Indigo dye

Indigo dye is an organic compound with

a distinctive blue color (see indigo).
Historically, indigo was a natural dye
extracted from the leaves of certain
plants, and this process was important
economically because blue dyes were
once rare. A large percentage of indigo
dye produced today, several thousand
tonnes each year, is synthetic. It is the
blue often associated with denim cloth
and blue jeans.
 Indigo

Names

Other names
2,2'-Bis(2,3-dihydro-3- oxoindolyliden),
Indigotin

Identifiers
CAS Number 482-89-3  

3D model (JSmol) Interactive image

ChEMBL ChEMBL599552  

ChemSpider 4477009  
ECHA InfoCard 100.006.898
PubChem CID 5318432

RTECS number DU2988400

UNII 1G5BK41P4F  

InChI
InChI=1S/C16H10N2O2/c19-15-9-5-1-3-7-11(9)17-13(15)14-16(20)10-6-2-4-8-12(10)18-14/h1-8,17-18H/b14-13+ 
Key: COHYTHOBJLSHDF-BUHFOSPRSA-N 

InChI=1/C16H10N2O2/c19-15-9-5-1-3-7-11(9)17-13(15)14-16(20)10-6-2-4-8-12(10)18-14/h1-8,17-18H/b14-13+
Key: COHYTHOBJLSHDF-BUHFOSPRBQ

SMILES
c1ccc2c(c1)C(=O)/C(=C\3/C(=O)c4ccccc4N3)/N2

Properties
Chemical formula C16H10N2O2

Molar mass 262.27 g/mol

Appearance dark blue crystalline

powder

Density 1.199 g/cm3

Melting point 390 to 392 °C (734 to

738 °F; 663 to 665 K)

Boiling point decomposes

Solubility in water 990 µg/L (at 25 °C)

Hazards
EU classification (DSD) 207-586-9
(outdated)
R-phrases (outdated) R36/37/38

S-phrases (outdated) S26-S36

Related compounds
Related compounds Indoxyl
Tyrian purple
Indican
Except where otherwise noted, data are given
for materials in their standard state (at 25 °C
[77 °F], 100 kPa).

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Infobox references

Uses
Indigo dye

The primary use for indigo is as a dye for

cotton yarn, which is mainly for the
production of denim cloth for blue jeans.
On average, a pair of blue jean pants
requires 3–12 g of indigo. Small amounts
are used for dyeing wool and silk.

Indigo carmine, or indigo, is an indigo

derivative which is also used as a
colorant. About 20 thousand tons are
produced annually, again mainly for blue
jeans.[1] It is also used as a food colorant,
and is listed in the United States as FD&C
Blue No. 2.

Natural indigoes
Plant sources

A variety of plants have provided indigo

throughout history, but most natural
indigo was obtained from those in the
genus Indigofera, which are native to the
tropics, notably the Indian subcontinent.
The primary commercial indigo species
in Asia was true indigo (Indigofera
tinctoria, also known as I. sumatrana). A
common alternative used in the relatively
colder subtropical locations such as
Japan's Ryukyu Islands and Taiwan is
Strobilanthes cusia. Dyer's knotweed
(Polygonum tinctorum) was the most
important blue dye in East Asia until the
arrival of the Indigofera species from the
south, which yield more dye. In Central
and South America, the species grown is
anil. In Europe woad containing the same
dye was used for blue-dying. Several
plants contain indigo, but low
concentrations make them difficult to
work with and the color is then more
easily tainted by other dye substances,
typically leading to a greenish tinge.

Natural sources also include mollusks:

the Murex sea snails produce a mixture
of indigo and dibromoindigo (red) which
together produce a range of purple hues
known as Tyrian purple. Light exposure
during part of the dying process can
convert the dibromoindigo into indigo
resulting in blue hues known as royal
blue or hyacinth purple.

Extraction

The precursor to indigo is indican, a

colorless, water-soluble derivative of the
amino acid tryptophan. Indican readily
hydrolyzes to release β-D-glucose and
indoxyl. Oxidation by exposure to air
converts indoxyl to indigo. Indican was
obtained from the processing of the
plant's leaves, which contain as much as
0.2–0.8% of this compound. The leaves
were soaked in water and fermented to
convert the glycoside indican present in
the plant to the blue dye indigotin.[2] They
precipitate from the fermented leaf
solution was mixed with a strong base
such as lye, pressed into cakes, dried,
and powdered. The powder was then
mixed with various other substances to
produce different shades of blue and
purple.

