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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 A new application for vat dyes constituted


their use as organic pigments. Based on these in-
The elucidation of the structure of alizarine by sights, a whole new series of specialty pigments
C. Graebe and C. Liebermann in 1868 marks was developed.
the beginning of anthraquinone chemistry. After The synthesis of an anthraquinone dye gen-
Caro, Graebe, and Liebermann had worked erally involves a large number of steps. For ex-
out a commercial synthesis for alizarine, major ample, the preparation of a vat dye may require
efforts, especially by R. Bohn (Badische Anilin- as many as eight steps and may necessitate the
& Sodafabrik) and R. E. Schmidt (Farbenfab- preparation of seven different anthraquinone in-
riken Bayer, formerly Friedrich Bayer & Co.) termediates.
were directed toward the manufacture of Anthraquinone dyes are surpassed in im-
hydroxyanthraquinones. A sizeable collection portance only by azo dyes. The more compli-
of red, blue, and green mordant dyes was as- cated syntheses and lower tinctorial strengths of
sembled over a span of 20 years. The turn of the the anthraquinone dyes make production costs
century saw the development of the first acidic higher than for azo dyes. Therefore anthra-
anthraquinone dyes that could be used to dye quinone dyes tend to be used only when the re-
wool in fast red to green shades without the need quired properties and color fastness are extreme
for pretreatment with mordants. or when the colors desired are not obtained easily
In 1901 a new era of anthraquinone chem- with azo dyes (especially bright blue to turquoise
istry started with the discovery of the mercury- shades). Use of a dye in vat dyeing requires the
catalyzed α-sulfonation of anthraquinone. (Sub- presence of special structural features (quinoid
stituted anthraquinones are usually designated or indigoid). Therefore most vat dyes are derived
as α for substitution at positions 1, 4, 5, or 8 and from anthraquinone.
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 2. Methods of Production
acids.) About 80 % of the anthraquinone dyes are
still prepared via anthraquinonesulfonic acids, The production of anthraquinone intermedi-
even though emphasis is shifting at present to- ates and anthraquinone dyes generally proceeds
ward synthesis via nitroanthraquinones. Impor- from a few key products generated by elec-
tant early reactions of anthraquinone chemistry trophilic substitution of unsubstituted anthra-
include the Fischer reaction (replacement of a quinone or by synthesis of the nucleus. The
sulfonic acid group by chlorine) and high-pres- major methods employed to prepare anthra-
sure fusion with lime (replacement of sulfonic quinone derivatives substituted in the α posi-
acid by a hydroxy group). tion are sulfonation and nitration. Preparation of
Simultaneously, new fundamental develop- β-substituted anthraquinones and of quinizarin
ments took place in the area of anthraquinone (1,4-dihydroxyanthraquinone) generally is ac-
vat dyes, e.g., indanthrone, flavanthrone, vi- complished by synthesis of the nucleus starting
olanthrone, benzoylaminoanthraquinones, an- from phthalic anhydride and a benzene deriva-
thrimides, and anthrimidecarbazoles. Subse- tive.
quent work concentrated on closing gaps in the Until fairly recently, preparation of almost
offerings of vat and acid dyes and testing of 80 % of all important anthraquinones was based
potential applications in nontextile dye applica- on anthraquinonesulfonic acids. However, ni-
tions. tration of anthraquinone is gaining in impor-
The introduction of synthetic fibers, such tance presently, a development triggered mainly
as polyester, polyamide, and polyacrylonitrile by environmental considerations (e.g., produc-
fibers, initiated a new phase in the development tion of large volumes of waste dilute acids dur-
of anthraquinone dyes. This led to a number of ing anthraquinone sulfonation). However, great
substitution products of anthraquinone that were progress has been made recently in solving the
useful as disperse dyes or as basic dyes. With the problems associated with sulfonation.
appearance of the first fiber-reactive dyes, work Preparation of nearly all important anthra-
on acid anthraquinone dyes was intensified. quinones starts from the following key inter-
Anthraquinone Dyes and Intermediates 3

mediates: anthraquinonesulfonic acids, nitro- If mercury or mercury compounds are added


anthraquinones, and the products of nucleus as catalysts, sulfonation proceeds under much
synthesis, 1,4-dihydroxy-, 2-methyl-, or 2- milder conditions and substitution occurs pref-
chloroanthraquinone. The only exceptions are erentially at the α position. The mercury can
derivatives with condensed rings, e.g., benzan- be reclaimed during workup of the sulfonation
throne and derived products, which are prepared mixtures [17–25].
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 Although other catalysts, such as palladium,
anthraquinones, as, for example, from 1-amino- ruthenium, or rhodium, are also suitable for sul-
4-arylaminoanthraquinone-2-sulfonic acid. fonating anthraquinone at the α position, they
Desulfonation of the α position may be ac- are not used industrially [26–28].
complished by heating in 70 – 90 % sulfuric
acid in the presence of mercury. This method Anthraquinone-1-sulfonic acid [82-49-5],
is used to convert unnecessary α,α -disulfonic K salt, also called diamant salt, M r 288.3, is
acids back to anthraquinones [15], [16]. prepared by sulfonation in the presence of, e.g.,
Sulfonation of the β position of anthra- 0.5 % mercury in 20 % oleum, an amount of
quinone is at present of little importance, be- SO3 adequate for the sulfonation of about 60 %
cause β-substituted compounds (e.g., 2-ami- of the charge. The reaction is controlled in such
noanthraquinone) are prepared nowadays from a manner that about 50 % of the anthraquinone
2-chloroanthraquinone instead of the sulfonic remains unsulfonated. After mercury is precipi-
acid. tated as the sulfide, the unreacted anthraquinone
is precipitated by dilution and is collected by
Process Details. Sulfonation of anthra- filtration. After washing and drying, it is re-
quinones requires extreme conditions circulated as ‘reclaimed quinone‘. Mercury is
(≈ 150 ◦ C, 20 % oleum), which yield either removed completely from the filtrate, and the
mono- or disulfonic acids, depending on the anthraquinone-1-sulfonic acid is then precipi-
method of operation. Whereas nitration and tated as the potassium salt [23].
halogenation preferentially substitute the α po-
sition, direct sulfonation attacks the β position, Anthraquinone-2-sulfonic acid [84-48-0],
yielding anthraquinone-2-sulfonic acid or the Na salt, also called silver salt, M r 288.3, is pre-
2,6- or 2,7-disulfonic acid derivatives. 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 is used, for instance, in the preparation of start-
1,6- (or 1,7-) disulfonic acid by desulfonation at ing materials for the synthesis of pyranthrone
the α position in dilute sulfuric acid [15]. and flavanthrone (see Section 2.12.7).

Anthraquinone-1,5-disulfonic acid 2-Methylanthraquinone [84-54-8], Mr


[117-14-6], Thiol Acid, M r 368.3, and anthra- 222.2, mp 182 – 183 ◦ C, is prepared from ph-
quinone-1,8-disulfonic acid [82-48-4], Azine thalic anhydride and toluene (see also [1], [2,
Acid, M r 368.3, are produced by disulfonation p. 10], [5, p. 40]).
under conditions similar to those for mono-
sulfonation except for an increased concentra- 2-Ethylanthraquinone [84-51-5], Mr
tion of SO3 . After sulfonation of the anthra- 235.3, mp 108 ◦ C, is prepared from phthalic
quinone is complete, the 1,5-acid is precipitated anhydride and ethylbenzene [29].
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 2.3. Haloanthraquinones
treated with charcoal, and the anthraquinone-
1,5-disulfonic acid precipitated from the filtrate Haloanthraquinones are important intermedi-
as its disodium salt by addition of saturated ates for all classes of dyes, especially for vat
sodium chloride solution. The 1,8-acid is iso- and disperse dyes.
lated as the potassium salt from the sulfuric acid Unsubstituted halogenated anthraquinones
mother liquors and the wash acids (see also [1] are prepared mainly by replacement reac-
and [3, p. 10]). Mercury can be removed in a tions or by synthesis of the nucleus. Only
similar manner as given for anthraquinone-1- the chloro derivatives are of practical impor-
sulfonic acid (see, e.g., [23]). tance. Aminoanthraquinones, hydroxyanthra-
quinones, phenoxyanthraquinones, and an-
thrimides (dianthraquinonylamines) may be ob-
2.2. Alkyl- and Arylanthraquinones tained by replacing the chlorine atom. The β-
chloroanthraquinones are much more suitable
Alkyl- and arylanthraquinones are obtained for preparing β-aminoanthraquinones than the
from the corresponding benzene derivatives and corresponding sulfonic acids. In contrast to the
phthalic acid anhydride via the benzoylbenzoic 1,5- and the 1,8-dichloroanthraquinones, a sin-
acids. 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-
2-Methylanthraquinone is of great impor-
stituents, such as amino or hydroxy groups, per-
tance for the synthesis of dyes. 2-Alkylanthra-
mit selective halogenation of one or the other
quinones (e.g., 2-ethyl-, 2-isoamyl-, or 2-
nucleus by appropriate choice of reaction con-
tertamylanthraquinone) are used as oxygen car-
ditions. Only the chloro and bromo derivatives
riers in the preparation of hydrogen perox-
are commercial products.
ides (→ Peroxo Compounds, Inorganic). If α-
haloanthraquinones are heated in the presence
Process Details. Direct chlorination of
of copper in inert, high-boiling solvents, dimer-
anthraquinone with chlorine or sulfuryl chlo-
ization (Ullmann reaction) yields the corre-
ride, occurs preferentially at the α position;
sponding 1,1 -dianthraquinonyls. This reaction
Anthraquinone Dyes and Intermediates 5

however, the resulting product mixtures are diffi- responding benzoylbenzoic acids. Because β-
cult to separate. Only 1,4,5,8-tetrachloroanthra- anthraquinonesulfonic acids react slowly in the
quinone of about 60 % purity [30] and 1-chloro- Fischer reaction, industrial production of 2-
2methylanthraquinone are prepared commer- chloroanthraquinone starts generally from ph-
cially by this method [2, p. 60]. thalic anhydride and chlorobenzene [2, pp. 8,
Replacement of sulfonic acid groups by chlo- 11].
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.

1-Chloroanthraquinone [82-44-0], Mr
242.7, mp 162 ◦ C, is prepared from anthra-
The reaction is carried out by slowly quinone-1-sulfonic acid [4, p. 29], [39], or from
adding an aqueous solution of sodium chlo- 1-nitroanthraquinone [31], [32]. Purification by
rate to a hot hydrochloric acid solution of the high-temperature distillation [35], [36].
anthraquinonesulfonic acid. The resulting, only
slightly soluble chloroanthraquinones are iso- 2-Chloroanthraquinone [131-09-9], M r
lated by filtration. The almost quantitative reac- 242.7, mp 210 ◦ C, is prepared by synthesis of
tion is also used for the identification of anthra- the nucleus starting with phthalic anhydride and
quinonesulfonic acids. The Fischer reaction of chlorobenzene [2, pp. 8, 11].
disulfonic acids can be directed in such a way
that mostly monochloroanthraquinonesulfonic 1,5-Dichloroanthraquinone [82-46-2], M r
acids form. 277.1, mp 251 ◦ C, is prepared by Fischer re-
A nitro group can be replaced by a chlo- action from anthraquinone-1,5-disulfonic acid,
rine atom at high temperature, generally above by addition of chlorobenzenes [40], or from
200 ◦ C, using chlorine or ionic chlorides, such 1,5-dinitroanthraquinone [32] by replacement of
as lithium chloride, in organic solvents [33]. NO2 .
A proposed industrial method is the reaction
of chlorine with nitroanthraquinone in the melt 1,8-Dichloroanthraquinone [82-43-9], M r
[31]. Diluents for the high-melting nitroanthra- 277.1, mp 203 ◦ C, is prepared from anthra-
quinones are lower melting compounds, such quinone-1,8-disulfonic acid [3, p. 15] or from
as chloroanthraquinone [32], trichlorobenzene 1,8-dinitroanthraquinone [32].
[110], phthalic anhydride [42], and salt melts
[34]. Chloroanthraquinones can be purified [35] 1,4-Dichloroanthraquinone [602-25-5], M r
and separated [36] by high-temperature distilla- 277.1, mp 187 ◦ C, is prepared from 1,4-di-
tion. hydroxyanthraquinone [37], [38] or by syn-
1,4-Dichloroanthraquinone may be obtained thesis of the nucleus from phthalide and 1,4-
by replacing the hydroxy groups of 1,4-di- dichlorobenzene [41].
hydroxyanthraquinone (quinizarin) with chlo-
rine by heating with thionyl chloride [37] or with 2,3-Dichloroanthraquinone [84-45-7], M r
mixtures of phosphoryl chloride and phosphorus 277.1, is prepared by synthesis of the
pentachloride [38]. nucleus from phthalic anhydride and 1,2-
The replacement of amino groups by chlo- dichlorobenzene [2, p. 10].
rine through diazotization and treatment with
cuprous chloride (Sandmeyer reaction) is used 1,4,5,8-Tetrachloroanthraquinone [81-58-
commercially only in special cases (see Section 3], M r 346.0, mp 342 ◦ C, is prepared by chlo-
2.5). rination of anthraquinone in sulfuric acid [30]
A few chloroanthraquinones can be ob- or by sulfonation of 1,8-dichloroanthraquinone
tained by synthesis of the nucleus via the cor- followed by Fischer reaction [43].
6 Anthraquinone Dyes and Intermediates

1-Chloro-2-methylanthraquinone [129- during nitration with mixed acids by increas-


35-1], M r 256.7, mp 171 ◦ C, is prepared from ing the water content [50–52]. Other procedures
2-methylanthraquinone by direct chlorination in specify the presence of organic solvents, such as
oleum [2, p. 60] or organic solvents [44]. halogenated hydrocarbons [54], [55], [56], sul-
folane (tetrahydrothiophene-1,1-dioxide) [57],
2-Chloro-3-methylanthraquinone [14684- hydrofluoric acid [58], or phosphoric acid [59].
09-4], M r 256.7, is prepared by synthesis of Some of these methods can be adapted to con-
the nucleus from phthalic anhydride and 2- tinuous processing.
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 Mononitration of 2-methylanthraquinone
increasing importance because of environmental leads to 2-methyl-1-nitroanthraquinone [2,
considerations, this method offering an econom- p. 13]. Nitration of anthraquinone-1-sulfonic
ical alternative to α-sulfonation. acid produces a mixture of 1-nitroanthra-
1-Nitro-2-methylanthraquinone is the quinone-5-sulfonic acid and 1-nitroanthra-
starting material for 1-amino-4-bromo-2- quinone-8-sulfonic acid, whereas nitration of
methylanthraquinone, 1-aminoanthraquinone- anthraquinone-2-sulfonic acid produces a mix-
2-aldehyde, and 1-aminoanthraquinone-2- ture of 1-nitroanthraquinone-6-sulfonic acid and
carboxylic acid derivatives. 1-nitroanthraquinone-7-sulfonic acid.
Halogen exchange by nitrite is an unimpor-
Process Details. Substituted anthraquinones tant method of preparing nitroanthraquinones.
usually are nitrated in concentrated sulfuric acid There are only a few patents directed toward the
using stoichiometric quantities of nitric acid or synthesis of more highly substituted nitroanthra-
nitric – sulfuric mixed acid. This method always quinones, e.g., [82].
produces considerable amounts of dinitro com- Finally, preparations of nitroanthraquinones
pound in addition to the mononitro compound. by means of nuclear syntheses, for instance, by
Even the best methodology permits preparation addition of butadiene to 5-nitronaphthoquinone
of only 75 – 80 % of the theoretical amount of (or its oxime), have also been proposed [83],
1-nitroanthraquinone. Mononitration in highly [84].
concentrated nitric acid also has been developed Several methods have been developed to re-
to an acceptable procedure by avoiding concen- move 2-nitroanthraquinone and dinitroanthra-
tration levels that can lead to explosions [46– quinones from 1-nitroanthraquinone. The chem-
49]. Dinitration can be retarded significantly ical purification processes are based on the treat-
ment of the crude product with sodium sulfite
Anthraquinone Dyes and Intermediates 7

[60] or alkaline reagents, such as amines [61], 1-nitroanthraquinone may be finally purified by
alcoholates [62], or hydrazine [63], which cause high-temperature distillation [67], [68].
preferential conversion of the contaminants to
compounds that can be separated easily on the 1,5-Dinitro- and 1,8-dinitroanthra-
basis of their different solubilities. The more quinones [82-35-9], [129-39-5], M r 298.2, are
economical physical separation methods incor- prepared by nitration of anthraquinone with ni-
porate prepurification into the nitration process tric acid in sulfuric acid [72], [73], if necessary
(e.g., crystallization from nitric acid [64]), or by addition of organic solvents [74], or in hy-
the isolated crude 1-nitroanthraquinone is puri- drogen fluoride [75].
fied with organic solvents, such as nitrobenzene For isolation and purification of mixtures of
[65] or amides [66]. Pure 1-nitroanthraquinone 1,5- (and 1,8-) dinitroanthraquinone, see [80].
is then obtained by high-temperature distillation Isolation of 1,5- (and 1,8-) dinitroanthraquinone
[67], [68]. is described in [77–79].
Purification may also be deferred to the ami-
noanthraquinone stage (see page 13. 1-Nitroanthraquinone-5- (and -8-) sul-
Modification of nitration conditions permits fonic acids [82-50-8], [129-37-3], M r 333.3,
dinitration of anthraquinone. Nitration in highly are prepared by nitration of anthraquinone-1-
concentrated nitric acid, as cited in [69], is for sulfonic acid [81].
safety reasons unsuitable for industrial produc-
tion [70]. However, addition of sulfuric acid 2-Methyl-1-nitroanthraquinone [129-15-7],
makes it possible to work with a margin of safety M r 267.7, is prepared by nitration of 2-
[71]. The preferred method for dinitration is still methylanthraquinone [2, p. 13].
the use of mixed nitric – sulfuric acid [72], [73].
However, nitration in organic solvents [74] or
hydrofluoric acid [75] have been proposed also. 2.5. Aminoanthraquinones
Apart from approximately equal portions of
1,5- and 1,8-dinitroanthraquinones, dinitration 2.5.1. General Aspects
produces α,β-dinitroanthraquinone. The direct
isolation of 1,5- and 1,8-dinitroanthraquinone Aminoanthraquinones, especially 1-amino- and
is possible from the nitration mixtures [76] 1,5-diaminoanthraquinone, are key products for
or, starting from isolated crude dinitroanthra- essentially all classes of anthraquinone dyes.
quinone mixtures, by fractional crystallization Important production methods are the replace-
from organic solvents, e.g., nitrobenzene [77], ment of sulfonic acid and nitro groups or
N-methylpyrrolidone [78], or high-boiling ke- of halogen atoms by ammonia or primary
tones [79]. Other procedures that simply sep- or secondary amines. With 1,4-dihydroxy-,
arate the α,β-dinitroanthraquinones have been 1,4-aminohydroxy-, and 1,4-diaminoanthra-
described also [80]. quinones, the replacement of hydroxy and
amino groups is also successful. Primary amino-
1-Nitroanthraquinone [82-34-8], Mr anthraquinones are also prepared by reduc-
253.2, mp 228 ◦ C, is prepared by nitration of tion of nitroanthraquinones. Modifications of
anthraquinone in nitric acid (danger of explo- the amino functions also have industrial im-
sion!) [46–49], sulfuric acid [50–52], organic portance. These include alkylation, arylation,
solvents [54–57], phosphoric acid [59], or hy- acylation, and hydrolysis of acylaminoanthra-
drogen fluoride [58]. quinones. The choice of production method for
Purification from organic solvents by ad- a desired aminoanthraquinone depends on the
dition of bases, such as amines [61], alcoho- position and type of the amino function, as well
lates [62], or hydrazine [63], or from water by as on the availability of starting materials.
addition of sodium sulfite [60]. 1-Nitroanthra- A special method for the production of 1-ami-
quinone is crystallized from nitric acid [64], noanthraquinone consists in the catalytic hydro-
from organic solvents, for example, nitroben- genation of 5-nitro-1,4,4 a,9 a-tetrahydroanthra-
zene [65], or from amides [66]. The resulting quinone, which is obtained by reacting butadiene
and 5-nitronaphthoquinone (see [85]).
8 Anthraquinone Dyes and Intermediates

