Anthraquinone 1
Anthraquinone
Axel Vogel, Bayer AG, Leverkusen, Federal Republic of Germany
1. Introduction . . . . . . . . . . . . . . . . .
2. Properties . . . . . . . . . . . . . . . . . .
3. Production . . . . . . . . . . . . . . . . . .
3.1. Oxidation of Anthracene with
Chromic Acid . . . . . . . . . . . . . . . .
3.2. Vapor-Phase Oxidation of Anthracene
with Air . . . . . . . . . . . . . . . . . . . .
3.3. Naphthalene Process . . . . . . . . . . .
3.4. Synthesis from Phthalic Anhydride
and Benzene . . . . . . . . . . . . . . . . .
1. Introduction
Anthraquinone [84-65-1] is the parent com-
pound for a large palette of anthraquinone dyes
and so is the most important starting material in
their production. Furthermore, anthraquinone is
gaining importance as a catalyst in the pulping
of wood.
In 1835, anthraquinone was prepared for the
first time by Laurent, via oxidation of anthra-
cene, which at first went largely unnoticed. Its
special importance for the dye industry was rec-
ognized only in 1868 when Graebe and Lieber-
mann prepared anthracene from alizarin (1,2-
dihydroxyanthraquinone) and, in turn, alizarin
via anthraquinone. This laid the groundwork for
the synthesis route of this – at the time – im-
portant dye. Since then, science and technology
have extended the chemistry of anthraquinone
swiftly, first by the discovery of new mordant
dyes and acid dyes, later by the introduction of
vat dyes and disperse dyes, and, since 1950, by
the anthraquinone reactive dyes. At the same
time, anthraquinone chemistry has acted as a
stimulus for the rapid extension of the produc-
tion processes of chemicals, such as oleum and
chlorine.

c 2005 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim
10.1002/14356007.a02 347
1 3.5. Styrene Process . . . . . . . . . . . . . . . 6
1 3.6. Environmental Considerations . . . . . 7
3 4. Purification, Quality Requirements,
and Analysis . . . . . . . . . . . . . . . . . 7
4 5. Uses . . . . . . . . . . . . . . . . . . . . . . 7
6. Economic Aspects . . . . . . . . . . . . . 8
4 7. Toxicology . . . . . . . . . . . . . . . . . . 8
5 8. References . . . . . . . . . . . . . . . . . . 8
6
Since 1970, the industrial chemistry of
anthraquinone has been undergoing a revolu-
tion worldwide. Initiated by a growing short-
age of anthracene accompanied by an increas-
ing demand, new procedures of synthesis us-
ing naphthalene or styrene as starting materi-
als were developed. Moreover, further process-
ing of anthraquinone is changing; α-substituted
anthraquinones should no longer be prepared by
mercury-catalyzed sulfonation but by new nitra-
tion procedures.
A completely new use for anthraquinone was
established by Holton in 1977, when he dis-
covered the catalytic effect of anthraquinone on
the alkaline pulping of wood. This branch of
anthraquinone chemistry is experiencing a rapid
development and has good chances of outdis-
tancing the needs of the dye industry. The de-
mand for anthraquinone has risen continuously
since 1870. At present the annual demand is
≈ 30 000 t.
2. Properties
Physical Properties. Anthraquinone [84-65-1],
C14 H8 O2 , M r 208.20, mp 287 ◦ C, bp 377 ◦ C,
crystallizes as thin, light yellow to pale yellow
needles; it is almost colorless if finely divided, as
when precipitated from sulfuric acid. The faint
colors of the crystals are effected strongly by the
granular structure and in commercial products
often are covered up by trace impurities.
