •
1899 a8o
112,297
Soc. Anon.
. 1898 140
112,913
tt •
. 1898 140
113. on
B.A.S.F.
. 1899 196
113,291
Wilton . .
. 1899 17
113,292
B.A.S.F. .
. 1899 231
113.724
By.
. 1899 246, 283
113.934
B.A.S.F.
.
. 1899 196
114,197
Soc. Anon.
. 1898 140
114,198
J J
. 1898 140
114,199
By.
. 1899 200, 205, 274
114,263
it •
. 1899 272
114,840
B.A.S.F. .
. 1899 231
115,002
By.
. 1897 246
115,048
tt •
. 1899 228
116,746
tt •
. 1899 246, 283
116,867
j» '
. 1900 196
116,951
It •
. 1899 187
117.923
tt •
. 1899 276
119,228
tt "
. 1899 283
119,229
II
. 1900 246. 247, 389
II9.755
Simon
. 1899 250, 280
119.959
B.A.S.F. .
. 1899 284
121,155
It
. 1900 196, 226
121,315
II *
. 1898 246
121,684
»» •
. 1898 198
125,094
»»
. 1899 228, 229, 251
125,578
By.
. 1900 196, 198
125,579
l» •
. 1900 243, 277
125,666
It •
. 1900 196
125,698
II •
. 1900 203
126,015
H
. 1899 251
126,392
It •
. 1899 228
126,393
#» •
. 1899 228
126,444
It
• 1900 379
126,542
»»
. 1900 196
126,603
B.A.S.F. .
1900 251
126,803
By.
. 1900 198, 203
126,804
M.L.B. .
. 1901 194
127,295
It •
1900 58
127,399
By.
• 1901 50, 53, 67
127,458
tt •
1900 196
127.459
It •
1900 196
127,532
It •
. 1900 196
127,699
It •
. 1901 273, 274
128,196
B.A.S.F. .
. 1899 231
128,753
,, •
1900 203
128,845
>>
. 1900 173
129,845
,, •
. 1901 194, 343
129,846
II •
■
• 1901 343. 352
INDEX TO GERMAN PATENTS
405
D.R.P.
129,847
129,848
131.403
131.538
133,686
134.985
135.407
135.408
135.409
135.634
136,015
136.777
136,778
136,872
137.074
137.078
137.495
137.566
137.782
137,783
I38.II9
138.134
138,166
138,167
138.324
138,325
139.425
139.581
139.633
139.634
141,296
141,355
141.575
141,982
142,052
142.154
143,804
143.858
144,111
144.634
145,188
145.237
145.238
145.239
146,223
146,691
146,848
147,277
147.851
147,872
148,079
148,109
148,306
148,767
148,792
148,875
149,780
149,781
Patentee.
B.A.S.F
By. „
b.'a.s.f. '.'.
Deichler and Weizmann .
B.A.S.F
m.l'.'b.
By.
B.A.S.F
By
B.A.S.F. ..
By.
Sadler & Co
B.A.S.F. ..
By.
B.A.S.F. ..
Deichler and Weizmann .
M.L.B. ..
By
B.A.S.F
By.
M.L.B.
f f
By.
M.L.B.
By'.
BA.S.F.
By.
B.A.S.F.
By.
M.L.B.
Date,
Page.
1 901
352
1901
347
I901
273
1900
173, 286
1901
300
1900
148
I901
343
1901
300, 343. 345
1901
389
I901
206
1901
300
1900
197, 198
1900
197. 198
190I
79. 201
1901
229, 251
1901
196
1901
74
1900
203
1900
175
1898
229
1902
300
1900
231
1 901
231
1902
350
1900
149
1900
149
1902
277
1900
198
1900
300. 345
1901
302
1902
277
190I
300. 345
1902
355. 356
1902
358
1899
196
1902
206
1900
277
1902
277
1901
196
1900
198
1902
241,287
1902
193
1902
242
1902
196
1902
91, 269, 287
1900
228
1900
224, 226
1902
79. 201
1902
194
1902
351
1902
79. 201
1901
227
1902
203
1903
196, 198
1903
250
1903
241
1903
196
1903
24c, 295
4o6
D.R.P.
149,801
150.322
151,018
151.384
I5I0II
151. 512
^51.513
152,013
152,175
153.129
153.194
153.517
153,770
154.337
154.353
155.045
^55,415
155.440
155.572
156,477
156,759
156,762
156,803
156,960
157.123
157,449
157.685
158,076
15S.257
15S.277
158,278
158,287
158.413
158,474
158,531
158,891
158.951
159.129
159,942
160,104
160,169
161,026
161,923
161,954
162,035
162,792
162,824
163,041
163,042
163.447
163,646
163,647
164,129
164,292
164,791
165,140
165,728
165,860
INDEX TO
Paten lee
By.
M.L.B.
B.A.S.F.
I f
By.
Wed.
B.A.S.F.
Wed.
By.
B.A.S.F.
By.
B.A.S.F.
M.L.B.
By.
m.'l.b.
By.
B.A.S.F.
M.L.B.
By.
M.L.B.
By.
B.A.S.F.
By.
GERMAN PATENTS
Date.
Page.
• •
1902
177
. .
• • 1903
198, 200, 263, 281.
282
1902
203
. .
1900
203
1902
196
• . 1903
198
• • 1903
198
1900
1^4
1902
275, 276
• • 1903
261, 262
• ■ 1903
275. 276
■ • 1903
357
. .
1902
356
. .
• • 1903
261, 262, 263
• • 1903
258
■ ■ 1903
259
. .
■ • 1903
350
1903
258
• • 1903
203
■ • 1903
357
I901
224
• • 1903
287
. .
. . 1904
227
• • 1903
260
. .
• . 1903
17
• • 1903
350
. . 1904
343
1900
224, 226
. .
. . 1904
196
. .
. . I904
285
• . 1905
287
• • 1903
345, 346, 350
.. 1903
259
. .
• ■ 1903
346. 350
• • 1903
287
. .
• ■ 1903
242
. .
• ■ 1903
228
I901
196
. . 1904
352
• • 1903
179, 278
. . 1904
229
. . 1904
238, 260
. .
. . 1904
345
. . 1904
261, 262, 386
. . 1904
258
. . 1904
262
• • 1903
232
. .
. . 1904
238, 262
. . 1904
280
. . 1904
389. 391
. .
. . I901
196
. .
. . 1904
283, 284
. . 1904
288
• . 1903
178, 194
. .
. . I901
229
. . 1904
196
• • 1903
202
. . 1904
278
INDEX TO GERMAN
D.R.P,
Patentee
166,433
By.
166,748
t }
167.169
>> •
167,255
1* • *
167,410
>» • •
167,461
11 ■ *
167,699
M.L.B. . .
167,743
Wed.
168,042
B.A.S.F. .
I70.II3
By.
170,329
Wed.
170,562
By.
171.293
II
171.588
>t
171,836
ft
171,939
B.A.S.F. ..
172,105
M.L.B. . .
172,300
Wed.
172,464
M.L.B.
172,575
By.
172,609
B.A.S.F. ..
172,642
By.
172,684
>i ' '
172,688
>t ' '
172,733
it ' •
174,131
M.L.B. ..
174.494
B.A.S.F. ..
174,699
By.
174.984
B.A.S.F. ..
175,024
By.
175,067
B.A.S.F. ..
175,069
By.
175,626
tt
175,629
,, . .
175,663
Wed.
176,018
B.A.S.F. ..
176,019
*» • •
176,641
By.
176,955
»> • '
176,956
II * *
177,574
B.A.S.F. ..
178,129
By.
178,130
II • *
178,631
II
178,764
Agfa.
178,840
By.
179.608
) 1 • •
179,671
i» • •
179,893
B.A.S.F. ..
179,916
Wed.
180,016
By.
180,157
B.A.S.F. ..
181,176
»i • •
181,659
Wed.
181,722
By.
181,879
M.L.B. . .
183,332
• » ' "
183,395
»* • •
PATENTS
407
Date. Page.
1904 196
1904 287
1903 178. 194
1904 346, 350
1904 219. 225
1904 91, 269
1904 168. 242, 287
1904 274
1903 350
1904 204
1903 178. 241
1904 341
1904 363
1904 219. 225
1905 296
1904 294. 320, 332
1904 128
1905 274
1903 203
1905 188
1904 332
1903 240, 241
1905 343, 349
1904 179. 258, 259, 260.
278
1904 302
1905 208
1905 335
1905 232
1905 159
1902 206
1905 335
1905 210
1905 345
1905 188
1901 274
1904 275, 321
1904 321
1905 188
1905 188
1905 232
1905 331. 332
1905 233. 343
1905 343
1904 240
1906 17
1905 188
1905 188
1905 188
1905 94
1905 275
1905 188
1905 92
1904 321
1905 275
1903 206
1903 203
1906 250
1903 196
4o8 INDEX TO
GERMAN PATENTS
D.R.P. Patentee.
Date.
Page.
184,391 By.
. . 1905
341
184,495 B.A.S.F
. . 1905
91
184,768 M.L.B
. . 1906
270
184,807
. . 1906
270
184,808 M.L.B
1906
270
184,905 B.A.S.F
. . 1906
232
185,221
. . 1904
329
185,222
. . 1904
3JO
185,223
. . 1904
330
185,546 M.L.B
1906
196
185,548 By
. . 1906
290, 292
186,465 B.A.S.F
. . 1906
233. 343
186,526
. . 1904
255
186,596
. . 1906
335
186,636
. . 1906
345
186,637
1906
345 „
186,882 By.
1906
376. 378
186,990 B.A.S.F
. . 1906
188
187,495
. . 1904
321
187,685 Wed
• • 1903
274
188,189 M.L.B
. . 1906
270
188,193 B.A.S.F
. . 1905
329
188,596 M.L.B
1906
270
188,597
. . 1906
270
189,234
. . 1905
294. 295
189,937 Wed
. . 1903
276
190,476 By.
. . 1906
179
190,656 B.A.S.F
1906
96. 335
190,799 Scholl.
. . 1906
333
191,111 B.A.S.F
. . 1906
290
191,731 M.L.B.
. . 1903
196
192,201 By.
1906
290
192,436 B.A.S.F
. . 1906
306, 309
192,484
. . 1906
270
192,970
. . 1906
290
193,104 M.L.B.
. . 1906
280
193,121 By.
. . 1907
345, 346, 347.
351
193,272 K
. . 1907
100
193.959 B.A.S.F
1906
325
193.961 Heller.
. . 1906
134. 143
194,252 B.A.S.F
. . 1906
293. 331
194.253 By.
. . 1906
232, 235, 293
194,328 M.L.B.
. . 1906
132. 135
194.955 Wed.
. . 1906
253
195,028 M.L.B.
. . 1906
253
195.139 By.
. . 1907
196
195,874 Wed.
. . 1903
241. 283
196,752 By.
. . 1907
375
196,980 M.L.B.
. . 1907
253
197,082 By.
. . 1907
273, 274
197,554 B.A.S.F. ..
1907
232
197,607 By.
1904
241
197.649 .. .. .
. . 1904
240
197.933 Scholl
. . 1906
333
198,024 By.
1907
352
198,025 B.A.S.F. . .
1907
291, 292
198,048
1907
291
198.507
1907
345
D.R.P.
199,713
199.756
199.758
200,014
200,015
200,335
201,327
201,542
201,904
201,905
202,398
202,770
203,083
203,436
203,752
204,354
204,411
204,772
204,905
204,958
205,035
205,095
205,096
205,097
205,149
205,195
205,212
205,217
205,218
205,294
205,442
205,551
205,881
205,913
205,914
205,965
206,054
206,464
206.536
206,645
206,717
207,668
208,162
208,559
208,640
208,969
209,033
209,231
209,232
209,233
209,321
209,331
209,351
210,019
210,565
210,863
211.383
211.927
INDEX TO
Patentee
By.
B.A.S.F.
By.
B.A.S.F.
m.l!b.
By.
MX.B.
Wed.
By.
B.A.S.F.
M.L.B.
By.
B.A.S.F.
G.C.I.B.
M.L.B.
B.A.S.F.
M.L.B.
By.
M.L.B.
By.
G.C.I.B.
B.A.S.F.
By.
M.L.B.
By.
M.L.B.
Wed.
By.
B.A.S.F.
By.
B.A.S.F.
M.L.B.
By.
G.C.LB.
By.
M.L.B.
By.
G.C.LB.
