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, in the ruins of
Pompeii, and ancient
Athens and
Corinth. In the Middle Ages,
Charlemagne encouraged madder cultivation. Madder was widely used as a dye in Western Europe in the Late Medieval centuries. 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. 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, 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 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.
Age of synthetic alizarin Alizarin became the first natural dye to be synthetically duplicated. In 1868 the
German chemists
Carl Graebe and
Carl Liebermann, working for
BASF, found a way to produce it from
anthracene. The
Bayer AG company draws its roots from alizarin as well. 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. Synthetic alizarin can be produced for a fraction of the cost of the natural product, and the market for madder collapsed virtually overnight. One synthesis entailed bromination of anthraquinone to give 1,2-dibromoanthraquinone followed by substitution treatment of the latter with
potassium hydroxide at 170°C, and then followed by treatment with strong acid. It is now produced commercially by oxidation of anthraquinone or its sulfonate in alkali media. Alizarin, as a dye, has been largely replaced today by the more light-resistant
quinacridone pigments developed at
DuPont in 1958. ==Structure and properties==