2 Anthraquinone
Crystallographic class: monoclinic, space
group P 21 /a. Dimensions of the unit cell:
a = 1.583 nm, b = 0.397 nm, c = 0.789 nm,
β = 102.5
Density of the crystals at 20 ◦ C: 1.438 g/cm3 , of
the melt (at 293 ◦ C): 1.067 g/cm3
Vapor pressure: 10.0 kPa at 286 ◦ C, 20.0 kPa at
300 ◦ C, 48.0 kPa at 340 ◦ C
Molar heat capacity at constant pressure cp
(solid) 265 J mol−1 K−1
Enthalpy of formation −179 kJ/mol
Enthalpy of combustion at 25 ◦ C: 6449 kJ/mol
Melting enthalpy at 287 ◦ C: 32.57 kJ/mol
Flash point 185 ◦ C
The UV spectrum exhibits four bands –
251 nm (εmax 54000), 279 nm (εmax 17600),
321 nm (εmax 4800), and 377 nm (εmax 110) –
each with pronounced vibrational structure. Un-
like solutions of anthracene, most solutions of
anthraquinone do not show fluorescence. The
IR spectrum has very few bands (characteris-
tic bands at ν C→O = 1680 cm−1 ) because of the
high symmetry of the compound.
Anthraquinone is sublimed easily without
decomposition, a property exploited industrially
for purification.
Anthraquinone is practically insoluble in wa-
ter (0.006 g/L at 50 ◦ C) and nearly insoluble to
sparingly soluble in organic solvents at room
temperature. However, solubility in organic sol-
vents increases with temperature (in ethanol
0.05 g per 100 g ethanol dissolves at 18 ◦ C,
2.25 g per 100 g at 78 ◦ C; in toluene 0.19 g per
100 g toluene at 15 ◦ C, 2.56 g at 100 ◦ C). There-
fore anthraquinone generally can be recrystal-
lized from high-boiling solvents, particularly
from the polar solvents pyridine, aniline, nitro-
benzene, formamide, or dimethylformamide.
Anthraquinone dissolves in 90 % sulfuric acid
giving a yellow to orange solution, and in oleum
(20 % SO3 ), giving a red solution. It can be
precipitated from these solutions in a finely di-
vided form by dilution with water. The solubil-
ity increases with the concentration of the sul-
furic acid. Anthraquinone behaves similarly in
hydrofluoric acid; however, the solubility in al-
most 100 % phosphoric acid is relatively small.
Anthraquinone can form explosive dust mix-
tures with air. Friction causes anthraquinone to
become electrostatically charged.
Chemical Properties. Anthraquinone ex-
hibits an extraordinary thermal stability, even
in the presence of oxidizing agents. Therefore
it can be prepared by oxidizing anthracene in
the vapor phase. A yield of 90 % is obtained if
conversion is complete.
Anthraquinone is attacked by oxidizing
agents only under vigorous conditions. For ex-
ample, it can be converted to alizarin by fusion
with sodium hydroxide and sodium chlorate.
Anthraquinone can be converted to the poly-
hydroxyanthraquinones alizarin, quinizarin, an-
thrarufin, and purpurine (→ Anthraquinone
Dyes and Intermediates, Chap. 2.6.) by oxida-
tion with concentrated sulfuric acid in the pres-
ence of boric acid, persulfates, or metaarsenic
acid at temperatures generally above 200 ◦ C.
The oxidation can be carried out with oleum at a
lower temperature that depends on the SO3 con-
tent. Under the usual conditions, concentrated
nitric acid does not oxidize anthraquinone, ni-
tration taking place instead. Several mixtures of
anthraquinone with 94 – 100 % nitric acid with
specific anthraquinone concentrations are explo-
sive.
On the other hand, anthraquinone can be re-
duced easily by ordinary reducing agents or
by hydrogen in the presence of a catalyst. The
standard potential (in aqueous ethanolic hydro-
chloric acid) for the anthraquinone–anthra-
hydroquinone equilibrium is only 0.155 V. Es-
pecially the quinone nucleus is reduced. Sodium
hyposulfite in alkaline solution reduces anthra-
quinone to a blood-red sodium salt of anthra-
hydroquinone, which rearranges to its tau-
tomer oxanthrone (9-keto-10-hydroxy-9,10-di-
hydroanthracene) in acidic solution. More vig-
orous reduction (tin – hydrochloric acid or cat-
alytic hydrogenation at high pressure or high
temperature) leads to anthrone (2) [90-44-8] ,
which is in equilibrium with its tautomer anthrol
(3) (9-hydroxyanthracene) [529-86-2] , and then
to anthracene and hydroanthracene.
If zinc or sodium hydroxide is used, dianthra-
nol is obtained via dimerization.