Aminoanthraquinones may be purified by Halogen → NH2 or NHR. Of great impor-


recrystallization, distillation, or sublimation. tance industrially is the replacement of chlo-
However, purification is preferred at the stage rine and bromine atoms in the α or β po-
of the nitroanthraquinones or the anthra- sitions by amines in substituted and unsub-
quinonesulfonic acids. stituted haloanthraquinones. Reagents for this
In most situations the presence of the amino purpose are ammonia, aliphatic and aromatic
group facilitates the introduction of further sub- amines, aminoanthraquinones, and amides, such
stituents into the same ring. Reaction media and as p-toluenesulfonamide or phthalimide. Be-
conditions as well as type and position of the cause of the increased reactivity of the α po-
amino group determine the position of substitu- sitions, the halogen atoms at the α positions of
tion. α,β-dihaloanthraquinones may be reacted selec-
In addition to conversion of existing ami- tively.
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- The partial replacement of halogen in α,α-
cessfully with both unsubstituted and fur- and β,β-dihaloanthraquinones, for example, in
ther substituted anthraquinonesulfonic acids. 2,3-dichloroanthraquinone, is also a known pro-
Depending on the choice of reaction condi- cess.
tions, diaminoanthraquinones and aminoanthra- Haloanthraquinones without sulfonic acid
quinonesulfonic acids may be obtained from groups are reacted in the presence of excess
disulfonic acids. The α- and β-sulfonic acids amine or in such organic solvents as alco-
react both with ammonia. In the reaction with hol, halobenzene, nitrobenzene, naphthalene, or
alkylamines, only the α derivatives give com- N-ethylcarbazole. Reaction temperatures range
mercially important products. Yields are deter- from 100 to 250 ◦ C, and the reaction is carried
mined in part by the number of sulfonic acid out in the presence of acid-neutralizing agents.
groups and in part by the type of amine and are Alkali carbonates, acetates, and stearates are
on the order of 70 – 90 %. 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
The exchange reactions are carried out absolutely essential in these reactions. Its action
in aqueous medium at 120 – 200 ◦ C and un- is reputed to be enhanced by adding Fe(II) salts
der pressure. To avoid attachment of dis- [86].
placed sulfite, an oxidizing agent, e.g., m-
nitrobenzenesulfonic acid, is usually added.
Anthraquinone Dyes and Intermediates 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],
Of great industrial importance are the re- amides [94], xylene [95], chlorobenzene [96], or
actions of 1-amino-4-bromoanthraquinone-2- tetramethylene sulfone [97]. The use of ammo-
sulfonic acid (bromamine acid). Yields depend nium salts or urea in place of ammonia has also
strongly on the choice of the reaction conditions been proposed [94].
and the reactivity of the amine. Strongly ba- Replacement of nitro groups by alkylamines
sic amines require the addition of alkali-metal or arylamines is favored in the production of
hydroxides. Sterically hindered amines, such as secondary amines. Replacement reactions with
2,4,6-trimethylaniline, react very slowly. 1-aminoanthraquinone to form anthrimides are
also successful [98].

Amines with very low basicity are unreactive


or react slowly. A side reaction of the bromamine When dinitroanthraquinones are used as
acid reaction is the reductive elimination of the starting materials, the choice of reaction con-
halogen atom and formation of 1-aminoanthra- ditions makes a partial exchange possible. The
quinone-2-sulfonic acid or the replacement by reaction is carried out in water or organic sol-
a hydroxy group to form 1-amino-4-hydroxy- vents, or in an excess of the amine.
anthraquinone-2-sulfonic acid.
OH → NH2 or NHR (R = H, alkyl, aryl).
NO2 → NH2 or NHR. Aminoanthra- The replacement of the hydroxy group by the
quinones with primary amino groups may be amino group is limited to 1,4-dihydroxy- and
prepared by replacement reactions or, even more 1-amino-4-hydroxyanthraquinone. It occurs via
simply, by reduction of the corresponding nitro- the 2,3-dihydro compounds and is reversible.
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
Exchange reactions are carried out using am-
out in dilute sodium hydroxide solution, a purifi-
monia, aliphatic and aromatic amines, and mix-
cation effect may take place if the 1-nitroanthra-
tures of amines. The starting material is the
quinone is contaminated with dinitroanthra-
isolated 2,3-dihydro compound, generally as a
quinone. A stepwise reduction with purifica-
mixture with dihydroxyanthraquinone. Alterna-
10 Anthraquinone Dyes and Intermediates

tively, the intermediate may be prepared in- anthraquinones are reacted with chloroanthra-
situ by addition of reducing agents such as quinones or nitroanthraquinones. The reaction
zinc–hydrochloric acid or iron – acetic acid. is carried out in high-boiling solvents, such as
The reaction media are water, alcohol, or ex- naphthalene or nitrobenzene, at temperatures of
cess amine. The primary product, 2,3-dihydro- 150 – 250 ◦ C. Certain cases do not require a sol-
1,4-diaminoanthraquinone, is oxidized to 1,4- vent (so-called “baking process”).
diaminoanthraquinone either during the reaction Acid-binding agents used in the prepa-
mediated by dihydroxyanthraquinone or after- ration of anthrimides include alkali carbon-
wards, by reaction with air. It is also possible to ates, acetates, oleates, stearates, and alkaline-
isolate the dihydro compound and then oxidize it earth oxides. Catalysts in the reactions of
with oleum, manganese dioxide – sulfuric acid, haloanthraquinones are copper and copper salts.
or nitrobenzene in the presence of piperidine. Nitroanthraquinones also may be reacted with-
In 1,4-dihydroxyanthraquinone, both hy- out a catalyst. Anthrimides may be isolated by
droxy groups are replaced in an excess amine. filtration or distilling the solvent away. Inorganic
In the presence of additional diluents, such as salts are removed by boiling with water or dilute
alcohols, generally only one hydroxy group mineral acids.
is exchanged. As expected, sterically hindered A special reaction for the preparation of
amines are not very reactive. anthrimides is the oxidation of aminoanthra-
quinones in aqueous sulfuric acid: 1-ami-
NH2 → NHR. The amino groups of 1,4-di- noanthraquinone yields aminopolyanthrimides
aminoanthraquinones may be replaced by other [99]. Mixtures of 1-aminoanthraquinone
amino groups via the 2,3-dihydro compounds. and 1,4-diaminoanthraquinone yield diami-
nodianthrimide [100].
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
Various anthrimides are suitable as vat dyes,
aminoanthraquinones can be achieved by com-
but they find their main use in the preparation of
monly employed methods, e.g., with dimethyl
anthrimidecarbazoles (see Section 2.11.2).
sulfate, alkyl halides, or esters of toluenesulfonic
acid. A special process is the methylation with
methanol in sulfuric acid [108]. When used on NH2 → NH – Heteroaryl. Of importance
aminohydroxy- and diaminoanthraquinones this here are mostly the triazinylaminoanthra-
process gives mixed products of interest to dy- quinones, where R1 and/or R2 may constitute
ers. anthraquinonylamino residues.
Due to the high reactivity of chlorotri-
NH2 → NHR (R = aryl). The preparation of azines, one does not require a catalyst or, acid-
simple arylanthraquinones by arylation of ami- binding agents. In addition to high boiling or-
noanthraquinones with aromatic halides, such ganic solvents such as nitrobenzene, phenols
as chlorobenzenes or chloronaphthalenes, has have proved valuable in the preparation of
no industrial importance. However, arylation is trisanthraquinonylaminotriazines [101].
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-
Anthraquinone Dyes and Intermediates 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 .


The reaction may be accelerated by adding Acylaminoanthraquinones are hydrolyzed in
tertiary amines, and in special cases by adding dilute to concentrated sulfuric acid as well as in
catalytic quantities of a Lewis acid such as AlCl3 2 – 10 % aqueous sodium hydroxide at temper-
or FeCl3 . atures ranging from 20 to 150 ◦ C. The sulfon-
amides are more stable in alkaline medium than
NH2 → NH-CO-R. The most important in an acidic medium. They are especially easily
method of preparing acylaminoanthraquinones cleaved in concentrated sulfuric acid. Because
is the acylation of aminoanthraquinones with arylsulfonylaminoanthraquinones are smoothly
acid chlorides, preferably in an organic solvent, prepared from haloanthraquinones (see page
such as nitrobenzene or dichlorobenzene. A 19), this method is suitable for the production of
further method is the reaction of aminoanthra- aminoanthraquinones otherwise difficult to pre-
quinones with carboxylic acids or their anhy- pare. Hydrolysis of arylamino groups depends
drides in oleum. Depending on the position of also on additional substituents. For instance, al-
the amino groups and the nature of the acid kaline hydrolysis of 1,5-bis(benzoylamino)-4-
chloride, diaminoanthraquinones also may be hydroxyanthraquinone causes hydrolysis of the
acylated in one position only, giving 60 – 90 % 5-benzoylamino group, whereas acidic medium
yields: 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
NHR → NH2 . Secondary or tertiary alkyl of α-aminoanthraquinone with aqueous alkali-
aminoanthraquinones are converted into amino- metal sulfites.
anthraquinones by removal of the alkyl residue
under the influence of acid or alkaline agents. Nucleus H → Halogen. Aminoanthra-
This method is also applicable to cycloalkyl- quinones may be halogenated with the usual
[102] and aralkylaminoanthraquinones and fa- halogenation agents such as chlorine, bromine,
cilitates the preparation of certain aminoanthra- and sulfuryl chloride. Suggested reaction media
quinones that are accessible only with diffi-
12 Anthraquinone Dyes and Intermediates

are hydrochloric acid, oleum, glacial acetic acid, bromination in hydrochloric acid. In this case no
sodium chloride–aluminum chloride melts, and substitution occurs at the 2 position, but the 1-
inert solvents, such as chlorobenzene, nitroben- alkylamino-4-bromoanthraquinones are formed
zene, halogenated hydrocarbons, and amides. in more than 90 % yield. By contrast, chlori-
The reaction of 1-aminoanthraquinone with nation of 1-methylaminoanthraquinone in weak
chlorine or sulfuryl chloride [1] in inert sol- oleum [104] will give, in a manner similar to
vents such as nitrobenzene leads to 1-ami- that of 1-aminoanthraquinone, the 5,8-dichloro-
no-2,4-dichloroanthraquinone, whereas addi- 1-methylamino compound.
tion of tetraalkylureas [103] leads to 1-ami-
no-2,3,4-trichloroanthraquinone. However, if 1- Nucleus H → CH3 . Starting from 1-ami-
amino- or 1-phthalimidoanthraquinone is chlo- noanthraquinones, reaction with formaldehyde
rinated in oleum, a good yield of 1-amino-5,8- yields 1-amino-2-methylanthraquinones. The
dichloroanthraquinones is obtained, if necessary reaction proceeds in aqueous alkaline solutions
after hydrolysis of intermediates: 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
Use of 1-benzoylaminoanthraquinone as the 1-amino-2,4-dinitroanthraquinone, whereas 1-
starting material generally leads to substitution phthalimidoanthraquinone yields the 4,5- (or
at the 4 position. Hydrolysis then yields the 1- 4,8-) dinitro derivatives [105]. If 1,4-diami-
amino-4-chloroanthraquinone. This compound noanthraquinone is used as the starting material,
may be obtained in better yields by chlorination 1,4-diamino-2-nitroanthraquinone is formed via
of 1-formamidinoanthraquinone in oleum fol- the intermediate 1,4-bis(benzoylamino)anthra-
lowed by hydrolytic cleavage of the protective quinone. The nitro group enters the 5 position
group. if the intermediate is the cyclic disulfimide 1.

Bromination of 1-aminoanthraquinone
in hydrochloric acid yields 1-amino-2,4- The dioxamic acid (2) of the 1,5-diami-
dibromoanthraquinone. noanthraquinone yields 1,5-diamino-4,8-
Chlorination of 1,4-diaminoanthraquinone dinitroanthraquinone after nitration and hydrol-
in organic solvents with chlorine or sulfuryl ysis [106].
chloride yields 1,4-diamino-2,3-dichloroanthra-
SO3 H → H. In certain 4-substituted 1-ami-
quinone; in boric acid–oleum, the 5,8-dichloro
noanthraquinone-2-sulfonic acids, replacement
derivative is formed. In hydrochloric acid,
of the sulfonic acid by hydrogen is feasible
1-amino-2-methylanthraquinone and 1-ami-
by using reducing agents in aqueous alkaline
noanthraquinone-2-sulfonic acid are bromi-
medium. Sodium dithionite and glucose have
nated at the 4 position.
been applied successfully here. This procedure
The 1-alkylaminoanthraquinones behave dif-
is used in the preparation of 1-alkylamino- (or
ferently from the 1-aminoanthraquinones upon
1-arylamino-) 4-aminoanthraquinone:
Anthraquinone Dyes and Intermediates 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].
The procedure has certain advantages for
the preparation of 1,4-diaminoanthraquinones 1,5-Diaminoanthraquinone [129-44-2],
with sensitive amino residues. An electro- M r 238.2, mp 319 ◦ C, is prepared by SO3 H ex-
chemical reductive desulfonation of β-anthra- change from anthraquinone-1,5-disulfonic acid
quinonesulfonic acids has been proposed also (see page 8), [3, p. 14], [5, p. 43], by replacing
[107]. NO2 in 1,5-dinitroanthraquinone (see page 9),
[116], or by reducing 1,5-dinitroanthraquinone
with sodium sulfide or by catalytic hydrogena-
2.5.2. Individual Aminoanthraquinones tion [117].
1-Aminoanthraquinone [82-45-1], Mr 1,8-Diaminoanthraquinone [129-42-0],
223.2, mp 252 – 253 ◦ C, is prepared from anthra- M r 238.2, mp 262 ◦ C, is prepared by the meth-
quinone-1-sulfonic acid in aqueous ammonia by ods given for 1,5-diaminoanthraquinone.
replacement of SO3 H (see page 8), [5, p. 22],
from 1-nitroanthraquinone in organic solvents 1,4,5,8-Tetraaminoanthraquinone [2475-
by replacement of NO2 by ammonia (see page 45-8], M r 268.3, mp 332 ◦ C, is prepared from
9), [93–97]; by reduction of 1-nitroanthra- anthraquinone-1,5-dioxamic acid by nitration,
quinone with sodium sulfide in water [87] or in hydrolysis, and reduction [3, p. 53].
organic solvents [109], with hydrazine hydrate
[89], with metal powders [90], or by catalytic 1-Methylaminoanthraquinone [82-38-2],
hydrogenation. This last reaction can be carried M r 237.3, mp 170 ◦ C, is prepared from anthra-
out in organic solvents [91], in sodium hydrox- quinone-1-sulfonic acid by replacing SO3 H (see
ide solution [92], or in dilute sulfuric acid [111]. page 8), [3, p. 18], from 1-chloroanthraquinone
Purification is carried out by recrystallization by replacing chlorine (see page 8), [118], or
from organic solvents [112], [113] or sulfuric from 1-nitroanthraquinone by replacing NO2
acid [114]. The greatest purity is obtained by (see page 9) [119], [120].
distillation [68].
1-Isopropylaminoanthraquinone [27354-
2-Aminoanthraquinone [117-79-3], Mr 18-3], M r 265.3, mp 187 ◦ C, is prepared by re-
223.2, mp 302 – 303 ◦ C. Older methods used placement of SO3 H [121] or NO2 [120], [121].
anthraquinone-2-sulfonic acid as the starting
material, replacing the SO3 H group. The pre- 1,4-Bis(methylamino)anthraquinone
ferred method is replacement of the chlorine in [2475−44−7], M r 266.3, is prepared by re-
2-chloroanthraquinone (see page 8), [2, p. 20]. placement of the hydroxy groups from 1,4-
dihydroxyanthraquinone (see page 9) via the
1-Amino-2-methylanthraquinone [82-28- 2,3-dihydro compound [122].
0], M r 237.3, mp 202 ◦ C, is prepared by nitration
of 2-methylanthraquinone [2, p. 13] followed by 1-Methylamino-4-(3-dimethylaminopro-
reduction or by methylation of 1-aminoanthra- pylamino)anthraquinone, (3), M r 337.4, is
quinone with formaldehyde [115]. prepared from 4-bromo-1-methylaminoanthra-
quinone (see page 8), [123].
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].
14 Anthraquinone Dyes and Intermediates

1-Methylamino-4-(2-hydroxyethylami- 1,5-Bis(benzoylamino)anthraquinone
no)anthraquinone [2475-46-9], (4), M r 296.3, [82-18-8], Indanthren Yellow GK, M r 446.4,
is prepared (in admixture with symmetrical and mp 350 ◦ C, is prepared from 1,5-diaminoanthra-
half-reacted exchange products) by replacement quinone with benzoyl chloride [131] or from 1,5-
of NH2 from 2,3-dihydro-1,4-diaminoanthra- dichloroanthraquinone with benzamide [130],
quinone with a mixture of methylamine and [132].
ethanolamine [124].
1-Amino-4-benzoylaminoanthraquinone
1-Amino-4-methylaminoanthraquinone [81-46-9], M r 342.3, is prepared from 1,4-
[1220−94−6], M r 252.2, is prepared from diaminoanthraquinone with benzoyl chloride
1,4-diaminoanthraquinone by partial methyla- [3, p. 4].
tion [125], from 1-amino-4-methylaminoanthra-
quinone-2-sulfonic acid by reductive SO3 H 1-Amino-5-benzoylaminoanthraquinone
cleavage (see page 12), [126], from 2,3-dihydro- [117-06-6], M r 342.3, mp 244 – 245 ◦ C, is pre-
1,4-dihydroxyanthraquinone by hydroxyl re- pared from 1,5-diaminoanthraquinone with
placement (see page 9) [122], or from 2,3- benzoyl chloride [3, p. 4] or from 1-chloro-
dihydro-1,4-diaminoanthraquinone by replace- 5-benzoylaminoanthraquinone with arylsul-
ment of NH2 [127] (in admixture with 1,4- famides and subsequent hydrolysis [133].
bismethylaminoanthraquinone).