M.L.B.
G.C.I.B.
By.
B.A.S.F.
Wed.
B.A.S.F.
GERMAN PATENTS
Date. Page.
1907 290
• 1905 95
1907 229. 230
. 1907 326
. 1907 291. 292
• 1905 34. 321
• 1907 231
. 1907 96
• 1907 293
1907 201, 203
• 1903 178. 239. 241
• 1907 273
. 1906 248
• 1906 335
1907 290
. 1905 322
• 1907 391
. 1907 183. 187
■ 1907 345
. 1907 188
• 1907 354
• 1907 293
. 1907 201
• 1907 253
. 1907 201
• 1907 173
. 1907 188
. 1907 188
. 1907 188
• 1905 321
• 1906 335
1907 201
1903 202
• 1907 173
• 1907 355
• 1903 238, 278
. 1907 183
• 1907 300
. 1908 183, 187
. 1907 196
. 1908 232, 235
. 1908 250
1908 232, 235
. 1908 188
. 1907 183
. 1908 234
1907 290, 291
1907 188
1908 188
1908 188
. 1908 196
1907 188
1908 188
1908 213. 214
1908 345
1908 179, 238, 241,
278
1908 300
• 1908 335
409
410
INDEX TO Gl
IRMAN PATENTS
D.R.P.
Patentee, Date.
Page
211,958
B.A.S.F
. 1908
213
211,967
G.C.I.B. . .
• 1907
188
212,019
B.A.S.F. ..
. 1908
335
212,204
ft
• 1907
290
212,436
By.
1908
213, 214
212,470
B.A.S.F. ..
. 1908
232. 235
212,471
»* • •
. 1908
333
212,697
M.L.B, . .
■ 1907
265,
212,857
By.
1908
183
213,501
»> • •
. 1908
233. 343
213,506
G.C.I.B. . .
• 1907
188
213,960
By.
1908
186
214,150
i# • •
. 1908
173
214.156
Thiimmler
. 1909
178
214,714
B.A.S.F. ..
1908
174
215,006
>$ • •
1908
91, 173.387
215,182
»» • '
. 1908
214
215.294
By.
• 1907
211
216,071
B.A.S.F. ..
• 1907
174
216,083
M.L.B. . .
• 1907
231
216,268
>> • '
. 1908
286
216,280
B.A.S.F. ..
1908
232. 235
216,306
By.
1908
373
216,480
»> ' '
. 1908
317
216,597
B.A.S.F. ..
. 1908
290
216,668
By. ...
1908
232. 235
216,715
B.A.S.F. ..
• 1905
171, 172
216,772
By.
. 1908
213
216,773
»> • •
. 1908
196
216,891
B.A.S.F. ..
190S
352
216,980
By.
1908
213, 214
217.395
B.A.S.F. ..
• 1907
232. 293
217,396
tt
• 1907
232, 293
217.552
By.
1908
178
217,570
B.A.S.F. ..
. 1909
332
217,688
By.
. 1908
374
218,161
B.A.S.F. ..
• 1907
232, 293
218,162
/» • •
. 1909
335
218,476
It • •
1908
294
218,571
By.
. 1908
208
220,032
>» • •
. 1909
227
220,314
,,
1908
355
220,361
B.A.S.F. ..
. 1909
352
220,579
ft
. 1909
211
220,580
By.
. 1909
339
220,581
l> • •
• 1909
232, 234, 235
220,627
»» • •
. 1909
208
221,853
Ullmann
. 1909
306
222,205
B.A.S.F. ..
. 1909
210
222,206
l> • •
. 1909
211
223,069
By.
. 1909
213, 214, 219
223,103
>t • •
1908
253
223,176
G.C.I.B. . .
1901
188
223,210
Kinzlberger & Co
1908
115
223,510
By.
. 1908
213. 214
223.642
Ullmann . .
. 1909
178
224,019
M.L.B. . .
. 1908
180
224,490
*t • •
. 1909
219
INDEX TO GERMAN PATENTS
411
D.R.P.
224,500
224,589
224,808
224,982
225,232
225,982
226,215
226,230
226,879
226,940
226,957
227,104
227,324
227,398
227,790
228,876
228,901
229,110
229,111
229,165
229,166
229,316
■229.394
229,408
229,465
230,005
230.052
230,399
230,400
230,407
230,409
230,411
230,454
230.455
231,091
231.853
231.854
232,076
232,127
232.135
232,262
232.526
232,711
232,712
232.739
232,791
232,792
233.072
233,126
234,289
234.294
234.518
234.749
234,922
234.977
235.094
235,312
235.776
Patentee.
M.L.B.
By.
Ullmann
By.
b'.'a.s.f.
Geigy.
By.
Ullmann
By.
B.A.S.F.
By."
Agfa.
M.L.B.
Agfa.
B.A.S.F.
By.
B.A.S.F.
M.L.B.
Agfa.
M.L.B.
By.
B.A.S.F.
By."
B.A.S.F.
Ullmann
G.C.I. B.
M.L.B.
By.
M.L.B
By.
M.L.B.
Agfa.
M.L.B.
Agfa.
By.
Griinau, Landshoff, and
By.
B.A.S.F.
By.
Wed.
Meyer
Date.
Page
1909
350
1908
187
1908
213. 214
1909
197
1908
213, 218
1908
355
1910
330
1909
149
1909
188
1908
213, 214
1909
188
1908
213
1909
197
1909
213
1909
352
1910
174
1909
170
1909
188
1909
220, 222
1910
373
1909
347. 350
1909
287
1909
163
1909
220
1909
188
1910
341
1910
232
1909
211
1909
211
1909
234
1909
211
1909
211
1909
353
1910
144. 304
1909
196
1909
220
1909
318
1909
381
1909
208
1909
221
1909
233
1910
341
1910
373
1910
373
1909
219
1909
221
1909
221
1910
373
1909
293
1908
76
1909
350
1910
212
1910
332
1910
222
1909
312. 317
1910
381
1910
208
1909
199
412
INDEX TO GERMAN PATENTS
D.R.P.
236,375
236,442
236,769
236.857
236,978
236,979
236,980
236,981
236,982
236,983
236,984
237,751
237.946
238,158
238,253
238,488
238,550
238,551
238,552
238,553
238,979
238,980
238,981
238,982
238,983
239,211
239,543
239,544
239,671
239,762
240,002
240,079
240,080
240,192
240,265
240,276
240,327
240,520
240,792
241,472
241,624
240,631
241,786
241,805
241,806
241,822
241,837
241,838
241,985
242,029
242,063
242,291
242,292
242,379
242,386
242,621
243,077
243-489
Patentee
M.L.B.
B.A.S.F.
M.L.B.
B.A.S.F.
M.L.B.
G.E.
Wed.
B.A.S.F.
G.E.
By.
M.L.B.
B.A.S.F.
m.l!b.
By.
Ullmann
By.
M.L.B.
By.
SchoU
M.L.B.
B.A.S.F.
M.L.B.
By.
m!l.b.
B.A.S.F.
Agfa.
B.A.S.F.
Scholl
G.E.
B.A.S.F.
By.
M.L.B.
Casella
B.A.S.F.
M.L.B.
Ullmann
B.A.S.F.
Scholl
Agfa.
Date.
Page.
1909
220
1910
214
1910
209
1910
297
1909
220
1909
220
1909
220
1909
220
1909
221
1909
220
1909
220
1910
335
1909
188
I910
297
19IO
387
1910
235
1909
219, 220
1909
220
1909
220
1909
220
1910
345. 350
1910
335
19IO
220, 365
1910
366
1910
317
1910
343
1909
312, 313
19IO
379
1910
336
1909
183
1910
306
1909
218
1910
234. 361
1909
220
1909
350
19IO
232
1909
306
1910
160
1910
188. 350
1910
92, 159
1910
33. 143. 164
1910
335
1911
160
1911
223
1911
255
1909
219
I910
212
I910
212
1908
183
1910
188
I911
313
1909
221
1909
219, 221
1910
285
1910
318
1911
188
1911
164
1909
210, 211
INDEX TO GERMAN PATENTS
413
D.R.P.
243.586
243.587
243.649
243.750
243.751
243.788
244.372
245,014
245.191
245,768
245.875
245.973
245.987
246,079
246,085
246,086
246,477
246,867
246,966
247,187
247.245
247,246
247.352
247,411
247,412
247,416
248,169
248,170
248,171
248,289
248,469
248,582
248,655
248,656
248,838
248,996
248,997
248,998
248,999
249,225
249.368
249,721
249.938
250,075
250,090
250,271
250,272
250,273
250,274
250,742
250,885
251,020
251,021
251. 115
251.234
251.235
251.236
251.350
Patentee
M.L.B.
B.A.S.F.
G.C.I.B.
Ullmann
Wed.
M.L.B.
G.E.
By.
m!l.b.
B.A.S.F.
Agfa.
B.A.S.F.
J. Meyer
Wed.
By.
M.L.B.
B.A.S.F.
Casella
By.
B.A.S.F.
By.
M.L.B.
B.A.S.F.
By.
B.A.S.F.
Agfa.
B.A.S.F.
Ullmann
m.l!b.
By.
m!l.b.
K. Meyer
By.
Schaarschmidt
B.A.S.F.
G.E.
B.A.S.F.
M.L.B.
B.A.S.F.
M.L.B.
If
By.
M.L.B.
Date.
Page.
1909
306, 308, 313
1910
317.318
1910
286
1911
317
1911
188
1909
162
1910
199
1910
199
1910
387
1910
350
1910
306
1910
387
1911
255
1911
266
1910
387
1911
222
1911
223
1909
188, 350
1911
306
1911
322
1911
199
1911
366
1909
387
1911
196, 199
1911
184
1911
188
1911
359
1911
306
1913
189, 35
1908
213
1910
318
1911
353
1910
211
1911
223
1911
194
1911
313. 318
1911
214
1911
354
1911
92, 297, 302
1908
186
1911
255
1911
175
1910
233
1910
23.46
1911
371
1910
318
1910
319
1911
187
1911
387
1911
163
1911
291
1911
380
1911
234. 361
1911
187
1911
188
1911
188
1911
255
1911
234. 361
414
INDEX TO GERMAN PATENTS
D.R.P.
Patentee.
251,480
Schaarschmidt
251,695
By
251,696
B.A.S.F
251,709
>» • • • •
251,845
W.t.M
251,956
By.
252,529
I> • • • •
252,530
f, • • • •
252,578
B.A.S.F
252,759
By
252,839
»> • • • •
253,088
G.E
253.089
By
253.090
B.A.S.F
253.238
M.L.B
253,507
tl • • • •
253,683
1* • • " •
253,983
Sanders . .
254,033
Schaarschmidt
254,091
Agfa
254,097
B.A.S.F
254,098
G.C.I.B
254.185
M.L.B
254,186
t > • • • •
254.450
B.A.S.F
254.475
M.L.B
254.561
By
254.710
Griinau, Landshoff, and
254.743
UUmann . .
254.744
M.L.B
254,745
By
255,031
»» • • • '
255,121
f*
255.340
M.L.B
255.591
Ullmann and Goldberg
255.641
G.E
255.821
M.L.B
255.822
f> • • • •
256.297
>> • ' • •
256,344
B.A.S.F
256,515
,,
256,623
M.L.B
256,626
tP • * • •
256,667
By
256,761
M.L.B
256,900
By
257,811
M.L.B
257,832
Wed
258,343
Agfa
258,556
M.L.B
258,561
B.A.S.F
258,808
Agfa.
259,037
By
259,365
B.A.S.F
259.370
,,
259,432
G.E
259,881
M.L.B
260,020
B.A.S.F
Meyer
Date,
Page,
I910
365
I9II
62
I9II
316
I9II
187
19II
211
I911
341
I9II
341
I91I
378
I9II
173
I9II
74
I9II
368, 369, 372
19II
387
I91I
372
1911
308
I910
387
1908
186
1909
179, 230, 231
1911
317
19II
365
I9II
136
I912
353
I9II
188
I911
225
I9II
233
I9II
173
I9II
305
I912
186
1910
76
I9II
372
19IX
220
I912
388
I912
129, 138
1912
165
I910
387
I910
186
I912
364
I9II
210
1911
233
1911
292, 293
I912
196
1911
206
I9II
76
I9II
306, 313
I912
374
I912
390
I9II
222
1909
232
I912
286
I912
194
I9II
93
I910
318
I910
379
I9II
368, 372
I912
163
I912
331
I912
227
I912
95
1912
331
INDEX TO GERMAN PATENTS
415
D.R.P.