The reduction can be restricted to the two
outer nuclei by choice of reaction conditions.
1,2,3,4-Tetrahydroanthraquinone [28758-94-3]
or octahydroanthraquinone [23585-26-4] can be
obtained. Reactions of anthraquinone with the
usual ketone reagents take place with great dif-
ficulty or not at all.
If anthraquinone is heated with glycerol,
iron powder, and sulfuric acid, condensation
takes place at positions 1 and 9, provid-
ing the commercially important benzanthrone
[82-05-3] (→ Anthraquinone Dyes and Interme-
diates, Chap. 2.12.1.).
Chlorine halogenates anthraquinone in
oleum in steps, depending on the proportion
used, mainly at the α position. Heating anthra-
quinone with antimony pentachloride or a sim-
ilar chlorine-releasing reagent produces chlo-
rinated products, from monochloro- up to per-
chloroanthraquinone.
Sulfuric acid or oleum can sulfonate and/or
hydroxylate anthraquinone. Concentrated sul-
furic acid sulfonates only above 200 ◦ C; usu-
ally, anthraquinone is sulfonated with 20 – 45 %
oleum at 140 – 160 ◦ C. The major reaction prod-
ucts are β-sulfonic acids, i.e., anthraquinone-
2-sulfonic acid [84-48-0] , as well as anthra-
quinone-2,6-disulfonic acid [14486-58-9] , and
anthraquinone-2,7-disulfonic acid [84-49-1]. In
the presence of mercury, however, the sulfona-
tion takes place almost exclusively at the α po-
sition, providing anthraquinone-1-sulfonic acid
[82-49-5] , anthraquinone-1,5-disulfonic acid
[117-14-6] , and anthraquinone-1,8-disulfonic
acid [82-48-4].
The nitration of anthraquinone requires vig-
orous conditions, and provides mainly α-nitro-
anthraquinones along with 10 – 20 % β-nitro-
and α,β-dinitroanthraquinones. Both mono-
and dinitration take place, so that impure
nitration products are obtained. These can
be separated into 1-nitroanthraquinone, 1,5-di-
nitroanthraquinone, and 1,8-dinitroanthraquin-
one only by extensive processing. Trinitration
of anthraquinone does not take place.
1-Nitroanthraquinone [82-34-8] can be pre-
pared by nitrating anthraquinone in mixed acid
(H2 SO4 -HNO3 ) with excess nitric acid, in
nearly 30 mol 94 – 98 % nitric acid, or with an al-
most stoichiometric amount of the mixed acid in
the presence of chlorinated aliphatic hydrocar-
bons. The crude 1-nitroanthraquinone is purified
Anthraquinone 3
by recrystallization and, if necessary, by distil-
lation; likewise it is processed directly to crude
1-aminoanthraquinone [82-45-1] , which is then
purified by distillation.
1,5- and 1,8-dinitroanthraquinone are pre-
pared by exhaustive nitration of anthraquinone
in excess, nearly anhydrous mixed acid. Pure
1,5-dinitroanthraquinone [82-35-9] and 1,8-di-
nitroanthraquinone [129-39-5] are obtained by
recrystallizing the crude dinitroanthraquinone
mixtures from nitrobenzene (→ Anthraquinone
Dyes and Intermediates, Chap. 2.4.).
3. Production
Processes that are used in the industrial produc-
tion of anthraquinone:
1) Oxidation of anthracene with chromic acid
2) Vapor-phase oxidation of anthracene with air
3) Naphthalene process
4) Synthesis from phthalic anhydride and ben-
zene
Anthraquinone is produced from anthracene,
where this is available from coal tar, either by ox-
idation with chromic acid in 48 % sulfuric acid
or by oxidation with air in the vapor phase. The
oxidation with chromic acid is competitive, pro-
vided that the chromium(III) sulfate lye formed
can be processed to tanning agents. Anthracene
with purity of
94 % is required for both oxi-
dation processes; crude anthracene from coal tar
must be purified by recrystallization.