1-Cyclohexylaminoanthraquinone [1096- 1,1 -Dianthraquinonylamine [82-22-4],


48-6], M r 305.4, is prepared by replacing SO3 H, dianthrimide, (6), M r 429.4, is prepared
chlorine, or NO2 [119]. by reacting 1-aminoanthraquinone with 1-
chloroanthraquinone in nitrobenzene [4, p. 29]
1,5-Bis-(2-nitrophenylamino)anthra- or water [134]. Also from 1-aminoanthra-
quinone [21982-51-4], (5), M r 480.4, is pre- quinone and 1-nitroanthraquinone [98].
pared from 1,5-diaminoanthraquinone and 2-
chloronitrobenzene [128].

1-Benzoylaminoanthraquinone [3571-23- 4,4 -Diamino-1,1 -dianthraquinonyl-


1], M r 327.3, mp 248 – 249 ◦ C, is prepared from amine [128-87-0], (7), M r 459.4, is prepared
1-aminoanthraquinone and benzoyl chloride by nitration of dianthrimide followed by reduc-
[129] or from 1-chloroanthraquinone and benz- tion [4, p. 30], [5, p. 138] or by oxidation of
amide [130]. a mixture of 1-aminoanthraquinone and 1,4-
diaminoanthraquinone in aqueous sulfuric acid
1,4-Bis-(benzoylamino)anthraquinone [100].
[2987-68-0], Indanthren Red 5 GK, M r 446.4,
is prepared from 1,4-diaminoanthraquinone and 4,4 -Bis(benzoylamino)−1,1 -dianthra-
benzoyl chloride [4, p. 40]. 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- Alternatively, it can be prepared by a one-pot


pylamino)anthraquinone [51818-35-0], (11), process: sulfonation and bromination in sulfuric
M r 402.3, is prepared from 1-amino-2,4- acid without isolation of intermediates [152].
dibromoanthraquinone and dimethylaminopro-
pylamine by bromine exchange [142].

1,4-Diaminoanthraquinone-6-sulfonic
acid [64910-84-5], M r 318.3, is prepared by sul-
1,4-Diamino-2-nitroanthraquinone, M r fonation of 1,4-diaminoanthraquinone in oleum
283.2, is prepared from 1,4-bis(benzoylami- in the presence of boric acid.
no)anthraquinone by nitration in a solvent and
subsequent hydrolysis [143]. 1-Aminoanthraquinone-2,5- [4137-18-2],
(or -2,8-) disulfonic acid [58294-46-5], M r
1,4-Diamino-5-nitroanthraquinone [82- 383.4, is prepared from 1-aminoanthraquinone-
33-7], M r 283.2, is prepared from 1,4-diami- 5- (or -8-) sulfonic acid by sulfonation [145],
noanthraquinone via the cyclic disulfimide (the or from 1-cyclohexylaminoanthraquinone-5-
structure is shown in page 12), which is nitrated sulfonic acid in oleum [102].
in sulfuric acid and then hydrolyzed [3, p. 20].
1-Aminoanthraquinone-2,6- (or -2,7-)
1,5-Diamino-4,8-dinitroanthraquinone disulfonic acid, M r 383.4, is prepared from
[10262-79-0], M r 328.3, is prepared from 1-nitroanthraquinone-6- (or -7-) sulfonic acid
anthraquinone-1,5-bis-oxamidic acid by ni- and Na2 S by formation of 1-amino-2-mercapto-
tration and hydrolysis [106] or from anthra- anthraquinone-6- (or -7-) sulfonic acid followed
quinone-1,5-bis(formamidinium chloride) by by oxidation [153].
nitration and hydrolysis in dilute sulfuric acid
[144]. 1-Isopropylaminoanthraquinone-5-
sulfonic acid [33175-83-6], M r 345.4, is pre-
1,4-Diamino-2-bromo-5-nitroanthra- pared from anthraquinone-1,5-disulfonic acid
quinone, M r 362.1, is prepared from 1-ami- by replacement of one SO3 H [154].
no-2,4-dibromo-5-nitroanthraquinone and p-
toluenesulfonamide followed by hydrolysis 1-Cyclohexylaminoanthraquinone-5-
[145]. sulfonic acid [33175-82-5], M r 385.4, is pre-
pared from anthraquinone-1,5-disulfonic acid
1-Aminoanthraquinone-2-sulfonic acid by replacement of one SO3 H [155].
[83-62-5], M r 303.3, is prepared from 1-ami-
noanthraquinone by sulfonation with ClSO3 H 1,4-Bis-(p-toluidino)anthraquinone-2 ,2 -
in an organic solvent (if nitrobenzene, danger disulfonic acid [3443-90-1], (13), M r 578.6,
of explosion) [5, p. 214], [146], [147], [149], or is prepared from 1,4-dihydroxyanthraquinone
with oleum in the presence of Na2 SO4 [148]. and p-toluidine by replacement of hydroxyl fol-
lowed by sulfonation [5, p. 215].
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].
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- in the 4 position in 1-amino-2,4-dihaloanthra-


quinone-5-sulfonic acid, (22), M r 424.3, is quinone using boric–sulfuric acid. As the di-
prepared by bromination [397]. 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-
1-Amino-2-bromo-4-(4 -methylphenyl-
quinone ethers. In individual cases the hydroxy
sulfonamido)anthraquinone [26868-32-6],
groups also may be inserted at defined positions
(23), M r 471.3, is prepared from 1-amino-2,4-
by oxidation.
dibromoanthraquinone and p-toluenesulfon-
Amino groups in 1,4-diamino- (or ami-
amide [162].
nohydroxy-) anthraquinones are converted read-
ily into hydroxy groups by reduction in alka-
line medium via the 2,3-dihydro compounds
2.5.3. Diazotization of
or in an acid medium by oxidation via the
Aminoanthraquinones
quinoneimines.
Halogenation, nitration, and sulfonation of
Aminoanthraquinones may be diazotized by the
hydroxyanthraquinones present no special dif-
usual methods in sulfuric acid. On an indus-
ficulties. Modification of the hydroxy group
trial scale, the diazotization of an aminoanthra-
(boric acid esters, ethers) alters the mode of sub-
quinone is accomplished by the conversion of
stitution. Derivatives of the hydroxy groups fre-
1-amino-5-benzoylaminoanthraquinone into 1-
quently enable a different or more selective sub-
chloro-5-benzoylaminoanthraquinone by diazo-
stitution than the free hydroxy compounds.
tization followed by the Sandmeyer reaction.
Azo derivatives of anthraquinone, which
may be obtained by coupling diazotized ami-
2.6.1. General Aspects
noanthraquinones, are cited as colorants for
a variety of applications [163]. Among the 2.6.1.1. Synthesis of the Nucleus
hydrazino derivatives only anthraquinone-1-
hydrazinosulfonic acid is worth mentioning be- The preparation of quinizarin from phthalic an-
cause it is obtained as an intermediate in the syn- hydride and p-chlorophenol in boric–sulfuric
thesis of pyrazoloanthrone (see Section 2.12.2). acid has considerable industrial importance. The
boric acid removes the quinizarin formed by for-
mation of a stable boric acid ester which changes
2.6. Hydroxyanthraquinones, Alkoxy- the equilibrium and, thus, enables the complete
and Aryloxyanthraquinones replacement of chlorine atoms by the hydroxy
group.
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 - Other methods, such as condensation of
disulfonic acids into α,α -dihydroxyanthra- maleic anhydride with naphthohydroquinone
quinones and the direct hydrolysis of a halogen [164] and the reaction of phthalic anhydride
Anthraquinone Dyes and Intermediates 19

with hydroquinone in molten aluminum chlo- coholic alkali at 50 – 120 ◦ C. If higher tem-
ride/sodium chloride, have not yet reached any peratures are used, hydroxyanthraquinones are
level of importance. formed also. Anthraquinone aryl ethers are not
prepared readily by this method. Instead, they
are made from haloanthraquinones.
2.6.1.2. Replacement Reactions
Halogen → OR (R = H, alkyl, aryl). Apart
H → OH. Hydroxy groups may be intro- from the synthesis of quinizarin, direct replace-
duced into anthraquinones in acid or alkaline ment of halogen by hydroxy groups is of in-
media. Suitable oxidizing agents are manganese dustrial importance only for replacing halogen
dioxide, potassium peroxodisulfate, potassium in 1-amino-4-haloanthraquinones, e.g., 24→ 25
chlorate, or sodium nitrite. Whereas the synthe- in the presence of boric–sulfuric acid. In all
sis of 1,2-dihydroxyanthraquinone (alizarine) other cases, the haloanthraquinones are first con-
by oxidation of anthraquinone requires an al- verted with alcoholate or phenolate into the cor-
kaline medium, preparation of 1,2,4-trihydroxy- responding alkoxy- or phenoxyanthraquinones.
anthraquinone (purpurin) from 1,2- or 1,4-di- This procedure is suitable for replacing halogens
hydroxyanthraquinone is carried out in sulfuric in both the α and the β position. However, for
acid solution by oxidation with manganese diox- the preparation of β-alkoxyanthraquinones, it is
ide. If 1,8-dihydroxyanthraquinone is oxidized recommended to generate first the β-phenoxy
with oleum containing a high percentage of SO3 compound and then to subject this compound to
in the presence of boric acid, oxidation occurs an ether exchange reaction, e.g., 25 → 26 → 27.
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., 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
However, sulfonic acid groups in the β posi- by hydroxy groups and ether residues. However,
tion react only in an alkali melt at temperatures because direct replacement of hydroxy groups
of 150 – 200 ◦ C. If oxidizing agents are added, causes side reactions, only the reactions with
the α position is also hydroxylated, e.g., synthe- alcoholate or phenolate, leading to the corre-
sis of alizarine from anthraquinone-2-sulfonic sponding anthraquinone ethers, are of industrial
acid: 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-
Further, anthraquinonesulfonic acids may cause industrial synthesis of anthraquinone in-
be converted into alkoxyanthraquinones by al- 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-


Furthermore, hydroxyanthraquinones are ca-
version of aminoanthraquinones to hydroxy-
pable of undergoing the Mannich reaction.
anthraquinones is of little importance. Usual
Quinizarin, formaldehyde, and piperidine react,
methods may be used to convert the amino group
for instance, under formation of 1,4-dihydroxy-
to the hydroxy group by means of diazotization
2-(piperidinomethyl)anthraquinone [168]:
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 When the hydrogen atoms in the β posi-
with warm sodium dithionite–sodium hydrox- tion are activated sufficiently, direct arylation
ide, is used industrially for the manufacture of of 1,4-substituted anthraquinones is also possi-
leuco-1,4,5,8-tetrahydroxyanthraquinone from ble. This reaction is important in preparing ary-
4,8-diamino-1,5-dihydroxyanthraquinone-2,6- lated diaminodihydroxyanthraquinones, which
disulfonic acid: 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 21

acid. This requires that in the following step the fonic acid [173], and in the 5,8 positions in boric
sulfonic acid groups be cleaved [170] or the re- acid – oleum [174].
maining nitro groups be reduced [171]: 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
Nucleus H → SO3 H. Hydroxyanthra- in sulfuric acid or organic solvents is nitrated
quinones are sulfonated in oleum. When the 1,4- in the 2 position, whereas in boric acid–oleum
dihydroxyanthraquinone is used as the starting one gets only nitration in the 5 position. A dif-
material, addition of boric acid blocks sulfona- ferent behavior is shown by the boric or ar-
tion of the 2 position, and instead the sulfonic sonic acid esters of 1,2-dihydroxyanthraquinone
acid group enters the 5 or 6 position [3], [172]. (alizarine). Here nitration in sulfuric acid yields
In 1,5- (or 1,8-) dihydroxyanthraquinones, addi- the 3- and 4-nitro derivatives. 1,8-Dihydroxy-
tion of sodium sulfate to the oleum may prevent anthraquinone in sulfuric acid is dinitrated up to
an excessive sulfonation and the oxidation to 80 % in the 4 and 5 positions, whereas the iso-
higher hydroxylated products. meric 1,5-dihydroxy compound affords only un-
satisfactory yields of 1,5-dihydroxy-4,8-dinitro-
Nucleus H → Halogen. In general the anthraquinone.
choice of the halogenating agent has no influ- The α-nitration is more successful with
ence on the substitution. Bromination is often dimethoxyanthraquinones and yet more suc-
preferred because of the greater ease in replacing cessful with diphenoxyanthraquinones. In the
bromine. last case the benzene rings are also nitrated in
As hydroxy and amino groups generally en- their 2 and 4 positions, which then facilitates
hance the reactivity towards halogenation, boric ether hydrolysis in alkaline medium:
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-
22 Anthraquinone Dyes and Intermediates

Halogen → SO3 H. The remaining chlo- 2.6.2. Individual Hydroxyanthraquinones


rine atom in 1,4-diamino-3-chloro-2-phen-
oxyanthraquinone (obtained from 1,4-diamino- 1,2-Dihydroxyanthraquinone [8005-35-4],
2,3-dichloroanthraquinone by phenolate melt) is alizarine, (32), M r 240.2, mp 289 – 290 ◦ C, is
replaced readily in alkali sulfite to yield the sul- prepared from anthraquinone by alkali melt
fonic acid. [182] or from anthraquinone-2-sulfonic acid
with 50 % aqueous sodium hydroxide and
Halogen → NHR. Halohydroxyanthra- sodium nitrate at 190 – 200 ◦ C [3, p. 39], [5,
quinones can be converted into the correspond- p. 44].
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 1,4-Dihydroxyanthraquinone [81-64-1],
oleum. quinizarin, (33), M r 240.2, mp 198 ◦ C, is
The nitro group of 1-hydroxy-4-nitroanthra- prepared from phthalic anhydride and p-
quinone is replaced easily by amino residues. In chlorophenol by heating in oleum in the pres-
α-dihydroxydinitroanthraquinones, a stepwise ence of boric acid [1], [12]. Improved methods
substitution presents no special difficulties. In are cited in [183], [184].
1,8-dihydroxy-4,5-dinitroanthraquinone, the re-
action with aromatic amines in the presence 1,5-Dihydroxyanthraquinone [117-12-4],
of boric acid takes a different course. The anthrarufin, (34), M r 240.2, mp 280 ◦ C, is pre-
product is 5,8-diarylamino-1-hydroxy-4-nitro- pared from 1,5-anthraquinonedisulfonic acid by
anthraquinone [179]. 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].

