Article No : a14_149
Indigo and Indigo Colorants
ELMAR STEINGRUBER, Frankenthal, Germany
1. Physical Properties . . . . . . . . . . . . . ..... ..
2. Chemical Properties . . . . . . . . . . . . ..... ..
3. Occurrence and Raw Materials . . . . ..... ..
4. Production . . . . . . . . . . . . . . . . . . . . ..... ..
5. Environmental Protection . . . . . . . . ..... ..
6. Quality Specifications. . . . . . . . . . . . ..... ..
7. Chemical Analysis . . . . . . . . . . . . . . ..... ..
8. Storage and Transportation. . . . . . . ..... ..
Indigo (1) is a natural dye obtained from the
plants Indigofera tinctoria and Isatis tintoria,
which have been used to color textiles in India,
China, and Egypt for 4000 years. Since its dis-
covery, the cultivation, extraction, and use of
indigo have spread throughout the world, and
trade in indigo became a significant economic
factor, reaching a volume of about 8000 t in 1900.
With the development and technical realiza-
tion of chemical syntheses at the end of the
nineteenth century, indigo became an important
product of the growing chemical industry. After
the proof of its structure by ADOLF VON BAEYER in
1883, experiments to prepare indigo synthetical-
ly culminated in 1887 in the commercialization
and large-scale production of synthetic indigo by
the Badische Anilin- und Soda-Fabrik (now
BASF Aktiengesellschaft) in Ludwigshafen.
Today, more than 100 years later, synthetic
indigo is still an important product of the dye
manufacturing industry and has almost
completely replaced the natural indigo from
plants. Synthetic indigo is the largest single

2012 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim
DOI: 10.1002/14356007.a14_149.pub2
55 9. Uses . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .. 60
56 10. Commercial Forms . . . . . . . . . . . . . . . . . . .. 60
56 11. Economic Aspects . . . . . . . . . . . . . . . . . . . .. 60
58 12. Toxicology and Occupational Health . . . . . .. 61
59 13. Indigo Derivatives . . . . . . . . . . . . . . . . . . . .. 62
59 References . . . . . . . . . . . . . . . . . . . . . . . . . .. 63
60
60
textile dye in the world, supplied by only a small
number of producers to over 500 dye houses,
whose main product is blue denim (i.e., cotton
twill weave where the warp is dyed with indigo).
Indigo is used for the manufacture of approxi-
mately 109 pairs of blue jeans annually. The
apparently unending life cycle of indigo is, in
view of its moderate fixation on the fiber, a
phenomenon that is difficult to understand.
Worldwide acceptance of easily washed out,
faded, indigo blue garments, not only as work
clothes but also as fashionable sport and leisure
articles, opened up new markets for indigo and
ensured increasing demand for dyers and
outfitters.
Apart from indigo itself, only few derivatives
and related compounds, primarily halogenated
indigo and thioindigo, have reached a position of
steady economic importance (see Chap. 13).
The considerable list of publications concern-
ing indigo began nearly 170 years ago [1] and is
indicative of the unusual cultural, as well as
chemical, position occupied by this compound
up until recent times [210].
1. Physical Properties
0
Indigo [482-89-3], indigotin, (D2,2 -biindoline)-
3,30 -dione, 2-(1,3-dihydro-3-oxo-2, H-indol-2-
56 Indigo and Indigo Colorants Vol. 19

ylidene)-1,2-dihydro-3, H-indol-3-one, C16H10

N2O2, Mr 262.27, C.I. Vat Blue 1, C.I. 73000
exists at ambient temperature and pressure as dark
blueviolet needles or leaves with a reddish
bronze metallic appearance. It sublimes above
170
C (mp 390 392
C). Indigo is practically
insoluble in water, aqueous acid, aqueous base,
and nonpolar solvents, but slightly soluble in
high-boiling polar solvents, (e.g., aniline, nitro-
benzene, phenol, phthalic anhydride, dimethyl
formamide, and dimethyl sulfoxide); it crystal-
lizes in pure form from hot solutions. The color of
indigo is unusually intense, compared to conju-
gated molecules of similar size [11], and is influ-
enced strongly by solvents. Despite the possibility
of cis trans isomerism about the central CC
double bond, only the trans isomer, stabilized by
intra- and intermolecular hydrogen bonding, is
observed [12, 13]. This fact also explains the
extremely low solubility, high melting point, and
vibrational and electronic absorption spectra of
indigo. Bond orders and charge densities of the Leuco indigo can be di- and tetraacetylated as
indigo chromophore have been investigated and well as methylated at the nitrogen and oxygen
calculated [12, 14, 15] as has the X-ray crystal atoms.
structure [16, 17]. The action of oxidizing agents leads to dehy-
droindigo (4); oxidation with permanganate or
chromate cleaves the molecule at the central
double bond, forming isatin [91-56-5] (5).
