Wikipedia:WikiProject Chemicals/Chembox validation/VerifiedDataSandbox and Indigo dye: Difference between pages

{{short description|Chemical compound, food additive and dye}}

| Watchedfields = changed

| verifiedrevid = 477315345

| Name = Indigo

| ImageFile = Indian indigo dye lump.jpg

| ImageName = Piece of indigo plant dye from India, {{circa|{{convert|2+1/2|cm|0}}}} square.

| ImageAlt = Lump of Indian indigo dye

| ImageFile1 = Indigo skeletal.svg

| ImageSize1 = 220px

| ImageAlt1 = Skeletal formula of indigo dye

| ImageFile2 = Indigo dye 3D ball.png

| ImageSize2 = 220px

| ImageAlt2 = Ball-and-stick model of the indigo dye molecule

| PIN = [2(2')''E'']-[2,2'-Biindolylidene]-3,3'(1''H'',1'''H'')-dione

| OtherNames = 2,2'-Bis(2,3-dihydro-3-oxoindolyliden), Indigotin

| Section1 = {{Chembox Identifiers

| PubChem = 10215

| CASNo = 64784-13-0

| Section2 = {{Chembox Properties

| Formula = C₁₆H₁₀N₂O₂

| MolarMass = 262.27 g/mol

| Appearance = dark blue crystalline powder

| Density = 1.199 g/cm³

| Solubility = 990 µg/L (at 25 °C)

| MeltingPtC = 390 to 392

| BoilingPt = decomposes

| Section7 = {{Chembox Hazards

| ExternalSDS =

| GHSPictograms =

| GHSSignalWord =

| HPhrases = {{H-phrases}}

| PPhrases = {{P-phrases}}

| GHS_ref =<!-- none found in PubChem 10-12-2021 -->

| FlashPt =

| AutoignitionPt =

| Section8 = {{Chembox Related

| OtherCompounds = [[Indoxyl]]<br>[[Tyrian purple]]<br>[[Indican]]

'''Indigo dye''' is an [[organic compound]] with a distinctive [[indigo|blue color]]. Indigo is a [[natural dye]] extracted from the leaves of some plants of the [[Indigofera#Uses|''Indigofera'']] genus, in particular ''[[Indigofera tinctoria]]''. Dye-bearing ''Indigofera'' plants were commonly grown and used throughout the world, particularly in Asia, with the production of indigo dyestuff economically important due to the historical rarity of other blue dyestuffs.<ref name=Ullmann/>

Most indigo [[dye]] produced today is [[chemical synthesis|synthetic]], constituting around 80,000 tonnes each year, as of 2023.<ref>{{cite journal |last1=Linke |first1=Julia A. |last2=Rayat |first2=Andrea |last3=Ward |first3=John M. |date=2023 |title=Production of indigo by recombinant bacteria |journal=Bioresources and Bioprocessing |volume=10 |issue=1 |pages=20 |issn=2197-4365 |pmid=36936720 |doi=10.1186/s40643-023-00626-7 |doi-access=free |pmc=10011309 }}</ref> It is most commonly associated with the production of [[denim]] cloth and [[jeans|blue jeans]], where its properties allow for effects such as [[stone washing]] and [[stone washing#Acid-washed jeans|acid washing]] to be applied quickly, which is why clothing made with natural Indigo dye tends to be more expensive.

==Uses==

[[File:Indigo plant extract sample.jpg|thumb|140px|left|Indigo dye]]

The primary use for indigo is as a dye for cotton yarn, mainly used in the production of denim cloth suitable for blue jeans; on average, a pair of blue jeans requires {{convert|3|g}} to {{convert|12|g}} of dye. Smaller quantities are used in the dyeing of wool and silk.

[[Indigo carmine]], also known as indigo, is an indigo derivative which is also used as a colorant. About 20,000 tonnes are produced annually, again mainly for the production of blue jeans.<ref name=Ullmann>{{Ullmann|doi=10.1002/14356007.a14_149.pub2|title=Indigo and Indigo Colorants|year=2004|last1=Steingruber|first1=Elmar|isbn=3527306730}}</ref> It is also used as a food colorant, and is listed in the United States as [[FD&C]] Blue No.&nbsp;2.

==Sources==

===Natural sources===

{{see also|#Indigo derivatives}}

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 {{lang|ja-Latn|Ryukyu|italic=no}} Islands and Taiwan is ''[[Strobilanthes cusia]]''.