A special reaction constitutes the conversion 1,8-Dihydroxyanthraquinone [117-10-2],


of α-nitroanthraquinones into the corresponding chrysazin, (35), M r 240.2, mp 193 ◦ C, is pre-
1-amino-4-hydroxyanthraquinones mediated by pared by replacing SO3 H [5, p. 46], by di-
the action of sulfur or other reducing agents, e.g., rectly replacing nitro groups in sulfolane in
FeSO4 , in oleum or sulfuric acid monohydrate, the presence of calcium oxide [185], or, bet-
if necessary with addition of boric acid. This ter, via 1,8-dimethoxyanthraquinone and subse-
reaction is accompanied by a number of side re- quent hydrolysis of the ether [186].
actions. Satisfactory yields and purity levels are
achieved only in exceptional cases [180], [181];
see also [13, pp. 199 – 203].
Anthraquinone Dyes and Intermediates 23

1,2,4-Trihydroxyanthraquinone [81-54-9], 1,8-dichloroanthraquinone [198] or 1,8-dinitro-


purpurin, (36), M r 256.2, mp 257 – 259 ◦ C, is anthraquinone [195], [197] by reaction with al-
prepared from alizarine [5, p. 57], [187] or from kali phenolate.
quinizarin by oxidation [188].
5,8-Dichloro-1,4-dihydroxyanthra-
1,4,5-Trihydroxyanthraquinone [2961- quinone [2832-30-6], (39), M r 309.1,
04-8], M r 256.2, mp 270 – 271 ◦ C, is prepared mp 266 ◦ C, is prepared from 3,6-
from 1,8-dihydroxyanthraquinone with 80 % dichlorophthalic anhydride by synthesis of the
oleum and boric acid [189]. nucleus [199] or from quinizarin by chlorination
[174].
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], 2-Bromo-1,4-dihydroxyanthraquinone


(37), M r 268.3, mp 236 ◦ C, is prepared [81-52-7], (40), M r 319.1, sublimation at
from anthraquinone-1,5-disulfonic acid with 300 ◦ C, is prepared from quinizarin by bromi-
methanolic alkali-metal hydroxide [190] or nation in nitrobenzene [3, p. 66].
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-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].
1,5-Diphenoxyanthraquinone [82-21-3],
(38), M r 392.4, mp 215 ◦ C, is prepared from 1,4-Dihydroxy-5-nitroanthraquinone
1,5-dichloroanthraquinone and sodium pheno- [27573-16-6] M r 285.2, mp 244 – 245 ◦ C, is pre-
late without solvent [4, p. 8] or with an inert sol- pared from 1-hydroxy-10-chloroanthraquinone-
vent [194] or from 1,5-dinitroanthraquinone by (4,9) [201].
reaction with alkali phenolate in phenol [195] or
an inert solvent [196], [197]. 1,5-Dihydroxy-4,8-dinitroanthraquinone
[128-91-6], M r 330.2, is prepared from 1,5-di-
1,8-Dimethoxyanthraquinone [6407-55-2], phenoxyanthraquinone by nitration followed by
M r 268.3, mp 212 ◦ C, is prepared from anthra- alkaline hydrolysis [4, p. 8].
quinone-1,8-disulfonic acid with methanolic
alkali-metal hydroxide [190], from 1,8-dinitro- 1,8-Dihydroxy-4,5-dinitroanthraquinone
anthraquinone with methanolic alkali-metal hy- [81-55-0], M r 330.2, is prepared from 1,8-di-
droxide in the presence of amidosulfonic acid phenoxyanthraquinone by nitration followed by
[191], by passing air through the reaction mix- alkaline hydrolysis or, alternatively, by nitration
ture [192], [193]. of 1,8-dihydroxyanthraquinone in oleum in the
presence of boric acid and isolation after the
1,8-Diphenoxyanthraquinone [82-17-7], sulfuric acid concentration has been adjusted to
M r 392, mp 189 – 190 ◦ C, is prepared from 80 – 100 % [202] or, using the same procedure,
24 Anthraquinone Dyes and Intermediates

from 1,8-dimethoxyanthraquinone followed by reduction [4, p. 8]; a process improvement is


ether cleavage. described in [206]; or from 4,8-diamino-1,5-
dihydroxyanthraquinone-2,6-disulfonic acid by
1-Amino-4-hydroxyanthraquinone [116- desulfonation [207].
85-8], (42), M r 239.2, mp 208 ◦ C, is pre-
pared from 1-amino-4-hydroxyanthraquinone- 4,5-Diamino-1,8-dihydroxyanthra-
3-sulfonic acid by splitting off the SO3 H group quinone [128-94-9], M r 270.2, is prepared from
[203], from 1-benzoylamino-4-chloroanthra- 1,8-dihydroxy-4,5-dinitroanthraquinone by re-
quinone by treatment with boric–sulfuric acid, duction [208] or by cleavage of the sulfonic acid
or from 1-nitroanthraquinone by reduction with groups from the corresponding 2,7-disulfonic
FeCl2 in sulfuric acid and rearrangement of acid [207].
the hydroxylamine stage [180], from 1,4-diami-
noanthraquinone with MnO2 in sulfuric acid 1-Hydroxy-5-isopropylaminoanthra-
[204], or from 1-hydroxyanthraquinone by ni- quinone [33902-49-7], (44), M r 281.3, is pre-
tration followed by reduction with Na2 S [5, pared from 1-isopropylaminoanthraquinone-5-
p. 200]. sulfonic acid by replacement of SO3 H [175],
[176].

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- 1-Hydroxy-4-(p-methylphenylami-
tion with Na2 S [3, p. 3]. no)anthraquinone [81-48-1], (45), M r 329.4,
is prepared from the leuco form of quinizarin
4-Amino-1,3-dihydroxyanthraquinone and p-toluidine [209], [3, p. 48] or from 4-halo-
[81-51-6], M r 255.2, is prepared from 1,2,4- 1-hydroxyanthraquinone and p-toluidine.
trihydroxyanthraquinone (purpurin) and NH3
[13, p. 163]. 1-Hydroxy-5,8-bis-(p-methylphenylami-
no)anthraquinone [4392-68-1], M r 434.5, is
5-Amino-1,4-dihydroxyanthraquinone prepared from 1,4,5-trihydroxyanthraquinone
[23215-11-4], M r 255.2, is prepared from the and p-toluidine [3, p. 33] by replacing hydroxyl
5-nitro compound by reduction with SO2 [205]. or from 5,8-dichloro-1-hydroxyanthraquinone
[210] by chlorine replacement.
3-Amino-2-hydroxyanthraquinone [117-
77-1], (43), M r 239.2, is prepared from 5- 1,4-Dihydroxy-5,8-bis(phenylami-
benzoylbenzoxazolone-2 -carboxylic acid [2, no)anthraquinone, (46), M r 422.4, is prepared
p. 14]. 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.

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
Anthraquinone Dyes and Intermediates 25

1-Methoxy-4-(p-methylphenylami- 4-hydroxyanthraquinone and phenolate. This


no)anthraquinone, (47), M r 343.4, is prepared process was improved [218].
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- 4,8-Diamino-1,5-dihydroxy-3-(p-methox-
methoxybenzoylamino)anthraquinone, (48), yphenyl)anthraquinone, (52), (for the eluci-
M r 508.4, is prepared by mixed acylation of dation of the structure see [169]), M r 377.3,
4,8-diamino-1,5-dihydroxyanthraquinone with is prepared from 4,8-diamino-1,5-dihydroxy-
p-methoxybenzoyl chloride and benzoyl chlo- anthraquinone-2,6-disulfonic acid by addi-
ride [4, p. 8]. 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
1-Amino-4-hydroxy-2-hydroxyethoxy- by chlorination in oleum–boric acid [180]
anthraquinone [17869-07-7], (49), M r 299.3, or from 1-amino-4,5,8-trichloroanthraquinone
is prepared from 1-amino-4-hydroxy-2-phen- with boric–sulfuric acid [221].
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- 1-Amino-3-bromo-4-hydroxyanthra-
nol by chlorine replacement [3, p. 49]. 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
1-Amino-4-hydroxy-2-phenoxyanthra- process from 1-aminoanthraquinone (bromi-
quinone [17418-58-5], (51), M r 331.3, is pre- nation – hydrolysis) [222–224].
pared from 1-amino-2-chloro- (or -2-bromo-)
26 Anthraquinone Dyes and Intermediates

8-Bromo-1-hydroxy-5-isopropylamino- 1,8-Dihydroxy-4,5-dinitroanthraquinone-
anthraquinone, (55), M r 360.2, is prepared by 2,7-disulfonic acid [128-90-5], (59), M r 490.3,
bromination [175]. 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].

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- 4,8-Diamino-1,5-dihydroxyanthra-
furic acid [226]. 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-
1,4-Dihydroxyanthraquinone-2-sulfonic fonation, nitration, and reduction [229].
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]. 2.7. Mercaptoanthraquinones

1,5-Dihydroxyanthraquinone-2,6- Mercaptoanthraquinones are of little commer-


disulfonic acid [6492-85-9], M r 400.3, is pre- cial importance. However, they appear as uniso-
pared from 1,5-dihydroxyanthraquinone with lated intermediates. They are obtained by re-
oleum–Na2 SO4 [228]. placement of halogen [231] or sulfonic acid
groups with alkali sulfides, by addition of alkali
1,8-Dihydroxyanthraquinone-2,7- sulfides to 1-aminoanthraquinones [232], or by
disulfonic acid, M r 400.3, is prepared by heat- cleavage of thiocyanatoanthraquinones [233].
ing 1,8-dihydroxyanthraquinone in oleum [229]. More important are the anthraquinone
thioethers, which are obtained by usual meth-
1,5-Dihydroxy-4,8-dinitroanthraquinone- ods as replacement of halogen, nitro, or
2,6-disulfonic acid [6449-09-8], (58), sulfonic acid groups; by modification of
M r 490.3, is prepared from 1,5-dihydroxy- mercaptoanthraquinones; or by addition reac-
anthraquinone-2,6-disulfonic acid by nitration tions to hydroxy- and aminoanthraquinones or
in sulfuric acid [228]. to quinoneimine derivatives [234]. 1-Hydroxy-
4-nitroanthraquinones react especially well un-
der simultaneous reduction of the nitro group
[235].
Anthraquinone Dyes and Intermediates 27

2.7.1. General Aspects 1,4-Dihydroxy-2-phenylmercaptoanthra-


quinone, (64), M r 348.4, is prepared from 1,4-
SO3 H → SR (R = alkyl, aryl). The ex- dihydroxyanthraquinone and thiophenol [240].
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-, 1,8-Dihydroxy-4-nitro-5-phenylmercapto-
alkylmercapto-, and arylmercaptoanthra- anthraquinone, (65), M r 393.4, is prepared
quinones. Suitable reaction media are organic from 1,8-dihydroxy-4,5-dinitroanthraquinone
solvents: halogenated aromatic hydrocarbons and thiophenol [236].
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]. 1-Amino-4-hydroxy-2-phenylmercapto-
anthraquinone, (66), M r 347.4, is prepared
H → SR. The addition of mercaptans to ami- by displacement of bromine from 1-amino-2-
no- or hydroxyanthraquinones or to 1-hydroxy- bromo-4-hydroxyanthraquinone and thiophenol
4-nitroanthraquinones [235] that occurs via re- [241].
ductive steps has no industrial importance.

SH → SR. Mercaptoanthraquinones may be 1-Amino-2-mercaptoanthraquinone-6-


converted to alkylmercaptoanthraquinones with sulfonic acid, (67), M r 335.4, is prepared from
the usual alkylating agents under alkaline con- 1-nitroanthraquinone-6-sulfonic acid with aque-
ditions [237]. ous sodium sulfide [242].

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 1,4-Dihydroxy-2-(2-hydroxyethyl-
followed by reduction [238]. 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

1-Amino-2-(2-hydroxyethylmercapto)-4- Alkyl and aryl sulfone derivatives of anthra-


phenylaminoanthraquinone, (63), M r 390.4, quinone have reached a certain amount of im-
is prepared by displacement of SO3 H from the portance only as polyester dyes resistant to subli-
corresponding anthraquinone-2-sulfonic acid mation and as dyes for mixed polyester – cotton
[239].
28 Anthraquinone Dyes and Intermediates

fabrics. They are obtained by displacement of formed in this step can be hydrolyzed easily to
the halo [244] or nitro group with sulfinates, by the aldehyde but usually is used directly in fur-
sulfinic acid addition to quinoneimines [245], ther reactions.
or by oxidation of the corresponding thioethers 1-Aminoanthraquinone-2-aldehyde also may
with chromium(VI) oxide or hydrogen peroxide be prepared from 2-methyl-1-nitroanthra-
in such solvents as glacial acetic acid or sulfuric quinone by reaction with 65 % oleum followed
acid [246]. by reduction of the resulting isoxazole [250].

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-Aminoanthraquinone-2-aldehyde,
1-Amino-2-ethylsulfonyl-4-(p-isopropyl- M r 251.2, is prepared by oxidation of 1-ami-
phenylamino)anthraquinone [4839-56-9], no-2-methylanthraquinone with nitrobenzene in
(69 with R1 = –C6 H4 CH(CH3 )2 , R2 = –C2 H5 ), the presence of aniline and potassium carbonate,
M r 448.5, is prepared from the 2-bromo com- followed by hydrolysis of the 1-aminoanthra-
pound by halogen displacement with ethyl sul- quinone-2-aldehyde anil in sulfuric acid [251],
finate [237]. or by action of 65 % oleum on 2-methyl-1-nitro-
anthraquinone followed by reduction [250].
4,8-Diamino-1,5-dihydroxy-2- (and -3-
) phenylsulfonylanthraquinone (70 with 1-Amino-4-benzoylaminoanthraquinone-
R = C6 H5 ), M r 410.4, is prepared from 4,8- 2-aldehyde anil, (71), M r 445.5, is pre-
diamino-1,5-dihydroxyanthraquinone via the pared from 1-amino-4-benzoylamino-2-
quinoneimine [245]. methylanthraquinone by oxidation in nitroben-
zene in the presence of aniline and potassium
carbonate [252].
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 The azine of 1-amino-4-benzoylamino-
via the dihalomethyl compounds [249] into the anthraquinone-2-aldehyde, (72), M r 736.6, is
aldehydes. In industrial processes, 1-amino-2- prepared from the aldehyde anil in glacial acetic
methylanthraquinone is oxidized with nitroben- acid with hydrazine hydrate [252].
zene in the presence of aniline. The azomethine
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 [81-41-4], (77), M r 288.2, is prepared from 1,4-
halogenated in the 4 position in sulfuric acid diaminoanthraquinone-2-sulfonic acid [259],
[256]. However, under these conditions, anthra- [260] or from 1,4-diaminoanthraquinone-2,3-
quinone-2-carboxylic acid is nitrated or dichlo- disulfonic acid in aqueous alkaline solution
rinated in the 5,8 positions. [261] or in amides [262] by reaction with sodium
cyanide.
Cl → NHR, NO2 → SO3 H, NHR. Car-
boxyl groups and their derivatives facilitate the 1-Amino-2-cyano-4-cyclohexylamino-
replacement of nitro groups or halogen atoms anthraquinone, (78), M r 345.4, is prepared by
by a variety of substituents. displacement of SO3 H with potassium cyanide
in aqueous solution [3, p. 56].
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.

2.10.2. Individual Anthraquinonecarboxylic


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

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


Containing Imidazole, Oxazole, and
Thiazole Rings
2-Carboxyanthraquinone-1-sulfonic acid, Anthraquinone dyes with condensed imidazole,
(84), M r 332.3, is prepared from 1-nitroanthra- oxazole, or thiazole rings are prepared by dehy-
quinone-2-carboxylic acid with Na2 SO3 in drating ring closure from 2-aroylaminoanthra-
aqueous solution [257]. 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- ride and 2-amino-3-chloroanthraquinone and
zole derivatives. These are prepared from 2- Na2 S-sulfur.
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.

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-
Whereas the oxazole derivatives are ob- chloroanthraquinone by replacing the chlorine
tained directly from the 3-amino-2-hydroxy- atom by a mercapto group, followed by reaction
anthraquinone by acylation followed by ring clo- with glyoxal sulfate in concentrated sulfuric
sure with sulfuric acid [269], the preparation of acid [272], [2, p. 19].
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- 2,8-Diphenylthiazolo [5 ,4 : 7,8] anthra-
lowed by displacement of the nitro group with [2,1-d-] thiazole-6,12-quinone [129-09-9], Al-
ammonia and ring closure [2, p. 15], [269]. 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 are the corresponding thi- The following description uses the desig-
azole compounds: Indanthren Rubine B nations common in industrial circles. The
[6371-49-9], (92), [2, p. 15, 16], M r 486.5; carbazole of 1,1 -dianthrimide is referred
Indanthren Blue CLG [6371-50-2], (93), [2, to as 1,1 -dianthrimide-2,2 -carbazole. Other
p. 18], [270], M r 605.6; and Indanthren Blue terms for this carbazole would be: 1,2 : 7,8-
CLB [6492-78-0], (94), [2, p. 18], [271], diphthaloylcarbazole, 16H-dinaphtho [2,3-
M r 673.6. Compound 94 is prepared from 1- a : 2 ,3 -i] carbazole-5,10,15,17-tetraone, and
amino-4-nitroanthraquinone-2-carbonyl chlo- 16H-(bis{anthraceno-[1,2-b : 2 ,1 -d] pyrrole})
5,17 : 10,15-bisquinone.
Anthraquinone Dyes and Intermediates 33

1-Arylaminoanthraquinones may be con-


densed to coeramidonine derivatives, or they
may be subjected to a dehydrogenating cycliza-
tion to give carbazole derivatives.

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,
Coeramidonines are generally obtained on on whether the linkage is linear or branched,
heating in aqueous sulfuric acid. When simple and on the nature of the substituents. They are
1-arylaminoanthraquinones are treated with alu- prepared industrially by carbazolyation of di-,
minum chloride, frequently both types of prod- tri-, tetra-, and pentanthrimides. Even if car-
ucts are obtained [274]. Naphthylaminoanthra- bazolyation products of the higher anthrimides
quinones and anthrimides tend to form carbazole are generally cited as pure single compounds,
derivatives. The reaction proceeds via dihydro- carbazolyation reaction in many polyanthrim-
carbazoles, which are converted to the corre- ides by the usual methods must be considered
sponding carbazoles by subsequent oxidation incomplete.
with air, sodium dichromate, manganese diox- In its broadest sense, the term anthrimide in-
ide, sodium chlorate, sodium nitrite, or sodium cludes secondary amines, where anthraquinone
hypochlorite. The dehydrogenating cyclization has been replaced by anthraquinone derivatives
is generally termed carbazolyation. 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
Among the carbazole derivatives that are not
to rather contaminated products because of the
derived from anthrimides, Alizarin Light Brown
temperatures required (200 – 280 ◦ C) [279] and
BL (97) is an example. It is prepared from
is not practical because of the difficulties in mix-
1-benzoylamino-2-methyl-4-β-naphthylami-
ing the components intimately. The physical and
noanthraquinone by ring closure in concen-
chemical properties of the melts have been modi-
trated sulfuric acid with simultaneous sulfona-
fied by a variety of additives. In the so-called acid
tion [275].
melts, alkali–metal halides (NaCl, NaF, KCl),
sulfur dioxide [281], sodium hydrogen sulfite,
34 Anthraquinone Dyes and Intermediates

