Anthraquinone Dyes and Intermediates 1

Anthraquinone Dyes and Intermediates

Hans-Samuel Bien, Bayer AG, Leverkusen, Federal Republic of Germany
Josef Stawitz, Bayer AG, Leverkusen, Federal Republic of Germany
Klaus Wunderlich, Bayer AG, Leverkusen, Federal Republic of Germany

1. Introduction and History . . . . . 2 2.11.2. Anthraquinonecarbazole Deriva-

2. Methods of Production . . . . . . . 2 tives . . . . . . . . . . . . . . . . . . . . 32
2.1. Anthraquinonesulfonic Acids . . . 3 2.11.3. Anthraquinone Derivatives with
2.2. Alkyl- and Arylanthraquinones . 4 Acridone Substructure (Phthaloy-
2.3. Haloanthraquinones . . . . . . . . . 4 lacridones) . . . . . . . . . . . . . . . . 35
2.4. Nitroanthraquinones . . . . . . . . 6 2.11.4. Anthraquinone Derivatives with
2.5. Aminoanthraquinones . . . . . . . 7 Phenazine Substructure . . . . . . . . 37
2.5.1. General Aspects . . . . . . . . . . . . 7 2.12. Anthraquinone Derivatives with
2.5.1.1. Replacement Reactions . . . . . . . . 8 Meso Rings
2.5.1.2. Modifications of the Amino Func- (1,9-Cyclo-10-anthrones) . . . . . . 38
tions . . . . . . . . . . . . . . . . . . . 10 2.12.1. Benzanthrone and Its Derivatives . 38
2.5.1.3. Substitutions on the Aminoanthra-
2.12.2. Pyrazolanthrone and Its Derivatives 40
quinone Nucleus . . . . . . . . . . . . 11
2.5.2. Individual Aminoanthraquinones . . 13 2.12.3. 1,9-Anthrapyrimidine and Its
2.5.3. Diazotization of Derivatives (1,9(N-)-Pyrimidino-
Aminoanthraquinones . . . . . . . . 18 anthrone-10) . . . . . . . . . . . . . . 41
2.6. Hydroxyanthraquinones, Alkoxy- 2.12.4. 1,9-Anthrapyridone and Its Deriva-
and Aryloxyanthraquinones . . . 18 tives . . . . . . . . . . . . . . . . . . . . 42
2.6.1. General Aspects . . . . . . . . . . . . 18 2.12.5. Dibenzpyrenequinones . . . . . . . . 42
2.6.1.1. Synthesis of the Nucleus . . . . . . . 18 2.12.6. Anthanthrones . . . . . . . . . . . . . 43
2.6.1.2. Replacement Reactions . . . . . . . . 19 2.12.7. Pyranthrone and Flavanthrone . . . 44
2.6.1.3. Conversions of the Hydroxy Group 20 2.12.8. Violanthrone and Isoviolanthrone . 44
2.6.1.4. Substitutions on the Hydroxyanthra- 2.12.9. Acedianthrone . . . . . . . . . . . . . 46
quinone Nucleus . . . . . . . . . . . . 20 3. Dye Classes . . . . . . . . . . . . . . . 46
2.6.2. Individual Hydroxyanthraquinones 22
3.1. Neutral Dyes . . . . . . . . . . . . . . 47
2.7. Mercaptoanthraquinones . . . . . 26
3.1.1. Disperse Dyes . . . . . . . . . . . . . 47
2.7.1. General Aspects . . . . . . . . . . . . 27
2.7.2. Individual Mercapto Compounds 3.1.1.1. Dyes for Polyester Fibers . . . . . . 47
and Thioethers . . . . . . . . . . . . . 27 3.1.1.2. Dyes for Cellulose Ester and Syn-
2.8. Anthraquinonesulfones . . . . . . . 27 thetic Polyamide Fibers . . . . . . . 49
2.9. Anthraquinone Aldehydes and 3.1.1.3. Transfer Dyes . . . . . . . . . . . . . . 50
Their Derivatives . . . . . . . . . . . 28 3.1.1.4. Dyes for Cotton – Polyester Fabrics 50
2.10. Anthraquinonecarboxylic Acids 3.1.2. Dyes Soluble in Organic Solvents . 51
and Carboxylic Acid Derivatives 29 3.1.3. Vat Dyes . . . . . . . . . . . . . . . . . 51
2.10.1. General Aspects . . . . . . . . . . . . 29 3.1.4. Pigments . . . . . . . . . . . . . . . . . 56
2.10.2. Individual Anthraquinonecar- 3.2. Anionic Dyes . . . . . . . . . . . . . . 57
boxylic Acids . . . . . . . . . . . . . . 30
3.2.1. Acid Dyes . . . . . . . . . . . . . . . . 57
2.11. Anthraquinone Derivatives with
Condensed Rings . . . . . . . . . . . 31 3.2.2. Direct Dyes . . . . . . . . . . . . . . . 59
2.11.1. Anthraquinone Derivatives Contain- 3.2.3. Reactive Dyes . . . . . . . . . . . . . 60
ing Imidazole, Oxazole, and Thia- 3.3. Cationic Dyes . . . . . . . . . . . . . 61
zole Rings . . . . . . . . . . . . . . . . 31 4. References . . . . . . . . . . . . . . . 61