Until the introduction of ''Indigofera'' species from the south, ''[[Polygonum tinctorum]]'' (dyer's knotweed) was the most important blue dyestuff in East Asia; however, the crop produced less dyestuff than the average crop of indigo, and was quickly surpassed in favour of the more economical ''Indigofera tinctoria'' plant. In [[Central America|Central]] and South America, the species grown is ''[[Indigofera suffruticosa]]'', also known as ''anil'', and in India, an important species was ''[[Indigofera arrecta]]'', Natal indigo. In Europe, ''[[Isatis tinctoria]]'', commonly known as woad, was used for dyeing fabrics blue, containing the same dyeing compounds as indigo, also referred to as indigo.

Several plants contain indigo, which, when exposed to an oxidizing source such as atmospheric oxygen, reacts to produce indigo dye; however, the relatively low concentrations of indigo in these plants make them difficult to work with, with the color more easily tainted by other dye substances also present in these plants, typically leading to a greenish tinge.

The precursor to indigo is [[indican]], a colorless, water-soluble derivative of the amino acid [[tryptophan]], and ''Indigofera'' leaves contain as much as 0.2–0.8% of this compound. Pressing cut leaves into a vat and soaking hydrolyzes the indican, releasing β-{{sc|D}}-[[glucose]] and [[indoxyl]]. The indoxyl dimerizes in the mixture, and after 12–15 hours of [[fermentation]] yields the yellow, water soluble [[Leuco dye|leucoindigo]]. Subsequent exposure to air forms the blue, water-insoluble indigo dye.<ref>{{cite book |last=Schorlemmer |first=Carl |author-link=Carl Schorlemmer |title=A Manual of the Chemistry of the Carbon compounds; or, Organic Chemistry |url=https://archive.org/details/amanualchemistr02schogoog |location=London |year=1874}} Quoted in the [[Oxford English Dictionary]], second edition, 1989</ref><ref>{{cite book |last1=Freeman |first1=H. S. |title=Colorants for non-textile applications |last2=Peters |first2=A. T. |publisher=Elsevier |year=2000 |isbn=978-0-444-82888-0 |location=Amsterdam [Netherlands] New York |pages=382–455 |chapter=9 - Natural Dyes}}</ref> The dye precipitates from the fermented leaf solution upon oxidation, but may also be precipitated when mixed with a strong base<ref>{{cite web |url=https://www.coyuchi.com/the-naturalista/indigo_dyeing/ |title=Indigo Dyeing |website=Coyuchi Inc. |language=en |access-date=2019-05-24 |archive-date=2019-05-24 |archive-url=https://web.archive.org/web/20190524001631/https://www.coyuchi.com/the-naturalista/indigo_dyeing/ |url-status=dead}}</ref> such as [[sodium hydroxide|lye]]. The solids are filtered, pressed into cakes, dried, and powdered. The powder was then mixed with various other substances to produce different shades of blue and purple.

Natural sources of indigo also include mollusks: the ''[[Murex]]'' genus of sea snails produces a mixture of indigo and [[6,6'-Dibromoindigo|6,6'-dibromoindigo]] (red), which together produce a range of purple hues known as [[Tyrian purple]]. Light exposure during part of the dyeing process can convert the dibromoindigo into indigo, resulting in blue hues known as royal blue, hyacinth purple, or [[tekhelet]].

===Chemical synthesis===

{{Multiple image|direction=vertical|width=330

|image1=Indigo.Baeyer-Drewson.Synthesis.svg|caption1=Heumann's synthesis of indigo

|image2=Indigo Synthesis V.1.svg|caption2=Pfleger's synthesis of indigo}}

Given its economic importance, indigo has been prepared by many methods. The [[Baeyer–Drewsen 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 was highly useful for obtaining indigo and many of its derivatives on the laboratory scale, but proved impractical for industrial-scale synthesis. Johannes Pfleger<ref name="history.evonik.com"/> and {{ill|Karl Heumann|de}} eventually came up with industrial mass production synthesis from [[aniline]] by using [[mercury (element)|mercury]] as a catalyst. The method was discovered by an accident by Karl Heumann in Zurich which involved a broken thermometer.<ref name="ingenious.org.uk"/>

The first commercially practical route of producing indigo is credited to Pfleger in 1901. In this process, [[N-Phenylglycine|''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 {{convert|200|°C}} 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.<ref name=Ullmann/> The preparation of indigo dye is practised in college laboratory classes according to the original Baeyer-Drewsen route.<ref>{{cite journal |last1=McKee |first1=James R. |last2=Zanger |first2=Murray |year=1991 |title=A microscale synthesis of indigo: Vat dyeing |journal=Journal of Chemical Education |volume=68 |issue=10 |page=A242 |doi=10.1021/ed068pA242 |bibcode=1991JChEd..68..242M}}</ref>

