1,2,4-Trihydroxyanthraquinone

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1,2,4-Trihydroxyanthraquinone
1,2,4-trihydroxyanthracene-9,10-dione 200.svg
Purpurin-3D-balls.png
Names
Preferred IUPAC name
1,2,4-Trihydroxyanthracene-9,10-dione
Other names
Purpurin, Purpurine, Hydroxylizaric acid
Identifiers
3D model (JSmol)
ChEBI
ChEMBL
ChemSpider
ECHA InfoCard 100.001.237 OOjs UI icon edit-ltr-progressive.svg
KEGG
PubChem CID
UNII
  • InChI=1S/C14H8O5/c15-8-5-9(16)14(19)11-10(8)12(17)6-3-1-2-4-7(6)13(11)18/h1-5,15-16,19H Yes check.svgY
    Key: BBNQQADTFFCFGB-UHFFFAOYSA-N Yes check.svgY
  • InChI=1/C14H8O5/c15-8-5-9(16)14(19)11-10(8)12(17)6-3-1-2-4-7(6)13(11)18/h1-5,15-16,19H
    Key: BBNQQADTFFCFGB-UHFFFAOYAW
  • C1=CC=C2C(=C1)C(=O)C3=C(C2=O)C(=C(C=C3O)O)O
  • O=C2c1ccccc1C(=O)c3c2c(O)cc(O)c3O
Properties
C14H8O5
Molar mass 256.21 g/mol
Melting point 259 °C (498 °F; 532 K) [1]
Except where otherwise noted, data are given for materials in their standard state (at 25 °C [77 °F], 100 kPa).
X mark.svgN  verify  (what is  Yes check.svgYX mark.svgN ?)

1,2,4-Trihydroxyanthraquinone, commonly called purpurin, is an anthraquinone. It is a naturally occurring red/yellow dye. It is formally derived from 9,10-anthraquinone by replacement of three hydrogen atoms by hydroxyl (OH) groups.

Contents

Purpurin is also called verantin, smoke Brown G, hydroxylizaric acid, and C.I. 58205. It is a minor component of the classical lake pigment "madder lake" or Rose Madder.

History

Madder root has been used for dying cloth at least since 1500 BC. [2] Purpurin and alizarin were isolated from the root by Pierre Robiquet and Colin, two French chemists, in 1826. They were identified as anthracene derivatives by Gräbe and Liebermann in 1868. They also synthesized alizarin from bromoanthraquinone, which, together with the conversion of alizarin into purpurin published previously by M. F. De Lalande, provided the first synthetic route to purpurin. [3] The positions of the OH groups were determined by Bayer and Caro in 1874–1875. [4]

Natural occurrence

Purpurin occurs in the roots of the madder plant ( Rubia tinctorum ), together with alizarin (1,2-dihydroxyanthraquinone). The root actually contains colorless glycosides of the dyes.

Properties

Purpurin is a crystalline solid, that forms orange needles melting at 259 °C (498 °F), [5] but becomes red when dissolved in ethanol, and yellow when dissolved with alkalis in boiling water. It is insoluble in hexane but soluble in chloroform, and can be obtained from chloroform as reddish needles. [6] Unlike alizarin, purpurin is dissolved by boiling in a solution of aluminum sulfate, from which it can be precipitated by acid. This procedure can be used to separate the two dyes. [7]

Like many dihydroxy- and trihydroxyanthraquinones, pupurin has a purgative action, although only 1/20 as effective as 1,2,7-trihydroxyanthraquinone (anthrapurpurin). [8]

Uses

Purpurin is a fast dye for cotton printing and forms complexes with various metal ions. However it fades faster than alizarin on exposure to sunlight. [2]

A study published in Nature journal Scientific Reports suggests that the purpurin could replace cobalt in lithium-ion batteries. [9] Eliminating cobalt would mean eliminating a hazardous material, allow batteries to be produced at room temperature, and lower the cost of recycling batteries. Extracting purpurin from farmed madder is a simple task; alternately, the chemical could be synthesized in a lab. [10]

See also

Related Research Articles

<i>Rubia</i> Genus of flowering plants in the family Rubiaceae

Rubia is a genus of flowering plants in the family Rubiaceae. It contains around 80 species of perennial scrambling or climbing herbs and subshrubs native to the Old World. The genus and its best-known species are commonly known as madder, e.g. Rubia tinctorum, Rubia peregrina, and Rubia cordifolia.