organic solvents [282], nitrobenzene (danger of and 1,1 : 4,1 : 5,1 : 8,1 -pentanthrimide
explosion!) [283], nitriles [285], or acid chlo- at 140 – 220 ◦ C. Stirring the melt into a so-
rides [286] have been proposed. The so-called lution of sodium hydroxide or hydrochlo-
alkaline aluminum chloride melts are obtained ric acid, followed by oxidation with sodium
by addition of excess pyridine, picolines, quino- dichromate, for example, yields the dyes.
lines, isoquinolines, or dimethylaniline [287]. 3) Aluminum chloride – sulfur dioxide: melts
Aluminum chloride–pyridine complexes in a of aluminum chloride and sulfur diox-
molar ratio of  1 : 1 [288], possibly in the pres- ide, to which sodium chloride can be
ence of organic solvents, and with aluminum added if necessary, have low viscosity and
chloride–ammonia complexes, are equivalent in permit carbazolyation under mild condi-
their mode of action to the acid melts [289]. tions (20 – 100 ◦ C). This method is supe-
Carbazolyation with titanium tetrachloride in or- rior to other carbazolyation processes in
ganic solvents, such as halobenzenes [290] or, some cases, for instance, in treating 4 ,4 -
sulfolane [291], have been described. Finally, dibenzoylamino-1,1 : 5,1 -trianthrimide.
alkaline carbazolyation in potassium hydroxide The reagent is prepared by passing sulfur
melts, possibly with addition of sodium hydrox- dioxide into a melt of aluminum chloride and
ide, has been reported also [292]. sodium chloride (weight ratio ≈ 4 : 1) until
Each of the carbazolyation agents possesses the melt has low viscosity. After the anthrim-
specific properties and modes of action. The ide is added, the mixture is heated to the tem-
choice of an optimal carbazolyation process de- perature required for carbazolyation. Workup
pends largely on the structure of the anthrimide involves stirring into sodium hydroxide solu-
and the nature of the substituents. tion.
The following carbazolyation agents are used 4) Aluminum chloride – pyridine (or
commercially: methylpyridines): carbazolyation in alu-
minum chloride–pyridine melts (excess
1) Sulfuric acid: benzoylamino groups in pyridine) is applicable to many substi-
the α-position and an acridone substruc- tuted and unsubstituted anthrimides. Indus-
ture facilitate carbazolyation in concen- trially, this method is applied mainly to
trated sulfuric acid. For example, the 1,1 : 4,1 -trianthrimide, 5-benzoylamino-
4,4 -, 4,5 -, and 5,5 -dibenzoylamino- 1,1 : 4,1 -trianthrimide, 5-(benzanthron-3-
1,1 -dianthrimides; 4,5-dibenzoylamino-8- ylamino)−1,1 -dianthrimide, and 1-benzoyl-
methoxy-1,1 -dianthrimide; and the anthrim- amino-4,1 : 5,1 : 8,1 -tetraanthrimide. In
ide prepared from 1-amino-5-benzoylami- this process, aluminum chloride is added to
noanthraquinone and the 2,5,7-trichloro-3,4- pyridine (weight ratio ≈ 1 : 5) first, and then
phthaloylacridone are carbazolated in this the anthrimide is added. After heating to the
way. The reactions are carried out by adding temperature required for the carbazolyation,
the anthrimide to sulfuric acid and stirring at 100 – 170 ◦ C, and stirring until reaction is
20 – 40 ◦ C until reaction is complete, which completed, workup is carried out by adding
is generally indicated by a change in the to sodium hydroxide solution, and, if neces-
color of the solution. The melt is then poured sary, oxidative cleanup. The type of organic
into water, and the dihydrocarbazole oxi- base (pyridine, methylpyridine, quinoline,
dized. Posttreatment with sodium dichro- etc.) selected and the reaction conditions ex-
mate, sodium nitrite, sodium persulfate, ert a decisive influence on the quality of the
sodium chlorate, or sodium hypochlorite dye.
facilitates a certain degree of purification by
oxidizing impurities. Some important members of the anthra-
2) Aluminum chloride – alkali metal halide: quinonecarbazole series are listed below.
mixtures of aluminum chloride and dry
sodium chloride (weight ratio ≈ 4 : 1) form 1,1 -Dianthrimide-2,2 -carbazole [4229-
relatively low melting eutectics. Such melts 15-6], Indanthren Yellow FFRK, M r 427.4
are used mainly for the carbazolyation of (for formula see above), is prepared from
1,1 -dianthrimide, 1,1 : 5,1 -trianthrimide,
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 Acridone Substructure (Phthaloylacridones)
[14999-97-4], Indanthren Khaki GG, M r 1085.0
(for formula see Section 3.1.3, 210), is prepared The red to blue anthraquinone dyes with
from the corresponding pentanthrimide with acridone substructure are all derived from 3,4-
aluminum chloride [278] or with aluminum phthaloylacridone (99). Their use has been
chloride–sodium chloride [5, p. 133], [293]. mainly as vat dyes.
The basic structure provides red-violet dyes,
5,5 -Bisbenzoylamino-1,1 -dianthrimide- but with rather weak tinctorial strength. The
2,2 carbazole [128-70-1], Indanthren Golden- 3,4-phthaloylacridones are prepared from the
Orange 3 G, M r 665.6, is prepared from 5,5 - 1-arylaminoanthraquinone-o-carboxylic acids
bisbenzoylamino-1,1 -dianthrimide by ring clo- 100 or 101 by acid-catalyzed ring closure us-
sure in concentrated sulfuric acid [4, p. 15]. ing sulfuric acid, weak oleum, chloro- or fluoro-
sulfonic acid, polyphosphoric acid, or AlCl3 or
to a lesser extent phosgene, acetyl chloride, or
4,5 -Bisbenzoylamino-1,1 -dianthrimide-
phosphoryl chloride.
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].

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], Special methods for ring closure are
[281]. 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 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.
Indanthren Green 4 G [6661-46-7], (110),
Better suited for the oxidative dimerization
M r 709.1, is prepared from 2-amino-7-chloro-
of 1-aminoanthraquinone to indanthrone is a
3,4-phthaloylacridone and 2-phenyl-4-chloro-
melt of potassium phenolate at 200 – 210 ◦ C
6,7-phthaloylquinazoline, which itself is derived
in the presence of oxidizing agents [308] or
from 3-aminoanthraquinone-2-carboxylic acid,
passage of air in the presence of catalysts,
benzoic acid, and ammonia [4, p. 19], [305].
such as MnO2 or FeCl3 [309]. Dimerization
of 1- (or 2-) aminoanthraquinone to indan-
2.11.4. Anthraquinone Derivatives with throne can be achieved with good yields at
Phenazine Substructure 115 – 125 ◦ C in mixtures of dimethyl sulfox-
ide [310] or tetramethylurea [311] and 50 %
Among the anthraquinone derivatives with aqueous KOH.
phenazine substructure, the indanthrones are an 2) 2-Amino-1-halo- (or 1-amino-2-halo-)
important class of vat dyes. The blue color of anthraquinones condense to indanthrones
the unsubstituted unit may be shifted to green when heated in high-boiling solvents, such
by appropriate substitutions. Several synthetic as nitrobenzene or naphthalene, in the pres-
pathways are available: 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 in industrial dye circles. For example, the com-
GCD or BC). pound called benzanthrone in the “traditional”
nomenclature would be named as 7-oxo-7H-
3,3 -Dichloro-4,4 -diaminoindanthrone benz [d,e]anthracene by the new nomenclature
[1328-41-2], Indanthren Green BB, (112), rules).
M r 541.4, is prepared from 1,4-diamino-2,3- Such ring systems have been prepared in
dichloroanthraquinone in naphthalene in the nearly every feasible combination, but only the
presence of copper powder [313]. few listed below have attained importance in the
commercial synthesis of dyes.

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].

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,
Leuco-sulfuric ester of 3,3 -dichloroindan- such as acedianthrone, anthanthrone (145, for
throne [2519-28-0], Anthrasol Blue IBC, (114), formula see Section 2.12.6), pyranthrone (149,
M r 839.7, is prepared from the leuco-sulfuric for formula see Section 2.12.7), violanthrone
ester of 2-acetylamino-3-chloroanthraquinone (151, for formula see Section 2.12.8), and diben-
[315]. 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
2.12. Anthraquinone Derivatives with quinoline synthesis. Industrial synthesis com-
monly starts directly from anthraquinone, which
Meso Rings (1,9-Cyclo-10-anthrones) is first reduced to anthrone by an appropriate re-
This class includes anthraquinone derivatives ducing agent (e.g., iron) without isolation of the
that contain a condensed carbon or heterocyclic intermediate.
ring linking the α position and the neighbor- Dyes of the basic benzanthrone system are of
ing meso position bridging the 1 and 9 posi- little importance. Commercial dyes are almost
tions. (These derivatives are named in the fol- always benzanthrones with additional fused ring
lowing discussion by their “traditional” nomen- systems derived from benzanthrone and its sim-
clature, which is still the one in common use 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.
4,4 -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
4-Methylbenzanthrone [6409-46-7], (124), [81-94-7], (115), M r 451.5, is prepared from 1-
M r 244.3, is prepared from 2-methylanthra- aminoanthraquinone and 3-halobenzanthrone
quinone via methylanthrone with glycerol in sul- [2, p. 71], [332].
furic acid [327].
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-
3-Bromobenzanthrone [81-96-9], (125),
zene [317].
M r 309.2, is prepared by bromination in hy-
drochloric acid [2, p. 71]; process improvement
Indanthren Navy Blue R [6247-39-8],
is described in [328].
(118), M r 466.5, is prepared from 117 by mild
alkali fusion [317].
3,9-Dibromobenzanthrone [81-98-1],
Additional compounds are given in the sec-
(126), M r 388.1, is prepared by bromination in
tion on vat dyes, Section 3.1.3.
chlorosulfonic acid [2, p. 76], [12], [329].

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-
3-Cyanobenzanthrone, (127), M r 255.3, ous hydrochloric acid.
is prepared from 3-bromobenzanthrone with Hydrazinoanthraquinones are obtained from
CuCN in pyridine [330]. 1-aminoanthraquinones by diazotization, reduc-
tion with sodium hydrogen sulfite to the hydrazi-
Benzanthrone-3-carboxylic acid, (128), nosulfonic acid, and hydrochloric acid hydroly-
M r 274.3, is prepared from the nitrile by hy- sis. Other synthesis options are displacement of
drolysis [331]. 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 cial interest. Starting from 4-bromo-1-
the 1,5-diaminoanthraquinone is not assured. methylaminoanthraquinone, the 6-bromo-3-
methylanthrapyridone is obtained by acetylation
6-(4 -Chlorobenzoylamino)anthrapyrimi- and alkali-catalyzed ring closure [5, p. 217].
dine [4216-00-6], Indanthren Yellow 7 GK, In this compound, the halogen may be eas-
M r 385.8, is prepared by reacting 6-ami- ily displaced by amine functions [344]. Subse-
noanthrapyrimidine with 4-chlorobenzo- quent sulfonation yields lightfast red acid dyes
yl chloride in o-dichlorobenzene [337] or (Alizarine Rubinoles).
from N,N-dimethyl-N -[4-(4 -chlorobenzo-
ylamino)anthraquinonyl-(1)] formamidinium 6-Bromo-3-methylanthrapyridone, (136),
chloride and ammonium acetate in N- M r 340.2. For preparation see preceding para-
methylpyrrolidone [338]. graph [5, p. 217].

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].

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 -
Conversion into the acid chloride and conden- sulfonic acid, (138), M r 432.5, is pre-
sation with aminoanthraquinone affords fast pared by condensation of 6-bromo-3-
yellow vat dyes and pigments [340], [341]. methylanthrapyridone with aniline, followed
by monosulfonation [345].

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:

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].

Acetylation and subsequent ring closure may


also be combined by heating the aminoanthra- 2.12.5. Dibenzpyrenequinones
quinone with acetic anhydride in the presence of
alkali-metal acetates [344]. According to their chemical structure, diben-
Only the 6-arylamino derivatives of 3- zpyrenequinones should be classified as benzan-
methylanthrapyridone and 1-ethoxycarbonyl- throne derivatives, but conventionally they are
4methylanthrapyridone are of commer- treated as a separate group.
Anthraquinone Dyes and Intermediates 43

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].

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 -
The 7,14-dibenzpyrenequinone is used com- dicarboxylic acid in sulfuric acid at 50 ◦ C, fol-
mercially as a golden-yellow vat dye. Another, lowed by chlorination in the presence of FeSO4
now obsolete, method for preparing this com- [5, p. 96], or from anthanthrone by sparging with
pound is fusion of benzanthrone with benzoyl chlorine in the presence of iodine in sulfuric acid
chloride and aluminum chloride [349] and, if or organic solvents [353].
necessary, with aeration with oxygen [350].
4,10-Dibromoanthanthrone [4378-61-4],
7,14-Dibenzpyrenequinone [128-66-5], In- Indanthren Brilliant Orange RK, M r 464.1,
danthren Golden Yellow GK (141), M r 332.4, is prepared from 1,1 -binaphthyl-8,8 -
is prepared from 1,5-dibenzoylnaphthalene (it- dicarboxylic acid in sulfuric acid monohydrate
self prepared from naphthalene with benzoyl at 35 ◦ C, followed by bromination in the pres-
chloride – AlCl3 ) by fusion with AlCl3 -NaCl ence of iodine [5, p. 88]. It is also used as a
at 160 ◦ C and aeration with oxygen [5, p. 123], pigment.
[347], [348].
4,10-Bis-(4 -benzoylaminoanthraquino-
Dibromo-7,14-dibenzpyrenequinone nyl-1 -amino)anthanthrone [6049-19-0], In-
[1324-11-4], Indanthren Golden Yellow RK, danthren Grey BG, (146), M r 987.0, is prepared
M r 490.2, is prepared by bromination in the from 4,10-dibromoanthanthrone and 1-amino-
melt [5, p. 121]. 4-benzoylaminoanthraquinone in naphthalene
[354].
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].
44 Anthraquinone Dyes and Intermediates

2.12.7. Pyranthrone and Flavanthrone Flavanthrone is prepared from 1-chloro-


2-phthalimidoanthraquinone via the 2,2 -
Pyranthrone [128-70-1], (149), M r 406.4, diphthalimido-1,1 -bianthraquinonyl, using
is prepared by double ring closure of 2,2 -di- copper in boiling trichlorobenzene. The alkaline
methyl-1,1 -bianthraquinonyl (148), which is ring closure is accomplished by boiling with ex-
obtained from 1-chloro-2-methylanthraquinone cess 3 – 5 % sodium hydroxide, which cleaves
(147) by heating with copper powder in o- both phthalic acid residues simultaneously [5,
dichlorobenzene – pyridine. Ring closure occurs p. 174]. Only the unsubstituted flavanthrone is
under alkaline conditions, e.g., KOH – isobuta- used as a vat dye and pigment.
nol at 105 ◦ C [2, p. 60]; process improvements
are reported in [355], [356]. The unsubstituted
pyranthrone and its halogen derivatives are used 2.12.8. Violanthrone and Isoviolanthrone
as vat dyes and pigments.
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.

Brominated pyranthrones (the dibromo


derivative [1324-35-2], M r 564.3, is Indanthren Violanthrone may be brominated or chlori-
Orange RRTS [2, p. 61]; a mixture of di- and tri- nated in chlorosulfonic acid or organic solvents.
bromo derivatives is Indanthren Orange 4 R [2, Both reactions are used to obtain other hues. If
p. 62]) are prepared from pyranthrone by bromi- sulfur is added during halogenation in chloro-
nation in chlorosulfonic acid in the presence of sulfonic acid, derivatives containing sulfur and
iodine or sulfur. halogen are obtained.
Nitration of violanthrone yields a mixture
Flavanthrone [475-71-8], (150), M r 408.
of mono- and dinitroviolanthrones, which are
4. Strictly speaking, flavanthrone should not
reduced in the vat dyeing process to (di)ami-
be classified with the polycarbocyclic anthra-
noviolanthrones.
quinone derivatives, but it is described here be-
Alternatively, reduction of the nitro group
cause it is so similar to pyranthrone.
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 45

Direct potash fusion leads to side products, such 3,12,16,17-Tetrachloroviolanthrone


as isoviolanthrone and 4-hydroxybenzanthrone. [84617-19-6], Indanthren Navy Blue RB,
The crude product may be used directly or in M r 594.3, is prepared by chlorination in
mixtures with other dyes in vat dyeing. It is also trichlorobenzene [4, p. 27].
used to generate violanthrone derivatives. Sev-
eral processes have been developed to decrease Bromoviolanthrones, with one bromine
the amounts of undesirable side products of the atom (Indanthren Navy Blue BRF, M r 535.4)
direct potash fusion of benzanthrone or to purify or with two bromine atoms (Indanthren Navy
the bibenzanthronyl or the crude violanthrone Blue BF [1328-18-3], M r 614.3), are prepared
[357–359]. Especially effective is the addition by bromination of violanthrone in chlorosul-
of high-boiling solvents such as naphthalene, the fonic acid in the presence of sulfur [361] or
so-called low carbazole anthracene residues, or antimony [362].
sodium acetate to the melt. The quality of the
products prepared by these methods is satisfac- Nitroviolanthrone [57455-91-1], Indan-
tory for the production of almost all violanthrone thren Black BB, M r 501.5, is prepared by ni-
dyes. tration of violanthrone [363].
Violanthrone of high purity is obtained
from 4,4 -bibenzanthronyl (153) by alkaline or 16,17-Dimethoxyviolanthrone [128-58-5],
acid ring closure, preferably in the presence Indanthren Brilliant Green FFB, Caledon Jade
of oxidizing agents [359], [360]. If this ring Green, (157), M r 516.6, is prepared from 4,4 -
closure is carried out in sulfuric acid with bibenzanthronyl by ring closure and oxidation
an excess of manganese dioxide, the 16,17- followed by reduction and ether formation [1],
violanthronequinone (155) is obtained. This can [5, p. 81], [364].
be reduced readily with sodium hydrogen sul-
fite to 16,17-dihydroxyviolanthrone (156). Sub- Isoviolanthrone [128-64-3], (152),
sequent alkylation of the hydroxy groups yields M r 456.5. Formerly prepared from 3-
very fast navy-blue to brilliant-green vat dyes. halobenzanthrone by alcoholic potash melt.
The dimethyl ether (157) is the well-known Isomer-free isoviolanthrone is obtained by an
dye Caledon Jade Green or Indanthren Brilliant alcoholic potash melt of 3,3 -dibenzanthronyl
Green B and FFB (extremely pure form). 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 47

The effect of β-substituents on the hue is The Colour Index (C.I.) numbers given for
best demonstrated by the 1,4-diaminoanthra- the individual dyes in the following sections cor-
quinones: 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
Furthermore, the shade may be modified synthetics, including polyester, polyamide, and
strongly by ring closure and condensation re- acetate fibers having 2.5 or 3 acetate groups per
actions: 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:
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 The most important factors in the selection
acid groups. 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- 1,4-Diaminoanthraquinones (for prepara-
tion fastness considerably. On the other hand, tion see page 9). The poor light fastness of 1,4-
increased sublimation resistance generally de- diaminoanthraquinone can be improved by ap-
creases the affinity characteristics of the dye. propriate negatively charged substitutents. The
The affinity is greatly affected by the position 2-sulfophenyl ester is a sublimation-resistant,
and the hydrophilic characteristics of the sub- brilliant blue dye with a reddish cast and good
stituents. Mixtures of appropriate dyes or the light fastness. The introduction of a nitro group
presence of contaminants formed during synthe- into the 2 position shifts the shade into bluish
sis may increase affinity by synergistic action. green and improves resistance to sublimation
Introduction of negatively charged substituents, and fading. Introduction of chlorine atoms into
for instance, carboxylic esters, halogen, or sul- the β position considerably improves light fast-
fone groups, may improve light fastness. ness with little affect on the basic sublimation
characteristics.
1-Amino-4-hydroxyanthraquinones (for β-Phenoxy groups in the 2,3 positions shift
preparation see page 19) possess good light the shade to a bright, somewhat reddish violet
fastness and affinity for polyester fibers. They with good stability to fading and sublimation. A
are bright, red dyes, whose brilliance may be very bright turquoise color with excellent light
improved significantly by introduction of ether fastness and good resistance to sublimation are
groups ortho to the amino groups. The aliphatic properties of the 2,3-dicarboximides.
ethers surpass the aromatic ethers with respect Examples are 167a, C.I. Disperse Violet
to light fastness and are much more yellow and 28, 61102 [81-42-5] (e.g. Resolin Violet RL,
somewhat brighter. Additional substituents in Bayer); 163b, a red violet dye [3, p. 48]; 164a,
the side chains may improve sublimation resis- blue green [376]; 167b brilliant red blue [377].
tance. Isomeric compounds with alkyl or aryl Compounds 165 and 166 are both turquoise blue
ether groups in addition to hydroxyl entities are dyes [378], [379].
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].