==History==

[[File:Indigo-Historische Farbstoffsammlung.jpg|thumb|right|Indigo, historical dye collection of the [[Dresden University of Technology|Technical University of Dresden]], Germany]]

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===Indigo versus woad===

[[File:Meisje met de parel.jpg|thumb|[[Johannes Vermeer]] used natural ultramarine in his paintings, as in his ''[[Girl with a Pearl Earring]]''. The expense was probably borne by his wealthy patron [[Pieter van Ruijven]].<ref>{{cite web |title=Girl with a Pearl Earring |url=http://www.essentialvermeer.com/catalogue/girl_with_a_pearl_earring.html |publisher=essentialvermeer.com |url-status=live |archive-url=https://web.archive.org/web/20150630060601/http://www.essentialvermeer.com/catalogue/girl_with_a_pearl_earring.html |archive-date=2015-06-30}}</ref>]]

In Europe, [[Isatis tinctoria]], or woad, had been the main source of [[indigo dye]], and the most readily-available source; the plant was processed into a paste called pastel. This industry was threatened in the 15th century by the arrival from India of the same dye ([[indigo]]), obtained from a shrub widely grown in Asia, ''[[Indigofera tinctoria]]''. The plant produced indigo dye in greater and more colourfast quantities than woad, making its introduction a major source of competition for European-produced indigo dye.

In 1498, [[Vasco da Gama]] opened a trade route to import indigo from India to Europe. In India, the indigo leaves were soaked in water, fermented, pressed into cakes, dried into bricks, then carried to the ports London, Marseille, Genoa, and Bruges.<ref name=autogenerated3>Eva Heller, ''Psychologie de la couleur effets et symboliques'' p. 21</ref> Later, in the 17th century, the British, Spanish, and Dutch established indigo plantations in Jamaica, South Carolina, the Virgin Islands and South America, and began to import American indigo to Europe. Countries with large and prosperous pastel industries attempted to block the import and use of indigo; one government in Germany outlawed the use of indigo in 1577, describing it as a "pernicious, deceitful and corrosive substance, the Devil's dye."<ref>[https://www.gutenberg.org/files/13242/13242-8.txt ''Lippincott's Magazine of Popular Literature and Science'', Volume 17, No. 100, April 1876] {{webarchive|url=https://web.archive.org/web/20121106154802/http://www.gutenberg.org/files/13242/13242-8.txt |date=2012-11-06}}.</ref><ref>D G Schreber, ''Historische, physische und economische Beschreibung des Waidtes'', 1752, the appendix; Thorpe JF and Ingold CK, 1923, ''Synthetic colouring matters – vat colours'' (London: Longmans, Green), p. 23</ref> In France, [[Henry IV of France|Henry IV]], in an edict of 1609, forbade under pain of death the use of "the false and pernicious Indian drug".<ref>{{cite book |last=Foucaud |first=Édouard |editor-last=Frost |editor-first=John |title=The book of illustrious mechanics of Europe and America |publisher=D. Appleton |year=1846 |page=[https://archive.org/details/bookillustrious00foucgoog/page/n246 236] |url=https://archive.org/details/bookillustrious00foucgoog}}</ref> It was forbidden in England until 1611, when British traders established their own indigo industry in India and began to import it into Europe.<ref name=autogenerated4>Eva Heller, ''Psychologie de la couleur – effets et symboliques'' p. 28</ref>

The efforts to block indigo were in vain; the quality of indigo blue was too high and the price too low for pastel made from woad to compete. In 1737, both the French and German governments finally allowed the use of indigo. This ruined the dye industries in Toulouse and the other cities that produced pastel, but created a thriving new indigo commerce to seaports such as Bordeaux, Nantes and Marseille.<ref>F. Lauterbach, ''Der Kampf des Waides mit dem Indigo'', Leipzig, p. 25. Cited by Michel Pastoureau, Bleu – Histoire d'une couleur, pp.&nbsp;108–13.</ref>