c 2005 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim

10.1002/14356007.a02 355
2 Anthraquinone Dyes and Intermediates
1. Introduction and History
The elucidation of the structure of alizarine by
C. Graebe and C. Liebermann in 1868 marks
the beginning of anthraquinone chemistry. After
Caro, Graebe, and Liebermann had worked
out a commercial synthesis for alizarine, major
efforts, especially by R. Bohn (Badische Anilin-
& Sodafabrik) and R. E. Schmidt (Farbenfab-
riken Bayer, formerly Friedrich Bayer & Co.)
were directed toward the manufacture of
hydroxyanthraquinones. A sizeable collection
of red, blue, and green mordant dyes was as-
sembled over a span of 20 years. The turn of the
century saw the development of the first acidic
anthraquinone dyes that could be used to dye
wool in fast red to green shades without the need
for pretreatment with mordants.
In 1901 a new era of anthraquinone chem-
istry started with the discovery of the mercury-
catalyzed α-sulfonation of anthraquinone. (Sub-
stituted anthraquinones are usually designated
as α for substitution at positions 1, 4, 5, or 8 and
as β for substitution at positions 2, 3, 6, or 7. For
example, α,α
-anthraquinonedisulfonic acid is a
mixture of anthraquinone-1,5 and 1,8-disulfonic
acids.) About 80 % of the anthraquinone dyes are
still prepared via anthraquinonesulfonic acids,
even though emphasis is shifting at present to-
ward synthesis via nitroanthraquinones. Impor-
tant early reactions of anthraquinone chemistry
include the Fischer reaction (replacement of a
sulfonic acid group by chlorine) and high-pres-
sure fusion with lime (replacement of sulfonic
acid by a hydroxy group).
Simultaneously, new fundamental develop-
ments took place in the area of anthraquinone
vat dyes, e.g., indanthrone, flavanthrone, vi-
olanthrone, benzoylaminoanthraquinones, an-
thrimides, and anthrimidecarbazoles. Subse-
quent work concentrated on closing gaps in the
offerings of vat and acid dyes and testing of
potential applications in nontextile dye applica-
tions.
The introduction of synthetic fibers, such
as polyester, polyamide, and polyacrylonitrile
fibers, initiated a new phase in the development
of anthraquinone dyes. This led to a number of
substitution products of anthraquinone that were
useful as disperse dyes or as basic dyes. With the
appearance of the first fiber-reactive dyes, work
on acid anthraquinone dyes was intensified.
A new application for vat dyes constituted
their use as organic pigments. Based on these in-
sights, a whole new series of specialty pigments
was developed.
The synthesis of an anthraquinone dye gen-
erally involves a large number of steps. For ex-
ample, the preparation of a vat dye may require
as many as eight steps and may necessitate the
preparation of seven different anthraquinone in-
termediates.
Anthraquinone dyes are surpassed in im-
portance only by azo dyes. The more compli-
cated syntheses and lower tinctorial strengths of
the anthraquinone dyes make production costs
higher than for azo dyes. Therefore anthra-
quinone dyes tend to be used only when the re-
quired properties and color fastness are extreme
or when the colors desired are not obtained easily
with azo dyes (especially bright blue to turquoise
shades). Use of a dye in vat dyeing requires the
presence of special structural features (quinoid
or indigoid). Therefore most vat dyes are derived
from anthraquinone.
2. Methods of Production
The production of anthraquinone intermedi-
ates and anthraquinone dyes generally proceeds
from a few key products generated by elec-
trophilic substitution of unsubstituted anthra-
quinone or by synthesis of the nucleus. The
major methods employed to prepare anthra-
quinone derivatives substituted in the α posi-
tion are sulfonation and nitration. Preparation of
β-substituted anthraquinones and of quinizarin
(1,4-dihydroxyanthraquinone) generally is ac-
complished by synthesis of the nucleus starting
from phthalic anhydride and a benzene deriva-
tive.
Until fairly recently, preparation of almost
80 % of all important anthraquinones was based
on anthraquinonesulfonic acids. However, ni-
tration of anthraquinone is gaining in impor-
tance presently, a development triggered mainly
by environmental considerations (e.g., produc-
tion of large volumes of waste dilute acids dur-
ing anthraquinone sulfonation). However, great
progress has been made recently in solving the
problems associated with sulfonation.
Preparation of nearly all important anthra-
quinones starts from the following key inter-
 Anthraquinone Dyes and Intermediates
mediates: anthraquinonesulfonic acids, nitro-
anthraquinones, and the products of nucleus
synthesis, 1,4-dihydroxy-, 2-methyl-, or 2-
chloroanthraquinone. The only exceptions are
derivatives with condensed rings, e.g., benzan-
throne and derived products, which are prepared
directly from anthraquinone via anthrone.
2.1. Anthraquinonesulfonic Acids
Anthraquinonesulfonic acids generally are ob-
tained by sulfonation. Additional options, such
as displacement of substituents (e.g., chlorine
atoms or nitro groups) by sulfite or oxidation
of mercapto groups, are of little importance but
are used for the preparation of some substituted
anthraquinonesulfonic acids.
The sulfonic acid group in anthraquinone
enters readily into nucleophilic exchange reac-
tions, whereby the α position is much more reac-
tive than the β position. Sulfonic acid groups are
exchanged readily against amino, alkylamino,
hydroxy, and alkoxy groups. Exchange against
chlorine atoms also proceeds smoothly (Fischer
synthesis, see page 4).
Reduction also may be used to remove the
sulfonic acid group from certain substituted
anthraquinones, as, for example, from 1-amino-
4-arylaminoanthraquinone-2-sulfonic acid.
Desulfonation of the α position may be ac-
complished by heating in 70 – 90 % sulfuric
acid in the presence of mercury. This method
is used to convert unnecessary α,α
-disulfonic
acids back to anthraquinones [15], [16].
Sulfonation of the β position of anthra-
quinone is at present of little importance, be-
cause β-substituted compounds (e.g., 2-ami-
noanthraquinone) are prepared nowadays from
2-chloroanthraquinone instead of the sulfonic
acid.
Process Details. Sulfonation of anthra-
quinones requires extreme conditions
(≈ 150 ◦ C, 20 % oleum), which yield either
mono- or disulfonic acids, depending on the
method of operation. Whereas nitration and
halogenation preferentially substitute the α po-
sition, direct sulfonation attacks the β position,
yielding anthraquinone-2-sulfonic acid or the
2,6- or 2,7-disulfonic acid derivatives.
3
If mercury or mercury compounds are added
as catalysts, sulfonation proceeds under much
milder conditions and substitution occurs pref-
erentially at the α position. The mercury can
be reclaimed during workup of the sulfonation
mixtures [17–25].
Although other catalysts, such as palladium,
ruthenium, or rhodium, are also suitable for sul-
fonating anthraquinone at the α position, they
are not used industrially [26–28].
Anthraquinone-1-sulfonic acid [82-49-5],
K salt, also called diamant salt, M r 288.3, is
prepared by sulfonation in the presence of, e.g.,
0.5 % mercury in 20 % oleum, an amount of
SO3 adequate for the sulfonation of about 60 %
of the charge. The reaction is controlled in such
a manner that about 50 % of the anthraquinone
remains unsulfonated. After mercury is precipi-
tated as the sulfide, the unreacted anthraquinone
is precipitated by dilution and is collected by
filtration. After washing and drying, it is re-
circulated as ‘reclaimed quinone‘. Mercury is
removed completely from the filtrate, and the
anthraquinone-1-sulfonic acid is then precipi-
tated as the potassium salt [23].
Anthraquinone-2-sulfonic acid [84-48-0],
Na salt, also called silver salt, M r 288.3, is pre-
pared by sulfonation in the absence of mercury
(e.g., according to the procedure cited in [3,
4 Anthraquinone Dyes and Intermediates
p. 8]). The acid also can be obtained from the
1,6- (or 1,7-) disulfonic acid by desulfonation at
the α position in dilute sulfuric acid [15].
Anthraquinone-1,5-disulfonic acid
[117-14-6], Thiol Acid, M r 368.3, and anthra-
quinone-1,8-disulfonic acid [82-48-4], Azine
Acid, M r 368.3, are produced by disulfonation
under conditions similar to those for mono-
sulfonation except for an increased concentra-
tion of SO3 . After sulfonation of the anthra-
quinone is complete, the 1,5-acid is precipitated
by slow addition of dilute sulfuric acid, col-
lected, and washed with dilute sulfuric acid. The
filter cake is dissolved in hot water, the solution
treated with charcoal, and the anthraquinone-
1,5-disulfonic acid precipitated from the filtrate
as its disodium salt by addition of saturated
sodium chloride solution. The 1,8-acid is iso-
lated as the potassium salt from the sulfuric acid
mother liquors and the wash acids (see also [1]
and [3, p. 10]). Mercury can be removed in a
similar manner as given for anthraquinone-1-
sulfonic acid (see, e.g., [23]).
2.2. Alkyl- and Arylanthraquinones
Alkyl- and arylanthraquinones are obtained
from the corresponding benzene derivatives and
phthalic acid anhydride via the benzoylbenzoic
acids.
2-Methylanthraquinone is of great impor-
tance for the synthesis of dyes. 2-Alkylanthra-
quinones (e.g., 2-ethyl-, 2-isoamyl-, or 2-
tertamylanthraquinone) are used as oxygen car-
riers in the preparation of hydrogen perox-
ides (→ Peroxo Compounds, Inorganic). If α-
haloanthraquinones are heated in the presence
of copper in inert, high-boiling solvents, dimer-
ization (Ullmann reaction) yields the corre-
sponding 1,1
-dianthraquinonyls. This reaction
is used, for instance, in the preparation of start-
ing materials for the synthesis of pyranthrone
and flavanthrone (see Section 2.12.7).
2-Methylanthraquinone [84-54-8], Mr
222.2, mp 182 – 183 ◦ C, is prepared from ph-
thalic anhydride and toluene (see also [1], [2,
p. 10], [5, p. 40]).
2-Ethylanthraquinone [84-51-5], Mr
235.3, mp 108 ◦ C, is prepared from phthalic
anhydride and ethylbenzene [29].
2.3. Haloanthraquinones
Haloanthraquinones are important intermedi-
ates for all classes of dyes, especially for vat
and disperse dyes.
Unsubstituted halogenated anthraquinones
are prepared mainly by replacement reac-
tions or by synthesis of the nucleus. Only
the chloro derivatives are of practical impor-
tance. Aminoanthraquinones, hydroxyanthra-
quinones, phenoxyanthraquinones, and an-
thrimides (dianthraquinonylamines) may be ob-
tained by replacing the chlorine atom. The β-
chloroanthraquinones are much more suitable
for preparing β-aminoanthraquinones than the
corresponding sulfonic acids. In contrast to the
1,5- and the 1,8-dichloroanthraquinones, a sin-
gle chlorine atom of 2,3-dichloroanthraquinone
can be replaced by ammonia to give 2-amino-3-
chloroanthraquinone in good yield [5, p. 30].
Haloanthraquinones with additional sub-
stituents commonly are prepared by direct halo-
genation of the corresponding anthraquinones
in water, hydrochloric acid, sulfuric acid, or
organic solvents. Electron-withdrawing sub-
stituents, such as sulfonic acid or nitro groups,
direct the halogenation to the other nucleus.
Anthraquinones with electron-donating sub-
stituents, such as amino or hydroxy groups, per-
mit selective halogenation of one or the other
nucleus by appropriate choice of reaction con-
ditions. Only the chloro and bromo derivatives
are commercial products.
Process Details. Direct chlorination of
anthraquinone with chlorine or sulfuryl chlo-
ride, occurs preferentially at the α position;
 Anthraquinone Dyes and Intermediates
however, the resulting product mixtures are diffi-
cult to separate. Only 1,4,5,8-tetrachloroanthra-
quinone of about 60 % purity [30] and 1-chloro-
2methylanthraquinone are prepared commer-
cially by this method [2, p. 60].
Replacement of sulfonic acid groups by chlo-
rine is called the Fischer reaction in honor of its
discoverer, A. Fischer. Sulfonic acid groups in
both the α and β position are replaced.
The reaction is carried out by slowly
adding an aqueous solution of sodium chlo-
rate to a hot hydrochloric acid solution of the
anthraquinonesulfonic acid. The resulting, only
slightly soluble chloroanthraquinones are iso-
lated by filtration. The almost quantitative reac-
tion is also used for the identification of anthra-
quinonesulfonic acids. The Fischer reaction of
disulfonic acids can be directed in such a way
that mostly monochloroanthraquinonesulfonic
acids form.
A nitro group can be replaced by a chlo-
rine atom at high temperature, generally above
200 ◦ C, using chlorine or ionic chlorides, such
as lithium chloride, in organic solvents [33].
A proposed industrial method is the reaction
of chlorine with nitroanthraquinone in the melt
[31]. Diluents for the high-melting nitroanthra-
quinones are lower melting compounds, such
as chloroanthraquinone [32], trichlorobenzene
[110], phthalic anhydride [42], and salt melts
[34]. Chloroanthraquinones can be purified [35]
and separated [36] by high-temperature distilla-
tion.
1,4-Dichloroanthraquinone may be obtained
by replacing the hydroxy groups of 1,4-di-
hydroxyanthraquinone (quinizarin) with chlo-
rine by heating with thionyl chloride [37] or with
mixtures of phosphoryl chloride and phosphorus
pentachloride [38].
The replacement of amino groups by chlo-
rine through diazotization and treatment with
cuprous chloride (Sandmeyer reaction) is used
commercially only in special cases (see Section
2.5).
A few chloroanthraquinones can be ob-
tained by synthesis of the nucleus via the cor-
5
responding benzoylbenzoic acids. Because β-
anthraquinonesulfonic acids react slowly in the
Fischer reaction, industrial production of 2-
chloroanthraquinone starts generally from ph-
thalic anhydride and chlorobenzene [2, pp. 8,
11].
1-Chloroanthraquinone [82-44-0], Mr
242.7, mp 162 ◦ C, is prepared from anthra-
quinone-1-sulfonic acid [4, p. 29], [39], or from
1-nitroanthraquinone [31], [32]. Purification by
high-temperature distillation [35], [36].
2-Chloroanthraquinone [131-09-9], M r
242.7, mp 210 ◦ C, is prepared by synthesis of
the nucleus starting with phthalic anhydride and
chlorobenzene [2, pp. 8, 11].
1,5-Dichloroanthraquinone [82-46-2], M r
277.1, mp 251 ◦ C, is prepared by Fischer re-
action from anthraquinone-1,5-disulfonic acid,
by addition of chlorobenzenes [40], or from
1,5-dinitroanthraquinone [32] by replacement of
NO2 .
1,8-Dichloroanthraquinone [82-43-9], M r
277.1, mp 203 ◦ C, is prepared from anthra-
quinone-1,8-disulfonic acid [3, p. 15] or from
1,8-dinitroanthraquinone [32].
1,4-Dichloroanthraquinone [602-25-5], M r
277.1, mp 187 ◦ C, is prepared from 1,4-di-
hydroxyanthraquinone [37], [38] or by syn-
thesis of the nucleus from phthalide and 1,4-
dichlorobenzene [41].
2,3-Dichloroanthraquinone [84-45-7], M r
277.1, is prepared by synthesis of the
nucleus from phthalic anhydride and 1,2-
dichlorobenzene [2, p. 10].
1,4,5,8-Tetrachloroanthraquinone [81-58-
3], M r 346.0, mp 342 ◦ C, is prepared by chlo-
rination of anthraquinone in sulfuric acid [30]
or by sulfonation of 1,8-dichloroanthraquinone
followed by Fischer reaction [43].
6 Anthraquinone Dyes and Intermediates
1-Chloro-2-methylanthraquinone [129-
35-1], M r 256.7, mp 171 ◦ C, is prepared from
2-methylanthraquinone by direct chlorination in
oleum [2, p. 60] or organic solvents [44].
2-Chloro-3-methylanthraquinone [14684-
09-4], M r 256.7, is prepared by synthesis of
the nucleus from phthalic anhydride and 2-
chlorotoluene [45].
2.4. Nitroanthraquinones
Nitration of anthraquinones has considerable in-
dustrial importance. Examples of compounds
that may be nitrated are anthraquinone and the
halo-, hydroxy-, amino-, and acylaminoanthra-
quinones. As a rule the nitro group attacks at
the α position; choice of reaction conditions fre-
quently permits mono- or dinitration.
Prior to the discovery of α-sulfonation of
anthraquinone, nitration was the only use-
ful method for preparing α-substituted anthra-
quinones. The nitro group of α-nitroanthra-
quinones may be replaced in a manner simi-
lar to the sulfonic acid moiety, e.g., by chlorine
atoms and amino, hydroxy, alkoxy, or mercapto
groups. Reduction readily yields aminoanthra-
quinones. Nitration of anthraquinone has gained
increasing importance because of environmental
considerations, this method offering an econom-
ical alternative to α-sulfonation.
1-Nitro-2-methylanthraquinone is the
starting material for 1-amino-4-bromo-2-
methylanthraquinone, 1-aminoanthraquinone-
2-aldehyde, and 1-aminoanthraquinone-2-
carboxylic acid derivatives.
Process Details. Substituted anthraquinones
usually are nitrated in concentrated sulfuric acid
using stoichiometric quantities of nitric acid or
nitric – sulfuric mixed acid. This method always
produces considerable amounts of dinitro com-
pound in addition to the mononitro compound.
Even the best methodology permits preparation
of only 75 – 80 % of the theoretical amount of
1-nitroanthraquinone. Mononitration in highly
concentrated nitric acid also has been developed
to an acceptable procedure by avoiding concen-
tration levels that can lead to explosions [46–
49]. Dinitration can be retarded significantly
during nitration with mixed acids by increas-
ing the water content [50–52]. Other procedures
specify the presence of organic solvents, such as
halogenated hydrocarbons [54], [55], [56], sul-
folane (tetrahydrothiophene-1,1-dioxide) [57],
hydrofluoric acid [58], or phosphoric acid [59].
Some of these methods can be adapted to con-
tinuous processing.
Mononitration of 2-methylanthraquinone
leads to 2-methyl-1-nitroanthraquinone [2,
p. 13]. Nitration of anthraquinone-1-sulfonic
acid produces a mixture of 1-nitroanthra-
quinone-5-sulfonic acid and 1-nitroanthra-
quinone-8-sulfonic acid, whereas nitration of
anthraquinone-2-sulfonic acid produces a mix-
ture of 1-nitroanthraquinone-6-sulfonic acid and
1-nitroanthraquinone-7-sulfonic acid.
Halogen exchange by nitrite is an unimpor-
tant method of preparing nitroanthraquinones.
There are only a few patents directed toward the
synthesis of more highly substituted nitroanthra-
quinones, e.g., [82].
Finally, preparations of nitroanthraquinones
by means of nuclear syntheses, for instance, by
addition of butadiene to 5-nitronaphthoquinone
(or its oxime), have also been proposed [83],
[84].
Several methods have been developed to re-
move 2-nitroanthraquinone and dinitroanthra-
quinones from 1-nitroanthraquinone. The chem-
ical purification processes are based on the treat-
ment of the crude product with sodium sulfite
 Anthraquinone Dyes and Intermediates
[60] or alkaline reagents, such as amines [61],
alcoholates [62], or hydrazine [63], which cause
preferential conversion of the contaminants to
compounds that can be separated easily on the
basis of their different solubilities. The more
economical physical separation methods incor-
porate prepurification into the nitration process
(e.g., crystallization from nitric acid [64]), or
the isolated crude 1-nitroanthraquinone is puri-
fied with organic solvents, such as nitrobenzene
[65] or amides [66]. Pure 1-nitroanthraquinone
is then obtained by high-temperature distillation
[67], [68].
Purification may also be deferred to the ami-
noanthraquinone stage (see page 13.
Modification of nitration conditions permits
dinitration of anthraquinone. Nitration in highly
concentrated nitric acid, as cited in [69], is for
safety reasons unsuitable for industrial produc-
tion [70]. However, addition of sulfuric acid
makes it possible to work with a margin of safety
[71]. The preferred method for dinitration is still
the use of mixed nitric – sulfuric acid [72], [73].
However, nitration in organic solvents [74] or
hydrofluoric acid [75] have been proposed also.
Apart from approximately equal portions of
1,5- and 1,8-dinitroanthraquinones, dinitration
produces α,β-dinitroanthraquinone. The direct
isolation of 1,5- and 1,8-dinitroanthraquinone
is possible from the nitration mixtures [76]
or, starting from isolated crude dinitroanthra-
quinone mixtures, by fractional crystallization
from organic solvents, e.g., nitrobenzene [77],
N-methylpyrrolidone [78], or high-boiling ke-
tones [79]. Other procedures that simply sep-
arate the α,β-dinitroanthraquinones have been
described also [80].
1-Nitroanthraquinone [82-34-8], Mr
253.2, mp 228 ◦ C, is prepared by nitration of
anthraquinone in nitric acid (danger of explo-
sion!) [46–49], sulfuric acid [50–52], organic
solvents [54–57], phosphoric acid [59], or hy-
drogen fluoride [58].
Purification from organic solvents by ad-
dition of bases, such as amines [61], alcoho-
lates [62], or hydrazine [63], or from water by
addition of sodium sulfite [60]. 1-Nitroanthra-
quinone is crystallized from nitric acid [64],
from organic solvents, for example, nitroben-
zene [65], or from amides [66]. The resulting
7
1-nitroanthraquinone may be finally purified by
high-temperature distillation [67], [68].
1,5-Dinitro- and 1,8-dinitroanthra-
quinones [82-35-9], [129-39-5], M r 298.2, are
prepared by nitration of anthraquinone with ni-
tric acid in sulfuric acid [72], [73], if necessary
by addition of organic solvents [74], or in hy-
drogen fluoride [75].
For isolation and purification of mixtures of
1,5- (and 1,8-) dinitroanthraquinone, see [80].
Isolation of 1,5- (and 1,8-) dinitroanthraquinone
is described in [77–79].
1-Nitroanthraquinone-5- (and -8-) sul-
fonic acids [82-50-8], [129-37-3], M r 333.3,
are prepared by nitration of anthraquinone-1-
sulfonic acid [81].
2-Methyl-1-nitroanthraquinone [129-15-7],
M r 267.7, is prepared by nitration of 2-
methylanthraquinone [2, p. 13].
2.5. Aminoanthraquinones
2.5.1. General Aspects
Aminoanthraquinones, especially 1-amino- and
1,5-diaminoanthraquinone, are key products for
essentially all classes of anthraquinone dyes.
Important production methods are the replace-
ment of sulfonic acid and nitro groups or
of halogen atoms by ammonia or primary
or secondary amines. With 1,4-dihydroxy-,
1,4-aminohydroxy-, and 1,4-diaminoanthra-
quinones, the replacement of hydroxy and
amino groups is also successful. Primary amino-
anthraquinones are also prepared by reduc-
tion of nitroanthraquinones. Modifications of
the amino functions also have industrial im-
portance. These include alkylation, arylation,
acylation, and hydrolysis of acylaminoanthra-
quinones. The choice of production method for
a desired aminoanthraquinone depends on the
position and type of the amino function, as well
as on the availability of starting materials.
A special method for the production of 1-ami-
noanthraquinone consists in the catalytic hydro-
genation of 5-nitro-1,4,4 a,9 a-tetrahydroanthra-
quinone, which is obtained by reacting butadiene
and 5-nitronaphthoquinone (see [85]).
8 Anthraquinone Dyes and Intermediates
Aminoanthraquinones may be purified by
recrystallization, distillation, or sublimation.
However, purification is preferred at the stage
of the nitroanthraquinones or the anthra-
quinonesulfonic acids.
In most situations the presence of the amino
group facilitates the introduction of further sub-
stituents into the same ring. Reaction media and
conditions as well as type and position of the
amino group determine the position of substitu-
tion.
In addition to conversion of existing ami-
no groups to other amino functions, the ami-
no groups also may be replaced by halogen or
hydroxy substituents through diazotization fol-
lowed by the Sandmeyer reaction.
2.5.1.1. Replacement Reactions
SO3 H → NHR (R = H or alkyl). The re-
placement of sulfonic acid groups by amino
or alkylamino groups can be carried out suc-
cessfully with both unsubstituted and fur-
ther substituted anthraquinonesulfonic acids.
Depending on the choice of reaction condi-
tions, diaminoanthraquinones and aminoanthra-
quinonesulfonic acids may be obtained from
disulfonic acids. The α- and β-sulfonic acids
react both with ammonia. In the reaction with
alkylamines, only the α derivatives give com-
mercially important products. Yields are deter-
mined in part by the number of sulfonic acid
groups and in part by the type of amine and are
on the order of 70 – 90 %.
The exchange reactions are carried out
in aqueous medium at 120 – 200 ◦ C and un-
der pressure. To avoid attachment of dis-
placed sulfite, an oxidizing agent, e.g., m-
nitrobenzenesulfonic acid, is usually added.
Halogen → NH2 or NHR. Of great impor-
tance industrially is the replacement of chlo-
rine and bromine atoms in the α or β po-
sitions by amines in substituted and unsub-
stituted haloanthraquinones. Reagents for this
purpose are ammonia, aliphatic and aromatic
amines, aminoanthraquinones, and amides, such
as p-toluenesulfonamide or phthalimide. Be-
cause of the increased reactivity of the α po-
sitions, the halogen atoms at the α positions of
α,β-dihaloanthraquinones may be reacted selec-
tively.
The partial replacement of halogen in α,α-
and β,β-dihaloanthraquinones, for example, in
2,3-dichloroanthraquinone, is also a known pro-
cess.
Haloanthraquinones without sulfonic acid
groups are reacted in the presence of excess
amine or in such organic solvents as alco-
hol, halobenzene, nitrobenzene, naphthalene, or
N-ethylcarbazole. Reaction temperatures range
from 100 to 250 ◦ C, and the reaction is carried
out in the presence of acid-neutralizing agents.
Alkali carbonates, acetates, and stearates are
suitable for this purpose. The reaction is acceler-
ated by the addition of copper catalysts. In many
cases, for example, in the preparation of anthrim-
ides, the copper catalyst is necessary.
Acylation of 1-amino-4-haloanthraquinones
may increase the reactivity of the halogen atom.
Haloanthraquinones with sulfonic acid
groups generally are reacted with amines in wa-
ter or water–alcohol mixtures at temperatures
up to 100 ◦ C in the presence of alkali carbon-
ates, alkali hydrogen carbonates, acetates, or
hydroxides. The addition of a copper catalyst is
absolutely essential in these reactions. Its action
is reputed to be enhanced by adding Fe(II) salts
[86].
 Anthraquinone Dyes and Intermediates
Of great industrial importance are the re-
actions of 1-amino-4-bromoanthraquinone-2-
sulfonic acid (bromamine acid). Yields depend
strongly on the choice of the reaction conditions
and the reactivity of the amine. Strongly ba-
sic amines require the addition of alkali-metal
hydroxides. Sterically hindered amines, such as
2,4,6-trimethylaniline, react very slowly.
Amines with very low basicity are unreactive
or react slowly. A side reaction of the bromamine
acid reaction is the reductive elimination of the
halogen atom and formation of 1-aminoanthra-
quinone-2-sulfonic acid or the replacement by
a hydroxy group to form 1-amino-4-hydroxy-
anthraquinone-2-sulfonic acid.
NO2 → NH2 or NHR. Aminoanthra-
quinones with primary amino groups may be
prepared by replacement reactions or, even more
simply, by reduction of the corresponding nitro-
anthraquinones. The industrial reducing agents
are usually sodium sulfide or sodium hydrogen
sulfide [87]. Reduction also may be accom-
plished with sulfur dioxide in ≈ 60 % sulfuric
acid in the presence of catalytic quantities of
iodine [88]. Other methods, particularly for the
preparation of 1-aminoanthraquinone, include
reduction by hydrazine in aqueous sodium hy-
droxide [89], by metals such as iron in sulfuric
acid [90], and by hydrogenation in organic sol-
vents in the presence of palladium or Raney
nickel [91]. If catalytic hydrogenation is carried
out in dilute sodium hydroxide solution, a purifi-
cation effect may take place if the 1-nitroanthra-
quinone is contaminated with dinitroanthra-
quinone. A stepwise reduction with purifica-
9
tion at the hydroxylamino stage has been pro-
posed also [92]. Highly purified 1-aminoanthra-
quinone is obtained by high-temperature distil-
lation [68].
Replacement of nitro groups by amino groups
using ammonia leads to good yields and high
quality 1-aminoanthraquinone and 1,5-diami-
noanthraquinone. The reaction commonly is car-
ried out at 140 – 170 ◦ C, optionally under pres-
sure, in organic solvents, such as alcohols [93],
amides [94], xylene [95], chlorobenzene [96], or
tetramethylene sulfone [97]. The use of ammo-
nium salts or urea in place of ammonia has also
been proposed [94].
Replacement of nitro groups by alkylamines
or arylamines is favored in the production of
secondary amines. Replacement reactions with
1-aminoanthraquinone to form anthrimides are
also successful [98].
When dinitroanthraquinones are used as
starting materials, the choice of reaction con-
ditions makes a partial exchange possible. The
reaction is carried out in water or organic sol-
vents, or in an excess of the amine.
OH → NH2 or NHR (R = H, alkyl, aryl).
The replacement of the hydroxy group by the
amino group is limited to 1,4-dihydroxy- and
1-amino-4-hydroxyanthraquinone. It occurs via
the 2,3-dihydro compounds and is reversible.
Exchange reactions are carried out using am-
monia, aliphatic and aromatic amines, and mix-
tures of amines. The starting material is the
isolated 2,3-dihydro compound, generally as a
mixture with dihydroxyanthraquinone. Alterna-
10 Anthraquinone Dyes and Intermediates
tively, the intermediate may be prepared in-
situ by addition of reducing agents such as
zinc–hydrochloric acid or iron – acetic acid.
The reaction media are water, alcohol, or ex-
cess amine. The primary product, 2,3-dihydro-
1,4-diaminoanthraquinone, is oxidized to 1,4-
diaminoanthraquinone either during the reaction
mediated by dihydroxyanthraquinone or after-
wards, by reaction with air. It is also possible to
isolate the dihydro compound and then oxidize it
with oleum, manganese dioxide – sulfuric acid,
or nitrobenzene in the presence of piperidine.
In 1,4-dihydroxyanthraquinone, both hy-
droxy groups are replaced in an excess amine.
In the presence of additional diluents, such as
alcohols, generally only one hydroxy group
is exchanged. As expected, sterically hindered
amines are not very reactive.
NH2 → NHR. The amino groups of 1,4-di-
aminoanthraquinones may be replaced by other
amino groups via the 2,3-dihydro compounds.
OR → NHR. Replacement of ether func-
tions by amino groups occasionally offers ad-
vantages over the other methods, especially in
reactions with reducing amines.
2.5.1.2. Modifications of the Amino
Functions
NH2 → NHR (R = alkyl). The preparation
of alkylaminoanthraquinones by alkylation of
aminoanthraquinones can be achieved by com-
monly employed methods, e.g., with dimethyl
sulfate, alkyl halides, or esters of toluenesulfonic
acid. A special process is the methylation with
methanol in sulfuric acid [108]. When used on
aminohydroxy- and diaminoanthraquinones this
process gives mixed products of interest to dy-
ers.
NH2 → NHR (R = aryl). The preparation of
simple arylanthraquinones by arylation of ami-
noanthraquinones with aromatic halides, such
as chlorobenzenes or chloronaphthalenes, has
no industrial importance. However, arylation is
used for the preparation of dianthraquinonyl-
amines and similar compounds, which are clas-
sified under the term anthrimides, e.g., di-
anthrimide, see page 14. In this case amino-
anthraquinones are reacted with chloroanthra-
quinones or nitroanthraquinones. The reaction
is carried out in high-boiling solvents, such as
naphthalene or nitrobenzene, at temperatures of
150 – 250 ◦ C. Certain cases do not require a sol-
vent (so-called “baking process”).
Acid-binding agents used in the prepa-
ration of anthrimides include alkali carbon-
ates, acetates, oleates, stearates, and alkaline-
earth oxides. Catalysts in the reactions of
haloanthraquinones are copper and copper salts.
Nitroanthraquinones also may be reacted with-
out a catalyst. Anthrimides may be isolated by
filtration or distilling the solvent away. Inorganic
salts are removed by boiling with water or dilute
mineral acids.
A special reaction for the preparation of
anthrimides is the oxidation of aminoanthra-
quinones in aqueous sulfuric acid: 1-ami-
noanthraquinone yields aminopolyanthrimides
[99]. Mixtures of 1-aminoanthraquinone
and 1,4-diaminoanthraquinone yield diami-
nodianthrimide [100].
Various anthrimides are suitable as vat dyes,
but they find their main use in the preparation of
anthrimidecarbazoles (see Section 2.11.2).
NH2 → NH – Heteroaryl. Of importance
here are mostly the triazinylaminoanthra-
quinones, where R1 and/or R2 may constitute
anthraquinonylamino residues.
Due to the high reactivity of chlorotri-
azines, one does not require a catalyst or, acid-
binding agents. In addition to high boiling or-
ganic solvents such as nitrobenzene, phenols
have proved valuable in the preparation of
trisanthraquinonylaminotriazines [101].
 Anthraquinone Dyes and Intermediates
The reaction may be accelerated by adding
tertiary amines, and in special cases by adding
catalytic quantities of a Lewis acid such as AlCl3
or FeCl3 .
NH2 → NH-CO-R. The most important
method of preparing acylaminoanthraquinones
is the acylation of aminoanthraquinones with
acid chlorides, preferably in an organic solvent,
such as nitrobenzene or dichlorobenzene. A
further method is the reaction of aminoanthra-
quinones with carboxylic acids or their anhy-
drides in oleum. Depending on the position of
the amino groups and the nature of the acid
chloride, diaminoanthraquinones also may be
acylated in one position only, giving 60 – 90 %
yields:
NHR → NH2 . Secondary or tertiary alkyl
aminoanthraquinones are converted into amino-
anthraquinones by removal of the alkyl residue
under the influence of acid or alkaline agents.
This method is also applicable to cycloalkyl-
[102] and aralkylaminoanthraquinones and fa-
cilitates the preparation of certain aminoanthra-
quinones that are accessible only with diffi-
11
culty. In the reaction of sterically hindered ary-
lamines with 1-amino-4-bromoanthraquinone-
2-sulfonic acid (bromamine acid), this cleavage
occurs as an undesirable side reaction, forming
1,4-diaminoanthraquinone-2-sulfonic acid.
NH-CO-R and NH-SO2 -R → NH2 .
Acylaminoanthraquinones are hydrolyzed in
dilute to concentrated sulfuric acid as well as in
2 – 10 % aqueous sodium hydroxide at temper-
atures ranging from 20 to 150 ◦ C. The sulfon-
amides are more stable in alkaline medium than
in an acidic medium. They are especially easily
cleaved in concentrated sulfuric acid. Because
arylsulfonylaminoanthraquinones are smoothly
prepared from haloanthraquinones (see page
19), this method is suitable for the production of
aminoanthraquinones otherwise difficult to pre-
pare. Hydrolysis of arylamino groups depends
also on additional substituents. For instance, al-
kaline hydrolysis of 1,5-bis(benzoylamino)-4-
hydroxyanthraquinone causes hydrolysis of the
5-benzoylamino group, whereas acidic medium
causes cleavage of the 1-benzoylamino group.
2.5.1.3. Substitutions on the
Aminoanthraquinone Nucleus
Nucleus H → SO3 H. 1-Aminoanthra-
quinone- 2-sulfonic acids are prepared by sul-
fonation of aminoanthraquinones in oleum or
chlorosulfonic acid. In order to suppress the
sulfonation and oxidation of the 4 position as
much as possible, chlorosulfonic acid in or-
ganic solvents or, alternatively, oleum in the
presence of sodium sulfate is used. When 1,4-
diaminoanthraquinone is sulfonated in oleum,
addition of boric acid (to form cyclic boric acid
amides) directs the sulfonic acid group into the 6
position. Sulfonation of β-aminoanthraquinones
has no commercial importance.
An alternative method for the introduction of
sulfonic acid groups consists of the treatment
of α-aminoanthraquinone with aqueous alkali-
metal sulfites.
Nucleus H → Halogen. Aminoanthra-
quinones may be halogenated with the usual
halogenation agents such as chlorine, bromine,
and sulfuryl chloride. Suggested reaction media
12 Anthraquinone Dyes and Intermediates
are hydrochloric acid, oleum, glacial acetic acid,
sodium chloride–aluminum chloride melts, and
inert solvents, such as chlorobenzene, nitroben-
zene, halogenated hydrocarbons, and amides.
The reaction of 1-aminoanthraquinone with
chlorine or sulfuryl chloride [1] in inert sol-
vents such as nitrobenzene leads to 1-ami-
no-2,4-dichloroanthraquinone, whereas addi-
tion of tetraalkylureas [103] leads to 1-ami-
no-2,3,4-trichloroanthraquinone. However, if 1-
amino- or 1-phthalimidoanthraquinone is chlo-
rinated in oleum, a good yield of 1-amino-5,8-
dichloroanthraquinones is obtained, if necessary
after hydrolysis of intermediates:
Use of 1-benzoylaminoanthraquinone as the
starting material generally leads to substitution
at the 4 position. Hydrolysis then yields the 1-
amino-4-chloroanthraquinone. This compound
may be obtained in better yields by chlorination
of 1-formamidinoanthraquinone in oleum fol-
lowed by hydrolytic cleavage of the protective
group.
Bromination of 1-aminoanthraquinone
in hydrochloric acid yields 1-amino-2,4-
dibromoanthraquinone.
Chlorination of 1,4-diaminoanthraquinone
in organic solvents with chlorine or sulfuryl
chloride yields 1,4-diamino-2,3-dichloroanthra-
quinone; in boric acid–oleum, the 5,8-dichloro
derivative is formed. In hydrochloric acid,
1-amino-2-methylanthraquinone and 1-ami-
noanthraquinone-2-sulfonic acid are bromi-
nated at the 4 position.
The 1-alkylaminoanthraquinones behave dif-
ferently from the 1-aminoanthraquinones upon
bromination in hydrochloric acid. In this case no
substitution occurs at the 2 position, but the 1-
alkylamino-4-bromoanthraquinones are formed
in more than 90 % yield. By contrast, chlori-
nation of 1-methylaminoanthraquinone in weak
oleum [104] will give, in a manner similar to
that of 1-aminoanthraquinone, the 5,8-dichloro-
1-methylamino compound.
Nucleus H → CH3 . Starting from 1-ami-
noanthraquinones, reaction with formaldehyde
yields 1-amino-2-methylanthraquinones. The
reaction proceeds in aqueous alkaline solutions
via the leuco form of the aminoanthraquinone
[115].
Nucleus H → NO2 . In the nitration of ami-
noanthraquinones, which usually is carried out
in sulfuric acid, the amino group must be pro-
tected by acylation or by formation of cyclic sul-
fimides. Location and number of the inserted ni-
tro groups are determined to some extent by the
nature of the protective group. For example, 1-
ethoxycarbonylaminoanthraquinone yields the
1-amino-2,4-dinitroanthraquinone, whereas 1-
phthalimidoanthraquinone yields the 4,5- (or
4,8-) dinitro derivatives [105]. If 1,4-diami-
noanthraquinone is used as the starting material,
1,4-diamino-2-nitroanthraquinone is formed via
the intermediate 1,4-bis(benzoylamino)anthra-
quinone. The nitro group enters the 5 position
if the intermediate is the cyclic disulfimide 1.
The dioxamic acid (2) of the 1,5-diami-
noanthraquinone yields 1,5-diamino-4,8-
dinitroanthraquinone after nitration and hydrol-
ysis [106].
SO3 H → H. In certain 4-substituted 1-ami-
noanthraquinone-2-sulfonic acids, replacement
of the sulfonic acid by hydrogen is feasible
by using reducing agents in aqueous alkaline
medium. Sodium dithionite and glucose have
been applied successfully here. This procedure
is used in the preparation of 1-alkylamino- (or
1-arylamino-) 4-aminoanthraquinone:
 Anthraquinone Dyes and Intermediates
The procedure has certain advantages for
the preparation of 1,4-diaminoanthraquinones
with sensitive amino residues. An electro-
chemical reductive desulfonation of β-anthra-
quinonesulfonic acids has been proposed also
[107].
2.5.2. Individual Aminoanthraquinones
1-Aminoanthraquinone [82-45-1], Mr
223.2, mp 252 – 253 ◦ C, is prepared from anthra-
quinone-1-sulfonic acid in aqueous ammonia by
replacement of SO3 H (see page 8), [5, p. 22],
from 1-nitroanthraquinone in organic solvents
by replacement of NO2 by ammonia (see page
9), [93–97]; by reduction of 1-nitroanthra-
quinone with sodium sulfide in water [87] or in
organic solvents [109], with hydrazine hydrate
[89], with metal powders [90], or by catalytic
hydrogenation. This last reaction can be carried
out in organic solvents [91], in sodium hydrox-
ide solution [92], or in dilute sulfuric acid [111].
Purification is carried out by recrystallization
from organic solvents [112], [113] or sulfuric
acid [114]. The greatest purity is obtained by
distillation [68].
2-Aminoanthraquinone [117-79-3], Mr
223.2, mp 302 – 303 ◦ C. Older methods used
anthraquinone-2-sulfonic acid as the starting
material, replacing the SO3 H group. The pre-
ferred method is replacement of the chlorine in
2-chloroanthraquinone (see page 8), [2, p. 20].
1-Amino-2-methylanthraquinone [82-28-
0], M r 237.3, mp 202 ◦ C, is prepared by nitration
of 2-methylanthraquinone [2, p. 13] followed by
reduction or by methylation of 1-aminoanthra-
quinone with formaldehyde [115].
1,2-Diaminoanthraquinone [1758-68-5],
M r 238.2, mp 303 – 304 ◦ C, is prepared from 1-
aminoanthraquinone-2-sulfonic acid by SO3 H
exchange (see page 8, [5, p. 98].
13
1,4-Diaminoanthraquinone [128-95-0],
M r 238.2, mp 268 ◦ C, is prepared by hydroxyl
replacement from 1,4-dihydroxyanthraquinone
via the 2,3-dihydro compound and subsequent
oxidation of the intermediate 2,3-dihydro-1,4-
diaminoanthraquinone [5, p. 51].
1,5-Diaminoanthraquinone [129-44-2],
M r 238.2, mp 319 ◦ C, is prepared by SO3 H ex-
change from anthraquinone-1,5-disulfonic acid
(see page 8), [3, p. 14], [5, p. 43], by replacing
NO2 in 1,5-dinitroanthraquinone (see page 9),
[116], or by reducing 1,5-dinitroanthraquinone
with sodium sulfide or by catalytic hydrogena-
tion [117].
1,8-Diaminoanthraquinone [129-42-0],
M r 238.2, mp 262 ◦ C, is prepared by the meth-
ods given for 1,5-diaminoanthraquinone.
1,4,5,8-Tetraaminoanthraquinone [2475-
45-8], M r 268.3, mp 332 ◦ C, is prepared from
anthraquinone-1,5-dioxamic acid by nitration,
hydrolysis, and reduction [3, p. 53].
1-Methylaminoanthraquinone [82-38-2],
M r 237.3, mp 170 ◦ C, is prepared from anthra-
quinone-1-sulfonic acid by replacing SO3 H (see
page 8), [3, p. 18], from 1-chloroanthraquinone
by replacing chlorine (see page 8), [118], or
from 1-nitroanthraquinone by replacing NO2
(see page 9) [119], [120].
1-Isopropylaminoanthraquinone [27354-
18-3], M r 265.3, mp 187 ◦ C, is prepared by re-
placement of SO3 H [121] or NO2 [120], [121].
1,4-Bis(methylamino)anthraquinone
[2475−44−7], M r 266.3, is prepared by re-
placement of the hydroxy groups from 1,4-
dihydroxyanthraquinone (see page 9) via the
2,3-dihydro compound [122].
1-Methylamino-4-(3-dimethylaminopro-
pylamino)anthraquinone, (3), M r 337.4, is
prepared from 4-bromo-1-methylaminoanthra-
quinone (see page 8), [123].
14 Anthraquinone Dyes and Intermediates
1-Methylamino-4-(2-hydroxyethylami-
no)anthraquinone [2475-46-9], (4), M r 296.3,
is prepared (in admixture with symmetrical and
half-reacted exchange products) by replacement
of NH2 from 2,3-dihydro-1,4-diaminoanthra-
quinone with a mixture of methylamine and
ethanolamine [124].
1-Amino-4-methylaminoanthraquinone
[1220−94−6], M r 252.2, is prepared from
1,4-diaminoanthraquinone by partial methyla-
tion [125], from 1-amino-4-methylaminoanthra-
quinone-2-sulfonic acid by reductive SO3 H
cleavage (see page 12), [126], from 2,3-dihydro-
1,4-dihydroxyanthraquinone by hydroxyl re-
placement (see page 9) [122], or from 2,3-
dihydro-1,4-diaminoanthraquinone by replace-
ment of NH2 [127] (in admixture with 1,4-
bismethylaminoanthraquinone).
1-Cyclohexylaminoanthraquinone [1096-
48-6], M r 305.4, is prepared by replacing SO3 H,
chlorine, or NO2 [119].
1,5-Bis-(2-nitrophenylamino)anthra-
quinone [21982-51-4], (5), M r 480.4, is pre-
pared from 1,5-diaminoanthraquinone and 2-
chloronitrobenzene [128].
1-Benzoylaminoanthraquinone [3571-23-
1], M r 327.3, mp 248 – 249 ◦ C, is prepared from
1-aminoanthraquinone and benzoyl chloride
[129] or from 1-chloroanthraquinone and benz-
amide [130].
1,4-Bis-(benzoylamino)anthraquinone
[2987-68-0], Indanthren Red 5 GK, M r 446.4,
is prepared from 1,4-diaminoanthraquinone and
benzoyl chloride [4, p. 40].
1,5-Bis(benzoylamino)anthraquinone
[82-18-8], Indanthren Yellow GK, M r 446.4,
mp 350 ◦ C, is prepared from 1,5-diaminoanthra-
quinone with benzoyl chloride [131] or from 1,5-
dichloroanthraquinone with benzamide [130],
[132].
1-Amino-4-benzoylaminoanthraquinone
[81-46-9], M r 342.3, is prepared from 1,4-
diaminoanthraquinone with benzoyl chloride
[3, p. 4].
1-Amino-5-benzoylaminoanthraquinone
[117-06-6], M r 342.3, mp 244 – 245 ◦ C, is pre-
pared from 1,5-diaminoanthraquinone with
benzoyl chloride [3, p. 4] or from 1-chloro-
5-benzoylaminoanthraquinone with arylsul-
famides and subsequent hydrolysis [133].
1,1
-Dianthraquinonylamine [82-22-4],
dianthrimide, (6), M r 429.4, is prepared
by reacting 1-aminoanthraquinone with 1-
chloroanthraquinone in nitrobenzene [4, p. 29]
or water [134]. Also from 1-aminoanthra-
quinone and 1-nitroanthraquinone [98].
4,4
-Diamino-1,1
-dianthraquinonyl-
amine [128-87-0], (7), M r 459.4, is prepared
by nitration of dianthrimide followed by reduc-
tion [4, p. 30], [5, p. 138] or by oxidation of
a mixture of 1-aminoanthraquinone and 1,4-
diaminoanthraquinone in aqueous sulfuric acid
[100].
4,4
-Bis(benzoylamino)−1,1
-dianthra-
quinonylamine [128-79-0], (8), M r 667.7, is
prepared from 4,4
-diamino-1,1
-dianthrimide
with benzoyl chloride [4, p. 31], [5, p. 139].
 Anthraquinone Dyes and Intermediates 15

1-Benzoylamino-4-chloroanthraquinone
[81-45-8], M r 361.8, is prepared from 1-ami-
noanthraquinone by benzoylation in nitroben-
zene [3, p. 13] and subsequent chlorination with
sulfuryl chloride.

1-Benzoylamino-5-chloroanthraquinone
[117-05-5], M r 361.8, is prepared from 1-ami-
no-5-benzoylaminoanthraquinone by diazoti-
zation and Sandmeyer reaction with Cu2 Cl2
or by benzoylation of 1-amino-5-chloroanthra-
quinone in o-dichlorobenzene using benzoyl
chloride [4, p. 16].

1-Amino-2,4-dichloroanthraquinone
1,4-Bis-(1-anthraquinonylamino)anthra-
[13432-32-1], M r 292.1, mp 217 – 219 ◦ C, is
quinone [116-76-7], 1,1
,4
,1

-trianthrimide,
prepared by chlorination of 1-aminoanthra-
(9), M r 650.7, is prepared from 1 mol of
quinone in nitrobenzene [139].
1,4-diaminoanthraquinone and 2 mol of 1-
chloroanthraquinone [5, p. 102], [134].
1-Amino-5,8-dichloroanthraquinone
[3223-94-7], M r 292.1, mp 199 ◦ C, is prepared
N,N
-Bis-(1-anthraquinonyl)isophthal-
by chlorination of 1-aminoanthraquinone in
amide [3627-47-2], Indanthren Yellow 5 GK,
chlorosulfonic acid or in oleum with a low per-
(10), M r 576.6, is prepared from 1-aminoanthra-
centage of SO3 [140].
quinone and isophthaloyl chloride [12, p. 596].
1,4-Diamino-2,3-dichloroanthraquinone
[81-42-5], M r 307.1, is prepared by chlorina-
tion of 1,4-diaminoanthraquinone or leuco-1,4-
diaminoanthraquinone [4, p. 18] with sulfuryl
chloride.