260,562
260,662
260,765
260,899
260,905
261,270
261,271
261,495
261,557
261,737
261,885
262,076
262,469
262,477
262,478
262,788
263,078
263,340
263,395
263,423
263,424
263,621
264,010
264,043
264,139
264,290
264,940
264,941
264,943
265,194
265,647
265,725
265,727
266,521
266,563
266,945
266,946
266,952
267,081
267,212
267,414
267,415
267,416
267,417
267,418
267,445
267,522
267,523
267,544
267,546
267,833
268,049
268,219
268,224
268,454
268,504
268,505
268,646
Patentee.
Date.
Page
B.A.S.F. .
. 1912
49
M.L.13. .
. 1911
95
By.
1911
264
Agfa.
. 1912
194
B.A.S.F. .
1911
371. 372
»» •
1911
230
j»
. 1911
230
Casella
1911
360, 362
G.C.I.B. .
. 1912
188
B.A.S.F. .
. 191 1
366, 367
Agfa.
1912
196
G.E.
. 1912
227
By.
. 1912
379
M.L.B. .
1911
186
G.C.I.B. .
. 1912
326
M.L.B. .
. 1911
234
B.A.S.F. .
1912
313
M.L.B. .
. 1912
180
B.A.S.F. .
. 1911
179. 231
By.
1911
igii
287
196
Wed.
. 1911
286
By.
igi2
292
G.E.
. 1912
340
By.
. 1912
374
»» •
1912
367
»»
1912
185
ft
. 1912
185, 188
B.A.S.F. .
1912
373
G.C.I.B. .
. 1912
188
Wed.
. 1912
286
M.L.B. .
1912
196
B.A.S.F. .
. 1911
179, 231
M.L.B. .
. 1912
180
B.A.S.F. .
1911
1912
179. 231
356
J»
. 1912
356
B.A.S.F. .
. 1911
359
Afga.
1912
159
M.L.B.
1912
206
Casella
. 1912
210
n
1912
210
it
. 1912
210
M.L.B. .
. 1912
380
B.A.S.F. .
1912
331
By.
. 1912
225
M.L.B. .
. 1912
234. 361
B.A.S.F. .
1912
373
M.L.B. .
. 1911
173
»»
• 1909
95
M
1912
234. 360
B.A.S.F. .
. 1909
76
»i •
. 1912
306
»f
• 1913
331
M.L.B. .
. •-
1912
196
B.A.S.F. .
1912
339
By.
• 1913
365
Brass
. 1912
306
4i6 INDEX TO GERMAN PATENTS
D.R.P. Patentee. Date. Page. ,|
268,793 By. 1912 293 ]!
268,984 „ 1912 225
269.194 B.A.S.F 1911 314
269,215 Wed 1912 286
269,249 Agfa 1913 171
269,749 M.L.B 1913 196
269.800 Schaarschmidt 1912 307,317
269.801 Cassella 1912 210
269,842 By. 1913 365
269,850 B.A.S.F 1912 306
270,579 By. .. .. .*. .. 1912 213
270.789 M.L.B 1912 362
270.790 „ 1912 196
271,475 By. 1911 222
271,681 M.L.B 1911 173
271,790 „ 1913 165
271,902 Agfa 1912 354 '
271,947 G.E 1913 350
272.296 B.A.S.F 1913 307
272.297 „ 1913 308
272.298 By. 1911 186
272.299 „ 1912 280
272.300 „ . . . . . . 1912 186
272.301 „ 1913 264
272.613 M.L.B 1912 362
272.614 „ 1912 196
273.318 M.L.B 1912 76
273.319 ,. 1912 76
273,341 By 1913 163
273.443 G.E 1913 388
273.444 M.L.B 1913 356
273,809 Junghaus . . . . . . . . 1911 230
274,357 By. 19" 186
274.783 SchoU 1913 286
274.784 .. 1913 91
275,220 Kardos 1913 330. 384
275,248 „ 1913 384
275,299 By. 1912 231
275,517 M.L.B 1913 165
275.670 B.A.S.F 1912 360
275.671 .. 1913 307
276.357 Kardos 1913 33°
276.358 „ 1913 330
276,956 „ 1913 330
277.393 G.E 1913 179
277,439 M.L.B 1912 181, 186
277.733 Hofmann 1913 75
278,424 B.A.S.F 1913 335
278,660 Kardos 1913 33°. 384
279,198 M.L.B 1914 363
279.866 B.A.S.F 1913 226
279.867 „ 1913 232
280,092 „ 1913 69
280,190 M.L.B 1913 290, 362
280,646 Agfa 1913 196
280.710 B.A.S.F. .. 1913 331
280.711 Cassella . . 1913 315
280.712 „ 1913 307
INDEX TO GERMAN PATENTS
417
o
2
O
5
3
D. ?.
280 39
280 4^0
280 io
280^1
280,52
280,53
280, 5
281
281,
281,
282,:
282,.
282,41
282,€:
282,7:
282,8;
282,9 '
283,0
283,1.
283,2
283.31
283,4^
283,7^
283,72
284,08
284,08
284,17
284,18
284,20
284,20;
284,20c
284,21c
284,70c
284,790
284,976
286,092
286,093
286,094
286,095
286,096
286,098
286,468
287,005
287,270
287,523
287,590
287,614
287,615
287,867
288,464
288,474
288.665
288,824
288,825
288,842
288,878
289,112
289,279
Patentee
Kardos
By.
B.A.S.F.
M.L.B.
Agfa.
By.
UUmann
By.
UUmann
M.L.B.
Kardos
M.L.B.
Agfa.
B.A.S.F.
M.L.B.
G.E.
B.A.S.F.
Agfa.
B.A.S.F.
Cassella
G.E.
M.L.B.
Kardos
B.A.S.F.
M.L.B.
By.
•Cardos
"assella
J.A.S.F.
assella
[.L.B.
.A.S.F.
y-
.A.S.F.
y-
?fa.
:l.b.
l^L.B.
Date;
Page.
[913
330. 384
913
365
[913
330
f9l3
210
C913
373
[913
373
[913
285
[913
220
[913
183
914
167
913
164
914
127, 138
[914
276
^913
196
913
330. 384
t9i3
47
[913
222
913
321. 330
[912
43
[913
75
[913
330
914
288
913
307
^913
373
914
75
914
75
914
75
913
368
913
366
913
363
913
291
913
330. 384
913
331
913
44
913
173
913
1 96
913
368
913
368
914
312
914
307
914
330
914
330
914
373
913
254. 335. 343
914
373
913
350
914
306, 312
914
312
914
179, 279
914
206
914
179, 279
914
196
914
361
914
208
913
368
914
178
914
179, 279
914
35*5
27
4i8
INDEX TO GERMAN PATENTS
D.R.P.
290,079
290,084
290,814
290,879
290,983
290,984
291,984 _
292,066
292,127
292,247
292,356
292.395
292,457
292,590
292,681
293,100
293,156
293.567
293.970
293.971
295,624
296,019
296,091
296,192
296,207
296,841
297,079
297,080
297,261
297.567
298,182
298,183
298,345
298,706
299,510
301.452
301,554
302,259
302,260
305,886
307,399
308,666
311,906
Patentee
B.A.S.F.
G.E.
Agfa.
M.L.B.
By.
G.E.
Ullmann
G.E.
M.L.B.
B.A.S.F.
Agfa.
M.L.B.
Wed.
M.L.B.
By.
M.L.B.
By.
G.E.
Wed.
M.L.B.
Wed.
By.
M.L.B.
Wed.
By.
G.E.
By.
Scholl.
M.L.B.
Date.
Page
1914
329
1914
184
I914
224
1914
173
1913
355
1914
291
1914
222
19I4
13S
1915
350
I913
2B7
1914
48
1914
224
1914
183
1914
49
1914
76
1914
197
1913
171
1913
393
1913
88
1914
350
1912
196
1915
50
1915
84, 271
I915
350
1912
188
I914
350
1912
188
1912
188
1915
271
I913
188
1973
188
I913
188
1916
130, 157
1913
366
1913
188
1916
84, 271
1914
364
1914
364
1916
364
1917
84, 271
1916
297
1916
232
1913
188. 371
INDEX TO AUTHORS
AcHENBACH, 77, 78, 369
Aders, 285
Akt. Ges. f. Anilinl? Fabrikation
(Agfa), 17, 64-66. 136, 159, 173,
188, 194, 196, 210, 211. 220, 222.
288, 354, 373. 379
Akt. Ges. f. Teer u. Erdfil Indus-
trie, 17
Akt. Ges. Griinau, Landshoff u.
Meyer, 76
Anderson. 1, 2, 42, 43
Anschutz, 15, 29, 30. 36, 37
Appenrodt, 17, 18
Atack, 398
Athenberg, 14
Auerbach, 126, 294
Auffenberg, 229
Auwers, 18
Bach, 37, 86, 87
Badische Anilin u. Soda Fabrik
(B.A.S.F.). 7. 34, 49, 69, 76, 91,
92, 94. 159, 160. 163, 172-174,
179, 184. 187-189. 194, 196-199.
203, 206, 210. 211, 213, 214,
222-224. 226-235, 243, 246, 249,
251, 254, 255. 261-263, 270, 284,
290-297, 300, 306-309, 312-318,
320-322, 329-333, 335, 339, 343,
345, 347. 350-353. 359, 360, 366,
367, 371-373, 387
Baeyer, 21, 96. 98. 104. 109. 123.
127. 128
Bally, 4, 294, 320, 321, 325, 332
Baly. 18. 149, 268
Bamberger, 39, 269, 328
Barret Co., 76
Bayer u. Co. (By.), 7, 17, 62, 67. 74.
79. 84. 91. 92. 96, 130. 157, 163-
165, 169, 170, 173, 175, 177-180,
183, 186-188, 192, 194, 196-198.
200-214, 218, 219, 222, 224, 225,
227-229, 231-235, 238-244. 246-
248, 251, 253, 254, 258-266, 269-
274, 276-284, 287. 288, 290-293,
295, 296, 307, 312. 313, 31-7, 326,
335, 339, 341, 343, 345, 346,
349-352. 355, 357, 358. 361. 363,
365-376. 378-381. 388, 389, 391
Bechamp, 383
Behla, 69
Behr, 14, 125, 132
Benda, 382, 386
Benesh, 92, 301
Bentley, 132, 148, 149, 151, 152,
239
Berblinger, 228, 229, 247, 350, 351
Bernthsen, 347, 379
Berthelot, 1. 14
Billig, 49, 137, 306, 308, 311
Binder, 273
Birnkoff. 26, 34, 126, 128. 163
Bischoff, 64, 69
Bistrzycki, 97, 133, 139
Bliss, 116
Blumenfeld, 68, 70, 140, 165, 167,
207
Boeck, 65, 237, 266
Bohn, 3, 4, 5. 94
Bollert, 67, 68. 176
Bondy, 117, 334
Bornstein, 27, 164
Bottger, 167, 168, 192, 244, 249,
386
Brass, 211, 306
Braun, 396
Brewer. 375
British Dyes, Ltd., 7
British Dyestuffs Corporation, Ltd.,
7
Brunck, 296
Bucherer, 251
Buchka, 347, 375
Burchker, 133
Burg. 14
Butescu. 162
Byk. 25
Cameron. 24
Caro, 3, 127. 128, 176, 281
Cassella u. Co. (Cas.), 188, 210, 307,
315, 360, 362. 373. 397
Chem. Fabrik. Akt. Ges. Hamburg,
17
Chojnacki, 238
Ciamician, 27, 164
Clark, 17. 85, 87
Clans, 180, 192, 193. 244
419
420
INDEX TO AUTHORS
Clemmensen, 84
Colman, 134, 143
Conzetti, 138, 173, 248, 249, 274,
306, 386
Crafts, 29, 35-37, 133, 134
Crossley. 129, 176, 238
Dammann, 379
Dandridge, 345
Davis, 186
Decker, 187, 247, 275, 376-380
Dehnst, 176
Deichler, 139, 147-152
Delacre, 16
Dewar, 32, 36, 37
Dhar, 392
Dickhuth, 347
Diehl, 41, 42, 170, 238
Dienel, 65-69, 73, 162,105,237,266
Dimroth, 24. 50, 67, 92, 93, 116,
129, 139, 237, 238, 261, 263, 266,
269, 274
Dootson, 306
Doralle, 269
van Dorp, 14. 32, 125, 132
Drewson, 127
Dumas, 1, 14
Diinschmann, 177
Eberle, 168, 224, 226
Eckert, 82, 92, 95, 96, 98, 114-117,
160, 164, 165, 168, 170-172, 174,
175, 192, 207, 224, 232-234. 242,
249, 273, 280, 309-311, 313, 333,
334, 343
Ehrenreich, 360
Ehrhart, 17, 75
Elbs, 24, 26, 27, 29, 30, 32-35, 70,
81, 82, 132, 133-135. 143, 162, 164
Errera, 330
Ertl, 340
Eurich, 32, 33
FiCK, 129, 139, 238. 261, 263, 266
Fischer, O., 25-28, 39, 43, 47-49,
162-164, 168, 247, 248, 267, 268,
282, 285, 288
Fleisher. 70. 384
Freund. 77. 78, 369, 384
Ere}', 139, 196, 232, 248, 287, 317
Friedel, 29, 35, 36, 133, 134
Friedemann, 237
Friedl, 148, 149. 151. 152
Friedlander, 100
Friess, 181-183, 186, 187, 229, 273,
370, 374
Fritsch, 37
Fritzsche, 1, 24, 168, 195
Frobenius, 180, 238, 240, 241
Gabriel, 134, 143, 145-147, 150-
152
Gardner, 132
Gattermann, 183. 186. 187, 238,
239, 246, 309, 370, 374, 379, 386,
388, 389
Geigy & Co., 149, 206
Georgievics. 239, 258, 260, 271, 272
Ges. f. Chem. Ind. in Basel
(G.C.I.B.). J44, 188, 206, 326,
335, 350, 351
Gibbs, 75
Gimbel, 82, 114, 124
Girard, 281
Glock, 164, 165
Godchot, 39, 40, 41
Goldberg, 186
Goldmann, 67, 98, 105, 106
Goldschmidt, 77, 328
Gosch, 79
Graebe, 2, 3, 17, 24, 42, 43, 45, 46,
48, 61, 68-70, 74, 79, 82, 113,
133, 140, 143, 144, 165, 167, 168,
176, 178. 207, 239. 243. 247, 278,
285, 294. 296. 325. 330. 347
Grandmougin, 83, 113, 265
Grawitz, 281
Gresly, 27, 32, 34, 35, 132-134, 140.