About 85 % of world production is based
on the oxidation of anthracene. Since the mid-
1970s, anthracene production has fallen continu-
ously, creating a supply shortage. Therefore, the
complex naphthalene process is gaining in im-
portance. There is an adequate supply of naph-
thalene in coal tar. If necessary, additional naph-
thalene can be isolated from the residual oils of
gasoline reforming, a process common in the
United States.
In the new naphthalene processes developed
in Japan by Kawasaki and in Europe by Bayer
anthraquinone is synthesized in three steps:
Naphthoquinone is prepared by vapor-phase ox-
idation with air. Butadiene is added to this
naphthoquinone in a Diels-Alder reaction. The
tetrahydroanthraquinone formed is oxydehydro-
genated. In this naphthalene process a significant
4 Anthraquinone
amount of phthalic anhydride byproduct is pro-
duced.
In the synthesis of anthraquinone from ph-
thalic anhydride and benzene approximately
1.4 t of aluminum chloride and 4 – 6 t of sulfuric
acid per ton of anthraquinone are used. This pro-
cedure is used in areas where anthracene is not
available in sufficient amounts from coal tar. It
may become important again, as a result of the
shortage of anthracene. Phthalic anhydride has
become available at low prices and in sufficient
quantities following the introduction of the eco-
nomical oxidation of naphthalene or o-xylene
with air.
In the early 1970s another interesting anthra-
quinone process was developed by BASF.
Styrene is first dimerized to 1-methyl-3-
phenylindane in the presence of an acid catalyst,
which is then converted to anthraquinone in the
vapor phase by oxidation with air.
3.1. Oxidation of Anthracene with
Chromic Acid
The classic process of oxidizing anthracene with
chromic acid is still carried out industrially on a
large scale. In combination with the manufacture
of tanning agents this process involves virtually
no expense for the oxidizing agent. The batch
process is still in use.
Pure, finely pulverized 94 – 95 % anthra-
cene (2600 kg) is pasted with water (9000 kg)
in a 30000-L mixing vessel. A wetting agent
is added. For oxidation, portions of 48 % sul-
furic acid and 20 % sodium dichromate so-
lution are added alternately; the reaction be-
gins at 50 – 60 ◦ C. The temperature increases
to 100 – 105 ◦ C but should not be allowed to
increase any further. The temperature is con-
trolled by regulating the amount of reagents
added. Foaming is severe. A total of 10200 kg of
48 % sulfuric acid and 23 500 kg of 20 % sodium
dichromate solution are used. At the end of the
reaction there should be a small excess of ox-
idizing agent, which is reduced with hydrogen
sulfite. The oxidation takes 30 – 36 h [4].
The reaction mixture is filtered through a suc-
tion filter while being stirred, washed, suspended
with water, and filtered into a chambered rotary
filter. A yield of ≈ 3000 kg of 95 % crude anthra-
quinone is obtained. The product is dried, or it is
recrystallized from nitrobenzene, in which case
the retained water is evaporated first. A purity of
99 % is achieved.
3.2. Vapor-Phase Oxidation of
Anthracene with Air
The vapor-phase oxidation of anthracene with
air was described first by A. Wolf in 1916. The
catalysts are similar to those for the oxidation of
naphthalene or o-xylene to phthalic anhydride:
vanadium compounds, mainly iron vanadate [5]
or vanadic acid doped with substoichiometric
amounts of alkali metal or alkaline-earth metal
ions [6].
The conversion of the anthracene is nearly
quantitative. The major byproduct is a small
quantity of phthalic anhydride, which is sepa-
rated easily. The advantage of this procedure is
that it produces anthraquinone of 99 % purity. It
can be converted further without purification.
Details on a plant constructed by Aziendi
Colori Nazionali Affini, Milan, were published
[7]:
Anthracene is evaporated with a preheated
air–water vapor mixture, and the gas current is
mixed carefully with more air (danger of explo-
sion!) and led into a catalytic furnace from the
bottom at 325 ◦ C. The catalytic furnace consists
of 1400 L of catalyst piled in layers; temperature
is controlled by tubes in which pressurized water
circulates through these layers. The lower part
of the furnace, where the reaction takes place,
is cooled to 390 ◦ C; the upper part is heated to
339 ◦ C. The catalyst consists of iron vanadate
prepared from ammonium vanadate and iron(III)
chloride. The air flow rate is 2150 m3 /h, each

cubic meter containing 20 g of 94 % anthracene.