1-Amino-2,4-dibromoanthraquinone [81-
49-2], M r 381.0, mp 221 ◦ C, is prepared from
1-Amino-4-chloroanthraquinone [2872- 1-aminoanthraquinone by bromination in dilute
47-1], M r 257.7, mp 179 – 180 ◦ C, is prepared by mineral acids [3, p. 6].
chlorination of 1-benzoylaminoanthraquinone
with sulfuryl chloride [135] and subsequent hy-
4-Bromo-1-methylaminoanthraquinone
drolysis or by chlorination of anthraquinonyl-
[128-93-8], M r 316.1, mp 194 ◦ C, is prepared
1-formamidinium salt followed by hydrolysis
from 1-methylaminoanthraquinone by bromi-
[136].
nation [141].
2-Amino-3-chloroanthraquinone [84-46-
4-Bromo-1-isopropylaminoanthra-
8], M r 257.7, mp 280 – 283 ◦ C, is prepared from
quinone [23573-29-7], M r 344.2, is prepared
2,3-dichloroanthraquinone by chlorine replace-
from 1-isopropylaminoanthraquinone by bromi-
ment (see page 8) [5, p. 30].
nation [141].
1-Amino-4-chloro-2-methylanthra-
4-Bromo-1-cyclohexylaminoanthra-
quinone [3225-97-6], M r 271.7, mp 255 –
quinone [14233-28-4], M r 384.4, is pre-
256 ◦ C, is prepared from 1-amino-2-
pared from 1-cyclohexylaminoanthraquinone
methylanthraquinone by chlorination with sul-
by bromination [141].
furyl chloride [137] or chlorine [138].
16 Anthraquinone Dyes and Intermediates
1-Amino-2-bromo-4-(dimethylaminopro-
pylamino)anthraquinone [51818-35-0], (11),
M r 402.3, is prepared from 1-amino-2,4-
dibromoanthraquinone and dimethylaminopro-
pylamine by bromine exchange [142].
1,4-Diamino-2-nitroanthraquinone, M r
283.2, is prepared from 1,4-bis(benzoylami-
no)anthraquinone by nitration in a solvent and
subsequent hydrolysis [143].
1,4-Diamino-5-nitroanthraquinone [82-
33-7], M r 283.2, is prepared from 1,4-diami-
noanthraquinone via the cyclic disulfimide (the
structure is shown in page 12), which is nitrated
in sulfuric acid and then hydrolyzed [3, p. 20].
1,5-Diamino-4,8-dinitroanthraquinone
[10262-79-0], M r 328.3, is prepared from
anthraquinone-1,5-bis-oxamidic acid by ni-
tration and hydrolysis [106] or from anthra-
quinone-1,5-bis(formamidinium chloride) by
nitration and hydrolysis in dilute sulfuric acid
[144].
1,4-Diamino-2-bromo-5-nitroanthra-
quinone, M r 362.1, is prepared from 1-ami-
no-2,4-dibromo-5-nitroanthraquinone and p-
toluenesulfonamide followed by hydrolysis
[145].
1-Aminoanthraquinone-2-sulfonic acid
[83-62-5], M r 303.3, is prepared from 1-ami-
noanthraquinone by sulfonation with ClSO3 H
in an organic solvent (if nitrobenzene, danger
of explosion) [5, p. 214], [146], [147], [149], or
with oleum in the presence of Na2 SO4 [148].
1-Amino-4-bromoanthraquinone-2-
sulfonic acid [116-81-4], bromamine acid, (12),
M r 382.2, is prepared from 1-aminoanthra-
quinone-2-sulfonic acid by bromination in water
[5, p. 214], [151] or in dilute acid [149], [150].
Alternatively, it can be prepared by a one-pot
process: sulfonation and bromination in sulfuric
acid without isolation of intermediates [152].
1,4-Diaminoanthraquinone-6-sulfonic
acid [64910-84-5], M r 318.3, is prepared by sul-
fonation of 1,4-diaminoanthraquinone in oleum
in the presence of boric acid.
1-Aminoanthraquinone-2,5- [4137-18-2],
(or -2,8-) disulfonic acid [58294-46-5], M r
383.4, is prepared from 1-aminoanthraquinone-
5- (or -8-) sulfonic acid by sulfonation [145],
or from 1-cyclohexylaminoanthraquinone-5-
sulfonic acid in oleum [102].
1-Aminoanthraquinone-2,6- (or -2,7-)
disulfonic acid, M r 383.4, is prepared from
1-nitroanthraquinone-6- (or -7-) sulfonic acid
and Na2 S by formation of 1-amino-2-mercapto-
anthraquinone-6- (or -7-) sulfonic acid followed
by oxidation [153].
1-Isopropylaminoanthraquinone-5-
sulfonic acid [33175-83-6], M r 345.4, is pre-
pared from anthraquinone-1,5-disulfonic acid
by replacement of one SO3 H [154].
1-Cyclohexylaminoanthraquinone-5-
sulfonic acid [33175-82-5], M r 385.4, is pre-
pared from anthraquinone-1,5-disulfonic acid
by replacement of one SO3 H [155].
1,4-Bis-(p-toluidino)anthraquinone-2
,2

-
disulfonic acid [3443-90-1], (13), M r 578.6,
is prepared from 1,4-dihydroxyanthraquinone
and p-toluidine by replacement of hydroxyl fol-
lowed by sulfonation [5, p. 215].
 Anthraquinone Dyes and Intermediates 17

1-Amino-4-(p-methylaminomethyl-
anilino)anthraquinone-2-sulfonic acid
[64135-01-9], (18), M r 437.5, is prepared
from bromamine acid and N-(4-amino-benzyl)
methylamine [160].

1-Amino-4-(2,4-diethyl-6-methylphenyl-
amino)anthraquinone-2-sulfonic acid
1,4-Bis-(2,6-dimethylanilino)anthra-
[20074-70-8], (19), M r 464.5, is prepared
quinone-x
,x

-disulfonic acid, (14), M r 606.7,
from bromamine acid and 2,4-diethyl-6-
is prepared from 1,4-dihydroxyanthraquinone
methylaniline [161].
and 2,6-dimethylaniline followed by sulfona-
tion [156].
1-Amino-4-(4
-acetylaminoanilino)anthra-
quinone-2-sulfonic acid, a blue acid dye, (20),
1,5-Bis-(p-toluidino)anthraquinone-2
,2

-
M r 451.1, is prepared from bromamine acid and
disulfonic acid [117-04-4], (15), M r 578.6, is
4-acetylaminoaniline [2, p. 135].
prepared by replacement of NO2 [157] or Cl
[158] followed by sulfonation [159].

1,8-Bis-(p-toluidino)anthraquinone-2
,2

-
disulfonic acid, (16), M r 578.6, is prepared by
replacement of NO2 [157] or Cl followed by
sulfonation [159].

1-Amino-4-cyclohexylaminoanthra-
quinone-2-sulfonic acid [5617-28-7], is a bril-
liant blue acid dye (e.g., Alizarin Brilliant Pure
Blue R), (21), M r 400.5; it is prepared from
bromamine acid and cyclohexylamine in the
presence of NaOH [3, p. 30].

1-Amino-4-anilinoanthraquinone-2-
sulfonic acid [2786-71-2], (17), M r 394.4, is
prepared from bromamine acid and aniline [3,
p. 41]. Compound 17 is a blue acid dye (e.g.,
Alizarine Saphirol A).
18 Anthraquinone Dyes and Intermediates
4-Bromo-1-isopropylaminoanthra-
quinone-5-sulfonic acid, (22), M r 424.3, is
prepared by bromination [397].
1-Amino-2-bromo-4-(4
-methylphenyl-
sulfonamido)anthraquinone [26868-32-6],
(23), M r 471.3, is prepared from 1-amino-2,4-
dibromoanthraquinone and p-toluenesulfon-
amide [162].
2.5.3. Diazotization of
Aminoanthraquinones
Aminoanthraquinones may be diazotized by the
usual methods in sulfuric acid. On an indus-
trial scale, the diazotization of an aminoanthra-
quinone is accomplished by the conversion of
1-amino-5-benzoylaminoanthraquinone into 1-
chloro-5-benzoylaminoanthraquinone by diazo-
tization followed by the Sandmeyer reaction.
Azo derivatives of anthraquinone, which
may be obtained by coupling diazotized ami-
noanthraquinones, are cited as colorants for
a variety of applications [163]. Among the
hydrazino derivatives only anthraquinone-1-
hydrazinosulfonic acid is worth mentioning be-
cause it is obtained as an intermediate in the syn-
thesis of pyrazoloanthrone (see Section 2.12.2).
2.6. Hydroxyanthraquinones, Alkoxy-
and Aryloxyanthraquinones
Hydroxyanthraquinones are prepared primar-
ily by synthesis of the nucleus, by exchange
reactions, and by ether cleavage of alkoxy-
(or aryloxy-) anthraquinones. The most impor-
tant example of nucleus synthesis is the indus-
trial production of 1,4-dihydroxyanthraquinone
(quinizarin). Examples for exchange reac-
tions are the conversion of anthraquinone-α,α
-
disulfonic acids into α,α
-dihydroxyanthra-
quinones and the direct hydrolysis of a halogen
in the 4 position in 1-amino-2,4-dihaloanthra-
quinone using boric–sulfuric acid. As the di-
rect replacement of the nitro group by a hy-
droxy group frequently leads to side reactions,
nitroanthraquinones are converted to hydroxy-
anthraquinones most readily via the correspond-
ing alkyl or aryl ethers. In some cases, under
rather special reaction conditions, direct replace-
ment of one or more nitro groups is also possi-
ble. Replacement of halogen by hydroxy groups
in otherwise unsubstituted haloanthraquinones
is best carried out via the corresponding anthra-
quinone ethers. In individual cases the hydroxy
groups also may be inserted at defined positions
by oxidation.
Amino groups in 1,4-diamino- (or ami-
nohydroxy-) anthraquinones are converted read-
ily into hydroxy groups by reduction in alka-
line medium via the 2,3-dihydro compounds
or in an acid medium by oxidation via the
quinoneimines.
Halogenation, nitration, and sulfonation of
hydroxyanthraquinones present no special dif-
ficulties. Modification of the hydroxy group
(boric acid esters, ethers) alters the mode of sub-
stitution. Derivatives of the hydroxy groups fre-
quently enable a different or more selective sub-
stitution than the free hydroxy compounds.
2.6.1. General Aspects
2.6.1.1. Synthesis of the Nucleus
The preparation of quinizarin from phthalic an-
hydride and p-chlorophenol in boric–sulfuric
acid has considerable industrial importance. The
boric acid removes the quinizarin formed by for-
mation of a stable boric acid ester which changes
the equilibrium and, thus, enables the complete
replacement of chlorine atoms by the hydroxy
group.
Other methods, such as condensation of
maleic anhydride with naphthohydroquinone
[164] and the reaction of phthalic anhydride
 Anthraquinone Dyes and Intermediates
with hydroquinone in molten aluminum chlo-
ride/sodium chloride, have not yet reached any
level of importance.
2.6.1.2. Replacement Reactions
H → OH. Hydroxy groups may be intro-
duced into anthraquinones in acid or alkaline
media. Suitable oxidizing agents are manganese
dioxide, potassium peroxodisulfate, potassium
chlorate, or sodium nitrite. Whereas the synthe-
sis of 1,2-dihydroxyanthraquinone (alizarine)
by oxidation of anthraquinone requires an al-
kaline medium, preparation of 1,2,4-trihydroxy-
anthraquinone (purpurin) from 1,2- or 1,4-di-
hydroxyanthraquinone is carried out in sulfuric
acid solution by oxidation with manganese diox-
ide. If 1,8-dihydroxyanthraquinone is oxidized
with oleum containing a high percentage of SO3
in the presence of boric acid, oxidation occurs
in the 4 position to form 1,4,5-trihydroxyanthra-
quinone.
SO3 H → OR (R = H, alkyl). Hydroxy and
alkoxy groups may be introduced by reactions
similar to those employed for amino group dis-
placement of sulfonic acid groups. For example,
anthraquinone-α-sulfonic acids are converted
by heating the anthraquinonesulfonic acid with
an aqueous suspension of calcium hydroxide
and magnesium chloride under pressure at 200 –
250 ◦ C, to form α-hydroxyanthraquinones, e.g.,
However, sulfonic acid groups in the β posi-
tion react only in an alkali melt at temperatures
of 150 – 200 ◦ C. If oxidizing agents are added,
the α position is also hydroxylated, e.g., synthe-
sis of alizarine from anthraquinone-2-sulfonic
acid:
Further, anthraquinonesulfonic acids may
be converted into alkoxyanthraquinones by al-
19
coholic alkali at 50 – 120 ◦ C. If higher tem-
peratures are used, hydroxyanthraquinones are
formed also. Anthraquinone aryl ethers are not
prepared readily by this method. Instead, they
are made from haloanthraquinones.
Halogen → OR (R = H, alkyl, aryl). Apart
from the synthesis of quinizarin, direct replace-
ment of halogen by hydroxy groups is of in-
dustrial importance only for replacing halogen
in 1-amino-4-haloanthraquinones, e.g., 24→ 25
in the presence of boric–sulfuric acid. In all
other cases, the haloanthraquinones are first con-
verted with alcoholate or phenolate into the cor-
responding alkoxy- or phenoxyanthraquinones.
This procedure is suitable for replacing halogens
in both the α and the β position. However, for
the preparation of β-alkoxyanthraquinones, it is
recommended to generate first the β-phenoxy
compound and then to subject this compound to
an ether exchange reaction, e.g., 25 → 26 → 27.
The corresponding hydroxy compounds are
then accessible by acid hydrolysis of the alkoxy
derivatives or by alkaline hydrolysis of the ni-
trated phenoxy derivatives.
NO2 → OR (R=H, alkyl, aryl). Similar to
halogen atoms, the nitro group may be replaced
by hydroxy groups and ether residues. However,
because direct replacement of hydroxy groups
causes side reactions, only the reactions with
alcoholate or phenolate, leading to the corre-
sponding anthraquinone ethers, are of industrial
importance. Alkoxyanthraquinones can then be
converted to the hydroxyanthraquinones by acid
cleavage.
These methods are important, especially
for the preparation of 1,5- and 1,8-dialkoxy-,
diphenoxy-, and dihydroxyanthraquinones, be-
cause industrial synthesis of anthraquinone in-
termediates is shifting more and more to the
20 Anthraquinone Dyes and Intermediates

use of nitroanthraquinones. In several cases, it in aqueous alkaline sodium dithionite solutions,

is recommended that a sequence of reactions thereby alkylating the β position. Reaction of
be done on the dialkoxyanthraquinones and the benzaldehyde with quinizarin, after conversion
ether scission be performed at a later stage. into the leuco form, yields 2-benzyl-1,4-di-
In the case of 1,5-dihydroxy-4,8-dinitroanthra- hydroxyanthraquinone [166], [167]:
quinone, the replacement of one nitro group with
boric–sulfuric acid presents no special difficul-
ties, whereas the same method fails in the iso-
meric 1,8 compound.

NHR → OR (R=H, alkyl, aryl). The con-

version of aminoanthraquinones to hydroxy-
anthraquinones is of little importance. Usual
methods may be used to convert the amino group
to the hydroxy group by means of diazotization
and boiling of the reaction mixture.
The oxidative and the reductive degradation
of 1,4-diamino- (or 1-amino-4-hydroxy)anthra-
quinones to the corresponding 1,4-dihydroxy-
anthraquinones is used to elucidate the struc-
ture of certain anthraquinone dyes. The re-
ductive alkaline degradation, e.g., by treatment
with warm sodium dithionite–sodium hydrox-
ide, is used industrially for the manufacture of
leuco-1,4,5,8-tetrahydroxyanthraquinone from
4,8-diamino-1,5-dihydroxyanthraquinone-2,6-
disulfonic acid:
Furthermore, hydroxyanthraquinones are ca-
pable of undergoing the Mannich reaction.
Quinizarin, formaldehyde, and piperidine react,
for instance, under formation of 1,4-dihydroxy-
2-(piperidinomethyl)anthraquinone [168]:
When the hydrogen atoms in the β posi-
tion are activated sufficiently, direct arylation
of 1,4-substituted anthraquinones is also possi-
ble. This reaction is important in preparing ary-
lated diaminodihydroxyanthraquinones, which
can be accomplished by three methods: Addi-
tion to anthraquinonediquinone, aminohydroxy-
anthraquinone sulfonic acids, or hydroxynitro-
anthraquinones.
Generally applicable is the arylation of
diquinones and diquinoneimines of 1,4,5,8-ami-
nohydroxyanthraquinones:

2.6.1.3. Conversions of the Hydroxy Group

OH → Alkoxy, Alkoxy → OH. The O-

alkylation of hydroxyanthraquinone may be
carried out in the presence of acid-neutralizing
agents using dimethyl sulfate or esters of p-
toluenesulfonic acid. In the reverse reaction,
anthraquinone alkyl ethers may be hydrolyzed
with mineral acids to give hydroxyanthra-
quinones [165]. Special methods are available for prepar-
ing arylated 4,8-diamino-1,5-dihydroxyanthra-
quinones, e.g., 28, where the starting mate-
2.6.1.4. Substitutions on the rials 4,8-diamino-1,5-dihydroxyanthraquinone-
Hydroxyanthraquinone Nucleus 2,6-disulfonic acid (29) or 4,8-dinitro-1,5-di-
hydroxyanthraquinone (30) determine the posi-
Nucleus H → Alkyl, Aryl. α- tion of the substituent [169]. Both reactions are
Hydroxyanthraquinones react with aldehydes carried out at low temperature in boric–sulfuric
 Anthraquinone Dyes and Intermediates
acid. This requires that in the following step the
sulfonic acid groups be cleaved [170] or the re-
maining nitro groups be reduced [171]:
Nucleus H → SO3 H. Hydroxyanthra-
quinones are sulfonated in oleum. When the 1,4-
dihydroxyanthraquinone is used as the starting
material, addition of boric acid blocks sulfona-
tion of the 2 position, and instead the sulfonic
acid group enters the 5 or 6 position [3], [172].
In 1,5- (or 1,8-) dihydroxyanthraquinones, addi-
tion of sodium sulfate to the oleum may prevent
an excessive sulfonation and the oxidation to
higher hydroxylated products.
Nucleus H → Halogen. In general the
choice of the halogenating agent has no influ-
ence on the substitution. Bromination is often
preferred because of the greater ease in replacing
bromine.
As hydroxy and amino groups generally en-
hance the reactivity towards halogenation, boric
acid esters and boric ester amides of the 1,4-
dihydroxy- (or hydroxyamino-) anthraquinones
have a special function because they prevent sub-
stitution in the 2 and 3 positions. For example,
quinizarin is halogenated in the 2 position in
nitrobenzene and in the 5,8 positions in boric–
sulfuric acid. The amino group has an additional
effect on halogenation of aminohydroxyanthra-
quinones because halogenation is directed by ei-
ther the hydroxy or the amino group, depend-
ing on the acidity of the medium. 1-Amino-
4-hydroxyanthraquinone is halogenated at the
2 position in organic solvents or hydrochloric
acid, in the 3 position in oleum or chlorosul-
21
fonic acid [173], and in the 5,8 positions in boric
acid – oleum [174].
1-Alkylamino-5-hydroxyanthraquinones are
halogenated preferentially in the 8 position in
oleum [175] and only in the 4 position in hy-
drochloric acid [176].
A uniform monohalogenation product is
not obtained from α-diaminodihydroxyanthra-
quinone. Choice of reaction conditions makes it
possible to influence the isomer ratio (halogen
next to amino or next to hydroxy groups).
1,5-Dihydroxy-4,8-dinitroanthraquinone is
halogenated cleanly in the 2,6 positions in aque-
ous alkali [177]. In boric–sulfuric acid and in
the presence of a 1,3-alkanediol, one of the nitro
groups is replaced by a halogen [178].
Nucleus H → NO2 . The rules for the course
of the nitration of hydroxyanthraquinones are
similar to those for the halogenation. Quinizarin
in sulfuric acid or organic solvents is nitrated
in the 2 position, whereas in boric acid–oleum
one gets only nitration in the 5 position. A dif-
ferent behavior is shown by the boric or ar-
sonic acid esters of 1,2-dihydroxyanthraquinone
(alizarine). Here nitration in sulfuric acid yields
the 3- and 4-nitro derivatives. 1,8-Dihydroxy-
anthraquinone in sulfuric acid is dinitrated up to
80 % in the 4 and 5 positions, whereas the iso-
meric 1,5-dihydroxy compound affords only un-
satisfactory yields of 1,5-dihydroxy-4,8-dinitro-
anthraquinone.
The α-nitration is more successful with
dimethoxyanthraquinones and yet more suc-
cessful with diphenoxyanthraquinones. In the
last case the benzene rings are also nitrated in
their 2 and 4 positions, which then facilitates
ether hydrolysis in alkaline medium:
22 Anthraquinone Dyes and Intermediates
Halogen → SO3 H. The remaining chlo-
rine atom in 1,4-diamino-3-chloro-2-phen-
oxyanthraquinone (obtained from 1,4-diamino-
2,3-dichloroanthraquinone by phenolate melt) is
replaced readily in alkali sulfite to yield the sul-
fonic acid.
Halogen → NHR. Halohydroxyanthra-
quinones can be converted into the correspond-
ing aminohydroxyanthraquinones by the meth-
ods cited under aminoanthraquinones (see page
8).
NO2 → NHR (R = H, alkyl, aryl). The re-
duction of hydroxynitroanthraquinones is possi-
ble using the usual methods. A special industrial
process is a reduction with elemental sulfur in
oleum.
The nitro group of 1-hydroxy-4-nitroanthra-
quinone is replaced easily by amino residues. In
α-dihydroxydinitroanthraquinones, a stepwise
substitution presents no special difficulties. In
1,8-dihydroxy-4,5-dinitroanthraquinone, the re-
action with aromatic amines in the presence
of boric acid takes a different course. The
product is 5,8-diarylamino-1-hydroxy-4-nitro-
anthraquinone [179].
A special reaction constitutes the conversion
of α-nitroanthraquinones into the corresponding
1-amino-4-hydroxyanthraquinones mediated by
the action of sulfur or other reducing agents, e.g.,
FeSO4 , in oleum or sulfuric acid monohydrate,
if necessary with addition of boric acid. This
reaction is accompanied by a number of side re-
actions. Satisfactory yields and purity levels are
achieved only in exceptional cases [180], [181];
see also [13, pp. 199 – 203].
2.6.2. Individual Hydroxyanthraquinones
1,2-Dihydroxyanthraquinone [8005-35-4],
alizarine, (32), M r 240.2, mp 289 – 290 ◦ C, is
prepared from anthraquinone by alkali melt
[182] or from anthraquinone-2-sulfonic acid
with 50 % aqueous sodium hydroxide and
sodium nitrate at 190 – 200 ◦ C [3, p. 39], [5,
p. 44].
1,4-Dihydroxyanthraquinone [81-64-1],
quinizarin, (33), M r 240.2, mp 198 ◦ C, is
prepared from phthalic anhydride and p-
chlorophenol by heating in oleum in the pres-
ence of boric acid [1], [12]. Improved methods
are cited in [183], [184].
1,5-Dihydroxyanthraquinone [117-12-4],
anthrarufin, (34), M r 240.2, mp 280 ◦ C, is pre-
pared from 1,5-anthraquinonedisulfonic acid by
replacing the SO3 H groups [3, p. 16], [12] and
from 1,5-dinitroanthraquinone by directly re-
placing the nitro groups, e.g., in sulfolane with
calcium oxide [185] or, more effectively, via 1,5-
dimethoxyanthraquinone and subsequent hy-
drolysis of the ether linkage [186].
1,8-Dihydroxyanthraquinone [117-10-2],
chrysazin, (35), M r 240.2, mp 193 ◦ C, is pre-
pared by replacing SO3 H [5, p. 46], by di-
rectly replacing nitro groups in sulfolane in
the presence of calcium oxide [185], or, bet-
ter, via 1,8-dimethoxyanthraquinone and subse-
quent hydrolysis of the ether [186].
 Anthraquinone Dyes and Intermediates
1,2,4-Trihydroxyanthraquinone [81-54-9],
purpurin, (36), M r 256.2, mp 257 – 259 ◦ C, is
prepared from alizarine [5, p. 57], [187] or from
quinizarin by oxidation [188].
1,4,5-Trihydroxyanthraquinone [2961-
04-8], M r 256.2, mp 270 – 271 ◦ C, is prepared
from 1,8-dihydroxyanthraquinone with 80 %
oleum and boric acid [189].
1,4,5,8-Tetrahydroxyanthraquinone [81-
60-7], M r 272.2, mp above 300 ◦ C, is pre-
pared from 4,8-diamino-1,5-dihydroxyanthra-
quinone-2,6-disulfonic acid by treatment with a
mixture of sodium dithionite–sodium hydroxide
in aqueous medium [12].
1,5-Dimethoxyanthraquinone [6448-90-4],
(37), M r 268.3, mp 236 ◦ C, is prepared
from anthraquinone-1,5-disulfonic acid with
methanolic alkali-metal hydroxide [190] or
from 1,5-dinitroanthraquinone with methanolic
alkali-metal hydroxide in the presence of ami-
dosulfonic acid [191] or by passing air through
the reaction mixture [192], [193].
1,5-Diphenoxyanthraquinone [82-21-3],
(38), M r 392.4, mp 215 ◦ C, is prepared from
1,5-dichloroanthraquinone and sodium pheno-
late without solvent [4, p. 8] or with an inert sol-
vent [194] or from 1,5-dinitroanthraquinone by
reaction with alkali phenolate in phenol [195] or
an inert solvent [196], [197].
1,8-Dimethoxyanthraquinone [6407-55-2],
M r 268.3, mp 212 ◦ C, is prepared from anthra-
quinone-1,8-disulfonic acid with methanolic
alkali-metal hydroxide [190], from 1,8-dinitro-
anthraquinone with methanolic alkali-metal hy-
droxide in the presence of amidosulfonic acid
[191], by passing air through the reaction mix-
ture [192], [193].
1,8-Diphenoxyanthraquinone [82-17-7],
M r 392, mp 189 – 190 ◦ C, is prepared from
23
1,8-dichloroanthraquinone [198] or 1,8-dinitro-
anthraquinone [195], [197] by reaction with al-
kali phenolate.
5,8-Dichloro-1,4-dihydroxyanthra-
quinone [2832-30-6], (39), M r 309.1,
mp 266 ◦ C, is prepared from 3,6-
dichlorophthalic anhydride by synthesis of the
nucleus [199] or from quinizarin by chlorination
[174].
2-Bromo-1,4-dihydroxyanthraquinone
[81-52-7], (40), M r 319.1, sublimation at
300 ◦ C, is prepared from quinizarin by bromi-
nation in nitrobenzene [3, p. 66].
1-Hydroxy-4-nitroanthraquinone [81-65-
2], (41), M r 269.2, mp 268 ◦ C, is prepared from
1-hydroxyanthraquinone in sulfuric acid mono-
hydrate with nitric–sulfuric acid [200].
1,4-Dihydroxy-5-nitroanthraquinone
[27573-16-6] M r 285.2, mp 244 – 245 ◦ C, is pre-
pared from 1-hydroxy-10-chloroanthraquinone-
(4,9) [201].
1,5-Dihydroxy-4,8-dinitroanthraquinone
[128-91-6], M r 330.2, is prepared from 1,5-di-
phenoxyanthraquinone by nitration followed by
alkaline hydrolysis [4, p. 8].
1,8-Dihydroxy-4,5-dinitroanthraquinone
[81-55-0], M r 330.2, is prepared from 1,8-di-
phenoxyanthraquinone by nitration followed by
alkaline hydrolysis or, alternatively, by nitration
of 1,8-dihydroxyanthraquinone in oleum in the
presence of boric acid and isolation after the
sulfuric acid concentration has been adjusted to
80 – 100 % [202] or, using the same procedure,
24 Anthraquinone Dyes and Intermediates
from 1,8-dimethoxyanthraquinone followed by
ether cleavage.
1-Amino-4-hydroxyanthraquinone [116-
85-8], (42), M r 239.2, mp 208 ◦ C, is pre-
pared from 1-amino-4-hydroxyanthraquinone-
3-sulfonic acid by splitting off the SO3 H group
[203], from 1-benzoylamino-4-chloroanthra-
quinone by treatment with boric–sulfuric acid,
or from 1-nitroanthraquinone by reduction with
FeCl2 in sulfuric acid and rearrangement of
the hydroxylamine stage [180], from 1,4-diami-
noanthraquinone with MnO2 in sulfuric acid
[204], or from 1-hydroxyanthraquinone by ni-
tration followed by reduction with Na2 S [5,
p. 200].
3-Amino-1,2-dihydroxyanthraquinone
[3963-78-8], M r 255.2, mp above 300 ◦ C, is
prepared from the 3-nitro compound by reduc-
tion with Na2 S [3, p. 3].
4-Amino-1,3-dihydroxyanthraquinone
[81-51-6], M r 255.2, is prepared from 1,2,4-
trihydroxyanthraquinone (purpurin) and NH3
[13, p. 163].
5-Amino-1,4-dihydroxyanthraquinone
[23215-11-4], M r 255.2, is prepared from the
5-nitro compound by reduction with SO2 [205].
3-Amino-2-hydroxyanthraquinone [117-
77-1], (43), M r 239.2, is prepared from 5-
benzoylbenzoxazolone-2
-carboxylic acid [2,
p. 14].
4,8-Diamino-1,5-dihydroxyanthra-
quinone [145-49-3], M r 270.2, is prepared from
1,5-dihydroxy-4,8-dinitroanthraquinone by re-
duction with sodium sulfide; from 1,5-diphen-
oxyanthraquinone by nitration, cleavage, and
reduction [4, p. 8]; a process improvement is
described in [206]; or from 4,8-diamino-1,5-
dihydroxyanthraquinone-2,6-disulfonic acid by
desulfonation [207].
4,5-Diamino-1,8-dihydroxyanthra-
quinone [128-94-9], M r 270.2, is prepared from
1,8-dihydroxy-4,5-dinitroanthraquinone by re-
duction [208] or by cleavage of the sulfonic acid
groups from the corresponding 2,7-disulfonic
acid [207].
1-Hydroxy-5-isopropylaminoanthra-
quinone [33902-49-7], (44), M r 281.3, is pre-
pared from 1-isopropylaminoanthraquinone-5-
sulfonic acid by replacement of SO3 H [175],
[176].
1-Hydroxy-4-(p-methylphenylami-
no)anthraquinone [81-48-1], (45), M r 329.4,
is prepared from the leuco form of quinizarin
and p-toluidine [209], [3, p. 48] or from 4-halo-
1-hydroxyanthraquinone and p-toluidine.
1-Hydroxy-5,8-bis-(p-methylphenylami-
no)anthraquinone [4392-68-1], M r 434.5, is
prepared from 1,4,5-trihydroxyanthraquinone
and p-toluidine [3, p. 33] by replacing hydroxyl
or from 5,8-dichloro-1-hydroxyanthraquinone
[210] by chlorine replacement.
1,4-Dihydroxy-5,8-bis(phenylami-
no)anthraquinone, (46), M r 422.4, is prepared
from 5,8-dichloro-1,4-dihydroxyanthraquinone
and aniline [211] or from leuco-tetrahydroxy-
anthraquinone and aniline in water [212] or in
pure aniline [213] with the addition of boric
acid.
 Anthraquinone Dyes and Intermediates
1-Methoxy-4-(p-methylphenylami-
no)anthraquinone, (47), M r 343.4, is prepared
by methylation of 1-hydroxy-4-(p-methyl-
phenylamino)anthraquinone.
1,5-Dibenzoylamino-4-hydroxyanthra-
quinone [6370-96-3], M r 462.4, is prepared by
oxidation of 1,5-dibenzoylaminoanthraquinone
with MnO2 [214].
8-Benzoylamino-1,5-dihydroxy-4-(p-
methoxybenzoylamino)anthraquinone, (48),
M r 508.4, is prepared by mixed acylation of
4,8-diamino-1,5-dihydroxyanthraquinone with
p-methoxybenzoyl chloride and benzoyl chlo-
ride [4, p. 8].
1-Amino-4-hydroxy-2-hydroxyethoxy-
anthraquinone [17869-07-7], (49), M r 299.3,
is prepared from 1-amino-4-hydroxy-2-phen-
oxyanthraquinone by replacement of the phen-
oxy group [215], from the 2-chloro compound
by replacement of chlorine [216], or from the
1,4-dihydroxy derivative with ammonia [217].
1,4-Diamino-2,3-diphenoxyanthra-
quinone [6408-72-6], (50), M r 422.4, is pre-
pared from the 2,3-dichloro compound and phe-
nol by chlorine replacement [3, p. 49].
1-Amino-4-hydroxy-2-phenoxyanthra-
quinone [17418-58-5], (51), M r 331.3, is pre-
pared from 1-amino-2-chloro- (or -2-bromo-)
25
4-hydroxyanthraquinone and phenolate. This
process was improved [218].
4,8-Diamino-1,5-dihydroxy-3-(p-methox-
yphenyl)anthraquinone, (52), (for the eluci-
dation of the structure see [169]), M r 377.3,
is prepared from 4,8-diamino-1,5-dihydroxy-
anthraquinone-2,6-disulfonic acid by addi-
tion of anisole [219] and subsequent SO3 H
removal [170] or from 4,8-diamino-1,5-di-
hydroxyanthraquinone via the iminoquinone
and reaction with anisole [220].
4,8-Diamino-1,5-dihydroxy-2-(p-methox-
yphenyl)anthraquinone [4702-64-1], (for the
elucidation of the structure see [169]), M r 377.3,
is prepared from 1,5-dihydroxy-4,8-dinitro-
anthraquinone and anisole in boric–sulfuric acid
followed by reduction [171].
1-Amino-5,8-dichloro-4-hydroxyanthra-
quinone [2832-17-9], (53), M r 308.1, is pre-
pared from 1-amino-4-hydroxyanthraquinone
by chlorination in oleum–boric acid [180]
or from 1-amino-4,5,8-trichloroanthraquinone
with boric–sulfuric acid [221].
1-Amino-3-bromo-4-hydroxyanthra-
quinone, (54), M r 318.1, is prepared from 1-
amino-4-hydroxyanthraquinone and bromine in
chlorosulfonic acid [173].
1-Amino-2-bromo-4-hydroxyanthra-
quinone [116-82-5], M r 318.1, is prepared
from 1-amino-2,4-dibromoanthraquinone with
boric–sulfuric acid [3, p. 5] or in a one-pot
process from 1-aminoanthraquinone (bromi-
nation – hydrolysis) [222–224].
26 Anthraquinone Dyes and Intermediates
8-Bromo-1-hydroxy-5-isopropylamino-
anthraquinone, (55), M r 360.2, is prepared by
bromination [175].
1,8-Dihydroxy-5-nitro-4-phenylami-
noanthraquinone, (56), M r 376.3, is prepared
from 1,8-dihydroxy-4,5-dinitroanthraquinone
and aniline [225].
1,2-Dihydroxyanthraquinone-3-sulfonic
acid [83-61-4], (57), M r 320.3, is prepared from
1,2-dihydroxyanthraquinone with fuming sul-
furic acid [226].
1,4-Dihydroxyanthraquinone-2-sulfonic
acid [145-48-2], M r 320.3, is prepared from
1,4-dihydroxyanthraquinone with sodium hy-
drogen sulfite and oxidizing agents [3, p. 65] or
by sulfonation in oleum [227].
1,5-Dihydroxyanthraquinone-2,6-
disulfonic acid [6492-85-9], M r 400.3, is pre-
pared from 1,5-dihydroxyanthraquinone with
oleum–Na2 SO4 [228].
1,8-Dihydroxyanthraquinone-2,7-
disulfonic acid, M r 400.3, is prepared by heat-
ing 1,8-dihydroxyanthraquinone in oleum [229].
1,5-Dihydroxy-4,8-dinitroanthraquinone-
2,6-disulfonic acid [6449-09-8], (58),
M r 490.3, is prepared from 1,5-dihydroxy-
anthraquinone-2,6-disulfonic acid by nitration
in sulfuric acid [228].
1,8-Dihydroxy-4,5-dinitroanthraquinone-
2,7-disulfonic acid [128-90-5], (59), M r 490.3,
is prepared from 1,8-dihydroxyanthraquinone-
2,7-disulfonic acid by nitration [229].
4,8-Diamino-1,5-dihydroxyanthra-
quinone-2-sulfonic acid [5138-23-8], (60),
M r 350.3, is prepared by removal of one SO3 H
group from the 2,6-disulfonic acid [207], [230].
4,8-Diamino-1,5-dihydroxyanthra-
quinone-2,6-disulfonic acid [128-86-9], (61),
M r 430.3, (the sodium salt is the dye Acilan
Sapphirol B), is prepared from 1,5-dihydroxy-
anthraquinone by sulfonation, nitration, and
reduction [1, p. 607].
4,5-Diamino-1,8-dihydroxyanthra-
quinone- 2,7-disulfonic acid, M r 430.3, is pre-
pared from 1,8-dihydroxyanthraquinone by sul-
fonation, nitration, and reduction [229].
2.7. Mercaptoanthraquinones
Mercaptoanthraquinones are of little commer-
cial importance. However, they appear as uniso-
lated intermediates. They are obtained by re-
placement of halogen [231] or sulfonic acid
groups with alkali sulfides, by addition of alkali
sulfides to 1-aminoanthraquinones [232], or by
cleavage of thiocyanatoanthraquinones [233].
More important are the anthraquinone
thioethers, which are obtained by usual meth-
ods as replacement of halogen, nitro, or
sulfonic acid groups; by modification of
mercaptoanthraquinones; or by addition reac-
tions to hydroxy- and aminoanthraquinones or
to quinoneimine derivatives [234]. 1-Hydroxy-
4-nitroanthraquinones react especially well un-
der simultaneous reduction of the nitro group
[235].
 Anthraquinone Dyes and Intermediates
2.7.1. General Aspects
SO3 H → SR (R = alkyl, aryl). The ex-
change of sulfonic acid groups against mercapto
groups is especially suitable for the preparation
of alkylmercaptoanthraquinones. The prepara-
tive reactions are carried out in aqueous alkaline
medium at temperatures up to 100 ◦ C.
Halogen → SR (R = H, alkyl, aryl). Halo-
gen displacement is used to prepare mercapto-,
alkylmercapto-, and arylmercaptoanthra-
quinones. Suitable reaction media are organic
solvents: halogenated aromatic hydrocarbons
and especially amides in the presence of acid
binding agents, such as alkali – metal carbonates
and tertiary amines.
NO2 → SR. Displacement of nitro groups
occurs under conditions similar to those for the
replacement of halogens, insofar as addition re-
actions do not predominate [236].
H → SR. The addition of mercaptans to ami-
no- or hydroxyanthraquinones or to 1-hydroxy-
4-nitroanthraquinones [235] that occurs via re-
ductive steps has no industrial importance.
SH → SR. Mercaptoanthraquinones may be
converted to alkylmercaptoanthraquinones with
the usual alkylating agents under alkaline con-
ditions [237].
2.7.2. Individual Mercapto Compounds and
Thioethers
1,4-Diamino-2-mercaptoanthraquinone,
(62), M r 270.3, is prepared from 1,4-diamino-
2-bromoanthraquinone and sodium disulfide
followed by reduction [238].
1-Amino-2-(2-hydroxyethylmercapto)-4-
phenylaminoanthraquinone, (63), M r 390.4,
is prepared by displacement of SO3 H from the
corresponding anthraquinone-2-sulfonic acid
[239].
27
1,4-Dihydroxy-2-phenylmercaptoanthra-
quinone, (64), M r 348.4, is prepared from 1,4-
dihydroxyanthraquinone and thiophenol [240].
1,8-Dihydroxy-4-nitro-5-phenylmercapto-
anthraquinone, (65), M r 393.4, is prepared
from 1,8-dihydroxy-4,5-dinitroanthraquinone
and thiophenol [236].
1-Amino-4-hydroxy-2-phenylmercapto-
anthraquinone, (66), M r 347.4, is prepared
by displacement of bromine from 1-amino-2-
bromo-4-hydroxyanthraquinone and thiophenol
[241].
1-Amino-2-mercaptoanthraquinone-6-
sulfonic acid, (67), M r 335.4, is prepared from
1-nitroanthraquinone-6-sulfonic acid with aque-
ous sodium sulfide [242].
1,4-Dihydroxy-2-(2-hydroxyethyl-
mercapto)anthraquinone [3319-54-8], (68),
M r 316.3, is prepared from 2-nitro-, 2-halo-,
or 2-sulfo-1,4-dihydroxyanthraquinone with 2-
mercaptoethanol [243].
2.8. Anthraquinonesulfones
Alkyl and aryl sulfone derivatives of anthra-
quinone have reached a certain amount of im-
portance only as polyester dyes resistant to subli-
mation and as dyes for mixed polyester – cotton
28 Anthraquinone Dyes and Intermediates
fabrics. They are obtained by displacement of
the halo [244] or nitro group with sulfinates, by
sulfinic acid addition to quinoneimines [245],
or by oxidation of the corresponding thioethers
with chromium(VI) oxide or hydrogen peroxide
in such solvents as glacial acetic acid or sulfuric
acid [246].
1-Amino-2-phenylsulfonyl-4-p-tosyl-
aminoanthraquinone (69 with R1 = –
2
SO2 C6 H4 CH3 , R = –C6 H5 ), M r 456.6, is pre-
pared from the 2-bromo compound by halogen
displacement with benzene sulfinate [244].
1-Amino-2-ethylsulfonyl-4-(p-isopropyl-
phenylamino)anthraquinone [4839-56-9],
(69 with R1 = –C6 H4 CH(CH3 )2 , R2 = –C2 H5 ),
M r 448.5, is prepared from the 2-bromo com-
pound by halogen displacement with ethyl sul-
finate [237].
4,8-Diamino-1,5-dihydroxy-2- (and -3-
) phenylsulfonylanthraquinone (70 with
R = C6 H5 ), M r 410.4, is prepared from 4,8-
diamino-1,5-dihydroxyanthraquinone via the
quinoneimine [245].
2.9. Anthraquinone Aldehydes and
Their Derivatives
Only anthraquinone-2-aldehydes and their
derivatives have industrial importance. Start-
ing materials are mainly methylanthraquinones,
which are converted by direct oxidation with
manganese dioxide or chromic acid [248] or
via the dihalomethyl compounds [249] into the
aldehydes. In industrial processes, 1-amino-2-
methylanthraquinone is oxidized with nitroben-
zene in the presence of aniline. The azomethine
formed in this step can be hydrolyzed easily to
the aldehyde but usually is used directly in fur-
ther reactions.
1-Aminoanthraquinone-2-aldehyde also may
be prepared from 2-methyl-1-nitroanthra-
quinone by reaction with 65 % oleum followed
by reduction of the resulting isoxazole [250].
1-Aminoanthraquinone-2-aldehyde,
M r 251.2, is prepared by oxidation of 1-ami-
no-2-methylanthraquinone with nitrobenzene in
the presence of aniline and potassium carbonate,
followed by hydrolysis of the 1-aminoanthra-
quinone-2-aldehyde anil in sulfuric acid [251],
or by action of 65 % oleum on 2-methyl-1-nitro-
anthraquinone followed by reduction [250].
1-Amino-4-benzoylaminoanthraquinone-
2-aldehyde anil, (71), M r 445.5, is pre-
pared from 1-amino-4-benzoylamino-2-
methylanthraquinone by oxidation in nitroben-
zene in the presence of aniline and potassium
carbonate [252].
The azine of 1-amino-4-benzoylamino-
anthraquinone-2-aldehyde, (72), M r 736.6, is
prepared from the aldehyde anil in glacial acetic
acid with hydrazine hydrate [252].
 Anthraquinone Dyes and Intermediates 29

dioxide. From 1,4-diaminoanthraquinone-2,3-

disulfonic acids are also formed the correspond-
ing 2,3-dicyano compounds.
A related reaction is the forma-
tion of 1,4-diaminoanthraquinone-2,3-N-
alkyliminodicarboxylic imides (73) from 1-ami-
no-4-nitroanthraquinone-2-carboxylic amides
on reaction with cyanides followed by reduc-
tion [253].

2.10. Anthraquinonecarboxylic Acids

and Carboxylic Acid Derivatives

Whereas carboxylic acid and carbonyl chloride

groups linked directly to the anthraquinone nu-
cleus rarely appear outside the realm of dyestuff
Halogen → CN. A general method for
intermediates, the carboxylic esters, amides,
preparing cyanoanthraquinones is the dis-
imides, azoles, and nitriles exist in dyestuffs.
placement of halogen with CuCN in an or-
Anthraquinonecarboxylic acids may be ob-
ganic solvent, such as benzyl cyanide, di-
tained by ring closure of the correspond-
methylformamide, or quinoline.
ing o-benzoylbenzoic acids, by oxidation of
methylanthraquinones, or by hydrolysis of ni- CN → CONH2 → COOH. Cyanoanthra-
triles. The derivatives are prepared from the car- quinones are hydrolyzed by the action of min-
boxylic acids or nitriles by the usual methods. eral acids or alkalies to yield the corresponding
The nitrile group may be introduced by displac- carboxamides or the free carboxylic acids, de-
ing the halogen or sulfonic acid group, or by pending on the conditions.
addition. Iminoimides (74), imides (75) [254], an-
hydrides, or free dicarboxylic acids are
formed from 2,3-dicyanoanthraquinones. Reac-
2.10.1. General Aspects tion with alcoholic alkali forms the correspond-
ing methoxyimino imides (74, R=CH3 ) [255].
Synthesis of Nucleus. Benzophenone dicar-
boxylic acids may be cyclized in weak oleum
at 110 – 120 ◦ C. This is the method used to
prepare anthraquinone-2-carboxylic acid and 3-
chloroanthraquinone-2-carboxylic acid.

CH3 → COOH. 2-Methylanthraquinone

can be converted into anthraquinone-2-
carboxylic acid by an oxidizing agent, such as
chromic acid, in dilute sulfuric acid. Oxidation
of the isoxazole obtained from 2-methyl-1-nitro-
anthraquinone yields the 1-nitroanthraquinone-
2-carboxylic acid.
These hydrolysis products may be reacted
SO3 H → CN. 1,4-Diaminoanthraquinone- further with amines.
2-sulfonic acid is converted to 1,4-diamino-2,3-
dicyanoanthraquinone by reaction with alkali COOH → COCl → COOR or CONR2 .
cyanides in aqueous alkaline medium and in Anthraquinonecarboxylic acids may be con-
the presence of an oxidant, such as manganese verted by the usual methods (reaction with
thionyl chloride or phosphorus halides) to their
30 Anthraquinone Dyes and Intermediates

acid chlorides and further to carboxylic esters

and amides. Depending on their substituents,
the carboxylic arylamides and hydrazides may
be converted to azoles. For example, anthra-
quinonedicarboxylic acid dihydrazides are con-
verted into the corresponding oxazoles.

H → NO2 or Halogen. 1-Aminoanthra- 1,4-Diamino-2,3-dicyanoanthraquinone

quinone-2-carboxylic acid may be nitrated or
halogenated in the 4 position in sulfuric acid
[256]. However, under these conditions, anthra-
quinone-2-carboxylic acid is nitrated or dichlo-
rinated in the 5,8 positions.
Cl → NHR, NO2 → SO3 H, NHR. Car-
boxyl groups and their derivatives facilitate the
replacement of nitro groups or halogen atoms
by a variety of substituents.
SO3 H → Cl. The sulfonic acid group of 2-
carboxyanthraquinone-1-sulfonic acid, which
is obtained from 1-nitroanthraquinone-2-
carboxylic acid, is replaced easily by halogen.
[81-41-4], (77), M r 288.2, is prepared from 1,4-
diaminoanthraquinone-2-sulfonic acid [259],
[260] or from 1,4-diaminoanthraquinone-2,3-
disulfonic acid in aqueous alkaline solution
[261] or in amides [262] by reaction with sodium
cyanide.
1-Amino-2-cyano-4-cyclohexylamino-
anthraquinone, (78), M r 345.4, is prepared by
displacement of SO3 H with potassium cyanide
in aqueous solution [3, p. 56].

2.10.2. Individual Anthraquinonecarboxylic

Acids
Anthraquinone-2-carboxylic acid [117-
78-2], M r 252.5, is prepared from 4
-methyl-
benzophenone-2-carboxylic acid by oxidation
with potassium permanganate and ring closure
with 5 % oleum [3, pp. 8, 12].
1-Chloroanthraquinone-2-carboxylic acid
[82-23-5], M r 286.7, is prepared by Fischer re-
action from 2-carboxyanthraquinone-1-sulfonic
acid [257].
3-Chloroanthraquinone-2-carboxylic acid
[84-32-2], M r 286.7, is prepared from 3
-chloro-
4
-methylbenzophenone-2-carboxylic acid by
oxidation with potassium permanganate in alka-
line solution, followed by ring closure in oleum
[4, p. 19].
1-Aminoanthraquinone-2-carboxylic acid
[82-24-6], (79), M r 267.2, is prepared from 1-
nitroanthraquinone-2-carboxylic acid with am-
monia [2, p. 17] or from 2-methyl-1-nitroanthra-
quinone [263].
3-Aminoanthraquinone-2-carboxylic acid
[4831-47-4], M r 267.2, is prepared from 3-
chloroanthraquinone-2-carboxylic acid with
ammonia [4, p. 19].
1-Amino-4-cyclohexylaminoanthra-
quinone-2carboxamide [3443-93-4], (80),
M r 363.4, is prepared by partial hydrolysis of
the nitrile [3, p. 57].

1-Nitroanthraquinone-2-carboxylic acid
[128-67-6], (76), M r 297.2, is prepared from
2-methyl-1-nitroanthraquinone by oxidation in
sulfuric acid with sodium dichromate [2, p. 13],
[5, p. 69] or in nitric acid with chromic acid Ethyl-1,4-diaminoanthraquinone-2-car-
[258]. boxylate, (81), M r 310.3, is prepared from 1-
 Anthraquinone Dyes and Intermediates 31

amino-4-nitroanthraquinone-2-carbonyl chlo-
ride and ethanol followed by reduction [264].

1-Amino-4-nitroanthraquinone-2-
carboxylic acid [2058-02-8], (82), M r 312.2, is
prepared by nitration of 1-aminoanthraquinone-
2-carboxylic acid in sulfuric acid–formaldehyde
[2, p. 17].

1,4-Diaminoanthraquinone-2,3-di-
carbonyl imide [128-81-4], (83), M r 307.3,
is prepared from the corresponding dinitrile
[254] or from 1,4-diaminoanthraquinone-2-
carboxamide and NaCN in dimethylformamide
with aeration [265].

2.11.1. Anthraquinone Derivatives

2-Carboxyanthraquinone-1-sulfonic acid,
(84), M r 332.3, is prepared from 1-nitroanthra-
quinone-2-carboxylic acid with Na2 SO3 in
aqueous solution [257].
Containing Imidazole, Oxazole, and
Thiazole Rings
Anthraquinone dyes with condensed imidazole,
oxazole, or thiazole rings are prepared by dehy-
drating ring closure from 2-aroylaminoanthra-
quinones that carry an amino, hydroxy, or mer-
capto group in positions 1 or 3.

2.11. Anthraquinone Derivatives with

Condensed Rings

Anthraquinone derivatives with carbocyclic

condensed rings, e.g., (85), have not yet become
important as dye building blocks; however,
anthraquinone structures with heterocyclic con- Anthraquinone derivatives with condensed
densed rings are important components of many imidazole rings are the least important. The
vat dyes and also of disperse dyes and pigments. bisimidazole 90 prepared from 1,2-diami-
Phthaloyl carbazoles, especially the anthrimide noanthraquinone and terephthalyl chloride
carbazoles, such as 86, represent by far the most [266], [267] is a yellow vat dye.
important class of compounds. Other hetero-
cyclic systems used industrially include imid-
azole, oxazole, and thiazole derivatives (87); the
phthaloyl acridones (anthraquinone acridone,
88); and the azine derivatives of anthraquinone
(indanthrone, 89).
32 Anthraquinone Dyes and Intermediates
More important are the oxazole and thia-
zole derivatives. These are prepared from 2-
hydroxy- (or 2-halo-) 3-aminoanthraquinones
and 1-nitro- (or 1-amino-) anthraquinone-2-
carboxylic acid [268] or 1-amino-4-nitroanthra-
quinone-2-carboxylic acid.
Whereas the oxazole derivatives are ob-
tained directly from the 3-amino-2-hydroxy-
anthraquinone by acylation followed by ring clo-
sure with sulfuric acid [269], the preparation of
the thiazoles requires acylation of 3-chloro-2-
aminoanthraquinone followed by displacement
of chlorine by a mercapto group using sodium
sulfide, with simultaneous reduction of the 1-
nitro group. Concentrated sulfuric acid is used
for the ring closure in the same manner as for
the oxazoles.
2-(1-Amino-2-anthraquinonyl)anthra [2,3-
d-] oxazole-5,10-quinone [2379-79-5], Indan-
thren Red FBB, (91), M r 470.4, is prepared by
reacting 1-nitroanthraquinone-2-carbonyl chlo-
ride and 2-amino-3-hydroxyanthraquinone, fol-
lowed by displacement of the nitro group with
ammonia and ring closure [2, p. 15], [269].
The following are the corresponding thi-
azole compounds: Indanthren Rubine B
[6371-49-9], (92), [2, p. 15, 16], M r 486.5;
Indanthren Blue CLG [6371-50-2], (93), [2,
p. 18], [270], M r 605.6; and Indanthren Blue
CLB [6492-78-0], (94), [2, p. 18], [271],
M r 673.6. Compound 94 is prepared from 1-
amino-4-nitroanthraquinone-2-carbonyl chlo-
ride and 2-amino-3-chloroanthraquinone and
Na2 S-sulfur.
2,2
-Bisanthra [2,1-d-] thiazole-6,11-
quinonyl [6451-12-3], Algol Yellow 8 G,
(95), M r 528.6, is prepared from 2-amino-1-
chloroanthraquinone by replacing the chlorine
atom by a mercapto group, followed by reaction
with glyoxal sulfate in concentrated sulfuric
acid [272], [2, p. 19].
2,8-Diphenylthiazolo [5
,4
: 7,8] anthra-
[2,1-d-] thiazole-6,12-quinone [129-09-9], Al-
gol Yellow GC, (96), M r 474.6, is prepared
from 2,6-diaminoanthraquinone and benzalde-
hyde [273] or benzotrichloride [2, p. 59] and sul-
fur in molten naphthalene.
2.11.2. Anthraquinonecarbazole Derivatives
The following description uses the desig-
nations common in industrial circles. The
carbazole of 1,1
-dianthrimide is referred
to as 1,1
-dianthrimide-2,2
-carbazole. Other
terms for this carbazole would be: 1,2 : 7,8-
diphthaloylcarbazole, 16H-dinaphtho [2,3-
a : 2
,3
-i] carbazole-5,10,15,17-tetraone, and
16H-(bis{anthraceno-[1,2-b : 2
,1
-d] pyrrole})
5,17 : 10,15-bisquinone.
 Anthraquinone Dyes and Intermediates
1-Arylaminoanthraquinones may be con-
densed to coeramidonine derivatives, or they
may be subjected to a dehydrogenating cycliza-
tion to give carbazole derivatives.
Coeramidonines are generally obtained on
heating in aqueous sulfuric acid. When simple
1-arylaminoanthraquinones are treated with alu-
minum chloride, frequently both types of prod-
ucts are obtained [274]. Naphthylaminoanthra-
quinones and anthrimides tend to form carbazole
derivatives. The reaction proceeds via dihydro-
carbazoles, which are converted to the corre-
sponding carbazoles by subsequent oxidation
with air, sodium dichromate, manganese diox-
ide, sodium chlorate, sodium nitrite, or sodium
hypochlorite. The dehydrogenating cyclization
is generally termed carbazolyation.
Among the carbazole derivatives that are not
derived from anthrimides, Alizarin Light Brown
BL (97) is an example. It is prepared from
1-benzoylamino-2-methyl-4-β-naphthylami-
noanthraquinone by ring closure in concen-
trated sulfuric acid with simultaneous sulfona-
tion [275].
33
The vast majority of industrial carbazoles
are derivatives of α,α
-anthrimides. They in-
clude some of the most important anthraquinone
dyes with condensed heterocyclic rings. They
are used mainly as vat dyes. They have good to
excellent coloristic properties in this application
and are used for yellow, orange, brown, olive,
and gray colors. The particular shade depends
on the number of linked anthraquinone moieties,
on whether the linkage is linear or branched,
and on the nature of the substituents. They are
prepared industrially by carbazolyation of di-,
tri-, tetra-, and pentanthrimides. Even if car-
bazolyation products of the higher anthrimides
are generally cited as pure single compounds,
carbazolyation reaction in many polyanthrim-
ides by the usual methods must be considered
incomplete.
In its broadest sense, the term anthrimide in-
cludes secondary amines, where anthraquinone
has been replaced by anthraquinone derivatives
such as benzanthrone, anthrapyrimidine, pyra-
zolanthrone, and phthaloylacridone.
Carbazolyation of anthrimide can be carried
out with strong protic acids, metal halides, or
alkali–metal hydroxides. The acid most com-
monly used is concentrated sulfuric acid, but
chlorosulfonic acid or weak oleum are used also
[276]. Anhydrous hydrogen fluoride in the pres-
ence of manganese dioxide also has been pro-
posed [277]. Of the recommended metal halides
(AlCl3 , FeCl3 [278], ZnCl2 , TiCl4 , SnCl4 , etc.)
the most frequently used is aluminum chlo-
ride. Carbazolyation in pure molten aluminum
chloride has been used successfully but leads
to rather contaminated products because of the
temperatures required (200 – 280 ◦ C) [279] and
is not practical because of the difficulties in mix-
ing the components intimately. The physical and
chemical properties of the melts have been modi-
fied by a variety of additives. In the so-called acid
melts, alkali–metal halides (NaCl, NaF, KCl),
sulfur dioxide [281], sodium hydrogen sulfite,
34 Anthraquinone Dyes and Intermediates
organic solvents [282], nitrobenzene (danger of
explosion!) [283], nitriles [285], or acid chlo-
rides [286] have been proposed. The so-called
alkaline aluminum chloride melts are obtained
by addition of excess pyridine, picolines, quino-
lines, isoquinolines, or dimethylaniline [287].
Aluminum chloride–pyridine complexes in a
molar ratio of
1 : 1 [288], possibly in the pres-
ence of organic solvents, and with aluminum
chloride–ammonia complexes, are equivalent in
their mode of action to the acid melts [289].
Carbazolyation with titanium tetrachloride in or-
ganic solvents, such as halobenzenes [290] or,
sulfolane [291], have been described. Finally,
alkaline carbazolyation in potassium hydroxide
melts, possibly with addition of sodium hydrox-
ide, has been reported also [292].
Each of the carbazolyation agents possesses
specific properties and modes of action. The
choice of an optimal carbazolyation process de-
pends largely on the structure of the anthrimide
and the nature of the substituents.
The following carbazolyation agents are used
commercially:
1) Sulfuric acid: benzoylamino groups in
the α-position and an acridone substruc-
ture facilitate carbazolyation in concen-
trated sulfuric acid. For example, the
4,4
-, 4,5
-, and 5,5
-dibenzoylamino-
1,1
-dianthrimides; 4,5-dibenzoylamino-8-
methoxy-1,1
-dianthrimide; and the anthrim-
ide prepared from 1-amino-5-benzoylami-
noanthraquinone and the 2,5,7-trichloro-3,4-
phthaloylacridone are carbazolated in this
way. The reactions are carried out by adding
the anthrimide to sulfuric acid and stirring at
20 – 40 ◦ C until reaction is complete, which
is generally indicated by a change in the
color of the solution. The melt is then poured
into water, and the dihydrocarbazole oxi-
dized. Posttreatment with sodium dichro-
mate, sodium nitrite, sodium persulfate,
sodium chlorate, or sodium hypochlorite
facilitates a certain degree of purification by
oxidizing impurities.
2) Aluminum chloride – alkali metal halide:
mixtures of aluminum chloride and dry
sodium chloride (weight ratio ≈ 4 : 1) form
relatively low melting eutectics. Such melts
are used mainly for the carbazolyation of
1,1
-dianthrimide, 1,1
: 5,1