History of natural indigo

Indigo, historical dye collection of the Technical
University of Dresden, Germany

Indigo is among the oldest dyes to be

used for textile dyeing and printing. The
oldest known fabric dyed indigo dating to
6,000 years ago was discovered in 2009
at Huaca Prieta, Peru.[3] Many Asian
countries, such as India, Japan, and
Southeast Asian nations have used
indigo as a dye (particularly silk dye) for
centuries. The dye was also known to
ancient civilizations in Mesopotamia,
Egypt, Britain, Mesoamerica, Peru, Iran,
and Africa. Indigo was also cultivated in
India, which was also the earliest major
center for its production and
processing.[4] The I. tinctoria species was
domesticated in India.[4] Indigo, used as
a dye, made its way to the Greeks and the
Romans, where it was valued as a luxury
product.[4]

India was a primary supplier of indigo to

Europe as early as the Greco-Roman era.
The association of India with indigo is
reflected in the Greek word for the dye,
indikón (Ἰνδικόν, Indian). The Romans
latinized the term to indicum, which
passed into Italian dialect and eventually
into English as the word indigo.
Cake of indigo, about 2 cm

In Mesopotamia, a neo-Babylonian
cuneiform tablet of the seventh century
BC gives a recipe for the dyeing of wool,
where lapis-colored wool (uqnatu) is
produced by repeated immersion and
airing of the cloth. Indigo was most
probably imported from India. The
Romans used indigo as a pigment for
painting and for medicinal and cosmetic
purposes. It was a luxury item imported
to the Mediterranean from India by Arab
merchants.

Indigo remained a rare commodity in

Europe throughout the Middle Ages. A
chemically identical dye derived from the
woad plant (Isatis tinctoria) was used
instead. In the late 15th century, the
Portuguese explorer Vasco da Gama
discovered a sea route to India. This led
to the establishment of direct trade with
India, the Spice Islands, China, and
Japan. Importers could now avoid the
heavy duties imposed by Persian,
Levantine, and Greek middlemen and the
lengthy and dangerous land routes which
had previously been used. Consequently,
the importation and use of indigo in
Europe rose significantly. Much European
indigo from Asia arrived through ports in
Portugal, the Netherlands, and England.
Many indigo plantations were
established by European powers in
tropical climates. Spain imported the dye
from its colonies in South America, and it
was a major crop in Haiti and Jamaica,
with much or all of the labor performed
by enslaved Africans and African
Americans. In the Spanish colonial era,
intensive production of indigo for the
world market in the region of modern El
Salvador entailed such unhealthy
conditions that the local indigenous
population, forced to labor in pestilential
conditions, was decimated.[5] Indigo
plantations also thrived in the Virgin
Islands. However, France and Germany
outlawed imported indigo in the 16th
century to protect the local woad dye
industry.

Man wearing an indigo-dyed tagelmust

Indigo was the foundation of centuries-

old textile traditions throughout West
Africa. From the Tuareg nomads of the
Sahara to Cameroon, clothes dyed with
indigo signified wealth. Women dyed the
cloth in most areas, with the Yoruba of
Nigeria and the Mandinka of Mali
particularly well known for their
expertise. Among the Hausa male dyers,
working at communal dye pits was the
basis of the wealth of the ancient city of
Kano, and they can still be seen plying
their trade today at the same pits.[6]

In Japan, indigo became especially

important in the Edo period, when it was
forbidden to use silk, so the Japanese
began to import and plant cotton. It was
difficult to dye the cotton fiber except
with indigo. Even today indigo is very
much appreciated as a color for the
summer Kimono Yukata, as this
traditional clothing recalls Nature and the
blue sea.

Newton used "indigo" to describe one of

the two new primary colors he added to
the five he had originally named, in his
revised account of the rainbow in
Lectiones Opticae of 1675.[7]

In North America indigo was introduced

into colonial South Carolina by Eliza
Lucas Pinckney, where it became the
colony's second-most important cash
crop (after rice).[8] As a major export
crop, indigo supported plantation slavery
there.[9] When Benjamin Franklin sailed to
France in November 1776 to enlist
France's support for the American
Revolutionary War, 35 barrels of indigo
were on board the Reprisal, the sale of
which would help fund the war effort.[10]
In colonial North America, three
commercially important species are
found: the native I. caroliniana, and the
introduced I. tinctoria and I.
suffruticosa.[11]

Because of its high value as a trading

commodity, indigo was often referred to
as blue gold.[12]

Peasants in Bengal revolted against

unfair treatment by the East India
Company traders/planters in what
became known as the Indigo revolt in
1859, during the British Raj of India. The
play Nil Darpan by Dinabandhu Mitra is
based on the slavery and forced
cultivation of indigo.