The gases leaving the catalytic furnace first go
through heat exchangers and then through cool-
ing towers, cooling chambers, and dust filters.
The anthraquinone produced has an average pu-
rity of 99.6 %
The iron vanadate catalyst is prepared as fol-
lows [5]: 2.4 kg of red iron(III) oxide is dissolved
by heating it in 9.1 L of 30 % hydrochloric acid,
9.6 L of water, and 120 g of potassium sulfate.
The resulting solution is mixed with a solution of
30.1 kg of ammonium vanadate in 600 L of wa-
ter at 60 ◦ C. The solution is made alkaline with
ammonia and the water evaporated until precip-
itation begins. The pregnant iron vanadate solu-
tion is evaporated onto pumice at 110 – 130 ◦ C
in a heatable ball mill. The catalyst is calcined
at 330 – 350 ◦ C. The catalyst should be yellow
brown but not dark brown.
After a period of time the activity of the cat-
alyst falls off, resulting in a decline in the yield
of anthraquinone and an increase in phthalic an-
hydride. To keep the activity of the catalyst con-
stant or to reactivate it, a small amount of ammo-
nia is added to the oxidation air or the exhausted
catalyst is washed with a dilute alkali solution
[8].
3.3. Naphthalene Process
The naphthalene process developed by
Kawasaki Kasei Chemicals [9] consists of three
steps. In the first step naphthalene is oxidized
in the gas phase with air on a vanadium pentox-
ide catalyst to produce the relatively unstable
naphthoquinone (4). Large amounts of phthalic
anhydride form at the same time. Because most
of the naphthalene reacts, recycling of unreacted
naphthaline is not necessary [10–13].
The hot reaction mixture is precooled in a gas
cooler and then quenched and washed with wa-
ter in a tower. The naphthoquinone is obtained
mixed with phthalic acid anhydride (or phthalic
acid) as a suspension in water. The naphtho-
quinone is extracted with an aromatic solvent,
for example xylene or tetrahydroanthraquinone,
to separate it from the phthalic acid. The small
residue of acid is carefully removed by washing
with dilute alkali [14–16].
In the second step the naphthoquinone is
Anthraquinone 5
reacted with butadiene in a Diels-Alder reac-
tion to give 1,4,4 a,10 a-tetrahydroanthraquin-
one (5). The Diels-Alder product is separated
from unreacted naphthoquinone by extraction
with aqueous alkali, which converts the quinone
into a water-soluble alkali-metal salt. The or-
ganic phase, which contains naphthoquinone, is
recycled to the first step [10], [11], [17].
In the third step the aqueous tetrahydro-
anthraquinone solution is reacted with air. The
anthraquinone that forms is insoluble in aqueous
alkali and can be isolated by filtration. The aque-
ous alkali is recycled into the tetrahydroanthra-
quinone extraction step [18]. The anthraquinone
can be purified further by vacuum distillation
[9].
Phthalic acid is isolated from the aqueous ph-
thalic acid solution by crystallization and filtra-
tion. It is heated to convert it to phthalic acid
anhydride. The phthalic acid anhydride can be
further purified by distillation.
Kawasaki Kasei Chemicals operates a plant
based on the naphthalene process that produces
3000 t/a. The plant has been in operation since
1980.
In Bayer’s variation of the naphthalene pro-
cess, naphthalene is oxidized with a mixture of
air and recycled reaction gas on a vanadium
pentoxide catalyst to give naphthoquinone, ph-
thalic acid anhydride and unreacted naphtha-
lene [19–21]. The products of the oxidation
along with unreacted naphthalene are quenched
and condensed into a liquid reaction mixture,
which is reacted without purification with buta-
diene [22], [23]. The Diels-Alder product mix-
ture that contains tetrahydroanthraquinone is re-
acted with air. The tetrahydroanthraquinone is
6 Anthraquinone
oxydehydrogenated to give anthraquinone. The
naphthalene is removed by distillation [23–25].
The two end products, anthraquinone and ph-
thalic acid anhydride, are separated by fractional
distillation [26].