-trianthrimide,
and 1,1
: 4,1

: 5,1


: 8,1



-pentanthrimide
at 140 – 220 ◦ C. Stirring the melt into a so-
lution of sodium hydroxide or hydrochlo-
ric acid, followed by oxidation with sodium
dichromate, for example, yields the dyes.
3) Aluminum chloride – sulfur dioxide: melts
of aluminum chloride and sulfur diox-
ide, to which sodium chloride can be
added if necessary, have low viscosity and
permit carbazolyation under mild condi-
tions (20 – 100 ◦ C). This method is supe-
rior to other carbazolyation processes in
some cases, for instance, in treating 4
,4

-
dibenzoylamino-1,1
: 5,1

-trianthrimide.
The reagent is prepared by passing sulfur
dioxide into a melt of aluminum chloride and
sodium chloride (weight ratio ≈ 4 : 1) until
the melt has low viscosity. After the anthrim-
ide is added, the mixture is heated to the tem-
perature required for carbazolyation. Workup
involves stirring into sodium hydroxide solu-
tion.
4) Aluminum chloride – pyridine (or
methylpyridines): carbazolyation in alu-
minum chloride–pyridine melts (excess
pyridine) is applicable to many substi-
tuted and unsubstituted anthrimides. Indus-
trially, this method is applied mainly to
1,1
: 4,1

-trianthrimide, 5-benzoylamino-
1,1
: 4,1

-trianthrimide, 5-(benzanthron-3-
ylamino)−1,1
-dianthrimide, and 1-benzoyl-
amino-4,1
: 5,1

: 8,1


-tetraanthrimide. In
this process, aluminum chloride is added to
pyridine (weight ratio ≈ 1 : 5) first, and then
the anthrimide is added. After heating to the
temperature required for the carbazolyation,
100 – 170 ◦ C, and stirring until reaction is
completed, workup is carried out by adding
to sodium hydroxide solution, and, if neces-
sary, oxidative cleanup. The type of organic
base (pyridine, methylpyridine, quinoline,
etc.) selected and the reaction conditions ex-
ert a decisive influence on the quality of the
dye.
Some important members of the anthra-
quinonecarbazole series are listed below.
1,1
-Dianthrimide-2,2
-carbazole [4229-
15-6], Indanthren Yellow FFRK, M r 427.4
(for formula see above), is prepared from
 Anthraquinone Dyes and Intermediates 35

1,1
dianthrimide in AlCl3 -NaCl melts [4, p. 53]

or in AlCl3 – pyridine melts [287].

1,1
: 5,1

-Trianthrimide-2,2
: 6,2

-

carbazole [2172-33-0], Indanthren Yellow 3 R,
M r 646.6, is prepared from 1,1
: 5,1

-
trianthrimide in AlCl3 -NaCl melts [2, p. 121].

1,1
: 4,1

-Trianthrimide-2,2
: 3,2

-

carbazole [2475-33-4], (Indanthren Brown BR,
M 646.6, is prepared from 1,1
: 4,1

-
trianthrimide in AlCl3 – pyridine [5, p. 101].

1,1
: 4,1

: 5,1


: 8,1



-Pentanthrimide- 2.11.3. Anthraquinone Derivatives with

2,2
: 3,2
: 6,2


: 7,2



-carbazole
[14999-97-4], Indanthren Khaki GG, M r 1085.0
(for formula see Section 3.1.3, 210), is prepared
from the corresponding pentanthrimide with
aluminum chloride [278] or with aluminum
chloride–sodium chloride [5, p. 133], [293].
5,5
-Bisbenzoylamino-1,1
-dianthrimide-
2,2
carbazole [128-70-1], Indanthren Golden-
Orange 3 G, M r 665.6, is prepared from 5,5
-
bisbenzoylamino-1,1
-dianthrimide by ring clo-
sure in concentrated sulfuric acid [4, p. 15].
4,5
-Bisbenzoylamino-1,1
-dianthrimide-
2,2
carbazole [131-92-0], Indanthren Brown
R, M r 665.6, is prepared from 4,5
-bisbenzoyl-
amino-1,1
-dianthrimide by ring closure in con-
centrated sulfuric acid [4, p. 10].
Acridone Substructure (Phthaloylacridones)
The red to blue anthraquinone dyes with
acridone substructure are all derived from 3,4-
phthaloylacridone (99). Their use has been
mainly as vat dyes.
The basic structure provides red-violet dyes,
but with rather weak tinctorial strength. The
3,4-phthaloylacridones are prepared from the
1-arylaminoanthraquinone-o-carboxylic acids
100 or 101 by acid-catalyzed ring closure us-
ing sulfuric acid, weak oleum, chloro- or fluoro-
sulfonic acid, polyphosphoric acid, or AlCl3 or
to a lesser extent phosgene, acetyl chloride, or
phosphoryl chloride.

4,4
-Bisbenzoylamino-1,1
-dianthrimide-

2,2
-carbazole [2379-81-9], Indanthren Olive
R, M r 665.6, is prepared from 4,4
-bisbenzoyl-
amino-1,1
-dianthrimide by ring closure in con-
centrated sulfuric acid [4, p. 29].

4,4

-Bisbenzoylamino-1,1
: 5,1

-trian-

thrimide-2,2
: 6,2

-carbazole [6487-07-6],
Indanthren Red Brown GR, (98), M r 884.8, is
prepared from the corresponding trianthrimide
in aluminum chloride–sulfur dioxide [4, p. 42],
[281].
Special methods for ring closure are
the chlorination of 1-anilino-2-methylanthra-
quinone, which yields 1,2,5,6,7,8-hexachloro-
3,4-phthaloylacridone [294], [295], and the
acridone ring closure that occurs on vatting
of 1-anilinoanthraquinone-2
-carboxylate esters
[296].
36 Anthraquinone Dyes and Intermediates

The phthaloylacridones are chlorinated eas- of 3,4-phthaloylacridone in chlorosulfonic acid

ily. Depending on the chlorination conditions, in the presence of sulfur [297] or from the 5,7-
the unsubstituted 3,4-phthaloylacridone may be dichloro compound [303].
chlorinated in the 2,5,7 positions when Cl2 –
nitrobenzene–I2 is used or in the 5,7,8 po-
sitions when Cl2 –chlorosulfonic acid is used
[297]. The chlorine in position 2 of 2,5,7-
trichloro-3,4-phthaloylacridone is replaced eas-
ily by amines. Therefore, 2,5,7-trichloro-3,4-
phthaloylacridone reacts with aminoanthra-
quinones to form anthrimides [298].
Bromamine acid and (substituted) anthranilic
acid are used in the preparation of (substituted)
2-amino-3,4-phthaloylacridone (102). Ring clo- 1,2,5,6,7,8-Hexachloro-3,4-phthaloylacri-
sure in acid medium (oleum or chlorosulfonic done [1328-35-4], (106), Indanthren Pink B,
acid) and cleavage of the sulfonic acid group M r 532.0, is prepared by chlorination of 1-
yield 2-amino-3,4-phthaloylacridone. anilino-2-methylanthraquinone in trichloroben-
zene followed by hydrolysis [294].

6-Chloro-2-amino-3,4-phthaloylacridone
[6219-98-3], (107), Indanthren Turquoise Blue
GK, M r 374.8, is prepared from 1-amino-4(2
-
carboxy-5
-chlorophenylamino)anthraquinone-
2-sulfonic acid by ring closure in weak oleum
and cleavage of the sulfonic acid group [4, p. 21].

3,4-Phthaloylacridone, (103), M r 325.3,

is prepared from 1-anilinoanthraquinone-2-
carboxylic acid [299], [300] or from 1-(2
-
carboxyphenylamino)anthraquinone [301]. 2-Benzoylamino-6-trifluoromethyl-3,4-
phthaloylacridone [6219-97-2], Indanthren
Blue HCGK, (108), M r 512.4, is pre-
pared from bromamine acid (12) and 4-tri-
fluoromethylanthranilic acid followed by ring
closure and desulfonation in sulfuric acid mono-
hydrate [4, p. 34], [5, p. 143].

1,2 : 5,6-Diphthaloylacridone [10142-57-

1], Indanthren Orange F 3 R, (109), M r 455.4,
2,5,7-Trichloro-3,4-phthaloylacridone
is prepared from 1-nitro- (or chloro-) anthra-
[6373−31−5], Indanthren Red Violet RRK,
quinone-2-carboxylic acid and 2-aminoanthra-
(104), M r 428.6, is prepared by chlorination
quinone in dichlorobenzene followed by ring
of 3,4-phthaloylacridone in nitrobenzene with
closure in sulfuric acid [304].
sulfuryl chloride [302].

5,7,8-Trichloro-3,4-phthaloylacridone,
(105), M r 428.6, is prepared by chlorination
 Anthraquinone Dyes and Intermediates
Indanthren Green 4 G [6661-46-7], (110),
M r 709.1, is prepared from 2-amino-7-chloro-
3,4-phthaloylacridone and 2-phenyl-4-chloro-
6,7-phthaloylquinazoline, which itself is derived
from 3-aminoanthraquinone-2-carboxylic acid,
benzoic acid, and ammonia [4, p. 19], [305].
2.11.4. Anthraquinone Derivatives with
Phenazine Substructure
Among the anthraquinone derivatives with
phenazine substructure, the indanthrones are an
important class of vat dyes. The blue color of
the unsubstituted unit may be shifted to green
by appropriate substitutions. Several synthetic
pathways are available:
37
1) Aminoanthraquinones are dimerized to in-
danthrones in alkali melts (above 200 ◦ C)
in the presence of such oxidizing agents as
sodium nitrite or air. The oldest and most im-
portant method for preparing unsubstituted
indanthrone is the potash fusion of 2-ami-
noanthraquinone. A related process is the ox-
idation of the leuco-sulfuric ester of 2-ami-
noanthrahydroquinones in sodium hydroxide
with potassium permanganate [306]. How-
ever, this preparation method is useful only
for the preparation of leuco-sulfuric esters of
indanthrones.
Better suited for the oxidative dimerization
of 1-aminoanthraquinone to indanthrone is a
melt of potassium phenolate at 200 – 210 ◦ C
in the presence of oxidizing agents [308] or
passage of air in the presence of catalysts,
such as MnO2 or FeCl3 [309]. Dimerization
of 1- (or 2-) aminoanthraquinone to indan-
throne can be achieved with good yields at
115 – 125 ◦ C in mixtures of dimethyl sulfox-
ide [310] or tetramethylurea [311] and 50 %
aqueous KOH.
2) 2-Amino-1-halo- (or 1-amino-2-halo-)
anthraquinones condense to indanthrones
when heated in high-boiling solvents, such
as nitrobenzene or naphthalene, in the pres-
ence of copper or copper salts and acid-
binding agents (Kugel’s indanthrone synthe-
sis) [312]. This method, however, is impor-
tant only in the preparation of substituted
indanthrones.
Indanthrone [81-77-6], Indanthren Blue RS
and R, (111), M r 442.4, is prepared from 2- (or
1-) aminoanthraquinone by potash fusion [1,
p. 712], in potassium phenolate [307], [309], or
in 50 % potassium hydroxide [211], [310].
Chlorination of indanthrone in sulfuric acid
under addition of 1 % or 5 % manganese dioxide
(5 – 8 % or 13.8 – 14 % Cl) at 50 – 55 ◦ C affords
38 Anthraquinone Dyes and Intermediates
dyes of slightly greener shades (Indanthren Blue
GCD or BC).
3,3
-Dichloro-4,4
-diaminoindanthrone
[1328-41-2], Indanthren Green BB, (112),
M r 541.4, is prepared from 1,4-diamino-2,3-
dichloroanthraquinone in naphthalene in the
presence of copper powder [313].
Indanthrone-3,3
-dicarboxylic acid,
Cibanone Blue 2 G, (113), M r 530.4, is pre-
pared from2-aminoanthraquinone-3-carboxylic
acid by potash fusion [314].
Leuco-sulfuric ester of 3,3
-dichloroindan-
throne [2519-28-0], Anthrasol Blue IBC, (114),
M r 839.7, is prepared from the leuco-sulfuric
ester of 2-acetylamino-3-chloroanthraquinone
[315].
2.12. Anthraquinone Derivatives with
Meso Rings (1,9-Cyclo-10-anthrones)
This class includes anthraquinone derivatives
that contain a condensed carbon or heterocyclic
ring linking the α position and the neighbor-
ing meso position bridging the 1 and 9 posi-
tions. (These derivatives are named in the fol-
lowing discussion by their “traditional” nomen-
clature, which is still the one in common use
in industrial dye circles. For example, the com-
pound called benzanthrone in the “traditional”
nomenclature would be named as 7-oxo-7H-
benz [d,e]anthracene by the new nomenclature
rules).
Such ring systems have been prepared in
nearly every feasible combination, but only the
few listed below have attained importance in the
commercial synthesis of dyes.
Without additional substituents, these com-
pounds possess a relatively faint yellow color,
and have a yellowish green fluorescence in or-
ganic solvents or sulfuric acid. This group also
includes a number of polycyclic compounds
with additional side and/or meso-ring systems,
such as acedianthrone, anthanthrone (145, for
formula see Section 2.12.6), pyranthrone (149,
for formula see Section 2.12.7), violanthrone
(151, for formula see Section 2.12.8), and diben-
zpyrenequinone.
2.12.1. Benzanthrone and Its Derivatives
Benzanthrone is an important intermediate for
the synthesis of vat dyes. It is prepared from an-
throne (122), glycerol, and sulfuric acid under
conditions similar to those employed in Skraup’s
quinoline synthesis. Industrial synthesis com-
monly starts directly from anthraquinone, which
is first reduced to anthrone by an appropriate re-
ducing agent (e.g., iron) without isolation of the
intermediate.
Dyes of the basic benzanthrone system are of
little importance. Commercial dyes are almost
always benzanthrones with additional fused ring
systems derived from benzanthrone and its sim-
ple substituted derivatives.
 Anthraquinone Dyes and Intermediates 39

Benzanthrone is substituted easily. Elec- 3-Bromobenzanthrone reacts with sodium

trophilic reagents usually attack the 3 posi- sulfide to yield the mercaptan, which may be
tion first and then the 9 position, whereas nu- alkylated with chloroacetic acid to give the thio-
cleophilic substitution attacks the 4 position glycolic acid derivative. This product may then
or the 6 position. Therefore halogenation of be converted to an indigoid dye by oxidation and
benzanthrones first yields the 3-halo deriva- potash fusion [318]:
tives; more vigorous reaction conditions yield
the 3,9-disubstituted compounds. Direct syn-
thesis is used to generate derivatives bearing
halogen in other positions and to obtain 4-
methylbenzanthrone.
For halobenzanthrones, displacement reac-
tions are carried out most easily with the halo-
gen in positions 3 or 9. Condensation with ami-
noanthraquinone in inert solvents in the presence
of acid-binding agents and a copper catalyst will
yield condensation products of the anthrimide
type. Valuable vat dyes, e.g., 116, are derived by Treatment of 3-bromobenzanthrone with
periring-closure of 3-(1-anthraquinonylamino)- copper cyanide in an organic solvent yields 3-
benzanthrone (115) using a potash melt [316] or cyanobenzanthrone, which may be hydrolyzed
pyridine – aluminum chloride. to benzanthrone-3-carboxylic acid. This com-
The bromine atoms of 3,9-dibromobenzan- pound may then be converted further via the acid
throne can be replaced stepwise. chloride and condensation with 1-aminoanthra-
Pyrazolanthrones can be reacted with quinone to the carboxamide (120), which in an
halobenzanthrones in a manner similar to 1- alkali melt forms a ring by decarboxylation to
aminoanthraquinone [317]. give “Isoimide Green” (121) [319]:

Mild treatment of benzanthrone with alco-

holic alkalies leads to dimerization, giving 4,4
-
bibenzanthronyl (129), an important intermedi-
ate for the preparation of violanthrone dyes (see
Section 2.12.8).

Benzanthrone [82-05-3], (123), M r 230.3,

mp 170 ◦ C, is prepared commercially by react-
ing anthraquinone with glycerol, sulfuric acid,
and a reducing agent, usually iron. This in-
volves reduction of anthraquinone to anthrone
(122), which condenses immediately with the
acrolein formed by dehydration of glycerol, and
is finally oxidized by the sulfuric acid [1], [2,
p. 65], [320]. An improved process is described
in [321], [322]. More recently, the use of phos-
40 Anthraquinone Dyes and Intermediates
phorus or a phosphorus compound, e.g., sodium
hypophosphite, has been proposed as the re-
ducing agent [323]. Electrochemical procedures
have been also suggested [324], [325]. It is pos-
sible to start with anthrone prepared in a sepa-
rate step, e.g., by hydrogenation [326]. Benzan-
throne is best purified by sublimation.
4-Methylbenzanthrone [6409-46-7], (124),
M r 244.3, is prepared from 2-methylanthra-
quinone via methylanthrone with glycerol in sul-
furic acid [327].
3-Bromobenzanthrone [81-96-9], (125),
M r 309.2, is prepared by bromination in hy-
drochloric acid [2, p. 71]; process improvement
is described in [328].
3,9-Dibromobenzanthrone [81-98-1],
(126), M r 388.1, is prepared by bromination in
chlorosulfonic acid [2, p. 76], [12], [329].
3-Cyanobenzanthrone, (127), M r 255.3,
is prepared from 3-bromobenzanthrone with
CuCN in pyridine [330].
Benzanthrone-3-carboxylic acid, (128),
M r 274.3, is prepared from the nitrile by hy-
drolysis [331].
4,4
-Bibenzanthronyl [116-90-5], (129),
M r 458.5, is prepared by mild alcoholic al-
kali melt of benzanthrone (below 200 ◦ C in the
presence of excess alcohol) [1]. It is an interme-
diate in the synthesis of violanthrone dyes (see
Section 2.12.8).
3-(1-Anthraquinonylamino)benzanthrone
[81-94-7], (115), M r 451.5, is prepared from 1-
aminoanthraquinone and 3-halobenzanthrone
[2, p. 71], [332].
Indanthren Olive Green B [3271-76-9],
Imide Green, (116), M r 449.5, is prepared from
3-(anthraquinonyl-(1)-amino)benzanthrone by
alkali melt [2, p. 71], [316].
N-[Benzanthronyl-(3)]pyrazolanthrone
(117), M r 448.5, is prepared from pyrazolan-
throne and 3-bromobenzanthrone in nitroben-
zene [317].
Indanthren Navy Blue R [6247-39-8],
(118), M r 466.5, is prepared from 117 by mild
alkali fusion [317].
Additional compounds are given in the sec-
tion on vat dyes, Section 3.1.3.
2.12.2. Pyrazolanthrone and Its Derivatives
1,9-Pyrazolanthrones are generated easily from
the 1-hydrazinoanthraquinones [333] by ring
closure with dehydration. This may be accom-
plished in either concentrated sulfuric acid at
temperatures up to 100 ◦ C or by heating in aque-
ous hydrochloric acid.
Hydrazinoanthraquinones are obtained from
1-aminoanthraquinones by diazotization, reduc-
tion with sodium hydrogen sulfite to the hydrazi-
nosulfonic acid, and hydrochloric acid hydroly-
sis. Other synthesis options are displacement of
halogen or sulfonic acid groups by hydrazine.
 Anthraquinone Dyes and Intermediates 41

Only the unsubstituted pyrazolanthrone quinones by reaction with formamide [337] or

(130) is of commercial importance for the pro- with aqueous solutions of formaldehyde and am-
duction of benzanthrone dyes obtained by reac- monia in the presence of nitrobenzene sulfonic
tion with 3-bromobenzanthrone and subsequent acid as the oxidizing agent [335], [336].
ring closure. It is also the starting material for
the production of 2,2
-bipyrazolanthronyl (131).
Alkylation of this substance then yields the cor-
responding diethyl derivative (Indanthren Rubin
R, 132).

An equally smooth process starts by trans-

forming 1-aminoanthraquinone into its for-
mamidinium chloride by reaction with di-
methylformamide and thionyl chloride, fol-
lowed by ring closure in the presence of am-
monium salts of weak acids [338]:
1,9-Pyrazolanthrone [129-56-6], (130), M r
220.2, mp 285 – 286 ◦ C, is prepared by diazoti-
zation of 1-aminoanthraquinone, reaction of the
diazonium salt with sodium hydrogen sulfite,
and cyclization of the resulting hydrazinosul-
fonic acid [5, p. 160].

2,2
-Bipyrazolanthronyl [129-54-4], (131),

M r 438.5, is prepared from pyrazolanthrone in
an alkali melt [13, p. 345], [334].
Only the 6- and 8-amino derivatives of 1,9-
anthrapyrimidines are used as intermediates to
produce greenish-yellow vat dyes. Unsubsti-
tuted 1,9-anthrapyrimidine is faint yellow, the
6-amino derivative is yellow with a green cast,
and the 8-amino derivative is orange red.