Another war of the blues took place at the end of the 19th century, between indigo and [[Baeyer–Drewson indigo synthesis|synthetic indigo]], discovered in 1868 by the German chemist Johann Friedrich Wilhelm Adolf von Baeyer. The German chemical firm [[BASF]] put the new dye on the market in 1897, in direct competition with the British-run indigo industry in India, which produced most of the world's indigo. In 1897 Britain sold ten thousand tons of natural indigo on the world market, while BASF sold six hundred tons of synthetic indigo. The British industry took measures to ensure their economic viability with the new BASF dye, but it was unable to compete; the synthetic indigo was more pure, made a more lasting blue, and was not dependent upon good or bad harvests. In 1911, India sold only 660 tons of natural indigo, while BASF sold 22,000 tons of synthetic indigo. In 2002, more than 38,000 tons of synthetic indigo was produced, often for the production of blue jeans.<ref name=Ullmann>{{Ullmann|first=Elmar|last=Steingruber|title=Indigo and Indigo Colorants|date=2004|doi=10.1002/14356007.a14_149.pub2}}</ref>

<gallery mode="packed" heights="150px">

File:Isatis tinctoria02.JPG|''[[Isatis tinctoria]]'', or woad, was the main source of blue dye in Europe from ancient times until the arrival of indigo from Asia and America. It was processed into a paste called pastel.

File:Schreber woad mill 1752.JPG|A woad mill in [[Thuringia]], in Germany, in 1752. The woad industry was already on its way to extinction, unable to compete with indigo blue.

File:The Hunt of the Unicorn Tapestry 1.jpg|A Dutch tapestry from 1495 to 1505. The blue colour comes from [[woad]].

File:Indigofera tinctoria1.jpg|''[[Indigofera tinctoria]]'', a tropical shrub, is the main source of indigo dye. The chemical composition of indigo dye is the same as that of woad, but the colour is more intense.

File:Indigo-Historische Farbstoffsammlung.jpg|Cakes of indigo. The leaf has been soaked in water, fermented, mixed with lye or another base, then pressed into cakes and dried, ready for export.

</gallery>

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The oldest known fabric dyed indigo, dated to 6,000 years ago, was discovered in [[Huaca Prieta]], Peru.<ref>{{cite journal |vauthors=Splitstoser JC, Dillehay TD, Wouters J, Claro A |date=2016-09-14 |title=Early pre-Hispanic use of indigo blue in Peru |journal=[[Science Advances]] |volume=2 |issue=9 |pages=e1501623 |doi=10.1126/sciadv.1501623 |pmid=27652337 |pmc=5023320 |bibcode=2016SciA....2E1623S}}</ref> Many Asian countries, such as [[India]], China, Japan, and [[Southeast Asia]]n nations have used indigo as a dye (particularly for [[silk]]) for centuries. The dye was also known to ancient civilizations in [[Mesopotamia]], [[ancient Egypt|Egypt]], [[prehistoric Britain|Britain]], [[Mesoamerica]], [[Peru]], [[Iran]], and [[West Africa]]. Indigo was also cultivated in India, which was also the earliest major center for its production and processing.<ref name=k&c>Kriger & Connah, page 120</ref> The ''[[Indigofera tinctoria]]'' species was domesticated in India.<ref name=k&c/> Indigo, used as a dye, made its way to the [[ancient Greece|Greeks]] and the [[ancient Rome|Romans]], where it was valued as a luxury product.<ref name=k&c/>

[[File:Indigo cake.jpg|thumb|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 lazuli|lapis]]-colored wool (''uqnatu'') is produced by repeated immersion and airing of the cloth.<ref name="StClair"/> 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.

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'' ({{lang|grc|Ἰνδικόν}}, Indian).<ref name="StClair">{{cite book |title=The Secret Lives of Colour |last=St. Clair |first=Kassia |publisher=John Murray |year=2016 |isbn=9781473630819 |location=London |page=189 |oclc=936144129}}</ref> The Romans [[latin]]ized the term to ''indicum'', which passed into [[Venetian language|Italian dialect]] and eventually into English as the word indigo.

In [[Bengal Presidency|Bengal]] indigo cultivators revolted against exploitative working conditions created by European merchants and planters in what became known as the [[Indigo revolt]] in 1859. The Bengali play ''[[Nil Darpan]]'' by Indian playwright [[Dinabandhu Mitra]] was a fictionalized retelling of the revolt.