2. Chemical Properties Concentrated alkali at elevated temperature
leads to decomposition of indigo with formation
Indigo is very resistant to light and elevated of aniline, N-methylaniline, and anthranilic acid.
temperature, even in the presence of air. Substi- In biological systems, indigo is extremely
tution by electrophiles or nucleophiles is diffi- stable. For example, in a biological wastewater
cult; only sulfonation in concentrated sulfuric treatment plant, indigo is not degraded, but sim-
acid, to give the di- and tetrasulfonic acid, and ply adsorbed to the activated sludge, probably as
halogenation in nitrobenzene, to introduce up to a result of its low solubility; the elimination is
six halogen atoms, are successful (See Chap. 13). 90100 % [37]. This fact accounts for the low
With strong mineral acids, indigo forms salts that acute and chronic toxicity of indigo (see
decompose in water. Chap. 12).
Reducing agents (e.g., sodium dithionite,
hydroxyacetone, zinc, hydrogen or biological
material in fermentation, recently also electric 3. Occurrence and Raw Materials
current [18, 19]) convert indigo to the leuco
form indigo white [6537-68-4] (2), which dis- Natural indigo occurs worldwide in numerous
solves in sodium hydroxide solution to types of Indigofera, particularly in Indigofera
form the disodium salt [894-86-0] (3). This tinctoria (in Asia and America), and in Crucifer-
is the effective dyeing agent (vat indigo) ae such as Isatis tinctoria (dyers woad, in Eur-
which penetrates into the fiber and, after re- ope). The concentration of indican [487-60-5]
oxidation adheres rather superficially to the (6), a glucoside of indoxyl found in the stems
surface of cotton fibers; in contrast, bonding and leaves, amounts to only 0.2 0.8 %. After
to the polypeptide fibers of wool or silk is indoxyl is released with enzymes, it oxidizes
more saltlike. rapidly to indigo.
Vol. 19
Before the introduction of synthetic indigo in
1897 by BASF, the cultivation of indigo plants,
especially in India, on an area of more than 7000
km2 was a huge business with a reported output of
19 000 t of indigo in 1897. The natural indigo
production collapsed to 1000 t per year in 1914.
For the industrial synthesis of indigo, only two
starting materials are now important. The first is
N-phenylglycine [103-01-5] (7) produced from
aniline and chloroacetic acid, or by reaction of
aniline with formaldehyde and sodium cyanide
or hydrogen cyanide followed by saponification
of the nitrile (8). In an alternate reaction, the
addition product (9) of aniline, formaldehyde,
and sodium bisulfite is treated with sodium
cyanide to give the N-phenylglycine nitrile 8.
Another route to the nitrile [8] is the reaction of
aniline with hydroxyacetonitrile (10) [2022].
All four synthetic routes were used industri-
ally [23]: the aniline-formaldehyde-hydrogen
cyanide route by DyStar (which took over the
textile dye business from BASF, Germany), the
aniline-formaldehyde-sodium cyanide varia-
tion by Buffalo Color Corp. (USA; the plant
has been closed in the meantime), the bisulfite
version by Bann Qu
mica (Brazil), and the
chloroacetic acid route by Chinese manufac-
turers. ICI and Mitsui have dicontinued their
indigo manufacture.
The second raw material still used for the
industrial synthesis of indigo is anthranilic acid
[118-92-3] (11), which is either condensed with
chloroacetic acid and alkali to give the salt of N-
phenylglycine-o-carboxylic acid, or converted to
the nitrile (12) with formaldehyde and hydrogen
cyanide; subsequent saponification yields (13).