6-Aminoanthrapyrimidine, (134),
M r 247.3, is prepared from 1,4-diaminoanthra-
quinone with aqueous formaldehyde and am-
monia in the presence of nitrobenzenesulfonic
acid [2, p. 88].
N,N
,-Diethyl-2,2
-bipyrazolanthronyl
[4203-77-4], (132), Indanthren Rubin
R, M r 494.6, is prepared from 2,2
-
bipyrazolanthronyl by alkylation with diethyl
sulfate after treatment with potassium hydrox-
ide solution [5, p. 159]. For structure elucidation
see [11, C.I. 70320].
8-Aminoanthrapyrimidine, M r 247.3, is
2.12.3. 1,9-Anthrapyrimidine and Its prepared from 1,5-diaminoanthraquinone-2-
Derivatives (1,9(N-)-Pyrimidino- sulfonic acid with aqueous formaldehyde and
anthrone-10) ammonia in the presence of nitrobenzenesul-
fonic acid, followed by splitting off the sulfonic
The 1,9-anthrapyrimidines (133) are obtained acid group [2, p. 94]. In contrast to 1,4-diami-
easily from the corresponding 1-aminoanthra-
42 Anthraquinone Dyes and Intermediates
noanthraquinone, reaction at only one side of
the 1,5-diaminoanthraquinone is not assured.
6-(4
-Chlorobenzoylamino)anthrapyrimi-
dine [4216-00-6], Indanthren Yellow 7 GK,
M r 385.8, is prepared by reacting 6-ami-
noanthrapyrimidine with 4-chlorobenzo-
yl chloride in o-dichlorobenzene [337] or
from N,N-dimethyl-N
-[4-(4
-chlorobenzo-
ylamino)anthraquinonyl-(1)] formamidinium
chloride and ammonium acetate in N-
methylpyrrolidone [338].
1,9-Anthrapyrimidine-2-carboxylic acid,
(135), M r 276.2, is prepared from 1-amino-2-
methylanthraquinone with formamide or with
formaldehyde–ammonia (addition of an oxidiz-
ing agent), followed by oxidation of the 2-
methyl derivative to the 2-carboxylic acid [339].
Conversion into the acid chloride and conden-
sation with aminoanthraquinone affords fast
yellow vat dyes and pigments [340], [341].
2.12.4. 1,9-Anthrapyridone and Its
Derivatives
1-Acetylaminoanthraquinones are converted to
anthrapyridones by alkaline reagents [342] and
by direct heating [343], which is accompanied
by loss of water:
Acetylation and subsequent ring closure may
also be combined by heating the aminoanthra-
quinone with acetic anhydride in the presence of
alkali-metal acetates [344].
Only the 6-arylamino derivatives of 3-
methylanthrapyridone and 1-ethoxycarbonyl-
4methylanthrapyridone are of commer-
cial interest. Starting from 4-bromo-1-
methylaminoanthraquinone, the 6-bromo-3-
methylanthrapyridone is obtained by acetylation
and alkali-catalyzed ring closure [5, p. 217].
In this compound, the halogen may be eas-
ily displaced by amine functions [344]. Subse-
quent sulfonation yields lightfast red acid dyes
(Alizarine Rubinoles).
6-Bromo-3-methylanthrapyridone, (136),
M r 340.2. For preparation see preceding para-
graph [5, p. 217].
6-Anilino-3-methylanthrapyridone,
M r 352.4, is prepared from 6-bromo-3-
methylanthrapyridone and aniline [3, p. 47].
6-Anilino-3-methylanthrapyridone-4
-
sulfonic acid, (138), M r 432.5, is pre-
pared by condensation of 6-bromo-3-
methylanthrapyridone with aniline, followed
by monosulfonation [345].
1-Ethoxycarbonyl-6-bromo-4-methylan-
thrapyridone, (139), M r 412.3, is prepared
from 1-amino-4-bromo-2-methylanthraquinone
and diethyl malonate [346].
2.12.5. Dibenzpyrenequinones
According to their chemical structure, diben-
zpyrenequinones should be classified as benzan-
throne derivatives, but conventionally they are
treated as a separate group.
 Anthraquinone Dyes and Intermediates
Although the yield of benzanthrone
by dehydrogenating ring closure of 1-
benzoylnaphthalene in an aerated aluminum
chloride – sodium chloride melt is too low [13,
pp. 315 – 317], these conditions are suitable for
the double ring closure of 1,5- (or 1,4-) di-
benzoylnaphthalene [348] to yield 7,14- (or
5,8-) dibenzpyrenequinone, (141), (140), [347].
The 7,14-dibenzpyrenequinone is used com-
mercially as a golden-yellow vat dye. Another,
now obsolete, method for preparing this com-
pound is fusion of benzanthrone with benzoyl
chloride and aluminum chloride [349] and, if
necessary, with aeration with oxygen [350].
7,14-Dibenzpyrenequinone [128-66-5], In-
danthren Golden Yellow GK (141), M r 332.4,
is prepared from 1,5-dibenzoylnaphthalene (it-
self prepared from naphthalene with benzoyl
chloride – AlCl3 ) by fusion with AlCl3 -NaCl
at 160 ◦ C and aeration with oxygen [5, p. 123],
[347], [348].
Dibromo-7,14-dibenzpyrenequinone
[1324-11-4], Indanthren Golden Yellow RK,
M r 490.2, is prepared by bromination in the
melt [5, p. 121].
2.12.6. Anthanthrones
The intensely orange anthanthrone (145), which
has little fiber affinity when used in its un-
substituted form as a vat dye, is produced
by double ring closure of 1,1
-binaphthyl-8,8
-
dicarboxylic acid (144) in sulfuric acid [351].
Anthanthrone is prepared commercially from
naphthostyril (142), which is hydrolyzed to 143,
diazotized, and dimerized, losing N2 [352].
43
In sulfuric acid, anthanthrone may be dichlo-
rinated or dibrominated in the 4,10 positions.
This procedure yields a dye with greater affin-
ity and brighter, more intense red shades. In
commercial processes halogenation is carried
out immediately following the cyclization of
144without isolation of intermediates.
4,10-Dichloroanthanthrone [1324-02-3],
Indanthren Brilliant Orange GK, M r 375.2,
is prepared from 1,1
-binaphthyl-8,8
-
dicarboxylic acid in sulfuric acid at 50 ◦ C, fol-
lowed by chlorination in the presence of FeSO4
[5, p. 96], or from anthanthrone by sparging with
chlorine in the presence of iodine in sulfuric acid
or organic solvents [353].
4,10-Dibromoanthanthrone [4378-61-4],
Indanthren Brilliant Orange RK, M r 464.1,
is prepared from 1,1
-binaphthyl-8,8
-
dicarboxylic acid in sulfuric acid monohydrate
at 35 ◦ C, followed by bromination in the pres-
ence of iodine [5, p. 88]. It is also used as a
pigment.
4,10-Bis-(4
-benzoylaminoanthraquino-
nyl-1
-amino)anthanthrone [6049-19-0], In-
danthren Grey BG, (146), M r 987.0, is prepared
from 4,10-dibromoanthanthrone and 1-amino-
4-benzoylaminoanthraquinone in naphthalene
[354].
44 Anthraquinone Dyes and Intermediates
2.12.7. Pyranthrone and Flavanthrone
Pyranthrone [128-70-1], (149), M r 406.4,
is prepared by double ring closure of 2,2
-di-
methyl-1,1
-bianthraquinonyl (148), which is
obtained from 1-chloro-2-methylanthraquinone
(147) by heating with copper powder in o-
dichlorobenzene – pyridine. Ring closure occurs
under alkaline conditions, e.g., KOH – isobuta-
nol at 105 ◦ C [2, p. 60]; process improvements
are reported in [355], [356]. The unsubstituted
pyranthrone and its halogen derivatives are used
as vat dyes and pigments.
Brominated pyranthrones (the dibromo
derivative [1324-35-2], M r 564.3, is Indanthren
Orange RRTS [2, p. 61]; a mixture of di- and tri-
bromo derivatives is Indanthren Orange 4 R [2,
p. 62]) are prepared from pyranthrone by bromi-
nation in chlorosulfonic acid in the presence of
iodine or sulfur.
Flavanthrone [475-71-8], (150), M r 408.
4. Strictly speaking, flavanthrone should not
be classified with the polycarbocyclic anthra-
quinone derivatives, but it is described here be-
cause it is so similar to pyranthrone.
Flavanthrone is prepared from 1-chloro-
2-phthalimidoanthraquinone via the 2,2
-
diphthalimido-1,1
-bianthraquinonyl, using
copper in boiling trichlorobenzene. The alkaline
ring closure is accomplished by boiling with ex-
cess 3 – 5 % sodium hydroxide, which cleaves
both phthalic acid residues simultaneously [5,
p. 174]. Only the unsubstituted flavanthrone is
used as a vat dye and pigment.
2.12.8. Violanthrone and Isoviolanthrone
Both violanthrone (151) and isoviolanthrone
(152) are formally derived by symmetrical or
unsymmetrical condensation of two molecules
of benzanthrone. Both polycyclic quinones have
intense blue color and are used either by them-
selves or in the form of simple derivatives as fast
violet to green or black vat dyes and as pigments.
In contrast to isoviolanthrone, unsubstituted vi-
olanthrone is available as a commercial dye.
Violanthrone may be brominated or chlori-
nated in chlorosulfonic acid or organic solvents.
Both reactions are used to obtain other hues. If
sulfur is added during halogenation in chloro-
sulfonic acid, derivatives containing sulfur and
halogen are obtained.
Nitration of violanthrone yields a mixture
of mono- and dinitroviolanthrones, which are
reduced in the vat dyeing process to (di)ami-
noviolanthrones.
Alternatively, reduction of the nitro group
may be carried out during the original dye syn-
thesis.
Posttreatment of the resulting greenish fabric
color with an oxidizing agent, such as hypochlo-
rite, produces fast, deep black colors.
Violanthrone [116-71-2], Indanthren Dark
Blue BOA, (151), M r 456.5, is generated by
potash fusion of benzanthrone [11], [2, p. 75].
 Anthraquinone Dyes and Intermediates
Direct potash fusion leads to side products, such
as isoviolanthrone and 4-hydroxybenzanthrone.
The crude product may be used directly or in
mixtures with other dyes in vat dyeing. It is also
used to generate violanthrone derivatives. Sev-
eral processes have been developed to decrease
the amounts of undesirable side products of the
direct potash fusion of benzanthrone or to purify
the bibenzanthronyl or the crude violanthrone
[357–359]. Especially effective is the addition
of high-boiling solvents such as naphthalene, the
so-called low carbazole anthracene residues, or
sodium acetate to the melt. The quality of the
products prepared by these methods is satisfac-
tory for the production of almost all violanthrone
dyes.
Violanthrone of high purity is obtained
from 4,4
-bibenzanthronyl (153) by alkaline or
acid ring closure, preferably in the presence
of oxidizing agents [359], [360]. If this ring
closure is carried out in sulfuric acid with
an excess of manganese dioxide, the 16,17-
violanthronequinone (155) is obtained. This can
be reduced readily with sodium hydrogen sul-
fite to 16,17-dihydroxyviolanthrone (156). Sub-
sequent alkylation of the hydroxy groups yields
very fast navy-blue to brilliant-green vat dyes.
The dimethyl ether (157) is the well-known
dye Caledon Jade Green or Indanthren Brilliant
Green B and FFB (extremely pure form).
45
3,12,16,17-Tetrachloroviolanthrone
[84617-19-6], Indanthren Navy Blue RB,
M r 594.3, is prepared by chlorination in
trichlorobenzene [4, p. 27].
Bromoviolanthrones, with one bromine
atom (Indanthren Navy Blue BRF, M r 535.4)
or with two bromine atoms (Indanthren Navy
Blue BF [1328-18-3], M r 614.3), are prepared
by bromination of violanthrone in chlorosul-
fonic acid in the presence of sulfur [361] or
antimony [362].
Nitroviolanthrone [57455-91-1], Indan-
thren Black BB, M r 501.5, is prepared by ni-
tration of violanthrone [363].
16,17-Dimethoxyviolanthrone [128-58-5],
Indanthren Brilliant Green FFB, Caledon Jade
Green, (157), M r 516.6, is prepared from 4,4
-
bibenzanthronyl by ring closure and oxidation
followed by reduction and ether formation [1],
[5, p. 81], [364].
Isoviolanthrone [128-64-3], (152),
M r 456.5. Formerly prepared from 3-
halobenzanthrone by alcoholic potash melt.
Isomer-free isoviolanthrone is obtained by an
alcoholic potash melt of 3,3
-dibenzanthronyl
sulfide [365] or by the one-pot method [366].
Dichlorination of isoviolanthrone with sul-
furyl chloride, or alternatively bromination in
chlorosulfonic acid, affords brilliant violet vat
dyes and pigments.
Dichloroisoviolanthrone [1324-55-6], (In-
danthren Brilliant Violet RR and 4 R with chlo-
rine in the 6,15 positions), M r 524.4, is prepared
from isoviolanthrone by chlorination with sul-
furyl chloride [367].
46 Anthraquinone Dyes and Intermediates

Tribromoisoviolanthrone [1324-17-0], In- 3. Dye Classes

danthren Brilliant Violet 3 B and F 3 B,
M r 693.2, is prepared by bromination of isovi- The introduction of auxochromes into the al-
olanthrone in chlorosulfonic acid in the presence most colorless anthraquinone permits the tai-
of sulfur [4, p. 9]. loring of compounds to cover nearly all shades
of dye colors: types and positions of the sub-
stituents in the molecule determine the hue. As
2.12.9. Acedianthrone a rule the bathochromic shift in simple anthra-
quinones increases with increasing basicity of
The unusual ring system of acedianthrone the substituents. This generalization is clearly
[129-68-0], (158), is generated from anthrone shown by the wavelengths of the longest wave-
by condensation with glyoxal sulfate [368], fol- length absorption maximum of anthraquinones
lowed by alkaline oxidation of the glyoxal an- monosubstituted in the 1-position [371]:
throne [368] and subsequent ring closure cat- Subst. λ [mµ]
alyzed by sulfuric acid, or by direct fusion of the H 327
glyoxal anthrone with AlCl3 -NaCl [369], [370]. Cl 337
OCH3 380
OH 405
NHCOCH3 410
NHCOC6 H5 415
SCH3 438
NH2 465
N(CH3 )2 504
NHCH3 508
NHC6 H5 508

The wavelengths of the absorption maxima of

hydroxy- and aminoanthraquinones are a func-
tion of position and number of OH and NH2
groups [371]:
Position: 2 1 1,2 1,5 1,8 1,4

OH λ [mµ] 365 405 416 428 430 476

NH2 λ [mµ] 410 465 480 480 492 550

The large shift from the 1,8- to the 1,4-

This process has found industrial application in
disubstituted anthraquinones, which even ex-
the production of the dichloro compound from
ceeds that between the α- and the β-substituted
2-chloro-9-anthrone.
compounds, is remarkable. For α-substituents,
additional changes in shade and color fastness
Dichloroacedianthrone [6424-51-7], In-
occur on formation of hydrogen bonds to the
danthren Red Brown RR, (159), M r 475.3,
neighboring carbonyl group.
is prepared from 2-chloroanthrone and gly-
Alteration of color in isomeric compounds
oxal sulfate in chlorobenzene via 2,2
-
can be demonstrated by comparing various
dichloroanthroneethylene, followed by ring clo-
diaminohydroxyanthraquinones:
sure in sulfuric acid [4, p. 47], [5, p. 149].
 Anthraquinone Dyes and Intermediates
The effect of β-substituents on the hue is
best demonstrated by the 1,4-diaminoanthra-
quinones:
Furthermore, the shade may be modified
strongly by ring closure and condensation re-
actions:
Not every colored anthraquinone derivative
is a dye. In addition to tinctorial strength and
depending on the intended use, such other prop-
erties as affinity to the fiber and resistance to at-
mospheric conditions must be present also. The
choice of a particular textile dye is determined
also by its application properties and its fastness.
The three major dye types, i.e., neutral, an-
ionic, and cationic dyes, are subdivided by use.
Neutral dyes: disperse dyes, vat dyes, pig-
ments, and dyes soluble in organic solvents.
Anionic dyes: acid dyes, direct dyes, and re-
active dyes.
Cationic dyes: dyes for polyacrylonitrile
fibers and other fibers modified to contain
acid groups.
47
The Colour Index (C.I.) numbers given for
the individual dyes in the following sections cor-
respond to the numbering system of the Colour
Index [11] where additional references can be
found.
3.1. Neutral Dyes
3.1.1. Disperse Dyes
The disperse dyes are water-insoluble, col-
loidally dispersed materials that are used to dye
synthetics, including polyester, polyamide, and
acetate fibers having 2.5 or 3 acetate groups per
glucose subunit. Disperse dyes are used for dye-
ing polyacrylonitrile fibers when good leveling
of light shades is required. Although disperse
dyes were developed many decades ago for col-
oring cellulose acetate fibers, the most important
application is to dye polyester fibers.
The simple anthraquinone dyes, containing
hydroxy or amino functions as their major aux-
ochromes, are used for brilliant red to blue
shades. Yellow and orange shades are obtained
by other dye classes. Choosing appropriate sub-
stituents allows the best dyes for various fibers
and colors to be obtained.
3.1.1.1. Dyes for Polyester Fibers
Anthraquinone dyes for polyester fibers can be
classified into five basic types:
The most important factors in the selection
of anthraquinone dyes are affinity, light fastness,
and resistance to sublimation. Large substituents
48 Anthraquinone Dyes and Intermediates
in the side chain tend to improve the sublima-
tion fastness considerably. On the other hand,
increased sublimation resistance generally de-
creases the affinity characteristics of the dye.
The affinity is greatly affected by the position
and the hydrophilic characteristics of the sub-
stituents. Mixtures of appropriate dyes or the
presence of contaminants formed during synthe-
sis may increase affinity by synergistic action.
Introduction of negatively charged substituents,
for instance, carboxylic esters, halogen, or sul-
fone groups, may improve light fastness.
1-Amino-4-hydroxyanthraquinones (for
preparation see page 19) possess good light
fastness and affinity for polyester fibers. They
are bright, red dyes, whose brilliance may be
improved significantly by introduction of ether
groups ortho to the amino groups. The aliphatic
ethers surpass the aromatic ethers with respect
to light fastness and are much more yellow and
somewhat brighter. Additional substituents in
the side chains may improve sublimation resis-
tance. Isomeric compounds with alkyl or aryl
ether groups in addition to hydroxyl entities are
of little commercial interest because their shades
are more blue and duller.
Examples are 160 and 161 both bright
yellow reds [372], [373]; 162, bright blue
red (R = H: C.I. Disperse Red 60, C.I. 60756
[17418-58-5], e.g., Resolin Red FB, Bayer); for
b see [374]; for c see [375].
1,4-Diaminoanthraquinones (for prepara-
tion see page 9). The poor light fastness of 1,4-
diaminoanthraquinone can be improved by ap-
propriate negatively charged substitutents. The
2-sulfophenyl ester is a sublimation-resistant,
brilliant blue dye with a reddish cast and good
light fastness. The introduction of a nitro group
into the 2 position shifts the shade into bluish
green and improves resistance to sublimation
and fading. Introduction of chlorine atoms into
the β position considerably improves light fast-
ness with little affect on the basic sublimation
characteristics.
β-Phenoxy groups in the 2,3 positions shift
the shade to a bright, somewhat reddish violet
with good stability to fading and sublimation. A
very bright turquoise color with excellent light
fastness and good resistance to sublimation are
properties of the 2,3-dicarboximides.
Examples are 167a, C.I. Disperse Violet
28, 61102 [81-42-5] (e.g. Resolin Violet RL,
Bayer); 163b, a red violet dye [3, p. 48]; 164a,
blue green [376]; 167b brilliant red blue [377].
Compounds 165 and 166 are both turquoise blue
dyes [378], [379].
N-Substituted 4-Amino-1-hydroxyanthra-
quinones. Alkyl- (or aryl-) aminohydroxy-
anthraquinones, which show good affinity and
light fastness and give violet to blue shades,
generally do not satisfy the requirements with
 Anthraquinone Dyes and Intermediates
respect to sublimation fastness. Compared to
the dyes of the tetrasubstituted series, they
are of lower tinctorial strength. Such sub-
stituents as carboxylic esters, arylsulfonic es-
ters, amides, hydroxyethylether, and methoxy
groups in arylamino compounds improve sub-
limation resistance, whereas optimized blends
prevent lowering of affinity.
Examples are 167a, C.I. Disperse Violet 27,
60724 [19286-75-0]; 167b, C.I. Disperse Blue
72, 60725 [81-48-1], and 167c, a violet dye
[380].
Diaminodihydroxyanthraquinones (for
preparation see page 24). Derivatives of α-
diaminodihydroxyanthraquinones are the most
important disperse dyes with respect to shade
and affinity. The dye properties may be opti-
mized by introducing suitable substituents, se-
lecting the positions of the isomers, and blend-
ing. Some of these properties can be illustrated
with the three basic structures shown below:
The bathochromic shift from 168 to 170 af-
fects the color; the light fastness increases in
the order of 169 → 170 → 168; and the affinity
increases from 168 → 170 → 169. The sublima-
tion fastness of all three is moderate.
Halo, alkoxy, hydroxyaryl, and phenylmer-
capto derivatives have attained commercial im-
portance. Compared to substitution next to the
hydroxy group, substitution next to the amino
group leads to brighter dyes and improved affin-
ity.
Examples are 171, C.I. Disperse Blue 56,
63285 [12217-79-7] (e.g., Resolin Blue FBL,
49
Bayer) and 172, C.I. Disperse Blue 73, 63265
[12222-75-2].
Nitroarylaminodihydroxyanthraquinones.
These dyes are valued because of their greenish-
blue shade and their good fastness to light and
sublimation. Reduction improves their affinity
somewhat but decreases light fastness.
Example : 173 is a blue dye of this kind [381].
3.1.1.2. Dyes for Cellulose Ester and
Synthetic Polyamide Fibers
The first disperse dyes (Celliton) were devel-
oped for dyeing cellulose fibers, but the impor-
tance of these diminished considerably when
other synthetic fibers appeared on the market.
Synthetic polyamide fibers could be dyed with
dyes used for acetate fibers: very few new dyes
had to be developed specifically for polyamide
fibers.
The basic type of dye closely resembles that
used for dyeing polyester fibers, but the selec-
tion of compounds is based on other criteria. Re-
quirements regarding sublimation resistance are
not as stringent, whereas fastness to ozone, ex-
haust gases, and washing are important. Substi-
tution by amino, and especially by alkylamino,
groups tends to decrease light fastness of the
dyes in polyester fibers. This is not the case for
acetate and polyamide fibers.
The orange derivatives of 1-aminoanthra-
quinone are of little importance in this context
because of their low tinctorial strength. This
contrasts with the 1-amino-4-hydroxyanthra-
quinone derivatives, which provide brilliant red
dyes. The most important are dyes derived from
1,4-diaminoanthraquinone, with shades ranging
50 Anthraquinone Dyes and Intermediates
from violet to greenish blue. Affinity may be en-
hanced vastly by blending similar compounds.
Examples of this class of dyes are 174, a bril-
liant red dye [382]; 175, C.I. Disperse Blue 14,
61500 [2475-44-7] [3, p. 54] (e.g., Celliton Fast
Blue, BASF); 176, a brillant blue dye [383]; 177,
C.I. Disperse Blue 31, 64505 [1328-23-0] [3,
p. 53] (e.g., Celliton Blue 3 G, BASF); 178, C.I.
Disperse Blue 7, 62500 [3179-90-6] [5, p. 201]
(e.g., Celliton Blue Green B, BASF).
3.1.1.3. Transfer Dyes
In transfer printing the dye is supplied in the
form of a coating on transfer paper. The fab-
ric is pressed closely against the paper, and the
dye is sublimed at ≈ 200 ◦ C and diffuses into
fibers. This process is used primarily for print-
ing on polyester fabrics. Originally it relied on
available disperse dyes with good sublimation
characteristics. Dyes, specifically developed for
this process have also appeared on the market
(see also [6, vol. VIII, pp. 191 ff.]).
Examples are 179, C.I. Disperse Red 60,
60756 [17418-58-5], and 180, C.I. Disperse
Blue 26, 63305 [3860-63-7].
3.1.1.4. Dyes for Cotton – Polyester Fabrics
Anthraquinone dyes of medium molecular mass
are suitable for direct printing and dyeing of cel-
lulose fibers, especially cotton – polyester fab-
rics pretreated with water. Most of these dyes
are classified as disperse dyes having excel-
lent resistance to sublimation, but vat dyes of
low molecular mass are included also. The dyes
are applied generally together with higher boil-
ing, water-miscible solvents (glycol and glycol
derivatives [384] or boric acid esters of species
with one to six hydroxy groups [385]) to fab-
rics preswollen with water. Heat treatment at
≈ 200 ◦ C evaporates the water, and the dye en-
ters the fiber via its solution phase. The polyester
component of the fabric is dyed simultaneously.
Examples: Compounds 181 [384] and 182
[386] are blue dyes; 183 [387] is green.
Reactive disperse dyes also make it possible
to dye cotton–polyester fabrics in equal shades.
Fluorotriazine reactive dyes have been proposed
for this application [388–390].
Examples: Compound 184 [388] is a blue,
and 185 [389] a red dye.
 Anthraquinone Dyes and Intermediates
3.1.2. Dyes Soluble in Organic Solvents
Anthraquinone dyes of relatively simple struc-
ture are used for coloring gasoline, oil, and
plastics. For example, the highly soluble
bis(alkylamino)anthraquinones are suitable ad-
ditives for gasoline, whereas quinizarin and its
derivatives are used for marking heating oils.
Note: addition of alkali causes a color change.
Examples: Compound 186 is a blue dye for
the coloring of hydrocarbons, including gasoline
[391]. Compound 187 is a mixture of blue dyes
used to color gasoline and mineral oils [392].
Dyeing of amorphous thermoplastics – poly-
methacrylate, (modified) polystyrene, or poly-
carbonate – requires dyes soluble in these mate-
rials so that transparency can be retained. How-
ever, such dyes also are used in combination
with titanium dioxide or other materials to pro-
vide body colors for the thermoplastics. Ini-
tially compounds with relatively simple struc-
tures were used, many of them drawn from
stocks of existing intermediates. Since then new
products designed to satisfy the specific require-
ments have become available.
Examples are 188, C.I. Solvent Red 111,
60505 [82-38-2]; 189, C.I. Solvent Red 52,
51
68210 [81-39-0]; 190, C.I. Solvent Violet 13,
60725 [81-48-1]; 191, C.I. Solvent Green 3,
61565 [128-80-3].
Many relatively simple amino- and hydroxy-
anthraquinone derivatives show a high degree of
order in liquid crystalline systems and are there-
fore suitable as dichroic dyes for guest – host dis-
plays. Several new dyes for this application have
been described.
Example: Compound 192 is a blue dichroic
dye [393].
3.1.3. Vat Dyes
Vat dyes have been used for many decades to
color cotton and other cellulose fibers. Despite
their high cost and their muted colors, these dyes
are extremely important for certain textiles be-
cause of their superior fastness. Very few new
vat dyes have been developed over the past few
years.
Water-insoluble vat dyes are converted to sol-
uble “anthrahydroquinones” by reducing agents,
such as sodium dithionite (hydrosulfite) in the
presence of sodium hydroxide. The sodium salts
of these mostly deep colored leuco compounds
penetrate cellulose fibers. The insoluble dye is
attached firmly to the fiber after reoxidation
(→ Textile Dyeing). Representative of a spe-
cial form are the water-soluble sulfuric acid es-
52 Anthraquinone Dyes and Intermediates

ters of the “anthrahydroquinone” compounds

(→ Leuco Esters of Vat Dyes).
On the basis of their chemical constitutions
the anthraquinoid vat dyes may be classified in
the following major groups:
acylaminoanthraquinones
anthraquinoneazoles
anthrimides and other linked anthraquinones
anthrimidocarbazoles
phthaloylacridones
benzanthrone dyes
indanthrones
other polycondensed ring systems

Acylaminoanthraquinones. Acylation of
aminoanthraquinones with benzoic acid or ben-
zoyl chloride, for example, affords vat dyes
with satisfactory affinity for cellulose fibers.
The simplest dyes of this type, 1,4- (and 1,5-)
dibenzoylaminoanthraquinones, are no longer
important. Bridging linkages, such as the di-
carboxylic acids oxalic or phthalic acid, permit
coupling of two anthraquinone units; three ami-
noanthraquinones may be combined by use of a
triazine, such as cyanuric chloride.
Acylation of 1-amino- (or 1,5-diamino)
anthraquinones yields yellow vat dyes and af-
fords red to ruby colored dyes when 1,4-
diaminoanthraquinones are used. Use of 4,8-
diamino-1,5-dihydroxyanthraquinones gives vi-
olet to blue dyes. The relatively low light fastness
of the yellow acylaminoanthraquinones may be
improved greatly by using azodiphenyl-4,4
-
dicarboxylic acid. All acylaminoanthraquinones
are relatively sensitive to atmospheric condi-
tions, except the yellow acylation product ob-
tained from anthrapyrimidinecarboxylic acid
and 1-aminoanthraquinone.
Examples of this class of dyes are 193, C.I.
Vat Violet 15, 63355 [6370-58-7] [4, p. 8] (e.g.,
Indanthren Brilliant Violet BBK, Bayer); 194
C.I. Vat Yellow 12, 65405 [6370-75-8] [4, p. 56]
(e.g., Indanthren Yellow 3 GF, Bayer); 195, C.I.
Vat Orange 17, 65415 [6370-77-0] [394] (e.g.,
Indanthren Orange GG, Bayer); 196, C.I. Vat
Yellow 10, 65430 [2379-76-2] [5, p. 178] (e.g.,
Indanthren Yellow GGF, Cassella); 197, C.I. Vat
Yellow 20, 68420 [4216-01-7] [395] (e.g., In-
danthren Yellow 4 GF, BASF); 198, C.I. Vat
Red 28, 65710 [6370-82-7] [10, p. 353] (e.g.,
Cibanone Red G, Ciba-Geigy).
 Anthraquinone Dyes and Intermediates 53

Anthraquinoneazoles. In contrast to the

older yellow Algol dyes, which contain two
thiazole rings (see page 32), the red to
blue oxazoles and thiazoles derived from
1-aminoanthraquinone-2-carboxylic acid and
3-amino-2-hydroxy- (or -mercapto-) anthra-
quinones exhibit good light fastness. The good
fastness to atmospheric conditions and chlo-
rine of the blue derivatives of 1-amino-4-
aroylaminoanthraquinone-2-carboxylic acid de-
serves special mention.
Examples are 199, C.I. Vat Red 10, 67000
[2379-79-5] [5, p. 152] (e.g., Indanthren Red
FBB, BASF); 200, C.I. Vat Blue 30, 67110
[6492-78-0] [2, p. 17], [5, p. 72] (e.g., Indan-
thren Blue CLB, BASF).