The demand for indigo in the 19th

century is indicated by the fact that in
1897, 7,000 km2 (2,700 sq mi) were
dedicated to the cultivation of indican-
producing plants, mainly in India. By
comparison, the country of Luxembourg
is 2,586 km2 (998 sq mi).[1]

Synthetic indigo
Production of Indigo dye in a BASF plant (1890)

In 1865 the German chemist Adolf von

Baeyer began working on the synthesis
of indigo. He described his first synthesis
of indigo in 1878 (from isatin) and a
second synthesis in 1880 (from 2-
nitrobenzaldehyde). (It was not until 1883
that Baeyer finally determined the
structure of indigo.[13]) The synthesis of
indigo remained impractical, so the
search for alternative starting materials
at Badische Anilin- und Soda-Fabrik
(BASF) and Hoechst continued.
Johannes Pfleger[14] and Karl Heumann
eventually came up with industrial mass
production synthesis.[15]
The synthesis of N-(2-
carboxyphenyl)glycine from the easy to
obtain aniline provided a new and
economically attractive route. BASF
developed a commercially feasible
manufacturing process that was in use
by 1897, at which time 19,000 tons of
indigo were being produced from plant
sources. This had dropped to 1,000 tons
by 1914 and continued to contract. By
2011 50,000 tons of synthetic indigo
were being produced worldwide.[16]

Developments in dyeing
technology
Indigo white (leuco-indigo)

Yarn dyed with indigo dye

Indigo white
Indigo is a challenging dye because it is
not soluble in water. To be dissolved, it
must undergo a chemical change
(reduction). Reduction converts indigo
into "white indigo" (leuco-indigo). When a
submerged fabric is removed from the
dyebath, the white indigo quickly
combines with oxygen in the air and
reverts to the insoluble, intensely colored
indigo. When it first became widely
available in Europe in the 16th century,
European dyers and printers struggled
with indigo because of this distinctive
property. It also required several
chemical manipulations, some involving
toxic materials, and had many
opportunities to injure workers. In the
19th century, English poet William
Wordsworth referred to the plight of
indigo dye workers of his hometown of
Cockermouth in his autobiographical
poem "The Prelude". Speaking of their
dire working conditions and the empathy
that he felt for them, he wrote,

Doubtless, I should have then made

common cause
With some who perished; haply perished
too
A poor mistaken and bewildered offering
Unknown to those bare souls of miller
blue

A preindustrial process for production of

indigo white, used in Europe, was to
dissolve the indigo in stale urine. A more
convenient reductive agent is zinc.
Another preindustrial method, used in
Japan, was to dissolve the indigo in a
heated vat in which a culture of
thermophilic, anaerobic bacteria was
maintained. Some species of such
bacteria generate hydrogen as a
metabolic product, which convert
insoluble indigo into soluble indigo white.
Cloth dyed in such a vat was decorated
with the techniques of shibori (tie-dye),
kasuri, katazome, and tsutsugaki.
Examples of clothing and banners dyed
with these techniques can be seen in the
works of Hokusai and other artists.
Direct printing

Two different methods for the direct

application of indigo were developed in
England in the 18th century and
remained in use well into the 19th
century. The first method, known as
'pencil blue' because it was most often
applied by pencil or brush, could be used
to achieve dark hues. Arsenic trisulfide
and a thickener were added to the indigo
vat. The arsenic compound delayed the
oxidation of the indigo long enough to
paint the dye onto fabrics.
Pot of freeze-dried indigo dye

The second method was known as 'China

blue' due to its resemblance to Chinese
blue-and-white porcelain. Instead of
using an indigo solution directly, the
process involved printing the insoluble
form of indigo onto the fabric. The indigo
was then reduced in a sequence of baths
of iron(II) sulfate, with air-oxidation
between each immersion. The China blue
process could make sharp designs, but it
could not produce the dark hues possible
with the pencil blue method.
Around 1880, the 'glucose process' was
developed. It finally enabled the direct
printing of indigo onto fabric and could
produce inexpensive dark indigo prints
unattainable with the China blue method.

Since 2004, freeze-dried indigo, or instant

indigo, has become available. In this
method, the indigo has already been
reduced, and then freeze-dried into a
crystal. The crystals are added to warm
water to create the dye pot. As in a
standard indigo dye pot, care has to be
taken to avoid mixing in oxygen. Freeze-
dried indigo is simple to use, and the
crystals can be stored indefinitely as long
as they are not exposed to moisture.[17]
Chemical properties

Indigo

Indigo is a dark blue crystalline powder

that sublimes at 390–392 °C (734–
738 °F). It is insoluble in water, alcohol, or
ether, but soluble in DMSO, chloroform,
nitrobenzene, and concentrated sulfuric
acid. The chemical formula of indigo is
C16H10N2O2.
The molecule absorbs light in the orange
part of the spectrum (λmax = 613 nm).[18]
The compound owes its deep color to the
conjugation of the double bonds, i.e. the
double bonds within the molecule are
adjacent and the molecule is planar. In
indigo white, the conjugation is
interrupted because the molecule is
nonplanar.