The N-phenylglycine-o-carboxylic acid process
Indigo and Indigo Colorants 57
was applied by BASF in 1897 to produce the first
synthetic indigo on an industrial scale and em-
ployed in Ludwigshafen until 1924. The ring
closure used in this process to form indoxyl is
easier because no sodium amide is required, but
the overall cost is considerably higher than the
process based on aniline. The anthranilic acid
route to synthesize indigo is therefore no longer
of any commercial importance.
Other intermediates used in the pioneering
phase of synthetic indigo were N-(2-hydro-
xyethyl)aniline and N-ethyl-N-phenylglycine;
the use of these starting materials ceased in
1914 and 1904, respectively. The numerous other
synthetic routes to indigo have no commercial
importance. The Baeyer Drewsen process of
1882 is no longer in use; in this method, 2-
nitrobenzaldehyde was used to synthesize 4,40 -
dichloroindigo, which is inaccessible by direct
chlorination.
During the first 20 years of synthetic indigo
manufacture, the decision as to which interme-
diate to use depended on the availability of the
petrochemical raw materials benzene and naph-
thalene. These two chemicals, then accessible
only from coal tar, were converted to aniline via
nitrobenzene and anthranilic acid via phthalic
anhydride, respectively. Today, the decision is
influenced predominantly by the process tech-
nology available and the production costs; in this
respect, the aniline process requires a higher
expenditure for process equipment, but con-
sumes cheaper raw materials.
Since about 1980, attempts to manufacture
indigo by biosynthetic methods from glucose
have been successful, using recombinant micro-
organisms [2426]. The disadvantage of han-
dling dilute solutions in huge bioreactors, the
58 Indigo and Indigo Colorants
difficulties of separating indigo from biomass,
and the treatment of large volumes of organic
byproducts prevented a commercialization of
this process.
4. Production
The extraction and isolation of natural indigo are
described in detail in [27], [28]. The indigo plants
are cut and fermented in water for 15 h. The
glycoside indican (6) is enzymatically cleaved to
glucose and indoxyl. Oxidation of indoxyl with
air yields indigo. The most important producer
countries were India (particularly Bengal), Java,
and Guatemala. Purification, based on reduction
and reoxidation, or fractional precipitation from
sulfuric acid, was usually necessary because of
the low purity of the natural indigo of only 15
70 %.
The rapid success of synthetic indigo at the
beginning of the 20th century had a devastating
effect on the plantations of natural indigo; by
1925 the production in India had dropped to only
a few percent.
For the industrial synthesis of indigo the
most important and also the most economic
production process currently in use is ring
closure of N-phenylglycine with sodium amide
[7782-92-5] in anhydrous sodium hydroxide
and potassium hydroxide solvent. The original
process used by KARL HEUMANN in 1890 did
not employ sodium amide and gave an indigo
yield of only ca. 10 % [3].
After the observation by J. PFLEGER in 1901
that the addition of sodium amide resulted in a
high yield of indigo, this process was intro-
duced industrially by Farbwerke Hoechst. The
process was also used by BASF in Ludwig-
shafen in 1905 with cheaper calcium oxide as
desiccant. When the price of sodium dropped
sharply, BASF changed to sodium amide in
1926 [29].
The Heumann Pfleger process provides in-
digo of adequate purity in yields up to 90 %.
Investigation of reaction conditions and raw
material ratios is described in [2]. Ring closure
of alkali salts of N-phenylglycine is carried out
with about 2 mol of sodium amide at ca. 200
C
and releases ammonia. The indoxyl formed in the
anhydrous melt exists as the stable dialkali-metal
salt (14).
Vol. 19
After ring closure, the melt is dissolved in
water; the unstable indoxyl monoalkali salt is
converted to indigo by oxidation with air. Some
decomposition occurs, leading to aniline, N-
methylaniline, and anthranilic acid as bypro-
ducts. Further details concerning the indoxyl
melt are described extensively in [3, 23, 2734].
The crystalline indigo formed by oxidation is
separated from the aqueous alkali by filtration and
washed with water. The usual commercial forms
are indigo powder, prepared by drying the aque-
ous filter cake, and reduced indigo in the form of
indigo vat 40 % solution and 60 % grains; some
manufacturers offer a paste or liquid containing
20 % indigo. The filtrate of the oxidation mixture
can be concentrated and the alkali used again for
the indoxyl melt. The alkali solution concentrated
to 50% is filtered to remove precipitated anthra-
nilic acid, sodium carbonate, and other impurities.