[[File:Ridpath's history of the world; being an account of the ethnic origin, primitive estate, early migrations, social conditions and present promise of the principal families of men (1897) (14597001160).jpg|thumb|Indigo factory at [[Allahabad]], [[India]], drawn by {{Interlanguage link|Émile Thérond|fr|3=Émile Thérond}}, 19th century]]

The demand for indigo in the 19th century is indicated by the fact that in 1897, {{convert|7000|sqkm|sqmi|abbr=on}} were dedicated to the cultivation of indican-producing plants, mainly in [[India]]. By comparison, the country of [[Luxembourg]] is {{convert|2,586|sqkm|sqmi|abbr=on}}.<ref name=Ullmann/>

In Europe, indigo remained a rare commodity throughout the Middle Ages. A chemically identical dye derived from the woad plant ''([[Isatis tinctoria]])'' was used instead. In the late 15th century, the [[Portugal|Portuguese]] explorer [[Vasco da Gama]] discovered a sea route to India. This led to the establishment of direct trade with India, the [[Maluku Islands|Spice Islands]], China, and Japan. Importers could now avoid the heavy duties imposed by [[Iran|Persia]]n, [[Levant]]ine, 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 Central and 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.<ref>Fowler, Walter (6 August 1991). ''The Formation of Complex Society in Southeastern Mesoamerica''. CRC Press.</ref> 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. In central Europe, indigo resist dyeing is a centuries old skill that has received UNESCO Intangible Cultural Heritage of Humanity recognition.<ref>{{cite web |last=Denisyuk |first=Yulia |title=Europe's secret dyeing formula |url=https://www.bbc.com/travel/article/20230420-blaudruck-europes-secret-dyeing-formula |access-date=2023-04-21 |website=bbc.com |language=en}}</ref>

[[Isaac Newton|Newton]] used "indigo" to describe one of the two new [[primary color]]s he added to the five he had originally named, in his revised account of the rainbow in ''Lectiones Opticae'' of 1675.<ref>Quoted in {{cite book |last=Hentschel |first=Klaus |title=Mapping the spectrum: techniques of visual representation in research and teaching |publisher=Oxford University Press |location=Oxford, England |year=2002 |page=28 |isbn=978-0-19-850953-0}}</ref>

Because of its high value as a trading commodity, indigo was often referred to as blue gold.<ref>{{cite web |title=History of Indigo & Indigo Dyeing |url=http://www.wildcolours.co.uk/html/indigo_history.html |website=wildcolours.co.uk |publisher=Wild Colours and natural Dyes |access-date=30 December 2015 |quote=Indigo was often referred to as Blue Gold as it was an ideal trading commodity; high value, compact and long lasting}}</ref>

[[File:Touaregs at the Festival au Desert near Timbuktu, Mali 2012.jpg|thumb|[[Tuareg people|Tuaregs]] wearing the indigo-dyed [[tagelmust]]]]

Throughout West Africa, Indigo was the foundation of centuries-old textile traditions. From the [[Tuareg people|Tuareg]] nomads of the [[Sahara]] to [[Cameroon]], clothes dyed with indigo signified wealth. Women dyed the cloth in most areas, with the [[Yoruba people|Yoruba]] of [[Nigeria]] and the [[Mandinka people|Mandinka]] of [[Mali]] particularly well known for their expertise. Among the [[Hausa people|Hausa]] male dyers, working at communal dye pits was the basis of the wealth of the ancient city of [[Kano (city)|Kano]], and they can still be seen plying their trade today at the same pits.<ref>Kriger, Colleen E. & Connah, Graham (2006). ''Cloth in West African History''. Rowman Altamira. {{ISBN|0-7591-0422-0}}.</ref> The Tuareg are sometimes called the "Blue People" because the [[indigo]] pigment in the cloth of their traditional robes and turbans stained their skin dark blue.<ref name="GearonEamonn">Gearon, Eamonn, (2011) ''The Sahara: A Cultural History'' Oxford University Press, p. 239</ref>

In Japan, indigo became especially important during the [[Edo period]]. This was due to a growing textiles industry,<ref name="Ikegami2005">{{cite book |author=Eiko Ikegami |title=Bonds of Civility: Aesthetic Networks and the Political Origins of Japanese Culture |url=https://books.google.com/books?id=KsN81J1s70kC&pg=PA284 |date=28 February 2005 |publisher=Cambridge University Press |isbn=978-0-521-60115-3 |page=284}}</ref> and because commoners had been banned from wearing silk,<ref name="Sagers2018">{{cite book |author=John H. Sagers |title=Confucian Capitalism: Shibusawa Eiichi, Business Ethics, and Economic Development in Meiji Japan |url=https://books.google.com/books?id=1-1lDwAAQBAJ&pg=PA27 |date=20 July 2018 |publisher=Springer |isbn=978-3-319-76372-9 |page=27}}</ref> leading to the increasing cultivation of cotton, and consequently indigo – one of the few substances that could dye it.<ref name="Wassenaar2011">{{cite book |author=Trudy M. Wassenaar |title=Bacteria: The Benign, the Bad, and the Beautiful |url=https://books.google.com/books?id=YGtR43I93iMC&pg=PA105 |date=3 November 2011 |publisher=John Wiley & Sons |isbn=978-1-118-14338-4 |page=105}}</ref>