Chemical synthesis

Given its economic importance, indigo

has been prepared by many methods.
The Baeyer-Drewson indigo synthesis
dates back to 1882. It involves an aldol
condensation of o-nitrobenzaldehyde
with acetone, followed by cyclization and
oxidative dimerization to indigo. This
route is highly useful for obtaining indigo
and many of its derivatives on the
laboratory scale, but was impractical for
industrial-scale synthesis. Johannes
Pfleger[14] and Karl Heumann (de)
eventually came up with industrial mass
production synthesis.[15] The first
commercially practical route is credited
to Pfleger in 1901. In this process, N-
phenylglycine is treated with a molten
mixture of sodium hydroxide, potassium
hydroxide, and sodamide. This highly
sensitive melt produces indoxyl, which is
subsequently oxidized in air to form
indigo. Variations of this method are still
in use today. An alternative and also
viable route to indigo is credited to
Heumann in 1897. It involves heating N-
(2-carboxyphenyl)glycine to 200 °C
(392 °F) in an inert atmosphere with
sodium hydroxide. The process is easier
than the Pfleger method, but the
precursors are more expensive. Indoxyl-
2-carboxylic acid is generated. This
material readily decarboxylates to give
indoxyl, which oxidizes in air to form
indigo.[1] The preparation of indigo dye is
practiced in college laboratory classes
according to the original Baeyer-Drewsen
route.[19]
Heumann's original synthesis of indigo

Pfleger's synthesis of indigo

Indigo derivatives

Structure of Tyrian purple

Structure of indigo carmine.

The benzene rings in indigo can be

modified to give a variety of related
dyestuffs. Thioindigo, where the two NH
groups are replaced by S atoms, is deep
red. Tyrian purple is a dull purple dye that
is secreted by a common Mediterranean
snail. It was highly prized in antiquity. In
1909, its structure was shown to be 6,6'-
dibromoindigo. It has never been
produced on a commercial basis. The
related Ciba blue (5,7,5′,7′-
tetrabromoindigo) is, however, of
commercial value. Indigo and its
derivatives featuring intra- and
intermolecular hydrogen bonding have
very low solubility in organic solvents.
They can be made soluble using
transient protecting groups such as the
tBOC group, which suppresses
intermolecular bonding.[20] Heating of the
tBOC indigo results in efficient thermal
deprotection and regeneration of the
parent H-bonded pigment.

Treatment with sulfuric acid converts

indigo into a blue-green derivative called
indigo carmine (sulfonated indigo). It
became available in the mid-18th
century. It is used as a colorant for food,
pharmaceuticals, and cosmetics.

Indigo as an organic
semiconductor
Indigo and some of its derivatives are
known to be ambipolar organic
semiconductors when deposited as thin
films by vacuum evaporation.[21]

Safety and the environment

Indigo has a low oral toxicity, with an
LD50 of 5000 mg/kg in mammals.[1] In
2009, large spills of blue dyes had been
reported downstream of a blue jeans
manufacturer in Lesotho.[22]

The compound has been found to act as

an agonist of the aryl hydrocarbon
receptor.[23]
See also
Indigo revolt

References
1. Elmar Steingruber "Indigo and Indigo
Colorants" Ullmann's Encyclopedia of
Industrial Chemistry 2004, Wiley-VCH,
Weinheim. doi:
10.1002/14356007.a14_149.pub2
2. Schorlemmer, Carl (1874). A Manual of
the Chemistry of the Carbon compounds;
or, Organic Chemistry. London. Quoted in
the Oxford English Dictionary, second
edition, 1989
3. Splitstoser JC, Dillehay TD, Wouters J,
Claro A (2016-09-14). "Early pre-Hispanic
use of indigo blue in Peru" . Science
Advances. 2 (9).
Bibcode:2016SciA....2E1623S .
doi:10.1126/sciadv.1501623 . Retrieved
2016-09-15.
4. Kriger & Connah, page 120
5. Fowler, Walter (6 August 1991). The
Formation of Complex Society in
Southeastern Mesoamerica. CRC Press.
6. Kriger, Colleen E. & Connah, Graham
(2006). Cloth in West African History.
Rowman Altamira. ISBN 0-7591-0422-0.
7. Quoted in Hentschel, Klaus (2002).
Mapping the spectrum: techniques of
visual representation in research and
teaching. Oxford, England: Oxford
University Press. p. 28. ISBN 978-0-19-
850953-0.
8. Eliza Layne Martin. "Eliza Lucas
Pinckney:Indigo in the Atlantic World"
(PDF). Retrieved 2013-08-24.