Recovery of the alkali makes the process more
cost attractive because only a small amount of
alkali is lost from the production cycle.
The production of indigo based on the more
expensive anthranilic acid via N-phenylglycine-
o-carboxylic acid [13] or its salts is simpler
because no anhydrous alkali or dehydrating agent
like sodium amide is required. Nevertheless, the
reaction mixture is more viscous and therefore
requires considerably more alkali to carry out the
fusion [27, 28, 35].
Vol. 19
In this process, ring closure to the indoxyl
carboxylic acid also occurs at ca. 200
C. The
yield is 70 90 %, depending on reaction condi-
tions and the quality of the dicarboxylic acid (13).
The fusion mass is dissolved in water, decarbox-
ylation and oxidation by air yields indigo. Isolation
of indigo is similar to that in the N-phenylglycine
process; the product quality is also comparable.
The indoxyl fusion of N-phenylglycine [7]
under anhydrous conditions can be carried out
in carbon steel vessels, which suffer practically
no corrosion. Stainless steel is preferred for the
considerably more aggressive water-containing
melt from N-phenylglycine-o-carboxylic acid
[13]. Both indoxyl oxidation and isolation of
indigo use normal steel, which is sufficiently
resistant to dilute caustic alkali.
In addition to the two processes described
above, another synthetic route starts from N-
(2-hydroxyethyl)aniline. Although an easily ac-
cessible raw material is involved and the process
was used by BASF from 1907 to 1914, it is no
longer of industrial importance. A considerably
higher temperature is required, at which hydro-
gen is released spontaneously; the yield and
purity of the indigo are lower. Further process
improvements by Farbwerke Hoechst [23] could
not revive this route.
Indigo is also marketed as the leuco indigo
disodium salt [3]. Prepared originally by reduc-
tion of indigo with zinc or iron, it is now obtained
by catalytic hydrogenation of indigo. Until 1980
indigo white (2) was marketed as a 50 % paste
and used as a syrupy product, predominantly in
the Far East; it is no longer in use. Indigo vat 60 %
is a granular product obtained by drying a mix-
ture of the sodium salt [3] and molasses, adjusted
to an indigo content of 60 %. Since 2000, also a
40 % solution of indigo vat is manufactured and
sold; the prereduced indigo gained interest in the
dye houses by saving costs and reducing the salt
content in the effluent.
5. Environmental Protection
Because of their chemical properties and toxici-
ty, the chemicals used in the production of N-
phenylglycine and indigo (particularly aniline,
formaldehyde, hydrogen cyanide, potassium or
sodium hydroxide, sodium, ammonia, and sodi-
um amide), demand high standards for safe han-
Indigo and Indigo Colorants 59
dling and processing. These are achieved by
extensive use of closed systems.
Indigo possesses very low mammalian toxic-
ity [36], [37] (see Chap. 12) and does not have an
adverse effect on adapted activated sludge sys-
tems (e.g., in rivers or biological effluent treat-
ment plants). The rate of biological degradation
is quite low because of its low solubility, but
indigo is adsorbed on activated sludge and there-
by eliminated from wastewater.
Byproducts from indigo synthesis may be
present in wastewater resulting from filtrates,
wash water, and flue-gas scrubbers; the wastewa-
ter must then be purified. The byproducts aniline
and anthranilic acid are easily degraded in bio-
logical water treatment plants, but N-methylani-
line is degraded more slowly. The ammonia
released in the sodium amide process and in the
saponification of the nitriles 8 or 12 is preferably
recovered but can also be removed from waste
streams by nitrification. Any alkali reaching the
wastewater must be neutralized with acid.
The extraction of natural indigo also involves
ecological problems, because 98 % of the dry
plant material do not consist of indigo and have to
be degraded in the fermentation process or de-
posited in the indigo plantations.
6. Quality Specifications
Indigo is available in the following forms: tech-
nically pure powder, microgranules, or lumps
considered to contain 100 % indigo; liquid dis-
persions in water with an indigo content of 20
30 %; indigo vat 60 % grains and indigo vat 40 %
solution.
The powder and microgranules still contain
traces of byproducts from the synthesis, together
with small amounts of additives that influence the
dispersibility. The following parameters serve as
quality criteria: indigo content, dusting and wet-
ting properties, reduction rate, properties of the
vat solution, and dyeing characteristics.