163
Griesheim Elektron (G.E.), 75, 184,
222, 224, 227, 267, 304, 340, 350.
364, 387, 388
Grimm, 128
Gross, 285
Guyot. 87. 88. 97, 101, 103, 113.
133. 140, 393
Hagen. 66, 244
Halla, 306, 309-311, 313
Haller, 86-88, 90, 97, 101. 103. 113,
140, 393
Hallgarten, 107
Hammerschlag, 42-44, 46, 164
Hansgirg, 399
Hantzsch, 60, 168
Harrop, 132, 148, 149, 151, 175, 187,
197
Hartenstein, 157
Haslinger, 65, 173
Haworth, 398
Heffter, 62, 66
Heinemann, 76
Heller, 32, 33, 130, 132, 134, 137,
140, 143, 144, 150, 162. 164, 173.
175, 198, 200, 347
Hepp, 94, 172, 174, 180, 238, 240,
241
Herzenberg, 397
INDEX TO AUTHORS
421
Hinsberg, 181
Hodgkinson, 15
Hofmann, 75, 76, 82, 114-116, 138,
326
Holdermann, 168
HoUiday (L.B.) & Co.. Ltd., 7, 272,
276
Hormann, 64, 65, 237, 26()
Hovermann, 139, 248
Hutchison, 186
Iljinsky, 3, 5, 177
Imhoff, 43
I pat jew, 40
Isler. 4, 5
Jackson, 15
Jacowlew, 40
Jones, 33, 36, 37
Jowett, 27
Jnngermann, 38
Junghaus, 330
Kabacznik, 348
Kacer, 192, 341, 386
Kaiser, 135
Kalb, 322
Kalischer, 160, 315
Kalle & Co. (K.), 100, 126
Kardos, 330, 383-385
Kauffler, 43, 77, US, 121, 168, 173,
199, 209, 242, 349, 387
Kauffmann, 146
Kammerer, 237
Kehrmann, 66
Kempf, 76
Keppich, 70
Kinzlberger & Co., 117
Kircher, 49, 138, 172
Kirschbaum, 396
Klingenberg, 94, 159, 160, 172, 175
Klinger, 154
Klobukowski, 263
Knoevenagel, 91
Knuppel, 294
Konig, 210
Kopp, 74
Kraemer, 14, 27, 28, 34, 35
Kummerer, 25
Lagodzinski, 65-67, 73, 139
Lampe, 63, 65, 66, 81
Landshoflf, 55, 56
Laube, 173, 210, 247, 275, 287, 359,
376, 377
Laurent, 1,2
Lauth, 167, 192, 193. 385-387
Lavaux, 26, 29-33, 70, 79, 164
Law, 272, 276
Lawrence, 397
Le Royer, 137
Leonhardt, 140
Lesser, 92
Letny, 14
Leupold, 145-147, 150-152
Lever, 315
Levi, 86, 87
Levinstein, Ltd., 7
Lewis, 75
Libkind, 359
Liebermann, 2, 3, 5. 14, 21, 24, 27,
39, 42-52, 55-57, 61, 63-70, 74,
79-82, 96, 98, 99, 102, 104, 106,
108, 109, 113, 114, 118, 127, 128,
133, 147, 164, 165, 168. 176-178.
202, 237-239, 243, 244, 247, 265.
266, 278. 280, 347, 383, 385
Liebig, 116
Lifschiitz. 180, 192, 240, 244. 249
Limpricht, 1, 15, 28, 33. 133. 134,
141, 164
Lindemann. 51, 52, 57
Lindenbaum, 44. 104
Linebarger, 24, 393
Linke. 61. 65
Lippmann, 37, 48. 70. 71
Lodter, 39
Louise, 33, 34, 141
Maffelzzoli. 164, 165, 207
Majert, 293
Mamlock, 101
Mansfield, 351
Marchlewski, 77
Mayer, 315
Medenwald. 211, 224-226. 231. 342.
365
Meek. 267, 271
Meerwein, 100, 101
Megraw, 28
Meisenheimer. 50-54. 56-58, 60, 61,
67
Meister. Lucius u. Briinning
(M.L.B.). 4, 43, 47-50, 76. 93. 95,
128, 132, 135, 136, 138, 140, 165,
168, 173, 179-181. 183, 186, 188,
193, 194, 196. 198, 201, 203. 206,
208, 210. 212. 218-222, 224-227.
230-234. 240-242. 249, 250, 253,
258, 259, 263, 265, 270, 277, 280-
282, 284-287. 290-295. 306, 309.
312. 317. 318. 341, 350, 354-357,
360-363, 366. 368, 371, 372, 375,
380. 387, 390, 391. 400
Mettler. 132, 136, 249
Metzler. 326
Meyer. B., 324
Meyer. F., 32, 134
422
INDEX TO AUTHORS
Meyer, H., 83, 115, 117, 124, 334 '
Mever. J., 322
Mever, K., 21-23, 42-46, 54, 60,
61, 77, 81, 96, 98, 101, 107, 111,
117-120, 123, 124, 326, 394-398
Meyer, R., 15, 267, 268
Mej-er, V., 78 ■
Michael, 145
Mills, 156, 157 !
Mohlau, 273, 364, 389-391 '
Molinari, 17 j
Morton, 345 I
Miihle. 383
Nathanson, 146
Neovious, 141
Niementowski, 28, 295
Nienhaus, 242, 266
Nietzki, 28, 128, 164. 194
Noah, 239
Noelting, 192, 194, 195, 224
Norris, 132, 148, 149. 151, 175. 187,
197
Nourrison, 139
Orchardson, 148-152
Orndorf, 24, 28, 116. 375
Ort, 294
Oudemas, 28
Paar, 270
Pabst, 281
Padova, 39, 67, 86, 87, 98-100,
116-118
Parthey, 202
Pechmann, 133
Perger, 82, 110, 176, 201, 202, 278
Parkin, A. G., 50, 53, 54, 57, 60,
103, 164, 321, 326, 327, 329. 345,
Parkin, W. H., 3, 15, 43, 176, 178,
281
Perrier, 70
Peter, 144
Petersen, 167, 168. 192, 244, 249,
386
PhiUppi, 76, 156, 157
PhiUips, 296
Pisovschi, 65, 67, 68, 73
Plath, 265, 276, 282, 285
Pleus, 69, 81, 177, 265
Pollok, 37, 48, 71, 96
Pother, 27
Potschiwauscheg, 302, 334
Praetorius, 269
Prescott, 186
Prud'homme, 3, 202. 294
Przibram & Co., 192, 198, 278
Pschorr, 155
Qua, 133
Quoos, 75
Radulescu, 43, 46, 48
Rakitin, 40
Rath, 61, 69, 164
Ray, 393
Rebsamen, 248
Ree, 137
Reinkober, 39,*48, 164
Remmert, 20, 38, 88, 393
Remy, 17
Ritter, 75
Robiquet, 126
Romer, 67, 82, 94, 126, 167, 168.
172, 174, 176, 192, 193, 229, 240,
249, 253, 280, 281
Romig, 30
Rosentiel, 80, 126, 281
Roser, 145
Roux, 137
Russig. 157
Rubidge, 133
Sachs, 206
Sadler & Co., 74
Sander, 395
Sanders, 317
Sandmeyer, 168
Sapper, 163, 247
Sarauw, 347
Sava, 66
Schaarschmidt, 134, 140, 160, 161.
166, 168, 187, 192, 193, 196-198,
207, 295, 307-309, 312-314. 317,
318. 323, 324, 353, 365, 367. 369,
386-388, 397, 398
Schardinger, 280
Schenk, 379, 380
Schapper, 133, 139
SchifE, 126
Schilhng, 47, 49, 174
Schlank, 17, 18, 102
Schlossar, 394, 395
Schmidt, E., 24, 195
Schmidt, R. E., 3, 5, 65, 81, 177,
178, 180, 192. 206, 238, 239, 287,
241. 259, 389
Schmidt. W.. 138
Schneider, 75
Schoeller. 128
SchoU, 4, 5, 10, 28, 33, 80, 91, 92,
94, 95, 116, 133-136, 141. 143-
145, 156, 157, 164, 168, 173, 188,
192. 195, 202, 207, 224, 226, 228-
230. 269, 273, 286, 297. 300-303,
320, 321, 325. 328, 329, 331, 333-
336, 339-341, 343, 346-352, 358,
360, 363, 386, 389
INDEX TO AUTHORS
423
Schramm, 15
Schrobsdorf. 201, 238. 247. 266,
273, 275, 277. 280
Schuhmann, 396
Schiller, 65, 66
Schiilke, 130, 132-134, 137. 140,
143, 162
Schiiltz, 14, 27, 164
Schulze, 21-23, 82, 93, 114, 269. 274
Schumpelt, 75
Schunck, 77, 126. 176, 240. 253, 281
Schurmann, 181-183, 186, 187, 273.
370, 374
Schwazer, 43, 46, 82, 280
Scottish Dyes, Ltd., 7
Seer, 30, 32, 36, 84, 92, 133, 136,
141, 164, 165, 169, 184, 192, 207,
213, 214. 232. 233
Seuberlich, 126
Simon, 239. 250, 280
Simonis, 20. 38, 88, 393
Smiles, 186
Societe Anon, des Mat. Col., 62. 140
Sone, 353
Sonn. 220
Spilker, 14, 27, 28, 34. 35
StahUng. 87
Stahlschmidt, 192, 295
Staudinger, 14, 78
Strecker, 2
Stein, 315
Steiner, 170, 171, 175, 224, 232. 234,
273, 280, 343
StegmuUer. 348
Steinkopf. 348
Stewart, 268
Strobel, 281
Suchannek, 77, 118, 121
Terres, 163, 166, 193, 207. 340.
341, 343
Thai, 17, 18
Thomas, 148, 149, 151, 152
Thorner, 98
Thiimmler, 178
Tomaschek, 92, 98, 117, 333, 334
Troschke, 202
TschiUkin, 86, 87
Tuck, 149
Uffers, 97
Uhlenhuth, 94. 172, 174
Ullmann. 5. 49, 92, 94, 95, 127. 132.