3.4. Synthesis from Phthalic Anhydride
and Benzene
In the first step o-benzoylbenzoic acid (6) is pre-
pared from phthalic anhydride and benzene by
a Friedel-Crafts reaction. In the second step the
o-benzoylbenzoic acid is cyclized to anthraquin-
one by heating with concentrated sulfuric acid.
The primary product of the Friedel-Crafts reac-
tion is an aluminum chloride complex of the o-
benzoylbenzoic acid, which can harden easily to
form a compact mass in the reaction vessel. Sev-
eral methods have been proposed to overcome
this problem. Based on a process described by
G. Heller already in 1906, condensation is car-
ried out in excess benzene to give yields of more
than 95 %. Patents issued to Klipstein & Sons
and the I. G. Farbenindustrie from 1923 to 1927
describe a solvent-free process carried out in ball
mills. The problem posed by the reaction mix-
ture’s baking can be reduced by adding ethylene
glycol or 1,4-butanediol, which causes a reduc-
tion in the necessary excess benzene or makes a
solvent-free process possible.
Phthalic anhydride, benzene, and aluminum
chloride in a molar ratio of 1 : 1 : 2 are allowed
to react below 45 ◦ C in iron ball mills fitted with
hollow axles for the addition of benzene and the
removal of the hydrogen chloride formed dur-
ing the reaction, or in a vessel equipped with
a strong horizontal agitator, possibly propelled
from the bottom. The reaction mass, which is
heterogeneous at first, liquefies, then gradually
becomes viscous as hydrogen chloride is con-
tinuously lost, and eventually forms a powder.
During the reaction there is extensive foaming,
producing several times the original volume, a
fact that must be considered when the charge
is measured out. The reaction is complete after
1 mol of hydrogen chloride per mol phthalic an-
hydride has been evolved. The reaction product
is placed into dilute acid. The precipitated o-
benzoylbenzoic acid is separated, washed, and
dried, providing a yield of more than 95 %.
Pure o-benzoylbenzoic acid [85-52-9] crys-
tallizes from water with 1 mol of water of hy-
dration in triclinic crystals, mp 94 ◦ C. The anhy-
drous acid crystallizes from xylene, mp 127 ◦ C.
In the second step it is also possible to start
with the aluminum chloride complex formed
in the first step and cleave 1 mol of hydrogen
chloride by heating to 200 ◦ C. A good yield
of anthraquinone is obtained. In practice, how-
ever, the condensation of the precipitated dried
o-benzoylbenzoic acid with sulfuric acid is pre-
ferred.
The acid is dissolved in three to four times its
weight in 95 – 98 % sulfuric acid and heated to
115 – 140 ◦ C. The duration of heating depends
on the quantity and concentration of the sulfuric
acid and on the temperature. After completion
of the reaction the anthraquinone is precipitated
with water, filtered, and dried. A portion of the
product also can be obtained in coarsely crystal-
lized form by cooling the sulfuric acid solution
directly. The yield is almost quantitative.
The condensation solution can be used di-
rectly for the manufacture of benzanthrone or
anthraquinonesulfonic acids.
3.5. Styrene Process
This process was developed in pilot by BASF.

Styrene dimerizes in the presence of acid cat-
alysts, such as sulfuric acid [27], [28], phos-
phoric acid, or boric acid [29] , yielding pri-
marily 1,3-diphenyl-2-butene, which cyclizes
further on the same catalyst to 1-methyl-3-
phenylindane [6416-39-3]. The yields obtained
in this step are 85 – 90 %.
1-Methyl-3-phenylindane is converted di-
rectly to anthraquinone by oxidation with air in
the vapor phase [30].
Basically, the same catalysts are used as those
employed in the gas-phase oxidation of anthra-
cene with air, i.e., vanadium compounds, pri-
marily vanadium pentoxide in combination with
other oxides, such as thallium oxide and anti-
mony oxide [31].
Yields of ≈ 77 % are obtained in the oxida-
tion stage. Byproducts are still attached to the
precipitated reaction product, and further purifi-
cation is necessary.
3.6. Environmental Considerations
Chromium salts should not get into the waste
water from the chromic acid process. The
chromium(III) sulfate lye is disposed of by pro-
cessing it to tanning agents. The anthraquinone
must be carefully washed free of chromium with
small amounts of wash water.