In North America, indigo was introduced into colonial South Carolina by [[Eliza Lucas]], where it became the colony's second-most important cash crop (after rice).<ref>{{cite web |title=Eliza Lucas Pinckney: Indigo in the Atlantic World |author=Eliza Layne Martin |url=http://cwh.ucsc.edu/SocialBiog.Martin.pdf |access-date=2013-08-24 |url-status=dead |archive-url=https://web.archive.org/web/20100607061823/http://cwh.ucsc.edu/SocialBiog.Martin.pdf |archive-date=2010-06-07}}</ref> As a major export crop, indigo supported plantation slavery there.<ref>Andrea Feeser, ''Red, White, and Black Make Blue: Indigo in the Fabric of Colonial South Carolina Life'' (University of Georgia Press; 2013)</ref> In the May and June 1755 issues of ''[[The Gentleman's Magazine]],'' there appeared a detailed account of the cultivation of indigo, accompanied by drawings of necessary equipment and a prospective budget for starting such an operation, authored by South Carolina planter [[Charles Woodmason]]. It later appeared as a book.<ref>{{cite journal |last1=Jones |first1=Claude E. |year=1958 |title=Charles Woodmason as a Poet |journal=The South Carolina Historical Magazine |volume=59 |issue=4 |pages=189–194}}</ref><ref>David S. Shields. ''Oracles of Empire: Poetry, Politics, and Commerce in British America, 1690-1750''. (Chicago: University of Chicago Press, 2010), pp. 69, 249</ref> By 1775, indigo production in South Carolina exceeded 1,222,000 pounds.<ref>Walter B. Edgar, ed. ''The South Carolina Encyclopedia''. Columbia, SC: University of South Carolina Press, 2006), p. 9.</ref> 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 [[USS Reprisal (1776)|''Reprisal'']], the sale of which would help fund the war effort.<ref>{{cite book |last=Schoenbrun |first=David |date=1976 |title=Triumph in Paris: The Exploits of Benjamin Franklin |publisher=Harper & Row |location=New York |isbn=978-0-06-013854-7 |page=51}}</ref> In colonial North America, three commercially important species are found: the native ''I. caroliniana'', and the introduced ''I. tinctoria'' and ''I. suffruticosa''.<ref>{{cite journal |journal=Economic Botany |volume=33 |issue=2 |year=1979 |pages=128–134 |title=The indigo of commerce in colonial North America |author=David H. Rembert Jr. |doi=10.1007/BF02858281 |s2cid=2488865}}</ref>

===Synthetic development===

[[File:Indigoproduktion BASF 1890.JPG|thumb|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.<ref>Adolf Baeyer (1883) [https://gallica.bnf.fr/ark:/12148/bpt6k90697p/f512.image.langEN "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.</ref>) 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<ref name="history.evonik.com">{{cite web |url=https://history.evonik.com/sites/geschichte/en/personalities/pfleger-johannes/pages/default.aspx |title=Johannes Pfleger - Das Evonik Geschichtsportal - Die Geschichte von Evonik Industries |website=history.evonik.com |access-date=Jun 7, 2020 |archive-date=August 1, 2020 |archive-url=https://web.archive.org/web/20200801202949/https://history.evonik.com/sites/geschichte/en/personalities/pfleger-johannes/pages/default.aspx |url-status=dead}}</ref> and [[:de:Karl Heumann|Karl Heumann]] eventually came up with industrial mass production synthesis.<ref name="ingenious.org.uk">{{cite web |url=http://www.ingenious.org.uk/site.asp?s=RM&Param=1&SubParam=1&Content=1&ArticleID=%7BCBDF1082-9F5C-498F-A769-B33A7DA83B30%7D&ArticleID2=%7B3C4444FC-FC4D-4498-B0B4-8B8A47C5BA76%7D&MenuLinkID=%7BA54FA022-17E2-483C-B937-DEC8B8964C33%7D |title=The Synthesis of Indigo |access-date=2015-01-05 |archive-url=https://web.archive.org/web/20160304084155/http://www.ingenious.org.uk/site.asp?s=RM&Param=1&SubParam=1&Content=1&ArticleID=%7BCBDF1082-9F5C-498F-A769-B33A7DA83B30%7D&ArticleID2=%7B3C4444FC-FC4D-4498-B0B4-8B8A47C5BA76%7D&MenuLinkID=%7BA54FA022-17E2-483C-B937-DEC8B8964C33%7D |archive-date=2016-03-04 |url-status=dead}}</ref>