With the liquid dispersions, which usually
contain 20 30 % indigo and are free-flowing
liquids, quality criteria include indigo content,
alkali content (0 6 %), viscosity, specific grav-
ity, storage stability, sedimentation behavior, and
those parameters used for the powder (i.e., re-
duction behavior, the quality of the reduced
solution, and dyeing properties).
60 Indigo and Indigo Colorants
Indigo vat 60 % grains and indigo vat 40 %
solution are tested for indigo, alkali, and water
content, and for the amount of reoxidized material.
For natural indigo, the most important quality
criteria are its purity, solubility after reduction,
and dyeing behavior.
7. Chemical Analysis
Numerous methods have been suggested for the
determination of indigo content, some of which
have been developed in the era of natural indi-
go [27], [32]. The preferred method consists
of sulfonation of an indigo sample with concen-
trated sulfuric acid, followed by titration of the
diluted sulfonic acid with sodium dithionite
solution [38], [39]. Indigo sulfonic acid can also
be determined spectrophotometrically [40];
highly purified indigo, obtained by extraction
with nitrobenzene or phenol, or by recrystalliza-
tion, is used as a standard. Other quality criteria
are discussed in Chapter 6. The effective indigo
content of indigo vat 40 % and 60 % is obtained
after air oxidation of the vat solution and filtra-
tion, and of liquid paste indigo products, after
extraction with dilute mineral acids and filtration.
8. Storage and Transportation
No specific limitations have been placed on
indigo because of the low toxicity. The danger
of dust explosions must be considered in storing
indigo powder (dust explosion class 2). With a
particle size of (20 60)106 m, ignition may
occur at concentrations exceeding 50 g/m3. In-
digo powder, indigo grains, indigo vat, and neu-
tral liquid products are similarly regarded as
nonhazardous for transportation [37]. Alkaline
liquid forms with 1 5 % alkali are regarded as
corrosive for transportation because of the action
of alkali on aluminum [41].
9. Uses
Only small quantities of indigo are used for dyeing
woven fabrics of cotton, wool, and silk (e.g., wax
batik for fashionable hand-crafted objects). The
greater part of the indigo produced worldwide is
used in continuous dyeing of cotton yarn. The dyed
Vol. 19
cotton warps are woven with undyed weft in
various twill weaves to give the typical blue denim
cloth. The predominantly heavy, sailcloth-like
material is used by about 400 producers to manu-
facture mainly blue jeans. The jeans phenome-
non was examined in detail in 1981 from histori-
cal, economic, fashion, artistic, and business per-
spectives [42, 43]. Thanks to the popularity of
cotton clothes dyed with indigo (of which ca.
90 % are blue jeans and only ca. 10 % other fashion
articles including printed textiles), the consump-
tion of indigo has attained a continuous growth rate
worldwide since about 1975, which is above aver-
age of the textile industry.
In dye houses specializing in indigo dyeing,
continuously operated slasher or warp dyeing
machines are used in which the cotton yarn is
immersed successively in three to six dye baths of
vatted indigo. Indigo is reduced to the soluble
leuco form with alkali and hydrosulfite, or pre-
reduced indigo vat is used, or electric current is
used in specialized equipment to reduce the
indigo [18, 19]. After each immersion into the
indigo vat, the yarn is squeezed and the adsorbed
indigo oxidized by air [44]. Worldwide, more
than 100 dye houses run about 200 dyeing ma-
chines, with about 70 % being in the Far East,
particularly the Hong Kong area, followed by the
United States and Europe. In 1980, a Loop Dye
1 for 6 dyeing machine was introduced, in
which cotton yarn passes through the same vat
up to six times [45].
10. Commercial Forms
Commercial products based on indigo include
the following:
DyStar Indigo gran.