Alizarin Chemical compound and histologic stain

Alizarin is an organic compound with formula C
14
H
8
O
4
that has been used throughout history as a prominent red dye, principally for dyeing textile fabrics. Historically it was derived from the roots of plants of the madder genus. In 1869, it became the first natural dye to be produced synthetically.

Carl Gräbe

Carl Gräbe was a German industrial and academic chemist from Frankfurt am Main who held professorships in his field at Leipzig, Königsberg, and Geneva. He is known for the first synthesis of the economically important dye, alizarin, with Liebermann, and for contributing to the fundamental nomenclature of organic chemistry.

The quinones are a class of organic compounds that are formally "derived from aromatic compounds [such as benzene or naphthalene] by conversion of an even number of –CH= groups into –C(=O)– groups with any necessary rearrangement of double bonds, resulting in "a fully conjugated cyclic dione structure". The archetypical member of the class is 1,4-benzoquinone or cyclohexadienedione, often called simply "quinone". Other important examples are 1,2-benzoquinone (ortho-quinone), 1,4-naphthoquinone and 9,10-anthraquinone.

A lake pigment is a pigment made by precipitating a dye with an inert binder, or "mordant", usually a metallic salt. Unlike vermilion, ultramarine, and other pigments made from ground minerals, lake pigments are organic. Manufacturers and suppliers to artists and industry frequently omit the lake designation in the name. Many lake pigments are fugitive because the dyes involved are not lightfast. Red lakes were particularly important in Renaissance and Baroque paintings; they were often used as translucent glazes to portray the colors of rich fabrics and draperies.

A glucoside is a glycoside that is derived from glucose. Glucosides are common in plants, but rare in animals. Glucose is produced when a glucoside is hydrolysed by purely chemical means, or decomposed by fermentation or enzymes.

Henry Edward Schunck, also known as Edward von Schunck, was a British chemist who did much work with dyes.

Rose madder Red paint made from the madder plant

Rose madder is a red paint made from the pigment madder lake, a traditional lake pigment extracted from the common madder plant Rubia tinctorum.

Pierre Jean Robiquet French chemist

Pierre Jean Robiquet was a French chemist. He laid founding work in identifying amino acids, the fundamental building blocks of proteins. He did this through recognizing the first of them, asparagine, in 1806, in the industry's adoption of industrial dyes, with the identification of alizarin in 1826, and in the emergence of modern medications, through the identification of codeine in 1832, a opiate alkaloid substance of widespread use with analgesic and antidiarrheal properties.

<i>Rubia cordifolia</i> Species of flowering plant

Rubia cordifolia, often known as common madder or Indian madder, is a species of flowering plant in the coffee family, Rubiaceae. It has been cultivated for a red pigment derived from roots.

Carl Theodore Liebermann

Carl Theodore Liebermann was a German chemist and student of Adolf von Baeyer.

A trihydroxyanthraquinone or trihydroxyanthracenedione is any of several isomeric organic compounds with formula C
14
H
8
O
5
, formally derived from anthraquinone by replacing three hydrogen atoms by hydroxyl groups. They include several historically important dyes. The isomers may differ in the parent anthraquinone isomer and/or of the three hydroxyl groups.

1,3-Dihydroxyanthraquinone Chemical compound

1,3-Dihydroxyanthraquinone, also called purpuroxanthin or xanthopurpurin, is an organic compound with formula C
14
H
8
O
4
that occurs in the plant Rubia cordifolia. It is one of ten dihydroxyanthraquinone isomers. Its molecular structure can be viewed as being derived from anthraquinone by replacement of two hydrogen atoms (H) by hydroxyl groups (-OH).

1,4-Dihydroxyanthraquinone Chemical compound

1,4-Dihydroxyanthraquinone, also called quinizarin or Solvent Orange 86, is an organic compound derived from anthroquinone. Quinizarin is an orange or red-brown crystalline powder. It is formally derived from anthraquinone by replacement of two hydrogen atoms by hydroxyl (OH) groups. It is one of ten dihydroxyanthraquinone isomers and occurs in small amounts in the root of the madder plant, Rubia tinctorum.

<i>Rubia tinctorum</i> Species of flowering plant (rose madder)

Rubia tinctorum, the rose madder or common madder or dyer's madder, is a herbaceous perennial plant species belonging to the family Rubiaceae. The plant's roots yield a red dye that was widely used for thousands of years for dyeing cloth.