133, 137, 138, 159. 160. 162, 163,
165-167, 171-173, 175, 178. 180.
183, 186, 187. 192, 193, 196. 197,
200, 211, 224-226, 229, 231. 232.
248, 249, 274, 276, 287. 297, 302,
305-308. 311-318, 341, 342. 346.
350, 353, 354, 358, 359, 361, 365-
368, 372-374, 380, 381, 386
Unterkreuter, 399
tirmenyi, 315
VoswiNCKEL, 147, 152-154
W.^CKER, 192, 209, 389
Walker, 169
Walsch. 132, 175, 178, 192
Waschendorf, 27, 29, 164
Watson, 267, 271
Wedekind & Co. (Wed.), 178, 179.
188, 199, 238, 241. 253, 271, 273-
276, 278, 286
Weigert, 25
Weiler, 27, 164
Weiler ter Mer (W.t.M.). 211
Weitz. 99, 133
Weitzenbock, 154, 184, 207, 213,
214 322
Weizmann, 132. 147-153, 178, 187,
192, 197, 239
Welton, 17
Wende, 35, 126
Wheeler, 396
White, 15
Wiegand, 28, 134, 164
Wieiand, 39, 273
Willgerodt, 164, 165, 207
Willstatter, 396
Wirth, 17
Wislicenus, 146
Wittich, 29
WolbUng, 173, 238, 240. 248, 277
Wolfenstein, 270
Wortmann, 192, 194, 195. 224
Wiirsch, 187, 378
Zahn, 42-46
Ziegler. 25, 39. 43, 47, 49, 162, 168,
282, 285, 288
Zincke, 15, 29, 98, 152, 164, 181
Zinke. 273. 399
Zsuffa. 69, 383
INDEX TO SUBJECTS
For index purposes the prefix "mono" is not used. Where two or
more substituents are present they are usually arranged in ascending order
of mass, substituted amino groups being treated as amino groups, alkoxy
groups as hydroxy], and all alkyl groups as methyl. Both bromine and
iodine are treated as equivalent to chlorine.
ACEANTHRENE GrEEN, 384
zso-aceanthrene green, 385
quinone, 69, 162. 383
monoxime, 384
Acetamino anthracene, 68
anthraquinone, 224, 228, 230, 290
benzophenone carboxylic acid,
136
bromanthraquinone, 301
chloranthraquinone, 230, 373
nitroanthraquinone, 365
phthalic acid, 392
Acetchloramino anthraquinone, 228
Acetophenone, 133
Acetoxyanthracene, 66
anthrone, 21, 23
Acetyl nitroanthranol, 61
Acetylene, 15
tetrabromide, 15, 29, 36
Acid Alizarin Blue BB, 246, 279
Acid Dyes, 5
Aldehyde ammonia, 79
Algol, 7
Blue, 3G, K, 351
Brilhant Orange FR, 218
Violet 2B, 215, 218
R, 214
Orange R, 235
Pink R, 215, 216
Red B, 235
FF, 5G, 215
Scarlet G, 215, 216
Violet B, 215, 218
Yellow 3G, 191, 214
R, 215
WG, 191. 215, 216
Alizarin, 2, 16, 49, 91, 93, 128, 180,
202, 238-240, 252-255, 257,
260, 263. 260-269. 272. 276,
278-280, 285. 287, 343. 357
Alizarin Astrol, 204
Black, 295
Blue Black, 205
Blue, A, ABl. F, GW, R. RR,
WA, 295
S, 296
X, 3, 294-296
Bordeaux, 205, 238, 257, 259,
260, 264, 276, 277, 282
Brilliant Green G, 203, 204
carboxylic acid, 264
Cardinal, 284
Cyanine B. BS, 246. 279
G, 284
Green, 3, 5, 199, 203, 204
R, 239, 264, 284
2R, 264
3R, 260
RA Extra, 264
3RS, 246, 279
WRS, 246, 279
Cyanol Violet R, 203
dimethyl ether, 247
Direct Green G, 203, 204
Violet R, 203
disulphonic acid, 278
GD, 254
GI, 254
Garnet R, 284
Green, 295, 375
S, 296
X, 3, 296
Indigo Blue, 3, 296
Irisol, 5, 203
Maroon, 284
methyl ethyl ether, 247
mit Blaustich, 254
monomethyl ether, 247
No. 1, 254
Orange A, Cy, SW, W, 282
424
INDEX TO SUBJECTS
425
Alizarin Pure Blue, 198, 204
RA, RG, RR, RX, V. 254
Red S, 278, 279
SSS. 279
3WS. 279
SDG, SX, 254
Saphirol, 3, 190, 283, 284
sulphonic acid, 254, 259, 263,
278, 279
Viridine, 205
AUochrysoketone, 323
carboxylic acid, 323
Amino alizarin, 251, 284. 294, 295,
368 382
anthracene, 53, 67, 68, 294, 343
anthrapurpurin, 295
anthraquinone, 67, 68, 140, 190-
231, 258, 290-294, 300, 305,
307, 311, 320, 332, 343-346,
354-356, 359, 363, 382, 385-
387 393
aldehyde, 160, 392
carboxylic acid, 196, 197, 20"^,
305, 306, 309
raercaptan, 358, 359, 371
nitrile, 198
sulphonic acid. 193, 209. 241.
343. 352
anthrol, 67, 73
anthrone, 103, 117. 123
azoanthracene, 68
benzanthraquinone, 152
benzanthrone, 345
quinoline, 345
bromalizarin, 251
anthraquinone, 229-231. 301,
345
sulphonic acid, 231
chloranthraquinone, 78, 136, 166.
229
dianthraquinonylamine, 292, 343
dibromanthraquinone, 172, 198,
229, 230, 258, 259, 368. 372
dichloranthraquinone. 229
dihydroxyd ianthraquinonyl-
amine, 234
dinitroanthraquinone, 225, 226
e r V t h rohydroxvanthraquinonc,
' 93. 209. 241,"250. 279
flavopurpurin, 294
hydroxyanthraquinone, 93, 202,
209. 236, 241, 250, 266. 279.
294
benzanthraquinone. 151
bromanthraquinone, 351, 368
indanthrone, 292, 352
methyl anthraquinone, 160, 166,
365, 373, 392, 397
benzanthraquinone, 144
Amino nitroanthraquinone, 168, 193,
224, 225, 227
phthahc acid, 129
pyridanthrone, 293
quinizarin, 129, 295
violanthrone, 331
Amyl anthracene, 18
dihydroanthracene, 18
hydroxyanthrone, 38. 110
Angular structure, 10
Anihdo anthrone, 120
Anisol. 139
Anthracene, Action of nitric acid
on, 50
listimation of, 74
Halogenation of, 41-50
Oxidation of, 14, 16, 46, 50, 73-
76, 116
Purification of, 16, 17, 24
Sulphonation of, 61-64
Synthesis of, 1,2, 14, 15, 16
Structure of, 18, 19
aldehydes, 70
Blue SWX, 246. 279
WB, WG. 247
WR. 239, 247. 257. 260. 279
carboxylic acid. 25, 62. 64. 69,
162. See also Anthroic
acid,
dibromide, 43
dicarboxylic acid. 69. 384. 385
dichloride. 43. 47
disulphonic acid, 61-63, 66
Green, 375
hexabromide, 42
homologues, 26-28
indandion, 384
ketones, 70
mercaptans, 66
methyl nitrate, 53
nitrile, 62, 64. 69, 165
oil, 16
ozonide, 17
sulphinic acid, 63, 66
sulphamide, 62
sulphochloride, 62
sulphonic acid, 61-65, 69, 174
Anthrachrysazin, 4, 238. 257, 270.
282
Anthradiquinones, 73. 92-94, 274
Anthraflavene, 4
Anthrafiavic acid, 126, 238, 240,
253. 255, 268. 270, 271, 274-
277, 280, 284
ISO- Anthrafiavic acid, 126, 195, 238,
240, 253. 268. 276, 277, 280,
284
Anthraflavone G, 94
Anthraflavones, 80, 94
426
INDEX TO SUBJECTS
Antliragallic acid. See Anthra-
gallol.
Anthragallol, 126, 238, 250, 251,
260, 264, 269, 280
Anthramine. See Aminoanthra-
cene.
Anthranilic acid, 195
Anthranol, 22, 67, 77, 96, 98, 105,
115, 321, 394. See also Anthrone.
Tautomerism of, 118-124
acetate, 22
anthraquinone dihydroazine, 348
ethyl ether, 105, 395
methyl ether, 107, 395
Anthranthrone, 322
Anthraphenone, 70, 71
Anthrapinacone, 82, 114
Anthrapurpurin, 202, 238, 253-255,
260-263, 271, 275, 282
Anthraquinol, 21, 23, 46, 75, 81-83,
86, 96, 99, 103, 108, 113, 122.
See also Hydroxvanthrone.
Tautomerism of, 121, 124
anthraquinone dihydroazine, 347
diethyl ether. 111
dihydroazine, 348
dimethyl ether. 111
ethyl ether, HI
methyl ether. 111, 122
AnthraquinoUne. See Pyridino-
anthracene.
Anthraquinone (1.2) 65, 72, 73, 343
(1.4) 65, 72, 73
(1.5) 72
(2.3) 72
(2.6) 72
(9.10) 2, 16, 23, 46, 47, 50. 69, 71,
73 et seq., 133. 201, 267, 268
Oxidation of, 20, 77, 254-256,
259, 261, 262
Preparation of, 73-76
Reduction of, 75, 80 et seq., 114,
115, 124
Synthesis of, 2
acid amides, 165, 206, 207
chlorides, 165
acridine, 314
acridone, 137, 205, 353
sulphonic acid, 312
aldehyde, 159, 164
arsinic acid, 382
azine, 340-352
Blue SR Extra, 198
carbazol, 360-362
carboxylic acid, 62, 70, 94, 140,
156, 160, 162-166, 206, 321,
353, 367, 381, 383
diazonium salts, 91. 227, 232, 249,
385, 386, 389
Anthraquinone dicarboxylic acid,
30, 31, 33, 143, 144, 150, 164
dichloride. See Dichloranthrone.
dihydrazine, 364
dimercaptan, 183, 189
dicelenide, 188
disulphide, 181, 183, 184, 187, 381
disulphonic acid, 66, 176-1 '5 8,
183, 240, 241, 254, 278
disulphoxide, 181
ethers, 284
fluoresceine, 164
glycine, 207, 208
isatin, 307
imidazol, 365-368
imidazolon, 367
indazol, 364, 365
ketones, 160, 308, 353
monoxime, 57, 59, 77, 101
nitrile, 162, 165, 307, 365, 367
osotriazol, 361
oxazin, 355
sulphonic acid, 358
oxazol, 368, 388
phenanthridone, 297
phenylhydrazone, 77
pinacones, 161
pyrazols, 363
quinoUne. See Pyridinoanthra-
quinone.
ring syntheses, 125-141
selenophenol, 185
sulphamide, 181, 374
sulphenic acid, 180-182, 186
sulphinic acid, 180-182
sulphochloride, 180, 183, 370, 380
sulphonic acid, 63, 64, 79, 133,
176-180, 183, 201, 231, 239-
241, 252-254, 259, 263, 373
sulphoxylic acid. See sulphenic
acid,
sulphurbromide, 181
chloride, 181, 182, 374
tetrachloride, 44, 49
thiazine, 358
thiazol, 371
disulphide, 372
thiazoline, 372
thioxanthone, 317-319, 363
trisulphonic acid, 177
violet, 199
xanthones, 315-317
Anthraquinonvl acrylic acid, 160.
164, 165
aminoacridone, 379
anthraquinone. See Dianthra-
quinonylamine .
dianthraquinonylamine, 233 et
seq.
INDEX TO SUBJECTS
427
Authraquinonyl aininoacridone, 379
thioxanthone, 379
pyridanthrone, 293
anthraquinone imidazol, 367
arsenoxide, 383
azide, 369, 388
iso-cyanate, 219
glycylaminoanthraquinone, 214
hydrazine, 340-352, 363, 364. 389
sulphonic acid, 389, 390
hvdroxylamine, 343, 389
mercaptan, 181-187, 358, 359,
370, 371, 373, 381
oxaminic acid, 226
piperidine, 195
pyridazoneanthrone, 354
selenocj^anide, 185, 374
sulphide, 186, 187
thiocyanate, 183, 374, 381
»50-thiocyanate, 222
thioglycollic acid, 370, 381
thiourea, 221
chloride, 222
urea, 191. 219-221
chloride, 219, 220, 221. 355
urethane, 219, 220, 225, 355
xanthate, 183, 374, 381
Anthrarufin. 63, 126, 209, 238, 243,
244, 253, 257. 259, 260, 267,
270, 273, 274, 277. 280, 376
dimethyl ether, 78
disulphbnic acid. 243, 277, 283
Anthratriquinone, 73
Anthrazine. 343, 349, 350
Anthrimide. See Dianthraquinonyl-
amine.