Anthrimide Carbazoles. Fast vat dyes are

Anthrimides and Other Linked An-
thraquinones. Among the anthrimides (di-
anthraquinonylamines), only the α,β deriva-
tives have reached a limited importance as vat
dyes. Coupling two anthraquinone molecules
via functional derivatives of the 2-aldehyde (or
2-carboxy) group offers another type of build-
ing block for vat dyes. Such compounds, e.g.,
1-aminoanthraquinones, are linked in the 2 po-
sition via an azine or oxadiazole group, and all
have good fastness.
Examples are 201, C.I. Vat Violet 16, 65020
[4003-36-5] [4, p. 14] (e.g., Indanthren Corinth
RK, Bayer); 202, C.I. Vat Red 18, 60705
[6409-68-3] [2, p. 64] (e.g., Indanthren Bor-
deaux B, BASF); 203, C.I. Vat Blue 64, 66730
[15935-52-1] [396] (e.g., Indanthren Blue ER,
Bayer); 204, C.I. Vat Red 13, 70320 [4203-77-4]
[5, p. 159] (e.g., Indanthren Rubine R, Cassella).
produced by carbazole ring closure from α,α-di-
anthraquinonylamines (anthrimides). The shade
is determined by the number and position of
the carbazole systems and by additional sub-
stituents, especially acylamino or alkoxy groups.
Anthraquinone carbazoles make it possible to
dye cellulose fibers in level, very fast yellow, or-
ange, brown, gray, and olive shades. However,
this series lacks dyes with bright shades.
Examples include 205, C.I. Vat Yellow 28,
69000 [4229-15-6] [4, p. 53] (e.g., Indanthren
Yellow FFRK, Hoechst); 206, C.I. Vat Orange
15, 69025 [2379-78-4] [4, p. 15], [5, p. 119]
(e.g., Indanthren Golden Orange 3 G, Bayer);
207, C.I. Vat Brown 3, 69015 [131-92-0] [4,
p. 10] (e.g., Indanthren Brown FFR, Bayer); 208,
C.I. Vat Black 27, 69005 [2379-81-9] [4, p. 29],
[5, p. 135] (e.g., Indanthren Olive R, Bayer);
209, C.I. Vat Brown 1, 70800 [2475-33-4] [5,
p. 101] (e.g., Indanthren Brown BR, Bayer);
210, C.I. Vat Green 8, 71050 [14999-97-4] [4,
54 Anthraquinone Dyes and Intermediates
p. 23] [5, p. 129] (e.g., Indanthren Khaki GG,
Hoechst).
Phthaloylacridones. Depending on the sub-
stituent in the 2 position, the 3,4-phthaloylacri-
dones supply shades varying between red and
green. The acridone vat dyes combine good light
fastness with somewhat poorer wash fastness.
Dyes of this series are especially suited for print-
ing purposes because of the ease of vatting.
Examples are 211, C.I. Vat Blue 21, 67920
[6219-97-2] [4, p. 34], [5, p. 143] (e.g., Indan-
thren Blue HCGK, Hoechst); 212, C.I. Vat Green
12, 70700 [6661-46-7] [4, p. 19].
Benzanthrone Dyes. Vat dyes derived from
benzanthrone can be subdivided into two ma-
jor groups: the peri ring-closure products of 3-
anthraquinonylaminobenzanthrone, referred to
as ‘imide-green’ dyes, and the dyes of the vi-
olanthrone and the isoviolanthrone series.
The first class gives the muted colors olive
green, olive, khaki, and grey and excels in its re-
sistance to light and atmospheric conditions. The
blue color of violanthrone is shifted to a brilliant
green by introducing two alkoxy groups into the
16 and 17 positions. An additional shift may be
achieved by halogenation.
A redder and brighter shade is obtained with
isoviolanthrone. Its halogenation products are
marketed as brilliant violet dyes. Related to vi-
olanthrone is the alkaline ring closure product
of the 3-pyrazolanthronylbenzanthrone, which
is used as a navy blue vat dye.
Examples are 213, C.I. Vat Green 3, 69500
[3271-76-9] [2, p. 71] (e.g., Indanthren Olive
Green B, BASF); 214, C.I. Vat Black 25,
69525 [4395-53-3] [2, p. 76] (e.g., Indanthren
Olive T, BASF); 215, C.I. Vat Blue 25, 70500
[6247-39-8] [4, p. 26] (e.g., Indanthren Navy
Blue R, Hoechst); 216, C.I. Vat Blue 20, 59800
[116-71-2] [5, p. 108] (e.g., Indanthren Dark
Blue BOA, BASF); 217, C.I. Vat Green 1, 59825
[128-58-5] [2, p. 69], [5, p. 83] (e.g., Indanthren
Brilliant Green FFB, BASF); 218, C.I. Vat Vio-
let 1, 60010 [1324-55-6] [367] (e.g., Indanthren
 Anthraquinone Dyes and Intermediates
Brilliant Violet RR, BASF); 219, C.I. Vat Blue
26, 60015 [4430-55-1] [414] (e.g., Indanthren
Cyanine B, BASF).
Indanthrones. The blue indanthrone was the
first synthetic vat dye of the anthraquinone se-
55
ries. Because of its excellent fastness and bright
colors it has remained the most important vat
dye for a long time despite its low resistance
to chlorine. Its chlorine resistance can be im-
proved somewhat by post-halogenation. Intro-
duction of hydroxy or amino groups shifts the
shade to green.
Examples are 220, C.I. Vat Blue 4, 69800
[81-77-6] [2, p. 52], [5, p. 73] (e.g., Indanthren
Blue RS, BASF); 221, C.I. Vat Green 11, 69850
[1328-41-2] [4, p. 18] (e.g., Indanthren Green
BB, Bayer).
Highly Condensed Ring Systems. A valu-
able supplement to the anthraquinone vat dyes is
found in the more highly condensed carbocyclic
quinones dibenzpyrenequinone, anthanthrone,
and pyranthrone. These substances are yellow
to red vat dyes without additional auxochromic
substituents. Halogenation may improve their
substantivity and change their shades. The halo
derivatives can be converted to anthrimide-
like compounds by reaction with aminoanthra-
quinones. These are in themselves useful as vat
dyes and dye cotton in brown to grey shades but
can be subjected to further carbazolyation.
Examples are 222, C.I. Vat Orange 1, 59105
[1324-11-4] [2, pp. 117, 119] (e.g., Indanthren
Golden Yellow RK, Hoechst); 223, C.I. Vat Or-
ange 3, 59300 [4378-61-4] [2, p. 129], [5, p. 90]
(e.g., Indanthren Brilliant Orange RK, Cas-
sella); 224, C.I. Vat Black 29, 65225 [6049-19-0]
[2, p. 23] (e.g., Indanthren Grey BG, Bayer);
225, C.I. Vat Orange 2, 59705 [1324-35-2]
[2, p. 61], [5, p. 116] (e.g., Indanthren Orange
RRTS, BASF); 226, C.I. Vat Brown 45, 59500
56 Anthraquinone Dyes and Intermediates
[6424-51-7] [4, p. 47], [5, p. 149] (e.g., Indan-
thren Red Brown RR, Cassella); 227, C.I. Vat
Orange 9, 59700 [128-70-1] [2, p. 60], [5, p. 114]
(e.g., Indanthren Golden Orange G, BASF).
3.1.4. Pigments
Because of their low solubility in organic me-
dia, most vat dyes should also be usable as pig-
ments. However, for this type of use they must
be prepared with a high degree of purity and
with special physical properties (crystal modifi-
cation, particle size distribution, etc.). The rel-
atively high costs of synthesizing anthraquinone
pigments restrict their use to special applica-
tions where requirements for fastness are strin-
gent. Only a few of the known vat dyes satisfy
these requirements. Apart from some acylami-
noanthraquinones, mostly dyes with polycon-
densed ring systems, including indanthrones,
anthanthrones, pyranthrones, flavanthrone, and
their halogen derivatives, have some importance
as pigments. Beyond that a number of spe-
 Anthraquinone Dyes and Intermediates
cialty anthraquinone dyes have been developed
as pigments over the past 25 years: for exam-
ple, anthraquinone-azo, bianthraquinonyl, and
anthraquinonylaminotriazine derivatives.
Only of little interest at present are the
colored lakes, especially aluminum lakes of
the hydroxyanthraquinones, such as alizarine,
purpurin, and quinizarin and their sulfonic
acids. (For preparation see Chap. 2; for formula-
tion and application → Pigments, Organic, and
[398].)
Examples are, 228 C.I. Pigment Yellow 108,
68420 [4216-01-7]; 229 C.I. Pigment Blue 60,
69800 [81-77-6]; 230 C.I. Pigment Red 168,
59300 [4378-61-4]; 231 C.I. Pigment Orange
40, 59700 [128-70-1]; 231 C.I. Pigment Yel-
low 24, 70600 [475-71-8]; 233, yellow pig-
ment [399]; 234, C.I. Pigment Red 177, 65300
[4051-63-2]; 235, yellow pigment [400]; 236
Aluminum Lake, C.I. Pigment Violet 5 : 1;
58055 : 1 [145-48-2].
3.2. Anionic Dyes
The anionic anthraquinone dyes may be classi-
fied by type of application and dyeing procedure
into the following groups:
acid dyes
direct dyes
reactive dyes
3.2.1. Acid Dyes
Acid dyes are used for dyeing wool, synthetic
polyamides, and silk in aqueous media. They
may be subdivided into the following basic
types:
57
The majority of the acid anthraquinone dyes
available commercially give bright blue shades
not obtainable with azo dyes. The red and yel-
low anthraquinone dyes are of little importance.
Dyes of green shades obtained by combining
yellow and blue dyes possess mostly slight wash
fastness. Here, the uniformly dyeing green dyes
of the anthraquinone series have proved their
special value. The acid anthraquinone dyes are
classified for particular applications according
to their leveling characteristics, light fastness,
and wash fastness. Once synthetic polyamide
fibers were introduced in the market appro-
priate types were selected from the existing
stocks. Special acid dyes have been developed
for polyamides.
1-Aminoanthraquinone-2-sulfonic Acids.
Condensation of bromamine acid (1-amino-4-
bromoanthraquinone-2-sulfonic acid, see page
16) with aromatic or cycloaliphatic amines is
used to produce a large number of blue acid
dyes. The shade, leveling characteristics, wash
fastness, and light fastness may be varied over a
wide range by choosing particular amines. Cy-
cloaliphatic amines provide the same brightness
as aliphatic dyes but impart greater light fast-
ness. Arylamines substituted with alkyl, halo-
gen, aryl, aryloxy, or sulfonic ester groups yield
dyes with better wash fastness and affinity in
neutral media but less uniform leveling. Sub-
stituents at the o position cause a hypochromic
shift and increase brilliance.
The arylamino residue may be altered sub-
sequently by sulfonation, halogenation, acyla-
tion, or by the Einhorn reaction. Substitution of
anthraquinone in the 5, 6, 7, or 8 positions offers
an additional possibility to change the character-
istics of the dye. For instance, halogen atoms and
sulfonic acid groups cause bathochromic effects
that are most pronounced when the substituents
are introduced in the β position. The solubility
of the 2,6- (or 2,7-) disulfonic acids is higher
than that of the 2,5- (or 2,8-) series.
Examples are 237, C.I. Acid Blue 25, 62055
[6408-78-2] [3, p. 41] (e.g., Acilan Direct Blue
A, Bayer); 238, C.I. Acid Blue 62, 62045
[4368-56-3] [3, p. 30] (e.g., Alizarine Brilliant
Blue R, Bayer); 239, C.I. Acid Blue 129, 62058
[6397-02-0] [401]; 240, C.I. Acid Blue 40,
58 Anthraquinone Dyes and Intermediates
62125 [6424-85-7] [2, p. 135] (e.g., Anthralan
Blue G, Hoechst); 241 [402] and 242 [404] are
brilliant blue dyes.
Diaminodihydroxyanthraquinonesulfonic
Acids. These dyes belong to the oldest synthetic
acid wool dyes, but their importance has de-
creased considerably. An example for this class
is 243, C.I. Acid Blue 43, 63000 [2150-60-9]
[3, p. 42] (e.g., Acilan Saphirol SE, Bayer).
1,4-Diaminoanthraquinones with Exter-
nal Sulfonic Acid Groups. A common fea-
ture of dyes of this group is their manufacture
by sulfonation of the corresponding dye base
derived from quinizarin or haloaminoanthra-
quinones. The reaction products of quinizarin
with aromatic or araliphatic amines predomi-
nate in number and importance. The introduc-
tion of hydroxy groups into the 5 or the 5,8 po-
sitions brings about the expected bathochromic
shift. Wash fastness and leveling properties may
be altered by substitution. The shade can be
varied from brilliant blue to green by appro-
priate amines. Araliphatic and cycloaliphatic
amines lead to brilliant blue shades. A similar
effect is exhibited by sterically hindered aro-
matic amines such as mesidine. These prod-
ucts are more light fast than the derivatives
of bromamine acid. Among the unsymmetri-
cally substituted dyes derived from 1-amino-
(or 1-alkylamino-) 4-haloanthraquinones, the 1-
alkylaminoanthraquinones have the lower light
fastness. Exceptions are the derivatives of the
1-sec-alkylamino-4-haloanthraquinones. Intro-
duction of alkoxy- (or aryloxy) groups into po-
sition 2 shifts the shade of the 4-arylamino-1-
aminoanthraquinones to a bright violet.
Examples are 244, C.I. Acid Green 25, 61570
[4403-90-1] [5, p. 215] (e.g., Alizarine Cyanine
Green G, Bayer); 245, C.I. Acid Green 41, 62560
 Anthraquinone Dyes and Intermediates 59

[4430-16-4] [3, p. 35]; 246 [406] and 247 [407]
are greenish-blue dyes; 248, C.I. Acid Violet 42,
62026 [6408-73-7] [3, p. 48] (e.g., Supracen Vi-
olet 3 R, Bayer).
1-Amino-4-hydroxyanthraquinones with
External Sulfonic Acid Groups. By one-sided
reaction of quinizarin with arylamines, fol-
lowed by sulfonation, violet leveling dyes are
obtained. Derivatives of 1-amino-4-hydroxy-2-
phenoxyanthraquinones were developed spe-
cially for polyamide fibers.
Examples are 249, C.I. Acid Violet 43, 60730
[4430-18-6] [3, p. 48] (e.g., Supracen Violet 3 B,
Bayer); 250 bluish brilliant red dye [408].
whole series of specially developed products
is available. For instance, derivatives of the
anthrimide or carbazole series are known to
be very light-fast gray and brown wool dyes.
The post-sulfonation products of 1,5- (and 1,8-)
diarylaminoanthraquinones are violet dyes com-
monly applied as mixtures.
An example is 252, C.I. Acid Black 48, 65005
[1328-24-1] [5, p. 216] (e.g., Alizarine Light
Grey BBLW, BBL, Bayer).

3.2.2. Direct Dyes

Compared to direct azo dyes, the direct anthra-

quinone dyes have lower tinctorial strengths and
are therefore far less economical to use. They
have lost most of their importance. Only a few
Anthrapyridones. Of the anthraquinone
special green dyes have retained their impor-
dyes with meso rings only species sulfonated
tance. Direct green cotton dyes can be produced
in the arylamino or phenoxy groups de-
by coupling a blue bromamine acid dye and a
rived from 6-arylamino-3-methyl-, 6-arylami-
yellow azo dye via ureido or diaminotriazine
no-1-carbethoxy-4-methyl-, and 6-arylamino-1-
bridges.
benzoyl-4-phenoxy-anthrapyridones are known
An example is compound 253, C.I. Direct
to have been used commercially. They once were
Green 28, 14155 [6471-09-6].
very important as light-fast, red, leveling dyes
but have lost their position with the availability
of the fast, red, azo dyes.
An example is 251, C.I. Acid Red 82, 68205
[2611-80-5] [3, p. 40].

Other Acid Anthraquinone Dyes. In addi-

tion to the dyes in the preceding classes, a
60 Anthraquinone Dyes and Intermediates