Indigo Bann 20 (paste)
Indigo Bann 30 (paste)
DyStar Indigo Vat 60 % Grains
DyStar Indigo Vat 40 % Solution
DyStar Indigo Black 5006 (mixture of indigo
with a yellow dye)
11. Economic Aspects
From 1960 to 1980, the growing demand for blue
jeans resulted in a steady increase in the indigo
Vol. 19
production capacity worldwide. By 1988, the
world capacity had reached 14 000 t per year of
synthetic indigo and was still distributed over
more than ten countries, 12 000 t were supplied
by the five major manufactureres BASF (Ger-
many), Buffalo Color Corp. (USA), ICI (UK and
Brazil), Mitsui Toatsu (Japan) and Taisung (Tai-
wan). Smaller quantities were produced in China,
the Soviet Union, Mexico, Korea, and India.
Fierce price competition and globalization of
world trade started to cause major changes, begin-
ning about 1990. Local indigo production was
started in Brazil by Bann Qu
mica, and low price
indigo from China began to compete on all mar-
kets. In 1996, the Zeneca indigo plant in the UK
(formerly ICI), was sold to BASF, which then
reached a total capacity of 7000 t of indigo per
year. In 2000, BASF included its textile dye busi-
ness in the joint venture DyStar, which consisted of
the textile dye activities of Bayer and former
Hoechst. In the meantime, the UK plant was
closed, Mitsui terminated their indigo production
in Japan, and in 2004 also Buffalo Color Corp. in
the USA ended their operations. The world indigo
consumption had reached about 30 000 t in 2002.
The remaining indigo suppliers in the world
are DyStar with a 7000 t/a capacity, Bann
Qu
mica in Brazil with about 4000 t/a, and
manufacturers in China who constructed huge
new capacities, an estimated 40 000 t/a or more.
The indigo production coming from China into
the world market was expected to amount to 14
000 18 000 t in 2003.
The consumption of indigo for dyeing cotton
yarn amounts to only 1.5 3 % of the weight of
the cotton. The weight of blue denim varies from
ca. 150 to 450 g/m2. With 1.5 m2 of material per
pair of trousers, only 3 12 g of indigo are used
for each pair of blue jeans. The world consump-
tion of 30 000 t/a of indigo in 2003 allows the
production of 24  109 pairs of blue jeans with
an enormous sales value, of which indigo itself
represents only a small fraction.
As a result of the enormous indigo production
capacities in China and the export pressure onto
the world market, indigo market prices have
suffered a steep drop from $ 15 20 per kilo-
gram in 1988 to $ 7 8 per kilogram in 2003 in
Europe; Chinese indigo is even offered at less
than $ 4 per kilogram.
The estimated distribution of the indigo con-
sumption in 2002 is shown in Table 1. Since
Indigo and Indigo Colorants 61
Table 1. Indigo consumption in 2002 (t)
Europe 3300
USA, Canada 3300
Central America 2700
South America 2700
Turkey, Near East, Middle East 2000
Africa 480
India, Pakistan 1950
China 16 000
Rest of Asia 6300
Total 38 780
1988, the demand has increased particularly in
Turkey, India, and China. The Far East continues
to be the largest growing indigo market.
12. Toxicology and Occupational
Health
Despite the long use of natural and synthetic
indigo, only few toxicological data were known
until a few decades ago. Since 1962, however, the
toxicological properties of indigo have been
increasingly examined and reported, in connec-
tion with the application for registration of puri-
fied indigo as D & C Blue No. 6 for use in
pharmaceuticals and cosmetics [36].
The low acute oral toxicity (LD50>
5000 mg/kg) has been confirmed in mammals
[36] fish toxicity LC50 is > 1000 mg/L (96 h,
Leuciscus idus) [37]. Experiments to determine
the acute dermal and inhalation toxicity dem-
onstrated no toxic effects. Subchronic and
chronic feeding experiments on rats and dogs
with purified indigo at up to 3 % of feed weight
showed, after a certain adaptation time, no
serious negative effects other than coloring of
the organs. Similarly, no negative effects were
found in rats over three generations in studies of
reproduction or in teratogenic investigations.
Repeated application of purified indigo to the
skin yielded no negative effects. With alkaline
forms of commercial indigo, the corrosive ac-
tion of the alkali can be observed. No indication
of sensitization in humans was found after re-
peated skin application of neutral indigo.
The Ames test for mutagenicity towards bac-
teria was applied to synthetic indigo in 1979 and
1982 and revealed a minimal positive mutagenic
effect, which was later found to be due to impu-
rities [4648].