Anthroanthraquinone azine. 343
Anthroic acid. 69
Anthrol, 64-67. 140. 315, 316
Anthrone, 54, 81, 86. 96-105. 367,
380. See also Anthroiie.
tautomerism of, 118-124
azine, 349
dihydroazine, 349
Anthrylamine. See Aminoanthra-
cene.
Arsenic compounds, 383, 384
Arsenoanthraquinol, 382, 383
Aziminoanthraquinone, 388
Azoanthraquinone, 387
Azoxyanthraquinone, 344, 388, 389
Barnett's notation, 12
Basic dyes. 5
Benzal acetoacetic ester. 100
acetophenone, 101
malonic ester, 100
Benzalizarin. 327
ang. Benzanthracene. 143
lin. Benzanthracene, 147
anthradiquinone. 152-154
anthraquinone (1.2). 33, 80. 134,
142-145. 164. 321, 330, 335
(2.3). 142. 145-152
anthrene, 325
anthrone. 101. 164. 320-339
carboxylic acid. 323
quinohne. 332
anthronjdaminoanthraquinone,
333
dianthrone, 333
fluorenone, 323
Benzoic acid, 125
Benzoyl aminoanthraquinone, 191.
215
chloranthraquinone. 297
dianthraquinonylamine, 235
hydroxyanthraquinone,2 1 5, 2 1 7
nitroanthraquinone. 216. 217.
368
trihydroxyanthraquinone. 215.
218
anthracene, 70. 71
authraquinonyl mercaptan, 184,
187
benzoic acid, 20. 130, 131
chloride, 70
diaminoanthraquinone, 216
mesitylene. 33
mesitylenic acid, 34
methylaminoanthraquinone, 216,
217
naphthalene. 324
nitroanthranol. 61
propionic acid, 133
pyranthrone, 337
pyrene, 328, 337
Benzyl anthracene, 37
chloride, 15, 37
hydroxyanthrone. 86, 87
toluene, 14
trichloracetate, 16
Benzylidene aminoanthraquinone.
210
bromanthraquinone, 301. 309
chloranthraquinone, 297
anthrone. 86
mesitylene. 33
Bisangular structure. 10
Bisdiketohydrindene, 145, 146
Bisthiazoliiies, 373
Bromalizarin, 276
aminoanthraquinone, 228
anthracene, 25, 43
anthraquinol ethyl ether. 106
anthraquinone, 43, 106, 137, 187,
210
nitrile. 197
428
INDEX TO SUBJECTS
Bromalizarin anthrone, 98, 99, 101,
102, 108, 116, 117, 121-123
benzanthrone, 331
benzylbromide, 15
triphenyl carbinol, 38, 88
dianthrone, 99, 117
dibenzylanthracene, 37
erythrohydroxyanthraceiie, 273
methylanthraquinone, 172
bromanthrone, 395
quinizarin, 200, 205
thiodianthraquinonylamine, 358
toluene, 137
Butyl hydroxyanthr one, 110
Caledon, 7
Blue, GC, GCD, 351
R, 347
Brilliant Purple R, RR, 332
Dark Blue, 329
Green, 330
Red, 312
5G, 215
Violet RN Extra, 313
Yellow G, 302
Carbazol, 141, 360
Carbonyl chloride, 69
Carboxyphenyl anthraquinone car-
boxylic acid, 84
Carminic acid, 148, 269
Chloracetamino anthraquinone, 291
carboxylic acid, 207
hydroxyanthraquinone, 355
aUzarin, 175, 276
anthracene, 25, 43, 47
anthraquinone, 47, 49, 77, 98,
137, 170, 173, 175, 183, 186-
188, 197,, 210, 306, 309, 315,
354, 369, 373
aldehyde, 397
carboxylic acid, 140, 160, 196,
311, 316, 354, 392, 398
diazonium chloride, 387
monoxime, 77, 78, 369
nitrile, 166
anthraquinonyl hydrazine, 390
Chloranthrene, 7
Chlor anthroic acid, 67
benzanthraquinone, 144, 150, 304
benzanthrone, 333
benzene, 136
benzophenone, 78
benzoylchloranthraquinone, 308
brom anthracene, 25
benzanthraquinone, 150
dianthranol, 117
dianthraquinone, 117
dibrommethyl anthraquinone, 94,
95, 172, 175
Chlor dichlormethylanthraquinone
397
dihydroxyanthraquinone, 276
erythrohydroxyanthraquinone,
127, 248, 274, 276
flavopurpurin, 275
naphthalene, 144, 150, 304
nitro alizarin, 175, 200
anthraquinone, 175, 203
Chloroform, iS, 29, 31
Chlor phenol, 127-129, 138
phthalic acid, 128
purpurin, 249
pyridanthrone, 292
quinizarin, 93, 248, 274
toluene, 26, 137, 140
tolyl methane, 15
Chrysarobin, 27
Chrysazin, 63. 209, 238, 242, 253,
257, 260, 262, 266, 273, 274,
277, 280, 282
disulphonic acid, 277
dimethyl ether, 280
zso-Chrysofluorenone, 325
Chrysol, 66
Cibanon, 7
Coccinic acid, 129, 140
Coeramidine, 379
carboxylic acid, 379
Cceroxene, 374—378
Coeroxenol, 377
Cceroxonol, 377
Coeroxonium salts, 376
Coerthiene, 378
Coerthienol, 378
Ccerthionol, 378
Coerthionium salts, 378
Ccerulein, 375
Colophonium, 27
Cresol, 26, 127, 128, 139, 140
Cyanthrene, 332
Cyanthrone, 327, 332
Deckahydroanthracene, 41
Diacetamino anthracene, 68
anthraquinone, 224
Diacetoxy anthracene, 66, 73
Diamino anthracene, 67, 73
anthrachrysazin disulphonic acid,
246
anthraiiavic acid disulphonic acid,
284
zso-anthraflavic acid disulphonic
acid, 284
anthraquinone, 78, 93, 193-195,
202, 207, 209, 226, 228-230,
250, 279, 282, 294, 308, 340-
343, 355, 365-367, 386, 388
per bromide, 228
INDEX TO SUBJECTS
429
Diamino anthrarulin, 93, 282
disulphonic acid, 283, 284
bromanthraquinonc, 367
chrysazin disulphonic acid, 284
dianthraquinonylaminc, 233, 234
dianthraquinonyl, 300, 301, 300
dianthryl, 115, 124
dihydroxy dianthraquinonyl-
amine, 233
dinitroanthraqiiinone, 194
indanthrone, 234
nitroanthraquinone, 225
phenylamino anthraquinone, 359
tetra brom anthraquinone, 198,
226, 229, 369
nitro anthraquinone, 224, 226
Diamyl anthracene, 38
Dianilido benzanthraquinone, 147
Dianthramines, 68
Dianthranol, 115-117, 120, 124
diacetate, 115, 117
dimethyl ether, 115
Dianthraquinone, 115-117
Dianthraquinonyl, 90-92, 135, 301.
333, 334
acetylene, 175
Dianthraquinonyl amine, 190, 191,
231-235, 305, 306, 361, 379
aminoanthraquinone, 190, 232
et seq.
carboxylic acid, 92
dialdehyde, 159, 335
dibromethylene, 175
dicarboxylic acid, 300
disulphide, 187
ether, 286
ethylene. See Anthraflavone.
diamine, 211
sulphide, 186, 178.
urea, 220
Dianthrene, 24, 25
Dianthrol, 83, 335
Dianthrone, 22, 24, 83, 99, 105, 116,
120, 124, 334, 335
Dianthryl, 82, 83, 91, 98, 114, 115,
124, 383
acridine, 314
Dibenzalanthracene, 37
iJs-Dibenzalanthracene, 37
Dibenz anthracene, 158
anthradiquinone, 156
anthraquinone, 135, 142, 143,
154-158
anthratriquinone, 157
Dibenzovl amino anthraquinone,
215, 216
anthrarufin, 215, 218
dianthraquinonyl, 218
hydroxj'anthraquinone, 215
Dibenzoyl anthracene, 70
benzene, 20
dianthraquinonyl, 335
dibenzylamino anthraquinone, 84
dinaphthyl, 329
indanthrone, 347 '
pyrene, 328, 331, 337
veratrol, 20
Dibenzyl amino anthracene, 37
anthraquinone, 84, 207
anthracene, 37
Dibenzylideneaminodianthra-
quinonyl, 301
Dibrom anthracene, 25, 43, 45
tetrabromide, 42, 43, 45
anthraflavone, 94
anthraquinone, 43, 170, 172, 247
anthrarufin disulphonic acid, 197,
283
anthrone, 77, 78, 101, 120
chrysazin, 247, 277
dinitro anthrarufin, 283
chrysazin, 284
erythrohydroxy anthraquinone,
273
ethoxy anthracene, 106
flavanthrone, 302
hystazarin, 275
indanthrone, 351
methyl anthraquinone, 95, 1 72, 1 75
chloranthraquinone, 172
oxythionaphthene, 100
purpuroxanthin, 276
pyranthrone, 335
iso-violanthrone, 332
Dichlor anthracene, 43, 44, 46-50,
172
dichloride, 43, 44, 49
hexachloride, 44
octachloride, 44
sulphonic acid, 49
tetrabromide, 46
tetrachloride, 41, 42, 44, 47
anthrachrvsazin disulphonic acid,
391.
Dichlor anthradiquinone, 93, 248
anthraflavic acid, 274, 275
anthraflavone, 95
anthraquinone, 44, 45, 49, 77,
170, 172, 173, 175, 189, 197,
203, 308, 359, 364, 390
carboxylic acid, 165
dioxime, 77
monoxime, 77
anthrarufin, 276
anthrone, 97, 98, 101. 103
benzanthrone, 147, 150
benzanthraquinone. 150
sulphonic acid, 144
430
INDEX TO SUBJECTS
Dichlor dihydroanthracene, 15, 31
erythrohydroxyanthraquinone,
248, 274
indanthrone, 351
method anthraquinone, 164, 171,
366, 367
nitroanthraquinone, 175
phthalic acid. 45, 49, 128, 137-
139, 144, 148
pyranthrone, 335
quinizarin, 248
Jso- violanthrone, 332
Diethoxy anthracene, 66
Diethyl amino anthroquinone sul-
phonic acid, 209
aniline, 141
anthrone, 106
dianthraquinonyl, 336
dihydroanthracene, 106
pjrranthrone, 336
Dihydro anthracene, 15, 16, 25, 31,
39, 40, 56, 80. 84
anthrazine, 342, 349
benzanthradiquinone. See Di-
hydroxy - lin - benzanthraqui-
none
benzanthrene, 325
benzanthrone, 325
flavanthranol, 303
flavanthraquinol. 304
hydrate. 303
flavanthrene hydrate, 302
methyl anthracene, 25
chloranthracene, 39
naphthacene. See Dihydrobenz-
anthracene.
nitroanthranol, 51, 52
pyranthridene, 299
Dih^'droxy anthracene, 66, 73
anthraquinol, 265
anthraquinone. 126, 238. 270,
276. See also special names
such as Alizarin. Quinizarin,
etc.
1.4-anthradiquinone, 398
benzanthraquinone, 147, 149, 150,
152. 153
benzanthrone. 327
benzoylbenzoic acid. 136
dianthraquinonyl, 91
amine, 233, 234
dianthr^'lmethane, 314
dibenzanthradiquinone. 157
dichlor anthraquinone, 136
benzoyl benzoic acid. 249
dinitrosodinitroflavanthrone, 302
dipyridinoanthraquinone, 295
hehanthrone, 333
hexachloranthraquinone, 229
Dihydroxy indanthrone, 351
methyl dianthryl methane, 316
naphthalene, 148
carboxylic acid, 157
nitroanthraquinone, 357
phenyl dianthryl methane, 316
trinitrobenzoic acid, 270
Diketohydrindine. 146
Dimethoxy anthracene. 66
anthraquinqjie, 78
anthrone, 59
dianthraquinonyl, 301
dianthrone. 122
diphenyl anthracene, 20. 38, 89
Dimethyl amino benzophenone car-
boxylic acid. 197
aniline. 141
anthracene. 15, 26, 28-35
anthraflavic acid, 126
anthragaUol, 126
anthramine, 68
anthraquinone, 29-34, 79, 134.