Anthraquinone dyes

Anthraquinone dyes are an abundant group of dyes comprising a anthraquinone unit as the shared structural element. Anthraquinone itself is colourless, but red to blue dyes are obtained by introducing electron donor groups such as hydroxy or amino groups in the 1-, 4-, 5- or 8-position. Anthraquinone dyestuffs are structurally related to indigo dyestuffs and are classified together with these in the group of carbonyl dyes.

Glossary of dyeing terms Wikipedia glossary

Dyeing is the craft of imparting colors to textiles in loose fiber, yarn, cloth or garment form by treatment with a dye. Archaeologists have found evidence of textile dyeing with natural dyes dating back to the Neolithic period. In China, dyeing with plants, barks and insects has been traced back more than 5,000 years. Natural insect dyes such as Tyrian purple and kermes and plant-based dyes such as woad, indigo and madder were important elements of the economies of Asia and Europe until the discovery of man-made synthetic dyes in the mid-19th century. Synthetic dyes quickly superseded natural dyes for the large-scale commercial textile production enabled by the industrial revolution, but natural dyes remained in use by traditional cultures around the world.

Alizarin Red S Chemical compound and histologic dye

Alizarin Red S is a water-soluble sodium salt of Alizarin sulfonic acid with a chemical formula of C
14
H
7
NaO
7
S
. Alizarin Red S was discovered by Graebe and Libermann in 1871. In the field of histology alizarin Red S is used to stain calcium deposits in tissues, and in geology to stain and differentiate carbonate minerals.

Synthetic colorant


A colorant is any substance that changes the spectral transmittance or reflectance of a material. Synthetic colorants are those created in a laboratory or industrial setting. The production and improvement of colorants was a driver of the early synthetic chemical industry, in fact many of today's largest chemical producers started as dye-works in the late 19th or early 20th centuries, including Bayer AG(1863). Synthetics are extremely attractive for industrial and aesthetic purposes as they have they often achieve higher intensity and color fastness than comparable natural pigments and dyes used since ancient times. Market viable large scale production of dyes occurred nearly simultaneously in the early major producing countries Britain (1857), France (1858), Germany (1858), and Switzerland (1859), and expansion of associated chemical industries followed. The mid-nineteenth century through WWII saw an incredible expansion of the variety and scale of manufacture of synthetic colorants. Synthetic colorants quickly became ubiquitous in everyday life, from clothing to food. This stems from the invention of industrial research and development laboratories in the 1870s, and the new awareness of empirical chemical formulas as targets for synthesis by academic chemists. The dye industry became one of the first instances where directed scientific research lead to new products, and the first where this occurred regularly.

This article explains the history of the color red.

References

  1. CRC Handbook of Chemistry & Physics, 90th Ed.
  2. 1 2 Madder Root Archived 2011-07-14 at the Wayback Machine catalog entry at Natural Pigments website. Accessed on 2010-01-22.
  3. Chemical news and journal of industrial science, Volume 30, Page 207
  4. Wahl, Andre; Atack, F. W (1919) The Manufacture Of Organic Dyestuffs. G. Bell And Sons, Limited. Online version accessed on 2010-01-22.
  5. CRC Handbook of Chemistry & Physics, 90th Ed.
  6. Vankar, Padma S.; Shanker, Rakhi; Mahanta, Debajit; Tiwari, S.C. (2008). "Ecofriendly sonicator dyeing of cotton with Rubia cordifolia Linn. using biomordant". Dyes and Pigments. 76 (1): 207–212. doi:10.1016/j.dyepig.2006.08.023.
  7. Irving Wetherbee Fay (1919) The chemistry of the coal-tar dyes. Van Nostrand Online version accessed on 2010-01-22.
  8. Hugh Alister McGuigan (1921), An introduction to chemical pharmacology; pharmacodynamics in relation to chemistry. P. Blakiston's son, Philadelphia. Online version at archive.org, accessed on 2010-01-30.
  9. Reddy, Arava Leela Mohana; Nagarajan, Subbiah; Chumyim, Porramate; Gowda, Sanketh R; Pradhan, Padmanava; Jadhav, Swapnil R; Dubey, Madan; John, George; Ajayan, Pulickel M; Ajayan, Pulickel M (2012). "Lithium storage mechanisms in purpurin based organic lithium ion battery electrodes". Scientific Reports. 2: 960. Bibcode:2012NatSR...2E.960R. doi:10.1038/srep00960. PMC   3518813 . PMID   23233879.
  10. Richard Chirgwin (12 December 2012). "Dying to make greener batteries". The Register. Retrieved 12 December 2012.