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.<ref>{{cite journal |title=Chemists go green to make better blue jeans |journal=Nature |year=2018 |volume=553 |issue=7687 |page=128 |doi=10.1038/d41586-018-00103-8 |bibcode=2018Natur.553..128. |doi-access=free}}</ref>

==Dyeing technology==

[[File:Leucoindigo structure.png|thumb|Indigo white (leuco-indigo)]]

[[File:IndigoDyedYarn.JPG|thumb|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 ([[redox|reduction]]). Reduction converts indigo into "white indigo" ([[leuco dye|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 presented 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:

{{Poem quote|

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 pre-industrial process for production of indigo white, used in Europe, was to dissolve the indigo in stale urine, which contains ammonia. A more convenient reductive agent is zinc. Another pre-industrial method, used in Japan, was to dissolve the indigo in a heated vat in which a culture of [[thermophile|thermophilic]], [[anaerobic digestion|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.

[[File:IndigoDyePotOnStove.JPG|thumb|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 drying|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.<ref>{{cite web |title=Directions for Instant Indigo |author=Judith McKenzie McCuin |url=http://www.paradisefibers.com/instantindigo.htm |access-date=2008-05-06 |url-status=dead |archive-url=https://web.archive.org/web/20041116195957/http://paradisefibers.com/instantindigo.htm |archive-date=2004-11-16}}</ref>

==Chemical properties==

[[File:Indigo3D.png|thumb|170px|Indigo, space-filling]]

Indigo dye is a dark blue crystalline powder that [[Sublimation (chemistry)|sublimes]] at {{convert|390|–|392|°C}}. It is insoluble in water, [[ethanol|alcohol]], or [[diethyl ether|ether]], but soluble in [[dimethyl sulfoxide|DMSO]], [[chloroform]], [[nitrobenzene]], and concentrated [[sulfuric acid]]. The [[chemical formula]] of indigo is [[carbon|C]]₁₆[[hydrogen|H]]₁₀[[nitrogen|N]]₂[[oxygen|O]]₂.

The molecule absorbs light in the orange part of the spectrum (''λ''_max=613&nbsp;nm).<ref>{{cite journal |last1=Wouten |first1=J. |last2=Verhecken |first2=A. |year=1991 |title=High-performance liquid chromatography of blue and purple indigoid natural dyes |journal=Journal of the Society of Dyers and Colourists |volume=107 |issue=7–8 |pages=266–269 |doi=10.1111/j.1478-4408.1991.tb01351.x}}</ref> The compound owes its deep color to the conjugation of the [[double bond]]s, 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 non-planar.

===Indigo derivatives===

[[File:Tyrian-Purple.svg|thumb|200px|Structure of Tyrian purple]]

[[File:Indigo carmine.svg|thumb|230px|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]] (red). 6-bromoindigo (purple) is a component as well.<ref name="indigo-bromo">{{cite journal |last1=Ramig |first1=Keith |last2=Lavinda |first2=Olga |last3=Szalda |first3=David J. |last4=Mironova |first4=Irina |last5=Karimi |first5=Sasan |last6=Pozzi |first6=Federica |last7=Shah |first7=Nilam |last8=Samson |first8=Jacopo |last9=Ajiki |first9=Hiroko |last10=Massa |first10=Lou |last11=Mantzouris |first11=Dimitrios |last12=Karapanagiotis |first12=Ioannis |last13=Cooksey |first13=Christopher |title=The nature of thermochromic effects in dyeings with indigo, 6-bromoindigo, and 6,6'-dibromoindigo, components of Tyrian purple |journal=Dyes and Pigments |date=June 2015 |volume=117 |pages=37–48 |doi=10.1016/j.dyepig.2015.01.025}}</ref> 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 group]]s such as the [[Tert-butyloxycarbonyl protecting group|tBOC group]], which suppresses intermolecular bonding.<ref>{{cite journal |last1=Głowacki |first1=Eric Daniel |last2=Voss |first2=Gundula |last3=Demirak |first3=Kadir |last4=Havlicek |first4=Marek |last5=Sünger |first5=Nevsal |last6=Okur |first6=Aysu Ceren |last7=Monkowius |first7=Uwe |last8=Gąsiorowski |first8=Jacek |last9=Leonata |first9=Lucia |last10=Sariciftcia |first10=Niyazi Serdar |display-authors=5 |date=2013 |title=A facile protection–deprotection route for obtaining indigo pigments as thin films and their applications in organic bulk heterojunctions |journal=Chemical Communications |volume=49 |issue=54 |pages=6063–6065 |doi=10.1039/C3CC42889C |pmid=23723050}}</ref> 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.<ref>{{cite journal |doi=10.1002/adma.201102619 |pmid=22109816 |title=Indigo - A Natural Pigment for High Performance Ambipolar Organic Field Effect Transistors and Circuits |year=2012 |last1=Irimia-Vladu |first1=Mihai |last2=Głowacki |first2=Eric D. |last3=Troshin |first3=Pavel A. |last4=Schwabegger |first4=Günther |last5=Leonat |first5=Lucia |last6=Susarova |first6=Diana K. |last7=Krystal |first7=Olga |last8=Ullah |first8=Mujeeb |last9=Kanbur |first9=Yasin |last10=Bodea |first10=Marius A. |last11=Razum |first11=Vladimir F. |last12=Sitter |first12=Helmut |last13=Bauer |first13=Siegfried |author14-link=Niyazi Serdar Sarıçiftçi |last14=Sarıçiftçi |first14=Niyazi Serdar |journal=Advanced Materials |volume=24 |issue=3 |pages=375–380 |bibcode=2012AdM....24..375I |s2cid=205241976}}</ref>