In the gas-phase oxidation of anthracene with
air and the naphthalene process, on the other
hand, the emphasis is placed on purifying the
large quantity of waste air.
The production of anthraquinone via the
Friedel-Crafts reaction from phthalic anhydride
and benzene is accompanied by a release of
waste water containing 1.4 t of aluminum chlo-
ride and 4 – 6 t of sulfuric acid per ton of anthra-
quinone. Moreover, carcinogenic benzene must
be eliminated from the waste air by thermal post-
treatment.
4. Purification, Quality
Requirements, and Analysis
Anthraquinone is most often purified by recrys-
tallization, preferably from nitrobenzene. Other
purification methods include sublimation or vac-
uum destillation.
Anthraquinone 7
At present, a degree of purity of at least 99 %
is required for the major uses of anthraquin-
one, i.e., production of nitroanthraquinones and
anthraquinonesulfonic acids. A content of 98 –
99 % is sufficient for use as catalyst in wood
pulping. The admission of anthraquinone by the
U.S. Food & Drug Administration (FDA) as cat-
alyst in the manufacture of food packing paper
requires a content of at least 98 % [32].
Today the main method of analyzing the con-
tent is gas chromatography: The other com-
ponents and solvents, which are present in
ppm quantities, are detected directly. High-pres-
sure liquid chromatography is another suitable
method of analysis.
According to the classic analytical processes
the content is determined (1) by reduction
to soluble anthrahydroquinone, filtration, back-
oxidation, and weighing out the filtered anthra-
quinone or (2) by separating the anthraquinone
by column chromatography and analyzing the
eluate by UV spectroscopy.
5. Uses
Anthraquinone serves as the basis for the pro-
duction of a large number of acid and base
dyes, vat dyes, disperse dyes, and reactive dyes
(→ Anthraquinone Dyes and Intermediates).
Anthraquinone-1-sulfonic acid, anthraquin-
one-2-sulfonic acid, anthraquinone-1,5-di-
sulfonic acid, and anthraquinone-1,8-disulfonic
acid as well as 1-nitroanthraquinone, 1,5-di-
nitroanthraquinone, 1,8-dinitroanthraquinone,
anthrone, and benzanthrone are prepared in the
first processing step. For environmental reasons
the production of anthraquinone-2-sulfonic acid
and anthraquinone-1,5- and anthraquinone-1,8-
disulfonic acids is being replaced increasingly
by the production of 1-nitroanthraquinone and
1,5- and 1,8-dinitroanthraquinone.
In the second stage of processing, the sul-
fonic or nitro groups generally are replaced by
ammonia, amine, chlorine, alcoholate, pheno-
late, or other nucleophilic agents or are reduced
to an amino group. Some of the anthraquinone
dyes, however, are prepared from anthraquin-
one derivatives. These are synthesized not from
anthraquinone, but from smaller molecules.
On a small scale, anthraquinone is used in
the manufacture of denaturants to protect seed
8 Anthraquinone

from crows, in the modification of stand oils, to 7. Toxicology

brighten up colophoniy, and in the manufacture
of hydrogen peroxide. Based on present knowledge, anthraquinone, un-
The paper and pulp industry is another like the “emodins” (hydroxyanthraquinone gly-
rapidly expanding market for anthraquinone cosides) from anthraquinone drugs [36], is bio-
[33]. Anthraquinone is a redox catalyst in the logically completely “inert,” i.e., inactive, pre-
production of pulp; the intermediate anthra- sumably as a consequence of its insolubility in
hydroquinone catalyzes the alkaline hydrolysis water and lipids.
of the polymeric lignin. When 0.03 – 0.05 % There is no toxicologic information about
anthraquinone is added, the yield of pulp is in- anthraquinone. Even in the Toxic Substances List
creased 2.5 – 4 % and the cooking time is re- [37] no LD50 is found for anthraquinone. In con-
duced up to 30 % [34]. trast to benzoquinone, which causes severe local
The worldwide production capacity is ade- irritation and is included in the list of occupa-
quate to cover the actual demand for anthraquin- tional hazards because of its damaging effect on
one [35]. the cornea, a fine dust of anthraquinone to which
emulgators were added had no greater effect on
the eyes of rabbits than a talcum suspension, as
6. Economic Aspects was shown in a BASF study.
An MAK value of 10 mg/m3 was recom-
The production capacity for anthraquinone mended [38]; therefore, anthraquinone dust is
worldwide is at present 34000 t/a. About 50 % considered the same as inert dust.
of this capacity is in Western Europe.