62 Indigo and Indigo Colorants
13. Indigo Derivatives
In comparison with the use of indigo as a special
product for dyeing blue jeans, other indigoid dyes
(e.g., thioindigo and substituted indigo deriva-
tives) have considerably less economic
importance.
Thioindigo [522-75-8], C.I. Vat Red 41,
C.I. 73 300, C16H8O2S2, Mr 296.37, available
from thiophenol-o-carboxylic acid and chlor-
oacetic acid via 2-hydroxythionaphthene (15),
is not used for cotton dyeing because of its
poor color fastness and limited affinity for
cotton, but is a brilliant red disperse dye for
polyester (C.I. Disperse Red 364), marketed
by DyStar.
4,7,40 ,70 -Tetrachlorothioindigo, obtained
from the dichloro compound (16) by cyclization
or by direct chlorination of thioindigo, is an
industrially important pigment (see ! Pigments,
Organic, Chap. 13.).
Among the halogen derivatives, Tyrian pur-
ple was obtained from historic times to the
Middle Ages from various sea snails. Despite
its dull red-violet shade, this dye was much
sought after. In 1909 the compound was identi-
Vol. 19
fied as 6,60 -dibromoindigo [19201-53-7], but it
cannot be prepared by direct bromination of the
parent indigo.
The halogenated indigo dyes still in use today
are specialty products; their sales volume
amounts to much less than 1 % of the unsubsti-
tuted indigo products.
5,7,50 ,70 -Tetrabromoindigo [2475-31-2] , C.
I. Vat Blue 5, C.I. 73 065, is synthesized by
bromination of indigo in acetic acid. On account
of its interesting neutral blue color the product is
still sold as DyStar Brilliant Indigo 4 B (for
dyeing) and DyStar Indigo 4B sfx. (for print-
ing). The commercial forms consist of a mixture
of tri- and tetrabromoindigo with a low chlorine
content.
5,50 -Dibromo-4,40 -dichloroindigo, C.I. Vat
Blue 2, C.I. 73045, obtained by bromination of
4,40 -dichloroindigo and sold as Brilliant Indigo
4 G, had been a desirable dye for printing be-
cause of its interesting greenish blue shade. It is
no longer commercially available.
Among the sulfonation products of indigo the
disodium salt of 5,50 -indigodisulfonic acid
C16H8N2Na208S2 is known as indigotine I or
indigo carmine [860-22-0], C.I. Acid Blue 74,
C.I. 73015, Mr 466.36.
Vol. 19 Indigo and Indigo Colorants 63

Registered also as C.I. Food Blue 1 and in the 25 J. W. Frost, J. Lievense, New J. Chem. 1994 18, 341.
USA as FD&C Blue 2, it has found an application 26 H. Bialy, Nature Biotechnol. 1997 15, 110.
as colorant for food, cosmetics, drugs, and ani- 27 Ullmann, 1st ed. 6, 505 508.
28 Ullmann, 2nd ed. Urban & Schwarzenberg, Berlin, Wien
mals feeds. It is marketed by BASF as Sicovit
1930, 6, 244 246.
Indigotin 85 E 132. 29 Ullmann, 3rd ed., Urban & Schwarzenberg, Munchen,
Berlin 7, 1956, 113 114. 8 (1957) 748 763.
30 Kirk-Othmer, 2nd ed., 7, (1965) 621 625; 11, (1966)
References 562 580, Interscience Publishers, New York.
31 Kirk-Othmer, 3nd ed., 8, 363 368;
32 K. Venkataraman: Chemistry of Synthetic Dyes, vol. 2,
1 Dumas, Annalen der Pharmacie 21 (1837) 72 77.
Academic Press, New York 1952, pp. 1003 1022.
2 F. Henesey, J. Soc. Dyers Colour. 54 (1938) 105 115.
33 Ullmann, 4th ed, 13, 177 181.
3 K. Holzach, Angew. Chem. A/60 (1948) 200 204.
34 Ullmanns, 5th ed., A 14, 149 156.
4 H. Cassebaum, Melliand Textilber 48 (1967) 207.
35 M. Phillipps, J. Ind. Eng. Chem. 13 (1921) 759 762.
5 M. Seefelder: Indigo: Kultur, Wissenschaft und Technik,
36 K. H. Ferber, J. Environ. Pathol. Toxicol. Oncol. 7 (1987)
ecomed, Landsberg, 1994.
