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Names | |
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Preferred IUPAC name 1,2-Dihydroxyanthracene-9,10-dione | |
Other names 1,2-Dihydroxy-9,10-anthracenedione [1] 1,2-Dihydroxyanthraquinone Turkey red Mordant red 11 Alizarin B Alizarin red | |
Identifiers | |
3D model (JSmol) | |
3DMet | |
1914037 | |
ChEBI | |
ChEMBL | |
ChemSpider | |
ECHA InfoCard | 100.000.711 |
34541 | |
KEGG | |
PubChem CID | |
UNII | |
CompTox Dashboard (EPA) | |
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Properties | |
C14H8O4 | |
Molar mass | 240.214 g·mol−1 |
Appearance | orange-red crystals or powder |
Density | 1.540 g/cm3 |
Melting point | 289.5 °C (553.1 °F; 562.6 K) [1] |
Boiling point | 430 °C (806 °F; 703 K) |
slightly to sparingly soluble | |
Acidity (pKa) | 6.94 |
Hazards | |
GHS labelling: | |
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Warning | |
H302, H315, H319 | |
P264, P270, P280, P301+P312, P302+P352, P305+P351+P338, P321, P330, P332+P313, P337+P313, P362, P501 | |
Safety data sheet (SDS) | External MSDS |
Related compounds | |
Related compounds | anthraquinone, anthracene |
Except where otherwise noted, data are given for materials in their standard state (at 25 °C [77 °F], 100 kPa). |
Alizarin (also known as 1,2-dihydroxyanthraquinone, Mordant Red 11, C.I. 58000, and Turkey Red [2] ) is an organic compound with formula C
14H
8O
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. [3] In 1869, it became the first natural dye to be produced synthetically. [4]
Alizarin is the main ingredient for the manufacture of the madder lake pigments known to painters as rose madder and alizarin crimson. Alizarin in the most common usage of the term has a deep red color, but the term is also part of the name for several related non-red dyes, such as Alizarine Cyanine Green and Alizarine Brilliant Blue. A notable use of alizarin in modern times is as a staining agent in biological research because it stains free calcium and certain calcium compounds a red or light purple color. Alizarin continues to be used commercially as a red textile dye, but to a lesser extent than in the past.
Madder has been cultivated as a dyestuff since antiquity in central Asia and Egypt, where it was grown as early as 1500 BC. Cloth dyed with madder root pigment was found in the tomb of the Pharaoh Tutankhamun, [5] in the ruins of Pompeii [ citation needed ], and ancient Athens and Corinth. [6] In the Middle Ages, Charlemagne encouraged madder cultivation. Madder was widely used as a dye in Western Europe in the Late Medieval centuries. [7] In 17th century England, alizarin was used as a red dye for the clothing of the parliamentary New Model Army. The distinctive red color would continue to be worn for centuries (though also produced by other dyes such as cochineal), giving English and later British soldiers the nickname of "redcoats".
The madder dyestuff is combined with a dye mordant. Depending on which mordant is used, the resulting color may be anywhere from pink through purple to dark brown. In the 18th century, the most valued color was a bright red known as "Turkey Red". The combination of mordants and overall technique used to obtain the Turkey Red originated in the Middle East or Turkey (hence the name). It was a complex and multi-step technique in its Middle Eastern formulation, some parts of which were unnecessary. [8] The process was simplified in late 18th-century Europe. By 1804, dye maker George Field in Britain had refined a technique to make lake madder by treating it with alum, and an alkali, [9] that converts the water-soluble madder extract into a solid, insoluble pigment. This resulting madder lake has a longer-lasting color, and can be used more efficaciously, for example by blending it into a paint. Over the following years, it was found that other metal salts, including those containing iron, tin, and chromium, could be used in place of alum to give madder-based pigments of various other colors. This general method of preparing lakes has been known for centuries [10] but was simplified in the late 18th and early 19th centuries.