==Safety and the environment==

Indigo has a low oral toxicity, with an {{LD50}} of 5&nbsp;g/kg (0.5% of total mass) in mammals.<ref name=Ullmann/> In 2009, large spills of blue dyes had been reported downstream of a blue jeans manufacturer in [[Lesotho]].<ref name="st2009">{{cite web |title=Gap alarm |date=2009-08-09 |newspaper=[[The Sunday Times]] |url=http://www.timesonline.co.uk/tol/news/world/africa/article6788728.ece |access-date=2011-08-16}}</ref>

The compound has been found to act as an [[agonist]] of the [[aryl hydrocarbon receptor]].<ref name="pmid12540743">{{cite journal |vauthors=Denison MS, Nagy SR |title=Activation of the aryl hydrocarbon receptor by structurally diverse exogenous and endogenous chemicals |journal=Annu. Rev. Pharmacol. Toxicol. |volume=43 |pages=309–334 |year=2003 |pmid=12540743 |doi=10.1146/annurev.pharmtox.43.100901.135828}}</ref>

==See also==

* [[Champaran Satyagraha]]

* [[Haint blue]]

* [[Indigo revolt]]

* ''[[Red, White, and Black Make Blue]]''

==References==

{{Reflist}}

==Further reading==

*{{cite book |last=Balfour-Paul |first=Jenny |title=Indigo: Egyptian Mummies to Blue Jeans |publisher=British Museum Press |year=2016 |isbn=978-0-7141-1776-8 |location=London |pages=264 pages}}

*{{cite journal |last1=Ferreira |first1=E.S.B. |last2=Hulme A. N. |author2-link=Alison Hulme |last3=McNab H. |last4=Quye A. |year=2004 |title=The natural constituents of historical textile dyes |url=http://eprints.gla.ac.uk/109139/1/109148.pdf |journal=Chemical Society Reviews |volume=33 |issue=6 |pages=329–36 |doi=10.1039/b305697j |pmid=15280965}}

*Paul, Jenny Balfour. 2020. "Indigo and Blue: A Marriage Made in Heaven." ''Textile Museum Journal'' 47 (January): 160–85.

*{{cite journal |last=Sequin-Frey |first=Margareta |year=1981 |title=The chemistry of plant and animal dyes |url=http://jchemed.chem.wisc.edu/Journal/Issues/1981/Apr/jceSubscriber/JCE1981p0301.pdf |journal=Journal of Chemical Education |volume=58 |issue=4 |pages=301 |bibcode=1981JChEd..58..301S |doi=10.1021/ed058p301}}

==External links==

*[https://web.archive.org/web/20080509184103/http://www.plantcultures.org/plants/indigo_landing.html Plant Cultures: botany, history and uses of indigo]

*[https://www.accessdata.fda.gov/scripts/cdrh/cfdocs/cfcfr/CFRSearch.cfm?fr=74.102 FD&C regulation on indigotine]

{{Dyeing}}

{{Aryl hydrocarbon receptor modulators}}

{{Authority control}}

[[Category:Enones]]

[[Category:Indigo structure dyes]]

[[Category:Indolines]]

[[Category:Organic pigments]]

[[Category:Organic semiconductors]]