73 83.
6 H. Schmidt, Chemie in unserer Zeit 31 (1997) , 121 128.
37 Sicherheitsdatenblatt DyStar Indigo gran, DyStar Textil-
7 A. Dutly: Geschichte des Indigos, ETH Zurich, 2002,
farben GmbH & Co., Leverkusen, 01.08.2002.
http://www.dutly.ch/indigohtml/indigo 1.html.
38 BASF Indigo rein, BASF Aktiengesellschaft Ludwigsha-
8 P. Miederer in: K. Hunger (ed.), Industrial Dyes: Chem-
fen am Rhein 1907, p. 14.
istry, Properties, Applications. Wiley-VCH, Weinheim,
39 Badische Anilin- und Soda-Fabrik Z. Farben Ind. 8
Germany, 2003, p. 40 43, 204 214.
(1909) 121 127, 137 141.
9 H. Zollinger: Color Chemistry, 3rd. rev. ed. VHCH
40 Lunge-Berl: Chemisch-technische Untersuchungsmetho-
Verlag Helvetica Chimica Acta, Zurich, and Wiley-VCH,
den, 7th ed., Springer Verlag, Berlin 1924, pp. 1033
Weinheim, Germany, 2003, p. 259 268.
1059.
10 M. Seefelder: Indigo in Kultur, Wissenschaft und Technik,
41 Sicherheitsdatenblatt DyStar Indigo Vat 40% Lsg., DyS-
BASF Aktiengesellschaft, Ludwigshafen am Rhein 1982.
tar Textilfarben GmbH & Co., Leverkusen, 03.09.2002.
11 W. L uttke, M. Klessinger, Chem. Ber. 97 (1964) 2342
42 B. Wehdemeier-Pusch, A. Pusch, Das Ph anomen
2357.
Jeans, Universitat Bielefeld 1981.
12 M. Klessinger, W. Luttke, Tetrahedron 19 (1963)
43 Blaue Wunder fur individuelle Jeansmode, BASF-
Suppl. 2, no. 315 335.
Gruppe, 09.07.2003, http://www.pressi.com/de/Mittei-
13 M. Klessinger, W. Luttke, Chem. Ber. 99 (1966) 2136
lung/69301.html.
2145.
44 Process Data Sheet: Continuous Dyeing of Cotton Warps
14 E. Wille, W. Luttke, Angew. Chem. 83 (1971) 853;
with Indigo, BASF Aktiengesellschaft, Ludwigshafen am
Angew. Chem. Int. Ed. Engl. 10 (1971) 803.
Rhein 1976 (German 1983).
15 E. Wille, W. Luttke, Chem Ber. 106 (1973) 3240.
45 B. Kramrisch, Am. Dyest. Rep. (Nov. 1980) 34 38.
16 H. v. Eller, Bull. Soc. Chim. Fr. 1955, 1426 1444.
46 B. N. Ames, J. McCann, E. Yamasaki, Mutat. Res. 31
17 M. Klessinger, Dyes and Pigments 3, (1982) 235.
(1975) 347 364.
18 W. Schrott T. Bechtold, Textilveredlung 2003 (9/10),
47 J. M. Muzzall, W. L. Cook, Mutat. Res. 67 (1979) 1 8.
19 22.
48 W. F. Jongen, G. M. Alink, Fd. Chem. Toxic. 20 (1982)
19 T. Bechtold E. Burtscher O. Bobleter, Recent Res. Dev. in
917 920.
Electrochem. 1998, 245 264.
20 E. Knoevenagel, Ber. Dtsch. Chem. Ges. 37 (1904) 4080.
H. Bucherer, Ber. Dtsch. Chem. Ges. 39 (1906) 2800.
21 H. Bucherer, Ber. Dtsch. Chem. Ges. 39 (1906) 2800. Further Reading
22 BASF, GB 1 119 256, 1966 (E. Tolksdorf).
23 J. G. Kern, H. Stenerson, Chem. Eng. News 24 (1946) J. Balfour-Paul: Indigo, Archetype Publ., London 2006.
3164 3181. V. Prideaux: A Handbook of Indigo Dyeing, Search Press,
24 D. Murdock, B. D. Ensley, C. Serdar, M. Thalen, Bio- Tunbridge Wells 2007.
technology 1993 11, 381.