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 49

respect to sublimation fastness. Compared to Bayer) and 172, C.I. Disperse Blue 73, 63265
the dyes of the tetrasubstituted series, they [12222-75-2].
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 Nitroarylaminodihydroxyanthraquinones.
[380]. 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].

Diaminodihydroxyanthraquinones (for
preparation see page 24). Derivatives of α- 3.1.1.2. Dyes for Cellulose Ester and
diaminodihydroxyanthraquinones are the most Synthetic Polyamide Fibers
important disperse dyes with respect to shade
and affinity. The dye properties may be opti- The first disperse dyes (Celliton) were devel-
mized by introducing suitable substituents, se- oped for dyeing cellulose fibers, but the impor-
lecting the positions of the isomers, and blend- tance of these diminished considerably when
ing. Some of these properties can be illustrated other synthetic fibers appeared on the market.
with the three basic structures shown below: 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-
The bathochromic shift from 168 to 170 af- quirements regarding sublimation resistance are
fects the color; the light fastness increases in not as stringent, whereas fastness to ozone, ex-
the order of 169 → 170 → 168; and the affinity haust gases, and washing are important. Substi-
increases from 168 → 170 → 169. The sublima- tution by amino, and especially by alkylamino,
tion fastness of all three is moderate. groups tends to decrease light fastness of the
Halo, alkoxy, hydroxyaryl, and phenylmer- dyes in polyester fibers. This is not the case for
capto derivatives have attained commercial im- acetate and polyamide fibers.
portance. Compared to substitution next to the The orange derivatives of 1-aminoanthra-
hydroxy group, substitution next to the amino quinone are of little importance in this context
group leads to brighter dyes and improved affin- because of their low tinctorial strength. This
ity. contrasts with the 1-amino-4-hydroxyanthra-
Examples are 171, C.I. Disperse Blue 56, quinone derivatives, which provide brilliant red
63285 [12217-79-7] (e.g., Resolin Blue FBL, 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- 3.1.1.4. Dyes for Cotton – Polyester Fabrics
hanced vastly by blending similar compounds.
Examples of this class of dyes are 174, a bril- Anthraquinone dyes of medium molecular mass
liant red dye [382]; 175, C.I. Disperse Blue 14, are suitable for direct printing and dyeing of cel-
61500 [2475-44-7] [3, p. 54] (e.g., Celliton Fast lulose fibers, especially cotton – polyester fab-
Blue, BASF); 176, a brillant blue dye [383]; 177, rics pretreated with water. Most of these dyes
C.I. Disperse Blue 31, 64505 [1328-23-0] [3, are classified as disperse dyes having excel-
p. 53] (e.g., Celliton Blue 3 G, BASF); 178, C.I. lent resistance to sublimation, but vat dyes of
Disperse Blue 7, 62500 [3179-90-6] [5, p. 201] low molecular mass are included also. The dyes
(e.g., Celliton Blue Green B, BASF). 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.

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 Reactive disperse dyes also make it possible
available disperse dyes with good sublimation to dye cotton–polyester fabrics in equal shades.
characteristics. Dyes, specifically developed for Fluorotriazine reactive dyes have been proposed
this process have also appeared on the market for this application [388–390].
(see also [6, vol. VIII, pp. 191 ff.]). Examples: Compound 184 [388] is a blue,
Examples are 179, C.I. Disperse Red 60, and 185 [389] a red dye.
60756 [17418-58-5], and 180, C.I. Disperse
Blue 26, 63305 [3860-63-7].
Anthraquinone Dyes and Intermediates 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].

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 Many relatively simple amino- and hydroxy-
bis(alkylamino)anthraquinones are suitable ad- anthraquinone derivatives show a high degree of
ditives for gasoline, whereas quinizarin and its order in liquid crystalline systems and are there-
derivatives are used for marking heating oils. fore suitable as dichroic dyes for guest – host dis-
Note: addition of alkali causes a color change. plays. Several new dyes for this application have
Examples: Compound 186 is a blue dye for been described.
the coloring of hydrocarbons, including gasoline Example: Compound 192 is a blue dichroic
[391]. Compound 187 is a mixture of blue dyes dye [393].
used to color gasoline and mineral oils [392].

3.1.3. Vat Dyes

Vat dyes have been used for many decades to


color cotton and other cellulose fibers. Despite
Dyeing of amorphous thermoplastics – poly- their high cost and their muted colors, these dyes
methacrylate, (modified) polystyrene, or poly- are extremely important for certain textiles be-
carbonate – requires dyes soluble in these mate- cause of their superior fastness. Very few new
rials so that transparency can be retained. How- vat dyes have been developed over the past few
ever, such dyes also are used in combination years.
with titanium dioxide or other materials to pro- Water-insoluble vat dyes are converted to sol-
vide body colors for the thermoplastics. Ini- uble “anthrahydroquinones” by reducing agents,
tially compounds with relatively simple struc- such as sodium dithionite (hydrosulfite) in the
tures were used, many of them drawn from presence of sodium hydroxide. The sodium salts
stocks of existing intermediates. Since then new of these mostly deep colored leuco compounds
products designed to satisfy the specific require- penetrate cellulose fibers. The insoluble dye is
ments have become available. attached firmly to the fiber after reoxidation
Examples are 188, C.I. Solvent Red 111, (→ Textile Dyeing). Representative of a spe-
60505 [82-38-2]; 189, C.I. Solvent Red 52, 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


produced by carbazole ring closure from α,α-di-
Anthrimides and Other Linked An- anthraquinonylamines (anthrimides). The shade
thraquinones. Among the anthrimides (di- is determined by the number and position of
anthraquinonylamines), only the α,β deriva- the carbazole systems and by additional sub-
tives have reached a limited importance as vat stituents, especially acylamino or alkoxy groups.
dyes. Coupling two anthraquinone molecules Anthraquinone carbazoles make it possible to
via functional derivatives of the 2-aldehyde (or dye cellulose fibers in level, very fast yellow, or-
2-carboxy) group offers another type of build- ange, brown, gray, and olive shades. However,
ing block for vat dyes. Such compounds, e.g., this series lacks dyes with bright shades.
1-aminoanthraquinones, are linked in the 2 po- Examples include 205, C.I. Vat Yellow 28,
sition via an azine or oxadiazole group, and all 69000 [4229-15-6] [4, p. 53] (e.g., Indanthren
have good fastness. Yellow FFRK, Hoechst); 206, C.I. Vat Orange
Examples are 201, C.I. Vat Violet 16, 65020 15, 69025 [2379-78-4] [4, p. 15], [5, p. 119]
[4003-36-5] [4, p. 14] (e.g., Indanthren Corinth (e.g., Indanthren Golden Orange 3 G, Bayer);
RK, Bayer); 202, C.I. Vat Red 18, 60705 207, C.I. Vat Brown 3, 69015 [131-92-0] [4,
[6409-68-3] [2, p. 64] (e.g., Indanthren Bor- p. 10] (e.g., Indanthren Brown FFR, Bayer); 208,
deaux B, BASF); 203, C.I. Vat Blue 64, 66730 C.I. Vat Black 27, 69005 [2379-81-9] [4, p. 29],
[15935-52-1] [396] (e.g., Indanthren Blue ER, [5, p. 135] (e.g., Indanthren Olive R, Bayer);
Bayer); 204, C.I. Vat Red 13, 70320 [4203-77-4] 209, C.I. Vat Brown 1, 70800 [2475-33-4] [5,
[5, p. 159] (e.g., Indanthren Rubine R, Cassella). 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, fastness with somewhat poorer wash fastness.
Hoechst). 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
Phthaloylacridones. Depending on the sub- Blue BOA, BASF); 217, C.I. Vat Green 1, 59825
stituent in the 2 position, the 3,4-phthaloylacri- [128-58-5] [2, p. 69], [5, p. 83] (e.g., Indanthren
dones supply shades varying between red and Brilliant Green FFB, BASF); 218, C.I. Vat Vio-
green. The acridone vat dyes combine good light let 1, 60010 [1324-55-6] [367] (e.g., Indanthren
Anthraquinone Dyes and Intermediates 55

Brilliant Violet RR, BASF); 219, C.I. Vat Blue ries. Because of its excellent fastness and bright
26, 60015 [4430-55-1] [414] (e.g., Indanthren colors it has remained the most important vat
Cyanine B, BASF). 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
Indanthrones. The blue indanthrone was the RRTS, BASF); 226, C.I. Vat Brown 45, 59500
first synthetic vat dye of the anthraquinone se-
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 pigments restrict their use to special applica-


tions where requirements for fastness are strin-
Because of their low solubility in organic me- gent. Only a few of the known vat dyes satisfy
dia, most vat dyes should also be usable as pig- these requirements. Apart from some acylami-
ments. However, for this type of use they must noanthraquinones, mostly dyes with polycon-
be prepared with a high degree of purity and densed ring systems, including indanthrones,
with special physical properties (crystal modifi- anthanthrones, pyranthrones, flavanthrone, and
cation, particle size distribution, etc.). The rel- their halogen derivatives, have some importance
atively high costs of synthesizing anthraquinone as pigments. Beyond that a number of spe-
Anthraquinone Dyes and Intermediates 57

cialty anthraquinone dyes have been developed The majority of the acid anthraquinone dyes
as pigments over the past 25 years: for exam- available commercially give bright blue shades
ple, anthraquinone-azo, bianthraquinonyl, and not obtainable with azo dyes. The red and yel-
anthraquinonylaminotriazine derivatives. low anthraquinone dyes are of little importance.
Only of little interest at present are the Dyes of green shades obtained by combining
colored lakes, especially aluminum lakes of yellow and blue dyes possess mostly slight wash
the hydroxyanthraquinones, such as alizarine, fastness. Here, the uniformly dyeing green dyes
purpurin, and quinizarin and their sulfonic of the anthraquinone series have proved their
acids. (For preparation see Chap. 2; for formula- special value. The acid anthraquinone dyes are
tion and application → Pigments, Organic, and classified for particular applications according
[398].) to their leveling characteristics, light fastness,
Examples are, 228 C.I. Pigment Yellow 108, and wash fastness. Once synthetic polyamide
68420 [4216-01-7]; 229 C.I. Pigment Blue 60, fibers were introduced in the market appro-
69800 [81-77-6]; 230 C.I. Pigment Red 168, priate types were selected from the existing
59300 [4378-61-4]; 231 C.I. Pigment Orange stocks. Special acid dyes have been developed
40, 59700 [128-70-1]; 231 C.I. Pigment Yel- for polyamides.
low 24, 70600 [475-71-8]; 233, yellow pig-
ment [399]; 234, C.I. Pigment Red 177, 65300 1-Aminoanthraquinone-2-sulfonic Acids.
[4051-63-2]; 235, yellow pigment [400]; 236 Condensation of bromamine acid (1-amino-4-
Aluminum Lake, C.I. Pigment Violet 5 : 1; bromoanthraquinone-2-sulfonic acid, see page
58055 : 1 [145-48-2]. 16) with aromatic or cycloaliphatic amines is
used to produce a large number of blue acid
dyes. The shade, leveling characteristics, wash
3.2. Anionic Dyes fastness, and light fastness may be varied over a
wide range by choosing particular amines. Cy-
The anionic anthraquinone dyes may be classi-
cloaliphatic amines provide the same brightness
fied by type of application and dyeing procedure
as aliphatic dyes but impart greater light fast-
into the following groups:
ness. Arylamines substituted with alkyl, halo-
acid dyes gen, aryl, aryloxy, or sulfonic ester groups yield
direct dyes dyes with better wash fastness and affinity in
reactive dyes neutral media but less uniform leveling. Sub-
stituents at the o position cause a hypochromic
3.2.1. Acid Dyes shift and increase brilliance.
The arylamino residue may be altered sub-
Acid dyes are used for dyeing wool, synthetic sequently by sulfonation, halogenation, acyla-
polyamides, and silk in aqueous media. They tion, or by the Einhorn reaction. Substitution of
may be subdivided into the following basic anthraquinone in the 5, 6, 7, or 8 positions offers
types: 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 1,4-Diaminoanthraquinones with Exter-


Blue G, Hoechst); 241 [402] and 242 [404] are nal Sulfonic Acid Groups. A common fea-
brilliant blue dyes. ture of dyes of this group is their manufacture
by sulfonation of the corresponding dye base
Diaminodihydroxyanthraquinonesulfonic derived from quinizarin or haloaminoanthra-
Acids. These dyes belong to the oldest synthetic quinones. The reaction products of quinizarin
acid wool dyes, but their importance has de- with aromatic or araliphatic amines predomi-
creased considerably. An example for this class nate in number and importance. The introduc-
is 243, C.I. Acid Blue 43, 63000 [2150-60-9] tion of hydroxy groups into the 5 or the 5,8 po-
[3, p. 42] (e.g., Acilan Saphirol SE, Bayer). 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] whole series of specially developed products
are greenish-blue dyes; 248, C.I. Acid Violet 42, is available. For instance, derivatives of the
62026 [6408-73-7] [3, p. 48] (e.g., Supracen Vi- anthrimide or carbazole series are known to
olet 3 R, Bayer). be very light-fast gray and brown wool dyes.
The post-sulfonation products of 1,5- (and 1,8-)
1-Amino-4-hydroxyanthraquinones with diarylaminoanthraquinones are violet dyes com-
External Sulfonic Acid Groups. By one-sided monly applied as mixtures.
reaction of quinizarin with arylamines, fol- An example is 252, C.I. Acid Black 48, 65005
lowed by sulfonation, violet leveling dyes are [1328-24-1] [5, p. 216] (e.g., Alizarine Light
obtained. Derivatives of 1-amino-4-hydroxy-2- Grey BBLW, BBL, Bayer).
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].