141. 168
carboxyhc acid. 132, 140
anthraquinonyl sulphonium salts,
66
anthrone, 395
benzaldehyde. 36
benzoic acid, 32, 34. See also
Mesitylenic acid.
benzoyl benzoic acid, 32
dianthraquinonyl. 136, 254, 298,
300. 335, 336
dibenzanthraquinonyl. 145
dichlor anthraquinone. 175
dinitroanthraquinone, 175
dihydroxy dihydroanthracene, 87
dimethoxydihydroanthracene, 87
dinitroanthraquinone, 169
diphthaloyl thianthrene, 189
indanthrone, 350
malonyl chloride, 384
nitroanthraquinone, 169
pyranthrone, 336
tetrahydroxybenzanthraquinone,
147
trihydroxyanthraquinone, 34
Dinaphthanthradiquinone, 156
Dinaphthanthraquinone. See Di-
benzanthraquinone .
Dinaphthoyl p^Tene. 337
Dinaphthyl dicarboxylic acid, 322
Dinitramino tetrabromanthraqui-
none, 227
tetranitroanthraquinone, 226
Dinitro anthracene. 50. 64, 59
anthrachrysazin, 194
anthraflavic acid, 280
fso-anthraflavic, 280
INDEX TO SUBJECTS
43T
Dinitro anthraflavic acid disulphonic
acid, 199
anthraquinone, 167-169, 178,
193-195. 199, 242, 244-246,
261, 282, 389, 397
anthrarufin, 194, 243, 247
disulphonic acid, 243, 283
chrysazin, 283
dianthraquinonyl, 301
amine, 233, 243
dianthryl, 116, 124
dihydroanthracene, 57, 59
diphenj-lamine, 343
hystazarin, 280
naphthalene, 58
purpuroxanthin, 282
Diphenyl, 135
aminobenzanthraquinone, 147
anthracene, 20, 38, 88. 90, 102,
103, 106
anthrone, 88, 97, 103, 106
dichlordihydroanthracene, 90
dihydroanthracene, 393
dihydroxy dihydroanthracene, 85,
89, 90
ketene, 78
methylene anthrone, 99
pyranthrone, 335
Diphthaloyl acridone, 309, 313, 314
carbazol, 360-362
oxazine, 356-358
phenylxanthene, 316
thianthrene, 189
thiazine, 358-360
Diprop5'l dianthraquinonyl, 336
Dip\aidinoanthraquinone, 294
Disodioanthracene, 17, 18
Disulphonaminoanthraquinone, 225
Ditolyl, 136
aminoanthraquinone, 201, 379
hydroxyanthraquinone, 204
ethane, 27
methane, 27
propane, 27
Dixylyl, 136
Dodekahydroanthracene, 41
Duranthrene, 7
Dur>'lic acid, 35, 126
Dyeing, 5
Emodin, 27
Ervveco Acid Alizarin Blue R, 199
Alizarin Acid Red BS, 279
Erythrohydroxy anthraquinone, 78,
91, 128.238, 240, 244, 257.
260, 262, 265-268, 273, 274,
280, 395
sulphonic acid, 180
Ethoxy anthracene, 66, 105
Ethoxyanthrone, 395
Ethine diphthalidc, 145
iso-Ethine diphthalidc. See Dihy-
droxybenzanthraquinone.
Ethyl anthracene. 52
anthranol ethyl ether, 106
anthraquinone, 80, 94, 134
benzene, 80, 134
benzyl aniline, 141
dihydroanthracene, 62, 55
ethoxy anthracene, 106
hydrox}^ anthrone, 106, 110, 111
nitro anthracene, 55, 56
anthranol, 52, 55
trinitrodihydroanthracene, 56
Ethylidene bromide, 15, 30
chloride, 15
Flavanthranol hydrate, 302
Flavanthraquinol hydrate, 303
Flavanthrene, 4, 290, 302, 304
hydrate, 303, 304
Flavanthrenol hydrate, 303
Flavanthrine, 304
hydrate, 303
Flavanthrinol hydrate, 303
Flavanthrone, 92, 290, 298-304,
344, 345
Flavol, 66
Flavopurpurin, 238, 253-255, 260-
263, 271, 275, 281, 282
sulphonic acid, 279
Fluorane, 376
Furjd naphthyl ketone, 338
Gallein, 374, 375
Gallic acid, 34, 35, 126
Green oil, 16
Grignard's solution, 85-90
Halogen anthracenes, 41-50
anthraquinones, 136-138, 170-
175, 247
HeUanthrone, 92, 327, 328, 333-
335
Helindon, 7
Brown 3 GN, 221
Orange GKN, 221
Yellow 3 GX, 220, 221
Helio Fast Yellow, 215
Hemimellitic acid, 140, 162
Hemipinic acid. 139, 148, 238
Hepta bromanthracene, 42
anthraquinone, 170
chloranthracene. 42
anthraquinone. 170, 171
hydroxyanthraquinone, 239
432
INDEX TO SUBJECTS
Hexa brorn anthracene, 42, 43
chlor anthracene, 42, 47
anthraquinone, 170
anthrarufin, 251
chrysazin, 251
hydro anthracene, 39, 40, 84
anthrone, 41
flavanthrene, 304
hydrate, 303
hydroxyanthraquinone, 180, 239,
246, 247, 257. See also
special names such as
Anthracene Blue WR, etc.
disulphonic acid, 245, 279
methj-l anthracene, 36
phenyl ethane, 102
Hydranthrene, 7
Hydrindene, 396
Hydroanthracene nitrite, 56
Hydroanthracenes, 39-41, 265
Hydro] uglone, 396
Hydroquinone, 128, 129, 140. 263
diacetate, 129
dimethyl ether, 139
Hydroxy acetyl naphthaquinone,
270
anthracene, 61, 63, 64
anthragallol, 239
anthrapurpurin, 238, 262, 266
anthraquinol, 265, 395
^-Hydroxy anthraquinone, 78, 139,
266, 268, 271, 274. 280, 381,
396
diazonium sulphate, 261, 262,
386
sulphonic acid, 241
anthraquinonyl carbinol, 270
anthrarufin, 238, 241, 253, 257,
260
anthrone. 23, 46, 96, 97, 99, 106,
108-113, 120-124. See also
Anthraquinol.
Tautomerism of, 120-124
acetate, 22, 108
benzanthraquinone, 144, 147-150
benzoic acid, 126. See also
SalicyUc acid,
brom anthraquinone, 273
chlor anthraquinone, 127, 128,
138, 248, 274-276, 286
benzanthraquinone, 149
chrysazin, 238, 241, 253, 260
dianthraquinonj-lamine, 233
dibromanthraquinone, 273
dichloranthraquinone, 248, 274
dihydroanthracene, 81, 82, 110,
140
diketo hexahydroanthraquinol,
398
^-Hydroxy dinitroanthraquinone,
250, 280
diphenylamino anthraquinone,
205
ethyl aminoanthraquinone, 208
flavopurpurin, 238, 262, 266
hydroquinone triacetate, 129,
140
naphthoquinonyl acetic acid, 269
acryhc acid. 269
naphthoyl • benzoic acid, 139,
148
nitroanthraquinone, 250, 356
benzanthraquinone, 150
dihydroanthracene, 51
nitroso nitroanthraquinone. 169.
244
phthaUc acid. 129. 139, 140. 148,
263
purpurin, 238
pyridanthrone. See P5n4done-
anthrone.
pyridinoanthraquinone, 294-296
pyxidone anthrone, 291
toluic acid. 126
Hydroxy lamino anthraquinone, 1 69.
192
Hystazarin. 128. 130, 139. 238. 272.
275. 280
Indanthrene, 4, 7, 342
Blue GC. GCD, 351
R, 346, 350
RS. 347
Bordeaux B. 190, 235
R Extra, 235
Dark Blue BO, 329
BT, 332
Golden Orange G. R, 335
Green B, 330
Orange GN, 319
Red BN Extra, 312
G. 235
Scarlet G. 335
Violet R Extra, RR Extra. 332
RN Extra. 313
RT, 331
Yellow G. 290. 302
GN. 319
Indanthrone. 254. 300. 301. 341-
352
sulphonic acid, 352
Indenigo, 147
Indolanthrone, 363
lodoanthraquinone, 210
Isatin dichloride, 100
Isoxazols. 77, 78. 369, 370, 400
Kymric Green, 190. 203
INDEX TO SUBJECTS
433
Leucol, 7
Lignite tar oil, 14
Linear structure, 10
Malonyl chloride, 384
Mesitylene, 141
Mesitylenic acid, 36
Methanthrene, 28
Methoxy anthracene, 66
anthraquinone, 161, 168
anthrone, 99, 108, 111, 122
benzoyl aminoanthraquinone, 215
chloranthraquinone, 247
dianthraquinonylamine, 356
nitroanthracene, 59
phthaiic acid, 148
Methyl amino anthracene, 394
anthraquinone nitrile, 197
sulphonic acid, 209
bromanthraquinone, 350
anthracene, 16, 25-28, 30, 31, 39,
80, 162, 173
carboxylic acid, 30, 31
anthranol methyl ether, 107, 108,
395
anthraquinone, 26, 28, 79, 80, 94,
134, 159, 162, 163, 166, 168,
171
carboxylic acid, 30, 31
imidazol, 366
anthraquinonyl sulphoxide, 182
anthrone, 325
benzanthraquinone, 95, 145, 363
benzanthronc, 324
benzophenone, 98
benzoyl chloride, 30
bromanthraquinone, 137
chloranthracene dibromide, 47
cceramidonol, 380
dianthraquinonyl, 92
dianthraquinonylamine, 309
dihydroxy anthraquinone, 128
nitro anthraquinone, 249
dinitro anthraquinone, 168
erythrohydroxyanthr a q u in o n e,
127, 128
hydroxy anthraquinone, 26, 28
anthrone. 111
benzanthraquinone, 144
benzene tricarboxylic acid, 147
benzoic acid, 126
chloranthraquinone, 200, 248
nitroanthraquinone, 249, 282
methoxy anthracene, 108
anthraquinone, 282
naphthalene, 1 14
naphthalene, 143
nitroanthraquinone, 195, 247
pentabrom anthracene, 48
Methyl phenyl hydroxy methoxy
dihydroanthracene, 87
phthahc acid, 128
P5a'idanthrone, 292
anthraquinone, 298, 299
quinizarin, 128, 163, 248
tetrahydroxy anthraquinone, 126
thianthrene, 189
thiodianthraquinonylamine, 358
tolylanthraquinone, 84, 136
trihydroxyanthraquinone, 129
Methylene amino anthraquinone,
226
anthraquinone, 394
anthrone, 394
chloride, 15, 29, 31. 36
methyl hydroxy dihydroanthra-
cene, 87
methoxy dihydroanthracene,
87
phenyl methoxy dihydroanthra-
cene, 87
Mordant dyes, 5
Naphthacendiquinone. See Benz-
anthradiquinone .
Naphthacene. See Benzanthracene
Naphthacenquinone. See Benz-
anthraquinone.
Naphthadianthrone, 334
Naphthalene, 15, 134, 143, 144. 156
Naphthylanthraquinonyl ketone,
156
Naphthalene sulphonic acid, 63
Naphthanthraquinone. See Benz-
anthraquinone.
