Indigo

 Introduction
 Indigo (Indigofera tinctoria) is one of the most oldest blue dyes used by man.
 The dye takes its name from the Greek word Indikos, meaning ‘of India’ .
 The preparation of Indigo has been entirely superceded by Synthetic processes.
 Newton used "Indigo" to describe one of the two new primary colours he added to the five he had originally named, in his revised account of the
rainbow in Lectiones Opticae of 1675.1
 ln colonial North America, three commercially important species are found: the native I. caroliniana, and the introduced I. tinctoria and I.
suffruticosa.

 Structure

Cis form Trans form

X-ray analysis shows that ordinary Indigo is the more stable transform.
 Preparation
Natural
i. Cut plant is tied and placed in the vats made of brick lined with cement.
ii. Plants are then covered with clear fresh water and left to steep until fermentation ends, usually 10 to 15 hours.
iii. Liquor that is yellow in colour and is a result of fermentation is moved into beaters where it is treated with wooden oars or by machinery.
iv. Colour of the mass changes into green, then blue and then into the Indigo.
v. Mass settles to the bottom of the vat and is then extracted.
vi. Indigo mass is then boiled, filtered and pressed to be dry as much as possible.
vii. Final product is a dry mass cut into cubes.

Synthetic

1) Heumann’s Synthesis

2) Pfleger’s Synthesis

3) Isolation from Indigo Plant.

4) Baeyer’s Method
 5) Commercial synthesis

 History
 Indigo was earlier extracted from Indigo leaves.
 But since its cultivation led to soil pollution, thus
 In 1865 the German chemist Adolf von Baeyer began working on the Synthesis of Indigo.
 He described his first synthesis from Isatin 1878.
 Again in 1880, he described his Second Synthesis from ortho-nitrobenzaldehyde.
 This synthesis was not accepted until Bayer in1883, finally determined the structure of Indigo(Proof).
 But again this method was not applicable for Commercial Production.
 This method is now used in Colleges to prepare Indigo.
 Thus Search for Alternative starting materials at BASF(Badische Anilin-und Soda-Fabrik) and Hoechst continued.
 Johannes Pfleger in 1901,proposed his method from N-phenylglycine.
 Also Heumann in 1997described a viable method of synthesis using N-(2-carboxyphenyl)glycine.
 This method is easier than Pfleger’s but the precursors are more expensive.
 Because of its high value as a trading commodity, Indigo was often referred to as Blue Gold.

 Properties
Physical
 State Crystalline powder
 Colour Dark blue with a copper lustre
 Molar mass 262.27 g/mol
 Density 1.199 g/cm3
 Solubility Insoluble in Water(Bahl and Bahl), Ether and Alcohol.
It can be made soluble, using transient protecting groups i.e. tBOC etc., which suppresses intermolecular bonding.
Solubility in water 990 g/L (at 25℃ ) {Wikipedia}
Soluble in DMSO, chloroform, nitrobenzene, sulfuric acid ,etc.
 Melting pt.390℃
 Boiling pt. - (decomposes)

Chemical


 Uses
 Indigo is used a Blue dark dye, which is used in Jeans to make Denims.
 When Indigo treated with conc. H2SO4 ,a dye INDIGO CARMINE, which is blue green derivative, is prepared.
It is used as colorant in food, pharmaceutical and cosmetic .
 If the -NH group is replaced by -S ;THIOINDIGO, which is Deep red in colour, is used as a dye.
 Indigo absorbs light in Orange part of the Spectrum( max = 613nm).
 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.
 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 Process is 5,7,5’,7’-tetrabromoindigo
of Commercial Use.
 Direct printing :Two different methods for the direct application of indigo were developed in England in the 1 8th century and remained in use
well into the 19th century. Different Methods 1.Pencil Blue 2.China Blue 3.Glucose Process.

 Safety and the environment

 Indigo has a low oral toxicity, with an LD50 of 5000 mg/kg in mammals. ln 2009, large spills of blue dyes had been reported downstream of
a blue jeans manufacturer in Lesotho.
 The compound has been found to act as an agonist of the aryl hydrocarbon receptor.
 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 Mitrc:n is based on the slavery and forced cultivation of Indigo.

 Structures

 References
1. Elmar Steingruber "Indigo and Indigo CoIorants' Ullmanns Encyclopedia of Industrial Chemistry 2004, Wiley-VCH, Weinheim. tJpj:
10.100274356007.a14 749.pub2 2 $chorIemmer Carl (1874). A Manual of the Chemistry of the Carbon compounds; or, Organic Chemistry.
London. Quoted in the QrJmd! English Dictionary, second edition. 7989 3. Splitstoser JC, Dillehay TD, Wouters J, Clara A (2016-09-14).
'Earlypre-Hisjwnic use Qf in.digo blue in Peru' . Science Arjvances.
2. Bibcode:2016SciA 2E1623S . doi: 7 0.7 726sciadv.750762
3. Kriger Connah,page 120 5 FowleC Walter (6 August 1991).
4. FowleC Walter (6 August 1991). The Formation of Complex Society in South-eastern Mesoamerica. CRC Press.
5. KrigeC Colleen E. Connah, Graham (2006). Cloth in West African History. Rowman Altamira. ISBN 0-7597-0422-0.
6. Quoted in Hentsche!, Klaus (2002). Mapping the spectrum: techniques of visual representation in research and teaching. Oxford, England: Oxford
University Press. p. 28. ISBN 978-0-79-850953-0.
7. Eliza Layne Martin. "Eliza Lucas Pinckney ‘Indigo in the Atlantic World" (PDF). Retrieved 207 3-08-24.
8. Andrea FeeseC Red, White, and Black Make Blue: Indigo in the Fabric of Colonial South Carolina Life (University of Georgia Press; 20 73)
9. Schoenbrun, David ('1976). Triumph in Paris: The Exploits of Benjamin Franklin. New York: Harper Row. p. 57. IS'BN 0-06- 0 73854-8,
10. "History of Indiqo Indigo Dyeinq" wildcolours.co.uk. Wild Colours and natura! Dyes. Retrieved 30 December 2015. "Indigo was often referred
to as Blue Gold as it was an ideal trading commodity; high va Iue, compact and long lasting"
11. Adolf Baeyer (7883) "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.
12. http:// history. evonik.comsitesgeschich tgZ ersonalitiespfleger- ohannespagesdefault.aspx
13. http:www.ingenious.org uksite.asp" sRMParam7Sub Param7Content -I ArticIeID7BCBDF1082-9F5C-498F-A 769- B33A7DA83B30
7DArticfeID2 7B3C444 4FC-FC4D-4498-BOB4- 8B8A47C5BA767DMenuLinkID7BA54 FA022-17E2-483C-B937-
14. "Chemists go green to make better blue ieans" . Nature. Nature Retrieved 7 9 February 20 7 8.
15. Judith McKenzie McCuin. "DirectiQns for Instant Indigo" . Archived from the original on 2004-7 7-7 6. Retrieved 2008-05-06.
16. A textbook of Organic Chemistry-By Arun Bahl,and B S Bahl