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 61

4. References
General References
1. Ullmann, 3rd ed., vol. 3, p. 662 – 732.
2. Bios Final Report 987.
3. Bios Final Report 1484.
3.3. Cationic Dyes 4. Bios Final Report 1493.
5. Fiat Final Report 1313 II.
Water-soluble cationic anthraquinone dyes have 6. K. Venkataraman: The Chemistry of Synthetic
become valuable for dyeing polyacrylonitrile Dyes, vol. I – VIII, Academic Press, New
York – London 1952 – 1978.
fibers. Dyes with external ammonium groups are
7. J. Houben: Das Anthracen und die
especially important. Dyes with quaternary am- Anthrachinone, G. Thieme, Leipzig 1929.
monium groups as well as salts of sufficiently 8. N. N. Woroshzow: Grundlagen der Synthese
basic amino derivatives are used also. The ma- von Zwischenprodukten und Farbstoffen,
jority of commercial dyes are alkylamino- or Akademie-Verlag, Berlin 1966.
arylaminoanthraquinones that carry an ammo- 9. P. Rys, H. Zollinger: Leitfaden der
nium group on the alkyl group, such as trialky- Farbstoffchemie, Verlag Chemie, Weinheim
lammonium, cycloammonium, or hydrazonium 1970.
residue. A protonated dialkylamino group also 10. H. R. Schweizer: Künstliche organische
may be present. Most of these dyes are derived Farbstoffe und ihre Zwischenprodukte,
from 1,4-diaminoanthraquinone. Springer, Berlin – Göttingen – Heidelberg
Examples are 262, a blue dye [307], 263, a 1964.
reddish-blue dye [284], 264, a greenish-blue dye 11. Colour Index, 3rd ed., vol. 1 – 5, Soc. of
[307], and compound 265, a blue dye used for Dyers & Colourists, Bradford/England 1971.
12. Ullmann 4th ed., vol. 7, p. 585 – 646.
wet-spun fibers while they are still gels [280].
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. 49. Bayer, DE-OS 2620486, 1976 (B. Thelen, W.
Ohm, J. Schroeder). Auge, K.-W. Thiem).
17. BASF, DE-OS 1593761, 1967 (H.-J. Nebel). 50. BASF, DE-OS 2039822, 1970 (E. Hartwig, O.
18. BASF, DE-OS 2102037, 1971 (H. Hiller, W. Ackermann, H. Eilingsfeld).
Jentzsch). 51. Sumitomo Chem., DE-OS 2727587, 1976 (A.
19. Bayer, DE-OS 2124261, 1971 (R. Schmitz). Fukasawa et al.).
20. Sumitomo Chem., DE-OS 2214948, 1971 (E. 52. Bayer, DE-OS 2646649, 1976 (W. Hohmann,
Hongo et al.). K. Wunderlich, H. Seidler).
21. Mitsubishi Chem., JP-KK 46-22335, 1969. 53. Sumitomo Chem., DE-OS 2751666, 1977 (A.
22. SU 138614, 1959 (W. A. Iwanowa et al.). Fukasawa, S. Masaki, N. Serizawa).
23. Bayer, DE-OS 2163674, 1971 (R. Schmitz, C. 54. Bayer, DE-OS 2233185, 1972 (A. Vogel).
Wittig). 55. Iwaki Seiyaku, DE-OS 2419726, 1973 (T.
24. ICI, GB 1420191, 1971 (N. Ackerley, R. Okada, K. Naito, T. Kikuchi).
Price). 56. Mitsui Toatsu Chem., JP-Kokai 54-19958,
25. ICI, GB 1416678, 1971 (A. Bennie, R. T. 1977.
Clarke, T. Hollis). 57. Ciba-Geigy, DE-OS 2349753, 1972 (Z. Scha,
26. Bayer, DE-OS 2041547, 1970 (R. Schmitz, K. T. Somlo).
Alberti). 58. Bayer, DE-OS 2219216, 1972 (E. Klauke, R.
27. Agency of Ind. Sci. Tech., Schmitz, H.-S. Bien).
JP-Kokai 51-100064, 1975. 59. Sandoz, DE-OS 2103360, 1970 (W. Frey, I.
28. Agency of Ind. Sci. Tech., Toth).
JP-Kokai 51-100063, 1975. 60. Sandoz, DE-OS 2206960, 1971 (F. Müller, R.
29. Reynolds Metals, US 2871244, 1955 (J. Winkler).
Kamlet). 61. BASF, DE-OS 2232446, 1972 (K.-H. Bantel,
30. Bayer, DE 228901, 1909; Friedländer, vol. 10, H. Eilingsfeld).
p. 578. 62. BASF, DE-OS 2233076, 1972 (K.-H. Bantel,
31. Bayer, DE-OS 2654650, 1976 (H. Seidler, N. H. Eilingsfeld, G. Stökelmann).
Majer, H. Judat). 63. BASF, DE-OS 2449219, 1974 (G. Epple).
32. Bayer, DE-OS 2455587, 1974 (N. Majer et al.). 64. Bayer, DE-OS 2343978, 1973 (K.-W. Thiem,
33. Bayer, DE-OS 2522177, 1975 (K.-J. Reubke). W. Auge, R. Neeff).
34. Inst. f. org. Zwischenprod. u. Farbst., 65. Bayer, DE-OS 2654649, 1976 (K. Wunderlich
SU 178390, 1963 (N. S. Dokunichin et al.). et al.).
35. Bayer, DE-OS 2458022, 1974 (B. Thelen et 66. BASF, DE-OS 2200088, 1972 (H. Eilingsfeld,
al.). O. Ackermann).
36. Bayer, DE-OS 2452014, 1974 (N. Majer et al.). 67. Bayer, DE-OS 2256644, 1972 (W. Auge et al.).
37. ICI, DE-OS 2240518, 1971 (D. A. S. Phillips). 68. Sumitomo Chem., DE-OS 3029302, 1979 (M.
38. Ciba-Geigy, DE-OS 1768593, 1967 (M. Takahashi et al.).
Grelat). 69. Bayer, DE-OS 2351590, 1973 (W. Hohmann).
39. Du Pont, US 3378572, 1964 (R. S. Wilder). 70. BASF, DE-OS 2853920, 1978 (S. Mensch, W.
40. Du Pont, US 2417027, 1943 (V. Weinmayr). Elser).
41. IG-Farbenind., DE 677327, 1935. 71. Bayer, DE-OS 2637732, 1976 (W. Hohmann,
42. Bayer, DE-OS 2720965, 1977 (H. Herzog, W. K. Wunderlich).
Hohmann, H. Seidler). 72. BASF, DE-OS 2459164, 1974 (D. Lach, H.
43. H. Schilling, Chem. Ber. 46 (1913) 1066. Eilingsfeld, G. Stöckelmann).
44. AG für Anilin-Fabrikation, DE 269249, 1913; 73. Mitsubishi Chem., JP-Kokai 54-100 362, 1978.
Friedländer, vol. 11, p. 548. AG für 74. Bayer, DE-OS 2346317, 1973 (A. Vogel).
Anilin-Fabrikation, DE 293156, 1913; 75. Inst. der Industrie für org. Chem., PL 52206,
Friedländer, vol. 12, p. 410. 1964 (S. Galinowski, S. Swiatly).
45. Du Pont, US 2033363, 1934 (J. M. Tinker, 76. Bayer, DE-OS 2400164, 1974 (A. Vogel).
V. M. Weinmayr). 77. Bayer, DE-OS 2637733, 1976 (K. Wunderlich,
46. Sandoz, DE-OS 2162538, 1970 (I. Toth). W. Hohmann, H.-S. Bien).
78. BASF, DE-OS 2545699, 1975 (H.
47. Sandoz, DE-OS 2227340, 1971 (I. Toth).
Bruenemann, H. Eilingsfeld, D. Lach).
48. Bayer, DE-OS 2232464, 1972 (W. Auge,
79. Mitsui Toatsu Chem., JP-Kokai 53-44551,
K.-W. Thiem, R. Neeff).
1976.
Anthraquinone Dyes and Intermediates 63

80. BASF, DE-OS 2524747, 1975 (H. Eilingsfeld, 112. SU 585156, 1976 (P. D. Jakuchny, T. I.
D. Lach). Komarenko, D. F. Schurygina).
81. Sandoz, DE-OS 2222638, 1971 (R. Winkler). 113. Mitsui Toatsu Chem., JP-Kokai 50-64257,
82. ICI, DE-OS 2227766, 1971 (J. Cheetham). 1973.
83. Ciba-Geigy, DE-OS 2412171, 1973 (T. Somlo, 114. Mitsui Toatsu Chem., JP-Kokai 50-134026,
J. Murphy). 1974.
84. Mitsui Toatsu Chem., DE-OS 2539631, 1974 115. Kuhlmann, DE 586515, 1932; Friedländer,
(Y. Torisu, S. Kaba, K. Mukai). vol. 20, p. 1302.
85. Mitsui Toatsu Chem., DE-OS 2514445, 1974 116. Bayer, DE-OS 2827197, 1978 (R. Braden et
(A. Iwamura et al.). al.).
86. Nippon Kayaku, JP-KK 47-36855, 1968. 117. Sandoz, DE-OS 2340114, 1972 (F. Krenmüller
87. Sumitomo Chem., DE-OS 2920441, 1978 (A. et al.).
Fukasawa et al.). 118. Bayer, DE 144634, 1901; Friedländer, vol. 7,
88. Bayer, DE-OS 1543605, 1966 (H. Pelster et p. 201.
al.). 119. Ciba-Geigy, DE-OS 2541663, 1974 (Z. Seha).
89. BASF, DE-OS 2452413, 1974 (G. Epple). 120. Bayer, EP 63298, 1981 (K.-J. Reubke).
121. IG-Farbenind., DE 736901, 1937 (W.
90. BASF, DE-OS 2164458, 1971 (K.-H. Bantel,
Zerweck, E. Heinrich).
H. Eilingsfeld).
122. H. Dreyfus, FR 602882, 1924.
91. Sumitomo Chem., DE-OS 2715072, 1976 (M.
123. Bayer, DE-AS 1150652, 1955 (G. Gehrke,
Yoshimura et al.).
L. Nüßler).
92. Mitsui Toatsu Chem., DE-OS 2557441, 1974
124. IG-Farbenind., DE 722593, 1933.
(Y. Hirai et al.). 125. Allied Chem. & Dye Corp., US 2443899, 1943
93. Sumitomo Chem., JP-Kokai 50-49267, 1973. (A. V. Erkkila, R. C. Hoare).
94. Sandoz, DE-OS 2211411, 1971 (M. Aerberli, 126. ICI, DE 511320, 1928; Friedländer, vol. 17,
I. Toth). p. 1191.
95. Bayer, DE-OS 2314218, 1973 (K.-W. Thiem, 127. Nat. Aniline, US 2207045, 1938 (R. S. Wilder).
W. Auge, R. Neeff). 128. Bayer, DE-OS 1644607, 1966 (K.-H. Peters,
96. Sumitomo Chem., JP-Kokai 51-32552, 1974. R. Neeff).
97. Bayer, DE-OS 2526651, 1975 (K.-J. Reubke, 129. Bayer, DE 225232, 1908; Friedländer, vol. 9,
H.-S. Bien). p. 1197.
98. Bayer, EP 49381, 1980 (K.-J. Reubke, J. 130. Du Pont, US 2346726, 1942 (E. C. Buxbaum).
Stawitz). 131. R. Wedekind, GB 14476, 1911; Friedländer,
99. IG-Farbenind., DE 555937, 1930 (R. E. vol. 11, p. 627.
Schmidt, K. Bamberger); Friedländer, vol. 19, 132. Ciba, BE 719645, 1967.
p. 2028. 133. IG-Farbenind., DE 623069, 1931 (K. Köberle);
100. Bayer, EP 81169, 1981 (J. Stawitz). Friedländer, vol. 21, p. 1085.
101. IG-Farbenind., DE 590163, 1930 (F. Wieners); 134. Du Pont, US 3040063, 1960 (R. L. Walker).
Friedländer, vol. 19, p. 2045. 135. IG-Farbenind., DE 518406, 1926 (W.
102. BASF, DE-AS 1205550, 1963 (W. Braun, M. Hartmann); Friedländer, vol. 17, p. 1211.
Ruske). 136. Bayer, DE-AS 1228274, 1965 (H. Leister, H.
103. Ciba-Geigy, BE 774901, 1971. Vollmann, H.-S. Bien)
104. Bayer, DE-AS 1154490, 1962 (H. Vollmann, 137. BASF, DE 158951, 1903; Friedländer, vol. 8,
W. Hohmann, F. Baumann). p. 277.
105. Scottish Dyes, GB 230116, 1923 (G. Beckett, 138. Ciba, BE 670204, 1964.
J. Thomas). 139. Ciba Geigy, DE-OS 2109058, 1970
106. Hoechst, DE 158076, 1900; Friedländer, (E. Mörgeli).
vol. 7, p. 776. 140. Bayer, DE-AS 1151517, 1962 (H. Vollmann,
107. Sandoz, DE-OS 1927785, 1968 (P. Buecheler). W. Hohmann, F. Baumann).
108. Bayer, DE 288825, 1914; Friedländer, vol. 12, 141. Ciba, DE-AS 1176668, 1962 (P. Sutter).
142. Du Pont, US 2716655, 1954 (S. N. Boyd).
p. 414.
143. Bayer, DE 267445, 1912; Friedländer, vol. 11,
109. Sumitomo Chem., JP-Kokai 53-44550, 1976.
p. 562.
110. BASF, DE 252578, 1911; Friedländer, vol. 11,
144. BASF, DE-AS 1221240, 1964 (H. Eilingsfeld).
p. 545.
145. Hoechst, DE-AS 1174925, 1961 (O. Fuchs, H.
111. Mitsubishi Chem., JP-Kokai 51-23250, 1974.
Rentél).
64 Anthraquinone Dyes and Intermediates

146. Nat. Aniline, US 2251688, 1938 (J. Ogilvie, 175. Bayer, DE-OS 1493739, 1965 (W. Hohmann,
R. X. Hoare). H. Vollmann, H.-S. Bien).
147. Du Pont, US 2135346, 1937 (H. R. Lee, D. C. 176. Bayer, DE-OS 1932646, 1969 (W. Hohmann,
Klein). K. Wunderlich, H.-S. Bien).
148. IG-Farbenind., DE 484997, 1927 (K. 177. Ciba, DE-AS 1134087, 1960 (P. Rhyner).
Weinand); Friedländer, vol. 16, p. 1248. 178. Sumitomo Chem., JP-KK 47-37252, 1970.
149. Sumitomo Chem., JP-Kokai 58-131964, 1982. 179. Bayer, DE-AS 1277475, 1963 (G. Gehrke).
150. Sumitomo Chem., JP-Kokai 57-77663, 1980. 180. BASF, DE-OS 1593780, 1967 (H.-J. Sturm, G.
151. ICI, GB 1291255, 1968 (J. H. Adam, D. N. Steinhoff).
Marsh). 181. Bayer, EP 69910, 1981 (V. Hederich, G.
152. Bayer, DE-OS 2740885, 1977 (R. Muders et Gehrke).
al.). 182. BASF, DE 186526, 1904; Friedländer, vol. 8,
153. Bayer, DE-AS 1226598, 1964 (F. Baumann, H. p. 237.
Vollmann, H.-J. Schulz). 183. Ciba-Geigy, DE-OS 2758397, 1976 (M.
154. Bayer, DE-OS 1768152, 1968 (K. Wunderlich, Grélat).
H.-S. Bien). 184. Bayer, DE-OS 2830554, 1978 (R. Schmitz).
155. Bayer, DE-AS 1222051, 1965 (H.-J. Schulz, 185. Mitsui Toatsu, JP-Kokai 54-22357, 1977.
H.-S. Bien). 186. Sumitomo Chem., JP-Kokai 49-5429, 1972.
156. Sandoz, DE 631518, 1934; Friedländer, 187. BASF, DE-AS 1165180, 1961 (K. Scherf).
vol. 23, p. 952. 188. Bayer, DE 81960, 1893; Friedländer, vol. 4,
157. BASF, DE 106227, 1898; Friedländer, vol. 5, p. 274.
p. 307. 189. Bayer, DE 161026, 1904; Friedländer, vol. 8,
158. Nat. Aniline, US 2210517, 1937 (R. S. Wilder). p. 256.
159. BASF, DE 108274, 1898; Friedländer, vol. 5, 190. Bayer, DE 156762, 1903; Friedländer, vol. 8,
p. 311. p. 240.
160. Bayer, GB 1014055, 1961 (J. Singer, H. W. 191. Bayer, DE-OS 2903851, 1979 (H. Seidler, G.
Schwechten). Gehrke).
161. Sandoz, FR 1509724, 1966 (J. Günthard). 192. Sumitomo Chem., JP-Kokai 50-131962, 1974.
162. Eastman Kodak, BE 661209, 1960. 193. Mitsubishi Chem. Ind., DE-OS 2607036, 1975
163. BASF, DE-AS 1227583, 1963 (W. Braun, I. (Y. Kimura et al.).
Paetzke); BASF, DE-OS 1960100, 1969 (P. 194. Toms River Chem., US 4255342, 1979 (A. D.
Dimroth, E. Schefczik); BASF, Olin).
DE-OS 2060557, 1970 (P. Dimroth, G. 195. Mitsubishi Chem. Ind., JP-Kokai 54-3051,
Henning); GAF, GB 1062388, 1965. 1977.
164. IG-Farbenind., DE 503717, 1926 (K. 196. Nippon Kayaku, JP-Kokai 53-37650, 1976.
Schirmacher, K. Zahn, H. Vollmann); 197. Bayer, DE-OS 2855939, 1978 (H. Herzog, G.
Friedländer, vol. 17, p. 695. Gehrke).
165. Sandoz, DE-OS 2224793, 1971 (R. Winkler). 198. ACNA, FR 1352537, 1962 (A. Crotti, P.
166. Kuhlmann, DE 583871, 1931; Friedländer, Mezzacappa).
vol. 20, p. 1299. 199. ICI, DE 568311, 1929; Friedländer, vol. 19,
167. BASF, DE-OS 1644439, 1965 (W. Braun, K. p. 1926.
Maier). 200. Bayer, DE 163042, 1904; Friedländer, vol. 8,
168. Hoechst, FR 1363216, 1962. p. 268.
169. K. Venkataraman, Indian. J. Chem. 9 (Oct. 201. Bayer, DE-OS 1543619, 1966 (R. Schmitz, H.
1971) 1060 – 1063. Leister, H.-S. Bien).
170. IG-Farbenind., DE 456235, 1925 (R. E. 202. Bayer, DE-OS 2 909481, 1979 (W. Steinbeck,
Schmidt); Friedländer, vol. 15, p. 674. G. Gehrke).
171. Bayer, BE 627010, 1962 (K. Wunderlich, 203. IG-Farbenind., DE 568760, 1925 (R. E.
H.-S. Bien). Schmidt); Friedländer, vol. 18, p. 1277.
172. ICI, GB 1471265, 1973 (R. T. Clarke, T. J. 204. IG-Farbenind., DE 554647, 1930 (R. E.
Smith, D. A. Stewart). Schmidt, K. Bamberger); Friedländer, vol. 19,
173. Bayer, DE-AS 1184879, 1962 (K. Klemm, G. p. 1949.
Gehrke). 205. Bayer, DE-OS 1543605, 1966 (H. Pelster et
174. Bayer, DE-AS 1199279, 1963 (H.-S. Bien, W. al.).
Hohmann, H. Vollmann). 206. Mitsui Toatsu, JP-Kokai 55-33407, 1978.
Anthraquinone Dyes and Intermediates 65