3.2.3. Reactive Dyes

The shades of the commercial reactive anthra-

quinone dyes range generally only from violet
to blue. These dyes are used specifically for the
production of fast brilliant blue shades on cel-
lulose fibers. Their synthesis begins with ba-
sic dyes linked to the reactive component via
an amino group. These amino or alkylamino
group may be positioned directly on the anthra-
quinone nucleus (rare) or on an aryl or cycloalkyl
residue. Another possible linkage involves ami-
nomethylarylaminoanthraquinones.
Nearly all reactive anthraquinone dyes are
derivatives of bromamine acid (see Section
3.2.1). To obtain a sufficiently soluble dye, at
least one additional sulfonic acid group must be
present in the molecule. This may be positioned
directly on the anthraquinone nucleus, in the 5
to 8 positions, or may be linked to the arylamino
substituent. It is also possible to introduce one
or two additional sulfonic acid groups together
with a reactive group.
A large number of fiber-reactive components
has been proposed for the preparation of reac-
tive anthraquinone dyes (→ Reactive Dyes). Re-
active carboxylic acid derivatives, such as 2,3-
dichloroquinoxaline-6-carbonyl chloride and α-
bromoacryloyl chloride, or reactive chloro or
fluoro heterocyclics, such as derivatives of tri-
azine or pyrimidine, have become important in-
dustrially.
Dyes with reactive vinylsulfonyl or β-
sulfatoethylsulfonyl groups are constructed on
a somewhat different principle.
The various options in printing or continuous
dyeing are affected more by the choice of the re-
active group than by the chromophoric system.
Examples of this class of dyes are 254, C.I.
Reactive Blue 2, 61211 [12236-82-7] (e.g., Pro-
cion Blue H-B); 255, C.I. Reactive Blue 4, 61205
[13324-20-4] (e.g., Procion Blue MX-R); 256,
reddish brilliant blue [409]; 257, brilliant blue
[410]; 258, blue [411]; 259, brilliant blue [412];
260, C.I. Reactive Blue 19, 61200 [2580-78-1]
(e.g., Remazol Brilliant Blue R, Hoechst); 261,
reddish brilliant blue for wool [413].
 Anthraquinone Dyes and Intermediates
3.3. Cationic Dyes
Water-soluble cationic anthraquinone dyes have
become valuable for dyeing polyacrylonitrile
fibers. Dyes with external ammonium groups are
especially important. Dyes with quaternary am-
monium groups as well as salts of sufficiently
basic amino derivatives are used also. The ma-
jority of commercial dyes are alkylamino- or
arylaminoanthraquinones that carry an ammo-
nium group on the alkyl group, such as trialky-
lammonium, cycloammonium, or hydrazonium
residue. A protonated dialkylamino group also
may be present. Most of these dyes are derived
from 1,4-diaminoanthraquinone.
Examples are 262, a blue dye [307], 263, a
reddish-blue dye [284], 264, a greenish-blue dye
[307], and compound 265, a blue dye used for
wet-spun fibers while they are still gels [280].
61
4. References
General References
1. Ullmann, 3rd ed., vol. 3, p. 662 – 732.
2. Bios Final Report 987.
3. Bios Final Report 1484.
4. Bios Final Report 1493.
5. Fiat Final Report 1313 II.
6. K. Venkataraman: The Chemistry of Synthetic
Dyes, vol. I – VIII, Academic Press, New
York – London 1952 – 1978.
7. J. Houben: Das Anthracen und die
Anthrachinone, G. Thieme, Leipzig 1929.
8. N. N. Woroshzow: Grundlagen der Synthese
von Zwischenprodukten und Farbstoffen,
Akademie-Verlag, Berlin 1966.
9. P. Rys, H. Zollinger: Leitfaden der
Farbstoffchemie, Verlag Chemie, Weinheim
1970.
10. H. R. Schweizer: Künstliche organische
Farbstoffe und ihre Zwischenprodukte,
Springer, Berlin – Göttingen – Heidelberg
1964.
11. Colour Index, 3rd ed., vol. 1 – 5, Soc. of
Dyers & Colourists, Bradford/England 1971.
12. Ullmann 4th ed., vol. 7, p. 585 – 646.
13. Houben-Weyl, 4/7, part 3 c.
14. P. F. Gordon, P. Gregory: Organic Chemistry in
Colour, Springer, Berlin–Heidelberg–New
York 1983.
Specific References
15. Bayer, DE 160104, 1903; Friedländer, vol. 8,
p. 236.
62 Anthraquinone Dyes and Intermediates
16. Bayer, DE-OS 3106933, 1981 (K. Ebke, J.
Ohm, J. Schroeder).
17. BASF, DE-OS 1593761, 1967 (H.-J. Nebel).
18. BASF, DE-OS 2102037, 1971 (H. Hiller, W.
Jentzsch).
19. Bayer, DE-OS 2124261, 1971 (R. Schmitz).
20. Sumitomo Chem., DE-OS 2214948, 1971 (E.
Hongo et al.).
21. Mitsubishi Chem., JP-KK 46-22335, 1969.
22. SU 138614, 1959 (W. A. Iwanowa et al.).
23. Bayer, DE-OS 2163674, 1971 (R. Schmitz, C.
Wittig).
24. ICI, GB 1420191, 1971 (N. Ackerley, R.
Price).
25. ICI, GB 1416678, 1971 (A. Bennie, R. T.
Clarke, T. Hollis).
26. Bayer, DE-OS 2041547, 1970 (R. Schmitz, K.
Alberti).
27. Agency of Ind. Sci. Tech.,
JP-Kokai 51-100064, 1975.
28. Agency of Ind. Sci. Tech.,
JP-Kokai 51-100063, 1975.
29. Reynolds Metals, US 2871244, 1955 (J.
Kamlet).
30. Bayer, DE 228901, 1909; Friedländer, vol. 10,
p. 578.
31. Bayer, DE-OS 2654650, 1976 (H. Seidler, N.
Majer, H. Judat).
32. Bayer, DE-OS 2455587, 1974 (N. Majer et al.).
33. Bayer, DE-OS 2522177, 1975 (K.-J. Reubke).
34. Inst. f. org. Zwischenprod. u. Farbst.,
SU 178390, 1963 (N. S. Dokunichin et al.).
35. Bayer, DE-OS 2458022, 1974 (B. Thelen et
al.).
36. Bayer, DE-OS 2452014, 1974 (N. Majer et al.).
37. ICI, DE-OS 2240518, 1971 (D. A. S. Phillips).
38. Ciba-Geigy, DE-OS 1768593, 1967 (M.
Grelat).
39. Du Pont, US 3378572, 1964 (R. S. Wilder).
40. Du Pont, US 2417027, 1943 (V. Weinmayr).
41. IG-Farbenind., DE 677327, 1935.
42. Bayer, DE-OS 2720965, 1977 (H. Herzog, W.
Hohmann, H. Seidler).
43. H. Schilling, Chem. Ber. 46 (1913) 1066.
44. AG für Anilin-Fabrikation, DE 269249, 1913;
Friedländer, vol. 11, p. 548. AG für
Anilin-Fabrikation, DE 293156, 1913;
Friedländer, vol. 12, p. 410.
45. Du Pont, US 2033363, 1934 (J. M. Tinker,
V. M. Weinmayr).
46. Sandoz, DE-OS 2162538, 1970 (I. Toth).
47. Sandoz, DE-OS 2227340, 1971 (I. Toth).
48. Bayer, DE-OS 2232464, 1972 (W. Auge,
K.-W. Thiem, R. Neeff).
49. Bayer, DE-OS 2620486, 1976 (B. Thelen, W.
Auge, K.-W. Thiem).
50. BASF, DE-OS 2039822, 1970 (E. Hartwig, O.
Ackermann, H. Eilingsfeld).
51. Sumitomo Chem., DE-OS 2727587, 1976 (A.
Fukasawa et al.).
52. Bayer, DE-OS 2646649, 1976 (W. Hohmann,
K. Wunderlich, H. Seidler).
53. Sumitomo Chem., DE-OS 2751666, 1977 (A.
Fukasawa, S. Masaki, N. Serizawa).
54. Bayer, DE-OS 2233185, 1972 (A. Vogel).
55. Iwaki Seiyaku, DE-OS 2419726, 1973 (T.
Okada, K. Naito, T. Kikuchi).
56. Mitsui Toatsu Chem., JP-Kokai 54-19958,
1977.
57. Ciba-Geigy, DE-OS 2349753, 1972 (Z. Scha,
T. Somlo).
58. Bayer, DE-OS 2219216, 1972 (E. Klauke, R.
Schmitz, H.-S. Bien).
59. Sandoz, DE-OS 2103360, 1970 (W. Frey, I.
Toth).
60. Sandoz, DE-OS 2206960, 1971 (F. Müller, R.
Winkler).
61. BASF, DE-OS 2232446, 1972 (K.-H. Bantel,
H. Eilingsfeld).
62. BASF, DE-OS 2233076, 1972 (K.-H. Bantel,
H. Eilingsfeld, G. Stökelmann).
63. BASF, DE-OS 2449219, 1974 (G. Epple).
64. Bayer, DE-OS 2343978, 1973 (K.-W. Thiem,
W. Auge, R. Neeff).
65. Bayer, DE-OS 2654649, 1976 (K. Wunderlich
et al.).
66. BASF, DE-OS 2200088, 1972 (H. Eilingsfeld,
O. Ackermann).
67. Bayer, DE-OS 2256644, 1972 (W. Auge et al.).
68. Sumitomo Chem., DE-OS 3029302, 1979 (M.
Takahashi et al.).
69. Bayer, DE-OS 2351590, 1973 (W. Hohmann).
70. BASF, DE-OS 2853920, 1978 (S. Mensch, W.
Elser).
71. Bayer, DE-OS 2637732, 1976 (W. Hohmann,
K. Wunderlich).
72. BASF, DE-OS 2459164, 1974 (D. Lach, H.
Eilingsfeld, G. Stöckelmann).
73. Mitsubishi Chem., JP-Kokai 54-100 362, 1978.
74. Bayer, DE-OS 2346317, 1973 (A. Vogel).
75. Inst. der Industrie für org. Chem., PL 52206,
1964 (S. Galinowski, S. Swiatly).
76. Bayer, DE-OS 2400164, 1974 (A. Vogel).
77. Bayer, DE-OS 2637733, 1976 (K. Wunderlich,
W. Hohmann, H.-S. Bien).
78. BASF, DE-OS 2545699, 1975 (H.
Bruenemann, H. Eilingsfeld, D. Lach).
79. Mitsui Toatsu Chem., JP-Kokai 53-44551,
1976.
 Anthraquinone Dyes and Intermediates
80. BASF, DE-OS 2524747, 1975 (H. Eilingsfeld,
D. Lach).
81. Sandoz, DE-OS 2222638, 1971 (R. Winkler).
82. ICI, DE-OS 2227766, 1971 (J. Cheetham).
83. Ciba-Geigy, DE-OS 2412171, 1973 (T. Somlo,
J. Murphy).
84. Mitsui Toatsu Chem., DE-OS 2539631, 1974
(Y. Torisu, S. Kaba, K. Mukai).
85. Mitsui Toatsu Chem., DE-OS 2514445, 1974
(A. Iwamura et al.).
86. Nippon Kayaku, JP-KK 47-36855, 1968.
87. Sumitomo Chem., DE-OS 2920441, 1978 (A.
Fukasawa et al.).
88. Bayer, DE-OS 1543605, 1966 (H. Pelster et
al.).
89. BASF, DE-OS 2452413, 1974 (G. Epple).
90. BASF, DE-OS 2164458, 1971 (K.-H. Bantel,
H. Eilingsfeld).
91. Sumitomo Chem., DE-OS 2715072, 1976 (M.
Yoshimura et al.).
92. Mitsui Toatsu Chem., DE-OS 2557441, 1974
(Y. Hirai et al.).
93. Sumitomo Chem., JP-Kokai 50-49267, 1973.
94. Sandoz, DE-OS 2211411, 1971 (M. Aerberli,
I. Toth).
95. Bayer, DE-OS 2314218, 1973 (K.-W. Thiem,
W. Auge, R. Neeff).
96. Sumitomo Chem., JP-Kokai 51-32552, 1974.
97. Bayer, DE-OS 2526651, 1975 (K.-J. Reubke,
H.-S. Bien).
98. Bayer, EP 49381, 1980 (K.-J. Reubke, J.
Stawitz).
99. IG-Farbenind., DE 555937, 1930 (R. E.
Schmidt, K. Bamberger); Friedländer, vol. 19,
p. 2028.
100. Bayer, EP 81169, 1981 (J. Stawitz).
101. IG-Farbenind., DE 590163, 1930 (F. Wieners);
Friedländer, vol. 19, p. 2045.
102. BASF, DE-AS 1205550, 1963 (W. Braun, M.
Ruske).
103. Ciba-Geigy, BE 774901, 1971.
104. Bayer, DE-AS 1154490, 1962 (H. Vollmann,
W. Hohmann, F. Baumann).
105. Scottish Dyes, GB 230116, 1923 (G. Beckett,
J. Thomas).
106. Hoechst, DE 158076, 1900; Friedländer,
vol. 7, p. 776.
107. Sandoz, DE-OS 1927785, 1968 (P. Buecheler).
108. Bayer, DE 288825, 1914; Friedländer, vol. 12,
p. 414.
109. Sumitomo Chem., JP-Kokai 53-44550, 1976.
110. BASF, DE 252578, 1911; Friedländer, vol. 11,
p. 545.
111. Mitsubishi Chem., JP-Kokai 51-23250, 1974.
63
112. SU 585156, 1976 (P. D. Jakuchny, T. I.
Komarenko, D. F. Schurygina).
113. Mitsui Toatsu Chem., JP-Kokai 50-64257,
1973.
114. Mitsui Toatsu Chem., JP-Kokai 50-134026,
1974.
115. Kuhlmann, DE 586515, 1932; Friedländer,
vol. 20, p. 1302.
116. Bayer, DE-OS 2827197, 1978 (R. Braden et
al.).
117. Sandoz, DE-OS 2340114, 1972 (F. Krenmüller
et al.).
118. Bayer, DE 144634, 1901; Friedländer, vol. 7,
p. 201.
119. Ciba-Geigy, DE-OS 2541663, 1974 (Z. Seha).
120. Bayer, EP 63298, 1981 (K.-J. Reubke).
121. IG-Farbenind., DE 736901, 1937 (W.
Zerweck, E. Heinrich).
122. H. Dreyfus, FR 602882, 1924.
123. Bayer, DE-AS 1150652, 1955 (G. Gehrke,
L. Nüßler).
124. IG-Farbenind., DE 722593, 1933.
125. Allied Chem. & Dye Corp., US 2443899, 1943
(A. V. Erkkila, R. C. Hoare).
126. ICI, DE 511320, 1928; Friedländer, vol. 17,
p. 1191.
127. Nat. Aniline, US 2207045, 1938 (R. S. Wilder).
128. Bayer, DE-OS 1644607, 1966 (K.-H. Peters,
R. Neeff).
129. Bayer, DE 225232, 1908; Friedländer, vol. 9,
p. 1197.
130. Du Pont, US 2346726, 1942 (E. C. Buxbaum).
131. R. Wedekind, GB 14476, 1911; Friedländer,
vol. 11, p. 627.
132. Ciba, BE 719645, 1967.
133. IG-Farbenind., DE 623069, 1931 (K. Köberle);
Friedländer, vol. 21, p. 1085.
134. Du Pont, US 3040063, 1960 (R. L. Walker).
135. IG-Farbenind., DE 518406, 1926 (W.
Hartmann); Friedländer, vol. 17, p. 1211.
136. Bayer, DE-AS 1228274, 1965 (H. Leister, H.
Vollmann, H.-S. Bien)
137. BASF, DE 158951, 1903; Friedländer, vol. 8,
p. 277.
138. Ciba, BE 670204, 1964.
139. Ciba Geigy, DE-OS 2109058, 1970
(E. Mörgeli).
140. Bayer, DE-AS 1151517, 1962 (H. Vollmann,
W. Hohmann, F. Baumann).
141. Ciba, DE-AS 1176668, 1962 (P. Sutter).
142. Du Pont, US 2716655, 1954 (S. N. Boyd).
143. Bayer, DE 267445, 1912; Friedländer, vol. 11,
p. 562.
144. BASF, DE-AS 1221240, 1964 (H. Eilingsfeld).
145. Hoechst, DE-AS 1174925, 1961 (O. Fuchs, H.
Rentél).
64 Anthraquinone Dyes and Intermediates
146. Nat. Aniline, US 2251688, 1938 (J. Ogilvie,
R. X. Hoare).
147. Du Pont, US 2135346, 1937 (H. R. Lee, D. C.
Klein).
148. IG-Farbenind., DE 484997, 1927 (K.
Weinand); Friedländer, vol. 16, p. 1248.
149. Sumitomo Chem., JP-Kokai 58-131964, 1982.
150. Sumitomo Chem., JP-Kokai 57-77663, 1980.
151. ICI, GB 1291255, 1968 (J. H. Adam, D. N.
Marsh).
152. Bayer, DE-OS 2740885, 1977 (R. Muders et
al.).
153. Bayer, DE-AS 1226598, 1964 (F. Baumann, H.
Vollmann, H.-J. Schulz).
154. Bayer, DE-OS 1768152, 1968 (K. Wunderlich,
H.-S. Bien).
155. Bayer, DE-AS 1222051, 1965 (H.-J. Schulz,
H.-S. Bien).
156. Sandoz, DE 631518, 1934; Friedländer,
vol. 23, p. 952.
157. BASF, DE 106227, 1898; Friedländer, vol. 5,
p. 307.
158. Nat. Aniline, US 2210517, 1937 (R. S. Wilder).
159. BASF, DE 108274, 1898; Friedländer, vol. 5,
p. 311.
160. Bayer, GB 1014055, 1961 (J. Singer, H. W.
Schwechten).
161. Sandoz, FR 1509724, 1966 (J. Günthard).
162. Eastman Kodak, BE 661209, 1960.
163. BASF, DE-AS 1227583, 1963 (W. Braun, I.
Paetzke); BASF, DE-OS 1960100, 1969 (P.
Dimroth, E. Schefczik); BASF,
DE-OS 2060557, 1970 (P. Dimroth, G.
Henning); GAF, GB 1062388, 1965.
164. IG-Farbenind., DE 503717, 1926 (K.
Schirmacher, K. Zahn, H. Vollmann);
Friedländer, vol. 17, p. 695.
165. Sandoz, DE-OS 2224793, 1971 (R. Winkler).
166. Kuhlmann, DE 583871, 1931; Friedländer,
vol. 20, p. 1299.
167. BASF, DE-OS 1644439, 1965 (W. Braun, K.
Maier).
168. Hoechst, FR 1363216, 1962.
169. K. Venkataraman, Indian. J. Chem. 9 (Oct.
1971) 1060 – 1063.
170. IG-Farbenind., DE 456235, 1925 (R. E.
Schmidt); Friedländer, vol. 15, p. 674.
171. Bayer, BE 627010, 1962 (K. Wunderlich,
H.-S. Bien).
172. ICI, GB 1471265, 1973 (R. T. Clarke, T. J.
Smith, D. A. Stewart).
173. Bayer, DE-AS 1184879, 1962 (K. Klemm, G.
Gehrke).
174. Bayer, DE-AS 1199279, 1963 (H.-S. Bien, W.
Hohmann, H. Vollmann).
175. Bayer, DE-OS 1493739, 1965 (W. Hohmann,
H. Vollmann, H.-S. Bien).
176. Bayer, DE-OS 1932646, 1969 (W. Hohmann,
K. Wunderlich, H.-S. Bien).
177. Ciba, DE-AS 1134087, 1960 (P. Rhyner).
178. Sumitomo Chem., JP-KK 47-37252, 1970.
179. Bayer, DE-AS 1277475, 1963 (G. Gehrke).
180. BASF, DE-OS 1593780, 1967 (H.-J. Sturm, G.
Steinhoff).
181. Bayer, EP 69910, 1981 (V. Hederich, G.
Gehrke).
182. BASF, DE 186526, 1904; Friedländer, vol. 8,
p. 237.
183. Ciba-Geigy, DE-OS 2758397, 1976 (M.
Grélat).
184. Bayer, DE-OS 2830554, 1978 (R. Schmitz).
185. Mitsui Toatsu, JP-Kokai 54-22357, 1977.
186. Sumitomo Chem., JP-Kokai 49-5429, 1972.
187. BASF, DE-AS 1165180, 1961 (K. Scherf).
188. Bayer, DE 81960, 1893; Friedländer, vol. 4,
p. 274.
189. Bayer, DE 161026, 1904; Friedländer, vol. 8,
p. 256.
190. Bayer, DE 156762, 1903; Friedländer, vol. 8,
p. 240.
191. Bayer, DE-OS 2903851, 1979 (H. Seidler, G.
Gehrke).
192. Sumitomo Chem., JP-Kokai 50-131962, 1974.
193. Mitsubishi Chem. Ind., DE-OS 2607036, 1975
(Y. Kimura et al.).
194. Toms River Chem., US 4255342, 1979 (A. D.
Olin).
195. Mitsubishi Chem. Ind., JP-Kokai 54-3051,
1977.
196. Nippon Kayaku, JP-Kokai 53-37650, 1976.
197. Bayer, DE-OS 2855939, 1978 (H. Herzog, G.
Gehrke).
198. ACNA, FR 1352537, 1962 (A. Crotti, P.
Mezzacappa).
199. ICI, DE 568311, 1929; Friedländer, vol. 19,
p. 1926.
200. Bayer, DE 163042, 1904; Friedländer, vol. 8,
p. 268.
201. Bayer, DE-OS 1543619, 1966 (R. Schmitz, H.
Leister, H.-S. Bien).
202. Bayer, DE-OS 2 909481, 1979 (W. Steinbeck,
G. Gehrke).
203. IG-Farbenind., DE 568760, 1925 (R. E.
Schmidt); Friedländer, vol. 18, p. 1277.
204. IG-Farbenind., DE 554647, 1930 (R. E.
Schmidt, K. Bamberger); Friedländer, vol. 19,
p. 1949.
205. Bayer, DE-OS 1543605, 1966 (H. Pelster et
al.).
206. Mitsui Toatsu, JP-Kokai 55-33407, 1978.
 Anthraquinone Dyes and Intermediates
207. Ciba, DE 589074, 1931; Friedländer, vol. 19,
p. 2001.
208. Bayer, DE 100138, 1897; Friedländer, vol. 5,
p. 245.
209. Du Pont, US 2419405, 1943 (D. X. Klein).
210. Bayer, FR 1445843, 1964 (W. Hohmann, H.-S.
Bien).
211. Bayer, FR 1468502, 1965 (W. Hohmann et al.).
212. Ciba, CH 146772, 1928.
213. IG-Farbenind., DE 445846, 1925 (C.
Weinand); Friedländer, vol. 15, p. 677.
214. Bayer, DE 238488, 1910; Friedländer, vol. 10,
p. 646.
215. Bayer, DE-OS 1939095, 1969 (P. Wegner et
al.).
216. Ciba, GB 1085685, 1965.
217. Nippon Kayaku, JP-Kokai 49-17425, 1972.
218. Ciba-Geigy, EP 71576, 1981 (P. Kniel).
219. IG-Farbenind., DE 445269, 1925 (R. E.
Schmidt, A. Jacobi); Friedländer, vol. 15,
p. 671.
220. Bayer, DE-AS 1228734, 1963 (K. Klemm, G.
Gehrke).
221. Bayer, GB 1029448, 1964 (W. Hohmann).
222. BASF, DE-AS 2713575, 1977 (J. Redeker, H.
Hiller, E. Spohler).
223. Sumitomo Chem., DE-OS 2817890, 1977 (M.
Nishikuri, A. Takeshita, H. Kenmochi).
224. Mitsui Toatsu Chem., JP-Kokai 56-123955,
1980.
225. Ciba, DE-AS 1065959, 1954 (P. Grossmann,
W. Jenny, W. Kern).
226. Österr. Alizarinfabr.-Ges., DE 3565, 1878;
Friedländer, vol. 1, p. 310.
227. American Aniline Products, US 3389151,
1966 (D. A. Zanella).
228. Bayer, DE 96364, 1897; Friedländer, vol. 5,
p. 246.
229. Bayer, DE 100136, 1897; Friedländer, vol. 5,
p. 247.
230. IG-Farbenind, DE 632 911, 1932 (K. Weinand,
C. Bamberger); Friedländer, vol. 21, p. 1038.
231. Ciba, DE 841313, 1944 (P. Grossmann).
232. Chem. Fabrik Griesheim-Elektron,
DE 290084, 1914; Friedländer, vol. 12, p. 439.
233. Bayer, DE 208640, 1907; Friedländer, vol. 9,
p. 701.
234. Geigy, FR 1522933, 1966.
235. Bayer, DE-AS 1180473, 1962 (H.-S. Bien, K.
Wunderlich, F. Baumann).
236. Bayer, DE-AS 1201933, 1962 (H.-S. Bien, K.
Wunderlich, F. Baumann).
237. ICI, DE-OS 2734828, 1976 (A. J. Logan, R. W.
Kenyon).
65
238. IG-Farbenind., DE 651104, 1935 (W. Zerweck,
W. Kunze); Friedländer, vol. 24, p. 991.
239. Celanese, US 2640059, 1949 (V. S. Salvin,
E. F. Landau).
240. Bayer, DE-AS 1190123, 1962 (H.-S. Bien, K.
Wunderlich, F. Baumann).
241. Allied Chem. Corp., US 3018154, 1959 (J. F.
Downey, R. C. Hoare).
242. Bayer, DE-AS 1226598, 1964 (F. Baumann, H.
Vollmann, H.-J. Schulz).
243. Nippon Kayaku, JP-KK 70-7037, 1967.
244. Bayer, DE-OS 1644578 (Example 104), 1964
(R. Neeff et al.).
245. Bayer, DE-OS 1293363, 1964 (R. Neeff et al.).
246. Mitsubishi Chem., JP-Kokai 55-73735, 1978.
247. Hoechst, BE 647171, 1963.
248. AG für Anilin-Fabrikation, DE 267081, 1912;
Friedländer, vol. 11, p. 593.
249. Hoechst, DE 361043, 1920; Friedländer,
vol. 14, p. 858.
250. IG-Farbenind., DE 533249, 1926 (K. Wilke);
Friedländer, vol. 18, p. 1245.
251. Cassella, DE 346188, 1915; Friedländer,
vol. 13, p. 395.
252. Bayer, DE 938435, 1953.
253. BASF, DE-AS 1918696, 1969 (E. Hartwig).
254. Mitsubishi Chem. Ind., JP-KK 47-26413,
1968.
255. Bayer, GB 879240, 1957.
256. BASF, DE-OS 1668870, 1968 (K. Maier).
257. American Cyanamid, US 2499003, 1946 (M.
Scalera).
258. BASF, DE 229394, 1909; Friedländer, vol. 10,
p. 601.
259. BASF, DE-AS 1108704, 1959 (W. Braun, M.
Ruske).
260. Sumitomo Chem., JP-Kokai 57-176944, 1981.
261. Bayer, DE 935669, 1953.
262. Bayer, DE-OS 2931981, 1979 (F. W. Kröck, R.
Neeff, H. Scheiter).
263. IG-Farbenind., DE 464863, 1926 (K. Wilke);
Friedländer, vol. 16, p. 1229.
264. BASF, DE-AS 1025079, 1955 (E. Anton, K.
Saftien).
265. BASF, DE-AS 1250031, 1963 (E. Hartwig, W.
Braun).
266. IG-Farbenind., DE 615756, 1934 (G.
Kränzlein, M. Corell, W. Schaich);
Friedländer, vol. 22, p.1078.
267. BASF, DE-AS 1100209, 1958 (H. Geeren, F.
Ebel, W. Braun).
268. IG-Farbenind., DE 475687, 1926 (M. A. Kunz,
G. v. Rosenberg, E. Goffarjé); Friedländer,
vol. 16, p. 1341.
269. IG-Farbenind., DE 604279, 1932 (P. Nawiasky
et al.); Friedländer, vol. 21, p. 1091.
66 Anthraquinone Dyes and Intermediates
270. IG-Farbenind., DE 623028, 1934 (E. Berthold,
J. Müller); Friedländer, vol. 22, p. 1081.
271. IG-Farbenind., DE 692750, 1938 (H.
Schlichenmaier, L. Berlin, E. Berthold).
272. BASF, DE 421236, 1922 (A. Lüttringhaus, F.
Kačev); Friedländer, vol. 15, p. 689.
273. AG für Anilin-Fabrikation, DE 232711, 1910;
Friedländer, vol. 10, p. 731.
274. J. Arient, V. Slavik, Collect. Czech. Chem.
Commun. 34 (1969) 3576.
275. Sandoz, DE 593867, 1932; Friedländer,
vol. 20, p. 1344.
276. Bayer, DE 239544, 1910; Friedländer, vol. 10,
p. 638.
277. Du Pont, US 2258394, 1939 (J. M. Tinker et
al.).
278. Hoechst, DE 251350, 1911; Friedländer,
vol. 11, p. 618.
279. A. K. Wick, Helv. Chim. Acta 54 (1971) 769.
280. ICI, GB 2048963, 1979 (P. Gregory, M.
Yelland).
281. IG-Farbenind., DE 746546, 1937 (F. Wieners,
W. Mieg); Friedländer, Suppl. vol. I/2, p. 392.
282. Ciba-Geiby, CH 528576, 1969 (A. Wick).
283. Kuhlmann, DE 566708, 1930; Friedländer,
vol. 19, p. 2120.
284. Bayer, DE 963502, 1955 (H. W. Schwechten,
O. Bayer).
285. IG-Farbenind., DE 696370, 1936 (W.
Burneleit, W. Mieg, F. Wieners).
286. Bayer, DE 630218, 1934 (W. Mieg, F.
Wieners); Friedländer, vol. 23, p. 1020.
287. IG-Farbenind., DE 451495, 1925 (W. Mieg);
Friedländer, vol. 16, p. 1345.
288. Ciba, DE-OS 1813729, 1967 (A. Wick).
289. Kuhlmann, FR 733440, 1931.
290. Výzkumný ústav organ. syntéz,
DE-OS 1817388, 1968 (J. Arient et al.).
291. Ciba-Geigy, EP 49873, 1980 (Z. Seha).
292. Hoechst, DE 208969, 1908; Friedländer,
vol. 9, p. 776.
293. Ciba, CH 191015, 1936.
294. IG-Farbenind., DE 525666, 1929 (W. Bruck);
Friedländer, vol. 18, p. 1310.
295. IG-Farbenind., DE 501746, 1929 (W. Bruck);
Friedländer, vol. 17, p. 1229.
296. BASF, DE 246966, 1911; Friedländer, vol. 10,
p. 725.
297. IG-Farbenind., DE 560236, 1929 (M. A. Kunz,
E. Berthold, K. Köberle); Friedländer, vol. 19,
p. 2088.
298. Bayer, DE 678499, 1937 (W. Bauer);
Friedländer, Suppl. vol. I/2, p. 382.
299. BASF, DE 237236, 1910; Friedländer, vol. 10,
p. 708.
300. American Cyanamid, US 2492802, 1945
(H. Z. Lecher, W. S. Forster).
301. IG-Farbenind., DE 590579, 1932 (E. Kramer);
Friedländer, vol. 20, p. 1293.
302. BASF, DE 258561, 1910; Friedländer, vol. 11,
p. 671.
303. IG-Farbenind., DE 555967, 1929 (M. A. Kunz,
E. Berthold, K. Köberle); Friedländer, vol. 19,
p. 2082.
304. BASF, DE 279867, 1913; Friedländer, vol. 12,
p. 445.
305. IG-Farbenind., DE 661152, 1936 (F. Baumann,
H. W. Schwechten); Friedländer, vol. 25,
p. 773.
306. IG-Farbenind., DE 470809, 1926 (K.
Schirmacher, W. Schaich, A. Wolfram);
Friedländer, vol. 16, p. 1316.
307. Bayer, DE-AS 1150652, 1955 (G. Gehrke,
L. Nüßler).
308. Ciba, DE-AS 1060526, 1953 (P. Sutter, W.
Fioroni).
309. Bayer, DE 904926 (Examples 5, 6), 1951 (H.
Thielert, F. Baumann).
310. Cassella, DE-AS 1215284, 1962 (W. Zerweck,
E. Schwamberger).
311. Cassella, DE-AS 1264648, 1963 (W. Zerweck,
E. Schwamberger).
312. Bayer, DE 158287, 1903; Friedländer, vol. 8,
p. 341.
313. Bayer, DE 193121, 1906; Friedländer, vol. 9,
p. 783.
314. Ciba, DE 423311, 1922; Friedländer, vol. 15,
p. 714.
315. IG-Farbenind., DE 580013, 1932; Friedländer,
vol. 20, p. 1377.
316. BASF, DE 212471, 1908; Friedländer, vol. 9,
p. 834.
317. IG-Farbenind., DE 490723, 1926 (K. Wilke);
Friedländer, vol. 16, p. 1368.
318. IG-Farbenind., DE 483154, 1927
(A. Lüttringhaus, P. Nawiasky, A. Ehrhardt);
Friedländer, vol. 16, p. 1490.
319. IG-Farbenind., DE 722868, 1937 (H. Scheyer,
H. Ritter); Friedländer, Suppl. vol. I/2, p. 451.
320. Du Pont, GB 364042, 1930.
321. Ciba-Geigy, EP 10525, 1978 (H. Jäger).
322. SU 401130, 1971 (E. M. Natanson et al.)
323. Bayer, DE-OS 2823160, 1978 (J. Schroeder).
324. Ciba-Geigy, EP 22062, 1979 (J. Bersier,
H. Jäger, H. Schwander).
325. Ciba-Geigy, EP 60437, 1981 (H. Jäger et al.).
326. Bayer, DE-OS 2830456, 1978 (B. Schroeder,
R. Neeff, R. Braden).
327. BASF, DE 200335, 1905; Friedländer, vol. 9,
p. 817.
 Anthraquinone Dyes and Intermediates
328. BASF, DE-OS 2631853, 1976 (A.
Schumacher, K. E. Kling).
329. Du Pont, US 2353049, 1942 (H. R. Lee, C. F.
Belcher).
330. Kalle, DE 467118, 1924 (M. P. Schmidt, W.
Neugebauer); Friedländer, vol. 16, p. 1453.
331. Hoechst, DE 420412, 1923 (A. Wolfram);
Friedländer, vol. 15, p. 736.
332. Bayer, DE 200014, 1907; Friedländer, vol. 9,
p. 760.
333. Bayer, DE 171293, 1904; Friedländer, vol. 8,
p. 304.
334. Chem. Fabrik Griesheim-Elektron,
DE 255641, 1912; Friedländer, vol. 11, p. 583.
335. Bayer, DE 220314, 1908; Friedländer, vol. 9,
p. 742.
336. IG-Farbenind., DE 711775, 1938 (E. Berthold,
W. Roland); Friedländer, Suppl. vol. I/2,
p. 280.
337. IG-Farbenind., DE 633207, 1931 (M. A. Kunz,
K. Köberle); Friedländer, vol. 21, p. 1143.
338. BASF, DE-AS 1159456, 1960 (H. Weidinger,
H. Eilingsfeld, G. Haese).
339. Kawasaki Kasei, JP-Kokai 52-95678, 1976.
340. BASF, DE-AS 1215843, 1962 (M. Bertl, F.
Graser).
341. BASF, DE-OS 2300019, 1973 (H. Hiller, W.
Jentzsch, A. Schuhmacher).
342. Bayer, DE 203752, 1907; Friedländer, vol. 9,
p. 735.
343. BASF, DE 216597, 1907; Friedländer, vol. 9,
p. 738.
344. Bayer, DE 201904, 1907; Friedländer, vol. 9,
p. 736.
345. Bayer, DE 233126, 1909; Friedländer, vol. 10,
p. 609.
346. Sandoz, DE 578995, 1930; Friedländer,
vol. 19, p.1964.
347. IG-Farbenind., DE 518316, 1927 (G.
Kränzlein, H. Vollmann); Friedländer, vol. 17,
p. 1301.
348. IG-Farbenind., DE 576253, 1927 (R.
Sedlmayer, W. Eckert); Friedländer, vol. 18,
p. 592.
349. Hoechst, DE 412053, 1922 (G. Kränzlein, M.
Corell, R. Sedlmayr); Friedländer, vol. 15,
p. 731.
350. Hoechst, DE 423720, 1924 (G. Kränzlein, R.
Sedlmayr); Friedländer, vol. 15, p. 733.
351. L. Kalb, DE 280787, 1913; Friedländer,
vol. 12, p. 498.
352. Cassella, DE 445390, 1925 (R. Herz, W.
Zerweck); Friedländer, vol. 15, p. 300.
353. Cassella, DE 458598, 1925 (R. Herz, W.
Zerweck); Friedländer, vol. 16, p. 1410.
67
354. IG-Farbenind., DE 485961, 1927 (R.
Heidenreich); Friedländer, vol. 16, p. 1422.
355. BASF, DE-OS 1951708, 1969 (G. Bock).
356. BASF, DE-OS 2115093, 1971 (F. Graser).
357. Du Pont, US 2872459, 1956 (A. A. Baum).
358. GAF, DE-AS 1068687, 1956 (T. A. Martin,
D. I. Randall, J. Taras).
359. Du Pont, US 2388743, 1944 (E. T. Howell).
360. IG-Farbenind., DE 450999, 1925
(A. Lüttringhaus, H. Neresheimer, H. J.
Emmer); Friedländer, vol. 15, p. 721.
361. IG-Farbenind., DE 608442, 1933 (H. Wolff,
W. Mieg); Friedländer, vol. 21, p. 1130.
362. IG-Farbenind., DE 595461, 1929 (M. A. Kunz,
K. Köberle, E. Berthold); Friedländer, vol. 20,
p. 1370.
363. BASF, DE 185222, 1904; Friedländer, vol. 9,
p. 830.
364. Scottish Dyes, DE 417068, 1920; Friedländer,
vol. 15, p. 760.
365. IG-Farbenind., DE 448262, 1924 (O.
Braunsdorf, P. Nawiasky, E. Holzapfel);
Friedländer, vol. 15, p. 728.
366. BASF, DE-AS 2704964, 1977 (W. S.
Schweckendiek, A. Schuhmacher, H. Hiller).
367. BASF, DE 217570, 1909; Friedländer, vol. 9,
p. 827.
368. IG-Farbenind., DE 453768, 1925 (R. Berliner,
B. Stein, W. Trautner); Friedländer, vol. 16,
p. 1283. IG-Farbenind., DE 470501, 1926 (H.
Scheyer); Friedländer, vol. 16, p. 1283.
369. IG-Farbenind., DE 550712, 1930 (H. Scheyer);
Friedländer, vol. 19, p. 2149.
370. IG-Farbenind., DE 576466, 1931 (H. Scheyer);
Friedländer, vol. 20, p. 1426.
371. H. Labhart, Helv. Chim. Acta 40 (1957) 1410.
372. BASF, DE-AS 1209680, 1962 (K. Maier).
373. Bayer, DE-OS 2531557, 1975 (V. Hederich,
H.-S. Bien, G. Gehrke).
374. Bayer, FR 1503492, 1965.
375. Sumitomo Chem., FR 1497689, 1965.
376. Bayer, DE-AS 1105837, 1958 (G. Gehrke).
377. Bayer, DE-AS 1644587, 1965 (M. Groll, K.
Wunderlich, H.-S. Bien).
378. Du Pont, US 2628963, 1951 (J. F. Laucius,
S. B. Speck).
379. BASF, DE-AS 1918696, 1969 (E. Hartwig).
380. Geigy, BE 650734, 1963.
381. Ciba, DE-AS 1065959, 1954 (P. Grossmann,
W. Jenny, W. Kern).
382. Ciba, FR 1594324, 1968.
383. Sandoz, FR 1490805, 1965 (M. F. Müller).
384. Du Pont, DE-AS 1811796, 1968 (J. Blackwell,
R. E. Starn, W. H. Gumprecht).
68 Anthraquinone Dyes and Intermediates
385. BASF, DE-OS 2524243, 1975 (H. Schwab, K.
Oppenlaender, A. Blum).
386. BASF, DE-OS 2654434, 1976 (W. Elser, H.
Eilingsfeld, G. Meyer).
387. BASF, DE-OS 2651975, 1976 (G. Epple, W.
Elser).
388. Bayer, DE-OS 2918881, 1979 (W. Harms et
al.).
389. Mitsubishi Chem. Ind., DE-OS 3218957, 1981
(T. Niwa, T. Hihara).
390. Mitsubishi Chem. Ind., JP-Kokai 55-164250,
1979.
391. Bayer, DE 849158, 1944 (K. Bähr).
392. BASF, DE-OS 1644482, 1967 (F. Graser, G.
Riedel).
393. Bayer, EP 93367, 1982 (M. Blunck et al.).
394. IG-Farbenind., DE 653386, 1935 (W. Mieg, F.
Wieners); Friedländer, vol. 24, p. 862.
395. IG-Farbenind., DE 696423, 1935 (K. Köberle);
Friedländer, Suppl. vol. I/2, p. 239.
396. Bayer, DE 911493, 1952 (H. W. Schwechten).
397. Bayer, BE 729177, 1968 (K. Wunderlich,
H.-S. Bien).
398. Ullmann, 4th ed., vol. 18, p. 661.
Anthraquinonesulfonic Acids → Anthraquinone Dyes and Intermediates
399. BASF, DE-AS 1544372, DE-AS 1544374,
1965 (W. Braun, I. Peatzke).
400. Ciba, DE-AS 1283542, 1961 (E. Mörgeli).
401. Sandoz, US 2121928, 1934 (A. Peter).
402. Ciba-Geigy, DE-OS 2850996, 1977 (R.
Lacroix, J.-M. Adam, J. Vincze).
403. Sandoz, CH 214909, 1939.
404. Bayer, GB 1099756, 1966 (J. Singer).
405. Geigy, BE 713252, 1967.
406. Sandoz, FR 1455722, 1964 (M. J. Günthard).
407. Geigy, FR 1461074, 1964.
408. Crompton & Knowles, FR 1478769, 1965
(M. R. W. Eltonhead).
409. Ciba, DE-OS 1925515, 1968 (K. Seitz, G.
Klahre, H. U. Schütz).
410. Bayer, DE-OS 1644204, 1967 (H.-S. Bien, E.
Klauke).
411. Bayer, DE-AS 1264647, 1961 (J. Singer, H. W.
Schwechten).
412. Bayer, DE-OS 2652119, 1976 (W. Harms, K.
Wunderlich, K. v. Oertzen).
413. Bayer, DE-OS 3142852, 1981 (K. v. Oertzen).
414. Scottish Dyes, FR 543910, 1921.