Naphthindandion, 330
Naphthindenon, 321, 330
Naphthol, 139, 148
sulphonic acid, 148
Naphthoquinol, 157
Naphthoquinone carboxylic acid,
307
Naphthoyl benzoic acid, 131, 134
Naphthylanthraquinonyl ketone,
338
New Anthracene Blue WR, 284
Nickel carbonyl, 32. 36
Nitramines. 226, 227
Nitramino anthraquinone, 227
dinitroanthraquinone, 226
nitroanthroquinone, 226, 227
tetrabromanthraquinone, 227
Nitro alizarin, 200, 247, 263, 281,
282, 284
anthracene, 50, 53, 57-59, 67
anthrapurpurin, 247, 282
anthraquinone. 167-169, 178,
192, 100, 231, 242. 243
28
434
INDEX TO SUBJECTS
Nitro alizarin aldehyde, 160
carboxylic acid, 165, 198
nitramine, 224
sulphonic acid, 169, 180, 193,
244
anthraquinonyl hydroxylamine,
389
anthrone, 52-54, 56, 59, 60, 103,
120, 267
anthrapurpurin, 282
benzanthraquinone, 145, 150, 389
chrv'sazin, 280
d'imethyl ether, 280
dianthraquinonyl, 92
amine, 343
erythrohvdroxyanthraquinone,
243, 250
disulphonic acid, 343
flavopurpurin, 247, 282
h\'stazarin, 280
naphthalene disulphonic acid,
58
phenj-laminoanthraquinone, 341
phthalic acid, 148, 397
purpurin, 263, 279, 281
pyridinoanthraquinone, 294
quinizarin, 261. 280, 282
toluene, 195
violanthrone, 330, 331
Nitroso anthraquinone, 169
sulphonic acid, 169
anthranol, 67
anthrone, 44
naphthol disulphonic acid, 58
nitro anthracene, 55
Nomenclature, 10
OCTABROMANTHRACENE, 42
Octachloranthracene, 42
anthraquinone, 229, 251
diaminoanthraquinone, 228, 229
Octahydro anthracene, 40
sulphonic acid, 40, 41
anthranol, 40
Octahydroxy anthraquinone, 239,
260,272
Opianic acid, 238
Oxalyl chloride, 69, 162, 383
Oxanthracene, 2
Oxazone anthrone, 381
Paranaphthalene, 1, 14
Paranaphthalose, 2
Paranthrene. See Dinathrene.
Pentabrom anthracene, 42
anthraquinone, 42, 170
Pentachlor anthracene, 47
anthraquinone, 170
benzophenone, 229
Pentahydroxy anthraquinone, 239,
247, 264. See also special
names _.j^ such as Ahzarin
Cyanine R.
Pentanitro dianthraquinonylamine,
233
Perchlorethylene, 15
Perhydroanthracene, 41
Peryiene, 327, S28, 399
Petroleum, 14
Pfaff's notation, 1
Phenanthrene, 135
Phenanthroyl benzoic acid, 135
Phenazine, 343
Phenol, 128
Phenyl amino anthraquinone, 199
indanthrone, 352
quinizarin, 200
anthracene, 21, 109
anthraquinone, 135
xantiaone, 316
anthrone, 96, 120, 123, 135
azo anthranol, 103
benzoylbenzoic acid, 135
chloranthraquinonj^ ketone, 160
chlor anthrone, 97, 102, 103
methylene anthrone, 99
coeroxene, 378
dichlormethyl anthrone, 99
diphenylmethane carboxyhc acid,
135
hydroxy anthranol, 104, 109
anthrone, 21, 98
methoxy anthrone, 87
methylene anthrone, 99
naphthalene dicarboxylic acid,
323
naphthyl ketone, 324, 338
pyridazone anthrone, 353
xylyl ketone, 27
Phosene, 1
Photene, 1, 24
Phthahc acid, 20, 28, 32, 34, 80,
127 et seq., 145 et seq.
synthesis, 130-141, 392
Phthaloyl acridone, 305-314
carbazol, 360-362
fluorenone, 399
hydrindene, 396
oxazine, 356-358
thiazine, 358-360
thioxanthone, 317-319
xanthone, 315
Piperidine, 195, 196
Propyl anthraquinone, 80, 94, 134
iso-Propyl anthraquinone, 134
Propyl benzene, 80
t50-Propyl benzene, 134
Propyl hydroxyanthrone, 110
INDEX TO SUBJECTS
435
Pseudocumene, 34, 30, 132, 134
Pseudopurpurin, 264
Purpurin, 93, 238, 239, 254, 259,
2G0, 2(52, 263, 265, 266,
268-270, 278, 281, 356, 357
carboxylic acid, 264
disulphonic acid, 278
sulphonic acid, 259, 263, 278
tso-Purpurin. See Anthrapurpurin.
Purpuroxanthin, 238, 244, 265, 272,
276, 282, 285
Pyranthrene, 4, 335, 339. See also
Pyran throne.
Pyranthridene, 299
Pyranthridone, 290, 297, 299
Pvranthrone, 254, 299, 327, 328,
335-337
Pyrazinoanthraquinone, 347
Pjnrazolanthrone, 363, 364
Pyrene, 327, 328, 336
Pyrenequinone, 328
PjTidanthrene, 289
Pyridanthrone, 289, 290-293
Pyridazineanthrone, 353-355
Pyridazoneanthrone, 353
Pyridine anthracene, 289, 294
anthradiquinone, 296
anthraquinone, 289, 293, 294,
32U
benzanthrone, 332
Pyridone anthrone carboxylic acid,
291
pyridinium chloride, 291, 292
P>T:imidone anthrone, 354
P>Trocatechol, 128, 130
Pyrrol anthrone, 362, 363
carboxyUc acid, 362
Pyromellitic acid, 156
QuiNALiZARiN. See Alizarin Bor-
deaux.
Quinizarin, 73, 91-93, 128, 129. 138,
139, 157, 184, 201, 203, 204,
209, 238. 248, 250, 259, 261.
262, 265, 267-269, 272, 274,
280, 287. 376, 395. 396
/fiMco-Quinizarin I. 265. 266, 396
II, 265, 266, 296
Quinizarin carboxylic acid, 163,
261
disulphonic acid, 259
Green. See AUzarin Cyanine
Green,
sulphonic acid, 204, 259
RuFiGALLic acid. See Rufigallol.
Rufigallol, 126, 239, 260, 263, 272
Rufiopin, 238
Rufol, (J6
Salicylamino antiiraquinone, 214
SalpetersaiJreanthracen, 51, 52, 56
Scholl's Peri synthesis, 324
iso-Sclenazolantlironc, 374
Semiazo compounds, 369, 388
Silver salt, 177
Sirius Yellow G, 143
Solway Blue, 190, 283
Blue-Black, 205
Purple, 203
Stilbene, 57
Styrene. 14. 15, 27. 34
Succinyl aminoanthraquinone, 191,
214, 216. 217
diaminoanthrarufin, 214
Sulphohydrazines, 380
Sulphonamide process, 197, 211
Tetraacetdiamino dibromanthra-
quinone, 229
tetrabromanthraquinone, 229
Tetrabenzoylamino anthraquinone,
218
Tetrabrom anthracene, 42, 43, 45
tetrabromide, 42
anthraquinone, 42, 43, 170
ethane. See Acetylene tetra-
bromide.
Tetrachlor anthracene, 41-45, 48,
49
anthraquinone, 42, 49, 138, 170-
173
anthratriquinone, 93
benzoylbenzoic acid, 49
phthahc acid, 42, 128, 138, 139.
148, 171
quinizarin, 248
Tetraethyl diamine diphenyl-
anthrone. 103
Tetrahydro anthracene, 39, 40
dianthrol, 83
flavanthrene, 303
hydrate, 303
Tetrahydroxv anthraquinone, 238,
239, 247, 248, 260, 262, 272,
277. See also special names
such as Alizarin Bordeaux,
etc.
dianthraquinonyl, 91, 269
dibenzanthraquinone, 157
dichloranthraquinone, 248
dinitroanthraquinone disulphonic
acid, 179
helianthrone, 333
Tetramethyl anthracene. 35-37
anthraquinone. 36. 84. 169
benzophenone, 35
diaminodiphenylanthrone, 103
dianthraquinonyl. 136
436
INDEX TO SUBJECTS
Tetramethyl diiiitroanthraquinone ,
169
tetranitroantliraquinone, 169
azine, 351
Tetramino dianthraquinoiiylamine,
234
dihydroxy flavanthrone, 302
tetrahydroxy indanthrone, 351
Tetranitro anthraflavic acid, 280
t50-anthraflavic acid, 280
anthraquinone dinitramine, 224
anthrapurpiirin, 263
chrysazin, 247, 282
dianthraquinonylamine, 233
flavopurpurin, 263
naphthalene, 58
Tetraphenyl dihydroanthracene,394
Thianthrene, 141, 188
Thiazine, 358
iso-Thiazolanthrone, 373, 374
Thiazols, 181, 371
ThiazoUnes, 372
Thienyl naphthj'l ketone, 338
Thiodianthxaquinonylamine, 358
Thiodiphenylamine, 141, 358
Thiopheneanthrone, 370, 371
Thiophenes, 182, 186, 370, 371
Toluene, 14, 15, 27-30, 32, 80, 133,
134, 156
Tolyl amino anthraquinone, 199,
379
naphthyl ketone, 324
xylyl ketone, 30, 31
Triamino anthraquinone, 341
trihj'droxy indanthrone, 351
Triazols, 387, 388
Tribenzoyl aminoanthraquinone,
218
anthracene, 70
pyrene, 328, 337
Tribrom anthracene, 42, 43, 45
anthraquinone, 350
indanthrone, 350
methylanthraquinone, 172, 174
Trichlor anthracene, 46, 48, 49
anthraflavic acid, 275
anthraquinone, 170
benzene, 171
trihydroxyanthraquinol, 265
Trihydroxy anthraquinone, 129,
238, 257, 260, 262, 266, 278.
See also special names such
as Purpurin.
sulphonic acid, 278
Trihydroxy benzanthraquinone, 148
dinitroso nitroanthraquinone
azine, 351
naphthalene, 395
Trimethyl anthracene, 35
anthragallol, 126
anthraquinone, 35, 134
benzoyl benzoic acid, 35, 132
trihydroxy»nthraquinone, 35
Trinitro benzene, 58
dianthraquinonylamine, 233
dihydroanthracene, 54, 56, 59,
267
naphthalene, 58
toluene, 58
Triphenyl dihydroanthracene, 88
hydroxy dihydroanthracene, 86,
88, 89
methane carboxylic acid, 88, 96,
123
methyl, 102
Turpentine, 14
Urethanes, 219, 220, 225
Untersalpetersaiireanthracen, 57
Vat dyes, 4, 6
Veratrol, 139
Vinyl bromide, 15
Violanthiene, 4. See also Viol-
anthrone.
BS, 329
R Extra, 332
Violanthrone, 327, 329, 330
jso- Violanthrone, 327, 331, 332
Viridanthrene B, 330
Wood tar oil, 14
Xanthopurpurin. See Purpuro-
xanthin.
Xylene, 15, 27, 30, 32, 34, 36. 133,
134, 138, 141, 393
Xyloyl benzoic acid, 34
Xylyl aminoanthraquinonyl ketone,
399
anthraquinonyl ketone, 399
chloranthraquinonyl ketone, 398,
399
chloride, 32
hydroxyanthraquinonyl ketone,
399
mesityl ketone, 36
Printed by William Clowes & Sons, Ltd., Beetles, /or
Bailliire, Tindalt & Cox, 8, Henrietta Stnet, Covtnt Garden, W-C. 2.
INDUSTRIAL CHEMISTRY
Being a Series of Volumes Giving a Comprehensive Survey of
THE CHEMICAL INDUSTRIES
Edited by SAMUEL RIDEAL, D.Sc. (Lond.), F. I. C, Fellow of
University College, London.
NOIV READY "
Silica and the Silicates . . J. A. Audley, B.Sc. (Lond.), F.LC.
388 pp. Price, $4.50
Organic Medicinal Chemicals M. Barrov^cliff, F.LC, and F. H. Carr,
F.LC. 346 pp. Price, $4.00
Anthracene and Anthraquinone . E. de Barry Barnett, B.Sc. A.LC.
447 pp. Price, $6.00
Coal-Tar Dyes and Intermediates
E. DE Barry Barnett, B.Sc, A.LC. 232 pp. Price, $3.50
Explosives E. de Barry Barnett, B.Sc, A.LC. 257 pp. Price, $5.00
Chemical Fertilizers and Parasiticides S. H. Collins 285 pp. Price, $3.50
Plant Products and Chemical Fertilizers
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The Industrial Gases . . . H. C. Greenwood, D.Sc. (Manchester).
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R. S. Morrell, M.Av, Ph.D.; A. E
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IN PREPARATION
Animal Proteids . . . . H. G. Bennett, M.Sc. (Leeds).
Economic Metallurgy . . A. E. Pr.att, B.Sc. (Lond.), As.soc. R.S.M.
The Rare Earths and Metals E. K. Rideal, M.A. (Cantab.), Ph.D..
F.I.C
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