207. Ciba, DE 589074, 1931; Friedländer, vol. 19, 238. IG-Farbenind., DE 651104, 1935 (W. Zerweck,
p. 2001. W. Kunze); Friedländer, vol. 24, p. 991.
208. Bayer, DE 100138, 1897; Friedländer, vol. 5, 239. Celanese, US 2640059, 1949 (V. S. Salvin,
p. 245. E. F. Landau).
209. Du Pont, US 2419405, 1943 (D. X. Klein). 240. Bayer, DE-AS 1190123, 1962 (H.-S. Bien, K.
210. Bayer, FR 1445843, 1964 (W. Hohmann, H.-S. Wunderlich, F. Baumann).
Bien). 241. Allied Chem. Corp., US 3018154, 1959 (J. F.
211. Bayer, FR 1468502, 1965 (W. Hohmann et al.). Downey, R. C. Hoare).
212. Ciba, CH 146772, 1928. 242. Bayer, DE-AS 1226598, 1964 (F. Baumann, H.
213. IG-Farbenind., DE 445846, 1925 (C. Vollmann, H.-J. Schulz).
Weinand); Friedländer, vol. 15, p. 677. 243. Nippon Kayaku, JP-KK 70-7037, 1967.
214. Bayer, DE 238488, 1910; Friedländer, vol. 10, 244. Bayer, DE-OS 1644578 (Example 104), 1964
p. 646. (R. Neeff et al.).
215. Bayer, DE-OS 1939095, 1969 (P. Wegner et 245. Bayer, DE-OS 1293363, 1964 (R. Neeff et al.).
al.). 246. Mitsubishi Chem., JP-Kokai 55-73735, 1978.
247. Hoechst, BE 647171, 1963.
216. Ciba, GB 1085685, 1965.
248. AG für Anilin-Fabrikation, DE 267081, 1912;
217. Nippon Kayaku, JP-Kokai 49-17425, 1972.
Friedländer, vol. 11, p. 593.
218. Ciba-Geigy, EP 71576, 1981 (P. Kniel).
249. Hoechst, DE 361043, 1920; Friedländer,
219. IG-Farbenind., DE 445269, 1925 (R. E.
vol. 14, p. 858.
Schmidt, A. Jacobi); Friedländer, vol. 15, 250. IG-Farbenind., DE 533249, 1926 (K. Wilke);
p. 671. Friedländer, vol. 18, p. 1245.
220. Bayer, DE-AS 1228734, 1963 (K. Klemm, G. 251. Cassella, DE 346188, 1915; Friedländer,
Gehrke). vol. 13, p. 395.
221. Bayer, GB 1029448, 1964 (W. Hohmann). 252. Bayer, DE 938435, 1953.
222. BASF, DE-AS 2713575, 1977 (J. Redeker, H. 253. BASF, DE-AS 1918696, 1969 (E. Hartwig).
Hiller, E. Spohler). 254. Mitsubishi Chem. Ind., JP-KK 47-26413,
223. Sumitomo Chem., DE-OS 2817890, 1977 (M. 1968.
Nishikuri, A. Takeshita, H. Kenmochi). 255. Bayer, GB 879240, 1957.
224. Mitsui Toatsu Chem., JP-Kokai 56-123955, 256. BASF, DE-OS 1668870, 1968 (K. Maier).
1980. 257. American Cyanamid, US 2499003, 1946 (M.
225. Ciba, DE-AS 1065959, 1954 (P. Grossmann, Scalera).
W. Jenny, W. Kern). 258. BASF, DE 229394, 1909; Friedländer, vol. 10,
226. Österr. Alizarinfabr.-Ges., DE 3565, 1878; p. 601.
Friedländer, vol. 1, p. 310. 259. BASF, DE-AS 1108704, 1959 (W. Braun, M.
227. American Aniline Products, US 3389151, Ruske).
1966 (D. A. Zanella). 260. Sumitomo Chem., JP-Kokai 57-176944, 1981.
228. Bayer, DE 96364, 1897; Friedländer, vol. 5, 261. Bayer, DE 935669, 1953.
p. 246. 262. Bayer, DE-OS 2931981, 1979 (F. W. Kröck, R.
229. Bayer, DE 100136, 1897; Friedländer, vol. 5, Neeff, H. Scheiter).
p. 247. 263. IG-Farbenind., DE 464863, 1926 (K. Wilke);
230. IG-Farbenind, DE 632 911, 1932 (K. Weinand, Friedländer, vol. 16, p. 1229.
C. Bamberger); Friedländer, vol. 21, p. 1038. 264. BASF, DE-AS 1025079, 1955 (E. Anton, K.
231. Ciba, DE 841313, 1944 (P. Grossmann). Saftien).
232. Chem. Fabrik Griesheim-Elektron, 265. BASF, DE-AS 1250031, 1963 (E. Hartwig, W.
DE 290084, 1914; Friedländer, vol. 12, p. 439. Braun).
266. IG-Farbenind., DE 615756, 1934 (G.
233. Bayer, DE 208640, 1907; Friedländer, vol. 9,
Kränzlein, M. Corell, W. Schaich);
p. 701.
Friedländer, vol. 22, p.1078.
234. Geigy, FR 1522933, 1966.
267. BASF, DE-AS 1100209, 1958 (H. Geeren, F.
235. Bayer, DE-AS 1180473, 1962 (H.-S. Bien, K.
Ebel, W. Braun).
Wunderlich, F. Baumann).
268. IG-Farbenind., DE 475687, 1926 (M. A. Kunz,
236. Bayer, DE-AS 1201933, 1962 (H.-S. Bien, K.
G. v. Rosenberg, E. Goffarjé); Friedländer,
Wunderlich, F. Baumann).
vol. 16, p. 1341.
237. ICI, DE-OS 2734828, 1976 (A. J. Logan, R. W. 269. IG-Farbenind., DE 604279, 1932 (P. Nawiasky
Kenyon). et al.); Friedländer, vol. 21, p. 1091.
66 Anthraquinone Dyes and Intermediates

270. IG-Farbenind., DE 623028, 1934 (E. Berthold, 300. American Cyanamid, US 2492802, 1945
J. Müller); Friedländer, vol. 22, p. 1081. (H. Z. Lecher, W. S. Forster).
271. IG-Farbenind., DE 692750, 1938 (H. 301. IG-Farbenind., DE 590579, 1932 (E. Kramer);
Schlichenmaier, L. Berlin, E. Berthold). Friedländer, vol. 20, p. 1293.
272. BASF, DE 421236, 1922 (A. Lüttringhaus, F. 302. BASF, DE 258561, 1910; Friedländer, vol. 11,
Kačev); Friedländer, vol. 15, p. 689. p. 671.
273. AG für Anilin-Fabrikation, DE 232711, 1910; 303. IG-Farbenind., DE 555967, 1929 (M. A. Kunz,
Friedländer, vol. 10, p. 731. E. Berthold, K. Köberle); Friedländer, vol. 19,
274. J. Arient, V. Slavik, Collect. Czech. Chem. p. 2082.
Commun. 34 (1969) 3576. 304. BASF, DE 279867, 1913; Friedländer, vol. 12,
275. Sandoz, DE 593867, 1932; Friedländer, p. 445.
vol. 20, p. 1344. 305. IG-Farbenind., DE 661152, 1936 (F. Baumann,
276. Bayer, DE 239544, 1910; Friedländer, vol. 10, H. W. Schwechten); Friedländer, vol. 25,
p. 638. p. 773.
277. Du Pont, US 2258394, 1939 (J. M. Tinker et 306. IG-Farbenind., DE 470809, 1926 (K.
al.). Schirmacher, W. Schaich, A. Wolfram);
278. Hoechst, DE 251350, 1911; Friedländer, Friedländer, vol. 16, p. 1316.
vol. 11, p. 618. 307. Bayer, DE-AS 1150652, 1955 (G. Gehrke,
279. A. K. Wick, Helv. Chim. Acta 54 (1971) 769. L. Nüßler).
280. ICI, GB 2048963, 1979 (P. Gregory, M. 308. Ciba, DE-AS 1060526, 1953 (P. Sutter, W.
Yelland). Fioroni).
281. IG-Farbenind., DE 746546, 1937 (F. Wieners, 309. Bayer, DE 904926 (Examples 5, 6), 1951 (H.
W. Mieg); Friedländer, Suppl. vol. I/2, p. 392. Thielert, F. Baumann).
282. Ciba-Geiby, CH 528576, 1969 (A. Wick). 310. Cassella, DE-AS 1215284, 1962 (W. Zerweck,
283. Kuhlmann, DE 566708, 1930; Friedländer, E. Schwamberger).
vol. 19, p. 2120. 311. Cassella, DE-AS 1264648, 1963 (W. Zerweck,
284. Bayer, DE 963502, 1955 (H. W. Schwechten, E. Schwamberger).
O. Bayer). 312. Bayer, DE 158287, 1903; Friedländer, vol. 8,
285. IG-Farbenind., DE 696370, 1936 (W. p. 341.
Burneleit, W. Mieg, F. Wieners). 313. Bayer, DE 193121, 1906; Friedländer, vol. 9,
286. Bayer, DE 630218, 1934 (W. Mieg, F. p. 783.
Wieners); Friedländer, vol. 23, p. 1020. 314. Ciba, DE 423311, 1922; Friedländer, vol. 15,
287. IG-Farbenind., DE 451495, 1925 (W. Mieg); p. 714.
Friedländer, vol. 16, p. 1345. 315. IG-Farbenind., DE 580013, 1932; Friedländer,
288. Ciba, DE-OS 1813729, 1967 (A. Wick). vol. 20, p. 1377.
289. Kuhlmann, FR 733440, 1931. 316. BASF, DE 212471, 1908; Friedländer, vol. 9,
290. Výzkumný ústav organ. syntéz, p. 834.
DE-OS 1817388, 1968 (J. Arient et al.). 317. IG-Farbenind., DE 490723, 1926 (K. Wilke);
291. Ciba-Geigy, EP 49873, 1980 (Z. Seha). Friedländer, vol. 16, p. 1368.
292. Hoechst, DE 208969, 1908; Friedländer, 318. IG-Farbenind., DE 483154, 1927
vol. 9, p. 776. (A. Lüttringhaus, P. Nawiasky, A. Ehrhardt);
293. Ciba, CH 191015, 1936. Friedländer, vol. 16, p. 1490.
294. IG-Farbenind., DE 525666, 1929 (W. Bruck); 319. IG-Farbenind., DE 722868, 1937 (H. Scheyer,
Friedländer, vol. 18, p. 1310. H. Ritter); Friedländer, Suppl. vol. I/2, p. 451.
295. IG-Farbenind., DE 501746, 1929 (W. Bruck); 320. Du Pont, GB 364042, 1930.
Friedländer, vol. 17, p. 1229. 321. Ciba-Geigy, EP 10525, 1978 (H. Jäger).
296. BASF, DE 246966, 1911; Friedländer, vol. 10, 322. SU 401130, 1971 (E. M. Natanson et al.)
p. 725. 323. Bayer, DE-OS 2823160, 1978 (J. Schroeder).
297. IG-Farbenind., DE 560236, 1929 (M. A. Kunz, 324. Ciba-Geigy, EP 22062, 1979 (J. Bersier,
E. Berthold, K. Köberle); Friedländer, vol. 19, H. Jäger, H. Schwander).
p. 2088. 325. Ciba-Geigy, EP 60437, 1981 (H. Jäger et al.).
298. Bayer, DE 678499, 1937 (W. Bauer); 326. Bayer, DE-OS 2830456, 1978 (B. Schroeder,
Friedländer, Suppl. vol. I/2, p. 382. R. Neeff, R. Braden).
299. BASF, DE 237236, 1910; Friedländer, vol. 10, 327. BASF, DE 200335, 1905; Friedländer, vol. 9,
p. 708. p. 817.
Anthraquinone Dyes and Intermediates 67

328. BASF, DE-OS 2631853, 1976 (A. 354. IG-Farbenind., DE 485961, 1927 (R.
Schumacher, K. E. Kling). Heidenreich); Friedländer, vol. 16, p. 1422.
329. Du Pont, US 2353049, 1942 (H. R. Lee, C. F. 355. BASF, DE-OS 1951708, 1969 (G. Bock).
Belcher). 356. BASF, DE-OS 2115093, 1971 (F. Graser).
330. Kalle, DE 467118, 1924 (M. P. Schmidt, W. 357. Du Pont, US 2872459, 1956 (A. A. Baum).
Neugebauer); Friedländer, vol. 16, p. 1453. 358. GAF, DE-AS 1068687, 1956 (T. A. Martin,
331. Hoechst, DE 420412, 1923 (A. Wolfram); D. I. Randall, J. Taras).
Friedländer, vol. 15, p. 736. 359. Du Pont, US 2388743, 1944 (E. T. Howell).
332. Bayer, DE 200014, 1907; Friedländer, vol. 9, 360. IG-Farbenind., DE 450999, 1925
p. 760. (A. Lüttringhaus, H. Neresheimer, H. J.
333. Bayer, DE 171293, 1904; Friedländer, vol. 8, Emmer); Friedländer, vol. 15, p. 721.
p. 304. 361. IG-Farbenind., DE 608442, 1933 (H. Wolff,
334. Chem. Fabrik Griesheim-Elektron, W. Mieg); Friedländer, vol. 21, p. 1130.
DE 255641, 1912; Friedländer, vol. 11, p. 583. 362. IG-Farbenind., DE 595461, 1929 (M. A. Kunz,
335. Bayer, DE 220314, 1908; Friedländer, vol. 9, K. Köberle, E. Berthold); Friedländer, vol. 20,
p. 742. p. 1370.
336. IG-Farbenind., DE 711775, 1938 (E. Berthold, 363. BASF, DE 185222, 1904; Friedländer, vol. 9,
W. Roland); Friedländer, Suppl. vol. I/2, p. 830.
p. 280. 364. Scottish Dyes, DE 417068, 1920; Friedländer,
337. IG-Farbenind., DE 633207, 1931 (M. A. Kunz, vol. 15, p. 760.
K. Köberle); Friedländer, vol. 21, p. 1143. 365. IG-Farbenind., DE 448262, 1924 (O.
338. BASF, DE-AS 1159456, 1960 (H. Weidinger, Braunsdorf, P. Nawiasky, E. Holzapfel);
H. Eilingsfeld, G. Haese). Friedländer, vol. 15, p. 728.
339. Kawasaki Kasei, JP-Kokai 52-95678, 1976. 366. BASF, DE-AS 2704964, 1977 (W. S.
340. BASF, DE-AS 1215843, 1962 (M. Bertl, F. Schweckendiek, A. Schuhmacher, H. Hiller).
Graser). 367. BASF, DE 217570, 1909; Friedländer, vol. 9,
341. BASF, DE-OS 2300019, 1973 (H. Hiller, W. p. 827.
Jentzsch, A. Schuhmacher). 368. IG-Farbenind., DE 453768, 1925 (R. Berliner,
342. Bayer, DE 203752, 1907; Friedländer, vol. 9, B. Stein, W. Trautner); Friedländer, vol. 16,
p. 735. p. 1283. IG-Farbenind., DE 470501, 1926 (H.
343. BASF, DE 216597, 1907; Friedländer, vol. 9, Scheyer); Friedländer, vol. 16, p. 1283.
p. 738. 369. IG-Farbenind., DE 550712, 1930 (H. Scheyer);
344. Bayer, DE 201904, 1907; Friedländer, vol. 9, Friedländer, vol. 19, p. 2149.
p. 736. 370. IG-Farbenind., DE 576466, 1931 (H. Scheyer);
345. Bayer, DE 233126, 1909; Friedländer, vol. 10, Friedländer, vol. 20, p. 1426.
p. 609. 371. H. Labhart, Helv. Chim. Acta 40 (1957) 1410.
346. Sandoz, DE 578995, 1930; Friedländer,
372. BASF, DE-AS 1209680, 1962 (K. Maier).
vol. 19, p.1964.
373. Bayer, DE-OS 2531557, 1975 (V. Hederich,
347. IG-Farbenind., DE 518316, 1927 (G.
H.-S. Bien, G. Gehrke).
Kränzlein, H. Vollmann); Friedländer, vol. 17,
374. Bayer, FR 1503492, 1965.
p. 1301.
375. Sumitomo Chem., FR 1497689, 1965.
348. IG-Farbenind., DE 576253, 1927 (R.
376. Bayer, DE-AS 1105837, 1958 (G. Gehrke).
Sedlmayer, W. Eckert); Friedländer, vol. 18,
377. Bayer, DE-AS 1644587, 1965 (M. Groll, K.
p. 592.
Wunderlich, H.-S. Bien).
349. Hoechst, DE 412053, 1922 (G. Kränzlein, M.
378. Du Pont, US 2628963, 1951 (J. F. Laucius,
Corell, R. Sedlmayr); Friedländer, vol. 15,
S. B. Speck).
p. 731.
379. BASF, DE-AS 1918696, 1969 (E. Hartwig).
350. Hoechst, DE 423720, 1924 (G. Kränzlein, R.
380. Geigy, BE 650734, 1963.
Sedlmayr); Friedländer, vol. 15, p. 733.
381. Ciba, DE-AS 1065959, 1954 (P. Grossmann,
351. L. Kalb, DE 280787, 1913; Friedländer,
W. Jenny, W. Kern).
vol. 12, p. 498.
352. Cassella, DE 445390, 1925 (R. Herz, W. 382. Ciba, FR 1594324, 1968.
Zerweck); Friedländer, vol. 15, p. 300. 383. Sandoz, FR 1490805, 1965 (M. F. Müller).
353. Cassella, DE 458598, 1925 (R. Herz, W. 384. Du Pont, DE-AS 1811796, 1968 (J. Blackwell,
Zerweck); Friedländer, vol. 16, p. 1410. R. E. Starn, W. H. Gumprecht).
68 Anthraquinone Dyes and Intermediates

385. BASF, DE-OS 2524243, 1975 (H. Schwab, K. 399. BASF, DE-AS 1544372, DE-AS 1544374,
Oppenlaender, A. Blum). 1965 (W. Braun, I. Peatzke).
386. BASF, DE-OS 2654434, 1976 (W. Elser, H. 400. Ciba, DE-AS 1283542, 1961 (E. Mörgeli).
Eilingsfeld, G. Meyer). 401. Sandoz, US 2121928, 1934 (A. Peter).
387. BASF, DE-OS 2651975, 1976 (G. Epple, W. 402. Ciba-Geigy, DE-OS 2850996, 1977 (R.
Elser). Lacroix, J.-M. Adam, J. Vincze).
388. Bayer, DE-OS 2918881, 1979 (W. Harms et 403. Sandoz, CH 214909, 1939.
al.). 404. Bayer, GB 1099756, 1966 (J. Singer).
389. Mitsubishi Chem. Ind., DE-OS 3218957, 1981 405. Geigy, BE 713252, 1967.
(T. Niwa, T. Hihara). 406. Sandoz, FR 1455722, 1964 (M. J. Günthard).
390. Mitsubishi Chem. Ind., JP-Kokai 55-164250, 407. Geigy, FR 1461074, 1964.
1979. 408. Crompton & Knowles, FR 1478769, 1965
391. Bayer, DE 849158, 1944 (K. Bähr). (M. R. W. Eltonhead).
392. BASF, DE-OS 1644482, 1967 (F. Graser, G. 409. Ciba, DE-OS 1925515, 1968 (K. Seitz, G.
Riedel). Klahre, H. U. Schütz).
393. Bayer, EP 93367, 1982 (M. Blunck et al.).
410. Bayer, DE-OS 1644204, 1967 (H.-S. Bien, E.
394. IG-Farbenind., DE 653386, 1935 (W. Mieg, F.
Klauke).
Wieners); Friedländer, vol. 24, p. 862.
411. Bayer, DE-AS 1264647, 1961 (J. Singer, H. W.
395. IG-Farbenind., DE 696423, 1935 (K. Köberle);
Schwechten).
Friedländer, Suppl. vol. I/2, p. 239.
396. Bayer, DE 911493, 1952 (H. W. Schwechten). 412. Bayer, DE-OS 2652119, 1976 (W. Harms, K.
397. Bayer, BE 729177, 1968 (K. Wunderlich, Wunderlich, K. v. Oertzen).
H.-S. Bien). 413. Bayer, DE-OS 3142852, 1981 (K. v. Oertzen).
398. Ullmann, 4th ed., vol. 18, p. 661. 414. Scottish Dyes, FR 543910, 1921.

Anthraquinonesulfonic Acids → Anthraquinone Dyes and Intermediates