The most important manufacturers of anthra-
quinone and their production capacities are 8. References
listed in Table 1.
General References
Table 1. Anthraquinone production capacities [32], [35] 1. Beilstein, VII, 781, VII (1), 407, VII (2), 709,
VII (3), 4059, VII (4), 2556.
Western Europe
Bayer 11000 t/a 2. E. de Barry Barnett: Anthracene and
ICI 2500 t/a Anthraquinone, Baillière, Tindall & Co.,
Ciba-Geigy 2200 t/a London 1921.
ACNA 1000 t/a
Ugine Kuhlmann 3. J. Houben: Das Anthracen und die
800 t/a Anthrachinone, Thieme Verlag, Leipzig 1929.
L. B. Holliday
200 t/a
Yorkshire Chem. 200 t/a Specific References
4. Fiat Final Rep. no. 1313, vol. 2, p. 19.
17900 t/a
United States 5. Fiat Final Rep. no. 1313, vol. 1, p. 332.
Toms River Chem. 1500 t/a 6. Ciba, DE 1016694, 1954.
American Cyanamid 400 t/a 7. Bios Misc. Rep. no. 104.
1900 t/a
8. Ciba, DE 1020617, 1954.
Japan 9. Kawasaki Kasei Chemicals Ltd., Research and
Kawasaki Kasei 3000 t/a Development in Japan awarded the Okochi
Nihon Joryn Kogyo 2000 t/a
Memorial Price, 1980, Okochi Memorial
5000 t/a Foundation.
Eastern Europe 10. Kawasaki, JP 5108256, 1974.
USSR 2600 t/a 11. Kawasaki, JP 5108257, 1974.
Poland 1800 t/a
Czechoslovakia 1200 t/a 12. Kawasaki, JP 5322559, 1978.
13. Kawasaki, DE 3033341, 1980.
5600 t/a 14. Kawasaki, JP 5251356, 1975.
Other Countries
Indian Dyestuff 3000 t/a
15. Kawasaki, GB 2039897, 1978.
Amar Dye (India) 250 t/a 16. Kawasaki, JP 5422246, 1979.
China 400 t/a 17. Kawasaki, US 4412954, 1981.
18. Kawasaki, JP 5652434, 1981.
3650 t/a
Worldwide 34050 t/a 19. Bayer, DE 2532422, 1975.

20. Bayer, DE 2453232, 1974.
21. Bayer, DE 2532365, 1975.
22. Bayer, DE 2532388, 1975.
23. Bayer, DE 2218316, 1972.
24. Bayer, DE 2245555, 1972.
25. Bayer, US 4284576, 1975.
26. Bayer, DE 2532450, 1975.
27. J. Risi, D. Gauvin, Can. J. Res. Sect. B. 14
(1936) 255.
28. P. E. Spoerri, M. J. Rosen, J. Am. Chem. Soc.
72 (1950) 4918.
29. BASF, DE 2064099, 1970.
30. BASF, DE 1934063, 1969.
Anthraquinone 9
31. BASF, DE 2135421, 1971.
32. A. Budzinski, Chem. Ind. (Düsseldorf) 33
(1981) 332.
33. H. H. Holton, Pulp Pap. Can. 78 (1977) 10.
34. G. Gellerstedt, Kem. Tidskr. 58 (1979) no. 2.
35. Eur. Chem. 1984, no. 27, 429.
36. H. Auterhoff, Arzneim. Forsch. 3 (1953) 23.
37. US-Department of Health; Toxic Substances
List, Nat. Instit. for Occup. Safety and Health,
Rockville, Maryland 1972.
38. V. H. Volodishenko, Biol. Abstr. 53 (1972)
no. 63983.