In 1826, the French chemist Pierre-Jean Robiquet found that madder root contained two colorants, the red alizarin and the more rapidly fading purpurin. [11] The alizarin component became the first natural dye to be synthetically duplicated in 1868 when the German chemists Carl Graebe and Carl Liebermann, working for BASF, found a way to produce it from anthracene. [12] The Bayer AG company draws its roots from alizarin as well. [13] About the same time, the English dye chemist William Henry Perkin independently discovered the same synthesis, although the BASF group filed their patent before Perkin by one day. The subsequent discovery (made by Broenner and Gutzhow in 1871) that anthracene could be abstracted from coal tar further advanced the importance and affordability of alizarin's artificial synthesis. [14]
The synthetic alizarin could be produced for a fraction of the cost of the natural product, and the market for madder collapsed virtually overnight. The principal synthesis entailed bromination of anthraquinone by bromine (in a sealed tube at 100 oC) to give 1,2-dibromoanthraquinone. Then the two bromine atoms were substituted by -OH by heating (170 oC) with KOH, followed by treatment with strong acid. [15] The incorporation of two bromine atoms in 1 and 2 position is not expected by an aromatic electrophilic substitution, and suggest the existence of an α,β unsaturated enol form of anthraquinone which suffer electrophilic addition by bromine.
Alizarin, as a dye, has been largely replaced today by the more light-resistant quinacridone pigments developed at DuPont in 1958.
Alizarin is one of ten dihydroxyanthraquinone isomers. It is soluble in hexane and chloroform, and can be obtained from the latter as red-purple crystals, melting point 277–278 °C. [3]
Alizarin changes color depending on the pH of the solution it is in, thereby making it a pH indicator. [17]
Alizarin Red is used in a biochemical assay to determine, quantitatively by colorimetry, the presence of calcific deposition by cells of an osteogenic lineage. As such it is an early stage marker (days 10–16 of in vitro culture) of matrix mineralization, a crucial step towards the formation of calcified extracellular matrix associated with true bone.[ citation needed ]
Alizarin's abilities as a biological stain were first noted in 1567, when it was observed that when fed to animals, it stained their teeth and bones red. The chemical is now commonly used in medical studies involving calcium. Free (ionic) calcium forms precipitates with alizarin, and tissue block containing calcium stain red immediately when immersed in alizarin. Thus, both pure calcium and calcium in bones and other tissues can be stained. These alizarin-stained elements can be better visualized under fluorescent lights, excited by 440–460 nm. [18] The process of staining calcium with alizarin works best when conducted in acidic solution (in many labs, it works better in pH 4.1 to 4.3). [19]
In clinical practice, it is used to stain synovial fluid to assess for basic calcium phosphate crystals. [20] Alizarin has also been used in studies involving bone growth, osteoporosis, bone marrow, calcium deposits in the vascular system, cellular signaling, gene expression, tissue engineering, and mesenchymal stem cells. [19]
In geology, it is used as a stain to differentiate the calcium carbonate minerals, especially calcite and aragonite in thin section or polished surfaces. [21] [22]
Madder lake had been in use as a red pigment in paintings since antiquity. [23]
A dye is a colored substance that chemically bonds to the substrate to which it is being applied. This distinguishes dyes from pigments which do not chemically bind to the material they color. Dye is generally applied in an aqueous solution and may require a mordant to improve the fastness of the dye on the fiber.
Rubia is the type genus of the Rubiaceae family of flowering plants, which also contains coffee. 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.
Carl Graebe 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.
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.
Heinrich Caro, was a German Jewish chemist.
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.
For the parent molecule 9,10-anthraquinone, see anthraquinone
Henry Edward Schunck, also known as Edward von Schunck, was a British chemist who did much work with dyes.
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 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, an opiate alkaloid substance of widespread use with analgesic and antidiarrheal properties.
Carl Theodore Liebermann was a German chemist and student of Adolf von Baeyer.
1,3-Dihydroxyanthraquinone, also called purpuroxanthin or xanthopurpurin, is an organic compound with formula C
14H
8O
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, 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.
Rubia tinctorum, the rose madder or common madder or dyer's madder, is a herbaceous perennial plant species belonging to the bedstraw and coffee family Rubiaceae.
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.
Natural dyes are dyes or colorants derived from plants, invertebrates, or minerals. The majority of natural dyes are vegetable dyes from plant sources—roots, berries, bark, leaves, and wood—and other biological sources such as fungi.
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 is a water-soluble sodium salt of Alizarin sulfonic acid with a chemical formula of C
14H
7NaO
7S. 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.
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.