9. Andrea Feeser, Red, White, and Black

Make Blue: Indigo in the Fabric of Colonial
South Carolina Life (University of Georgia
Press; 2013)
10. Schoenbrun, David (1976). Triumph in
Paris: The Exploits of Benjamin Franklin.
New York: Harper & Row. p. 51. ISBN 0-06-
013854-8.
11. David H. Rembert, Jr. (1979). "The
indigo of commerce in colonial North
America". Economic Botany. 33 (2): 128–
134. doi:10.1007/BF02858281 .
12. "History of Indigo & Indigo Dyeing" .
wildcolours.co.uk. Wild Colours and
natural Dyes. Retrieved 30 December
2015. "Indigo was often referred to as
Blue Gold as it was an ideal trading
commodity; high value, compact and long
lasting"
13. Adolf Baeyer (1883) "Ueber die
Verbindungen der Indigogruppe" [On the
compounds of the indigo group], Berichte
der Deutschen chemischen Gesellschaft
zu Berlin, 16 : 2188-2204 ; see especially
p. 2204.
14.
http://history.evonik.com/sites/geschicht
e/en/personalities/pfleger-
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15. http://www.ingenious.org.uk/site.asp?
s=RM&Param=1&SubParam=1&Content=
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8B8A47C5BA76%7D&MenuLinkID=%7BA5
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DEC8B8964C33%7D
16. "Chemists go green to make better
blue jeans" . Nature. Nature. Retrieved
19 February 2018.
17. Judith McKenzie McCuin. "Directions
for Instant Indigo" . Archived from the
original on 2004-11-16. Retrieved
2008-05-06.
18. Wouten, J.; Verhecken, A. (1991).
"High-performance liquid chromatography
of blue and purple indigoid natural dyes".
Journal of the Society of Dyers and
Colourists. 107: 266–269.
19. McKee, James R.; Zanger, Murray
(1991). "A microscale synthesis of indigo:
Vat dyeing". Journal of Chemical
Education. 68: A242.
Bibcode:1991JChEd..68..242M .
doi:10.1021/ed068pA242 .
20. Głowacki, Eric Daniel; Voss, Gundula;
Demirak, Kadir; Havlicek, Marek; Sünger,
Nevsal; et al. (2013). "A facile protection–
deprotection route for obtaining indigo
pigments as thin films and their
applications in organic bulk
heterojunctions". Chemical
Communications (54): 6063–6065.
doi:10.1039/C3CC42889C .
21. Irimia-Vladu, Mihai; Głowacki, Eric D.;
Troshin, Pavel A.; Schwabegger, Günther;
Leonat, Lucia; Susarova, Diana K.; Krystal,
Olga; Ullah, Mujeeb; Kanbur, Yasin; Bodea,
Marius A.; Razumov, Vladimir F.; Sitter,
Helmut; Bauer, Siegfried; Sarıçiftçi, Niyazi
Serdar (2012). "Indigo - A Natural Pigment
for High Performance Ambipolar Organic
Field Effect Transistors and Circuits".
Advanced Materials. 24 (3): 375.
doi:10.1002/adma.201102619 .
22. "Gap alarm" . The Sunday Times.
2009-08-09. Retrieved 2011-08-16.
23. Denison MS, Nagy SR (2003).
"Activation of the aryl hydrocarbon
receptor by structurally diverse
exogenous and endogenous chemicals".
Annu. Rev. Pharmacol. Toxicol. 43: 309–
34.
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Further reading
Balfour-Paul, Jenny (2016). Indigo:
Egyptian Mummies to Blue Jeans.
London: British Museum Press.
pp. 264 pages. ISBN 0-7141-1776-5.
Ferreira, E.S.B.; Hulme A. N.; McNab H.;
Quye A. (2004). "The natural
constituents of historical textile dyes".
 Chemical Society Reviews. 33 (6): 329–
36. doi:10.1039/b305697j .
PMID 15280965 .
Sequin-Frey, Margareta (1981). "The
chemistry of plant and animal dyes"
(PDF). Journal of Chemical Education.
58 (4): 301.
Bibcode:1981JChEd..58..301S .
doi:10.1021/ed058p301 .

External links
Plant Cultures: botany, history and
uses of indigo
FD&C regulation on indigotine
Textile Dyeing in Curlie.org
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