Alizarin
Encyclopedia
Alizarin or 1,2-dihydroxyanthraquinone (also known as Mordant Red 11 and Turkey Red) is an organic compound
with formula that has been used throughout history as a prominent dye
, originally derived from the roots of plants of the madder
genus.
Alizarin was used as a red dye for the English parliamentary "new model" army. The distinctive red color would continue to be worn for centuries, giving English and later British soldiers the nickname of "redcoat
". In 1869, it became the first natural pigment to be duplicated synthetically.
Different dyes were used by the British, at different times, as one dye name that is commonly cited is "cochineal". Cochineal
is derived from several related species of scale insect, endemic to South America.
Alizarin is the main ingredient for the manufacture of the madder lake pigments known to painters as Rose madder
and Alizarin crimson
. The term is also part of the name for a variety of related dyes, such as Alizarine Cyanine Green G and Alizarine Brilliant Blue R, and gave its name to alizarin crimson
, a particular shade of red. The word derives from the Arabic
al-usara "juice".
) and in various parts of Indian madder (Rubia cordifolia
).
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
and in the ruins of Pompeii
and ancient Corinth. In the Middle Ages, Charlemagne
encouraged madder cultivation. It grew well in the sandy soils of the Netherlands
and became an important part of the local economy.
By 1804, the English
dye maker George Field had refined the technique to 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.
In 1826, the French
chemist Pierre-Jean Robiquet found that madder root contained two colorants, the red alizarin and the more rapidly fading purpurin. 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
. 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 only 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.
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 oxidation of anthraquinone-2-sulfonic acid with sodium nitrate
in concentrated sodium hydroxide. Alizarin itself has been in turn largely replaced today by the more light-resistant quinacridone
pigments developed at DuPont
in 1958.
isomers. Its molecular structure can be viewed as being derived from anthraquinone
by replacement of two neighboring
hydrogen
atoms (H) by hydroxyl
groups (-OH).
It is soluble in hexane and chloroform, and can be obtained from the latter as red-purple crystals, m.p. 277–278 °C.
Alizarin changes color depending on the pH of the solution it is in, thereby making it a pH indicator.
, 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.
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. The process of staining calcium with alizarin works best when conducted in basic solution.
In clinical practice, it is used to stain synovial fluid
to assess for basic calcium phosphate
crystals. 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.
In geology, it is used as a stain to indicate the calcium carbonate
minerals, calcite
and aragonite
.
Organic compound
An organic compound is any member of a large class of gaseous, liquid, or solid chemical compounds whose molecules contain carbon. For historical reasons discussed below, a few types of carbon-containing compounds such as carbides, carbonates, simple oxides of carbon, and cyanides, as well as the...
with formula that has been used throughout history as a prominent dye
Dye
A dye is a colored substance that has an affinity to the substrate to which it is being applied. The dye is generally applied in an aqueous solution, and requires a mordant to improve the fastness of the dye on the fiber....
, originally derived from the roots of plants of the madder
Madder
Rubia is a genus of the madder family Rubiaceae, which contains about 60 species of perennial scrambling or climbing herbs and sub-shrubs native to the Old World, Africa, temperate Asia and America...
genus.
Alizarin was used as a red dye for the English parliamentary "new model" army. The distinctive red color would continue to be worn for centuries, giving English and later British soldiers the nickname of "redcoat
Red coat (British army)
Red coat or Redcoat is a historical term used to refer to soldiers of the British Army because of the red uniforms formerly worn by the majority of regiments. From the late 17th century to the early 20th century, the uniform of most British soldiers, , included a madder red coat or coatee...
". In 1869, it became the first natural pigment to be duplicated synthetically.
Different dyes were used by the British, at different times, as one dye name that is commonly cited is "cochineal". Cochineal
Cochineal
The cochineal is a scale insect in the suborder Sternorrhyncha, from which the crimson-colour dye carmine is derived. A primarily sessile parasite native to tropical and subtropical South America and Mexico, this insect lives on cacti from the genus Opuntia, feeding on plant moisture and...
is derived from several related species of scale insect, endemic to South America.
Alizarin is the main ingredient for the manufacture of the madder lake pigments known to painters as Rose madder
Rose madder
Rose Madder is the commercial name sometimes used to designate a paint made from the pigment Madder Lake - a traditional lake pigment, extracted from the common madder plant ....
and Alizarin crimson
Alizarin crimson (color)
The color alizarin crimson is a "cool" hue of the color red that is biased slightly more towards purple than towards orange on the color wheel. It is named after the organic dye alizarin, found in the madder plant, and the related synthetic lake pigment Alizarin Crimson .-Alizarin crimson in human...
. The term is also part of the name for a variety of related dyes, such as Alizarine Cyanine Green G and Alizarine Brilliant Blue R, and gave its name to alizarin crimson
Alizarin crimson (color)
The color alizarin crimson is a "cool" hue of the color red that is biased slightly more towards purple than towards orange on the color wheel. It is named after the organic dye alizarin, found in the madder plant, and the related synthetic lake pigment Alizarin Crimson .-Alizarin crimson in human...
, a particular shade of red. The word derives from the Arabic
Arabic language
Arabic is a name applied to the descendants of the Classical Arabic language of the 6th century AD, used most prominently in the Quran, the Islamic Holy Book...
al-usara "juice".
Occurrence
Alizarin occurs in the root of the common madder (Rubia tinctorumRubia tinctorum
Rubia tinctorum, the common madder or dyer's madder, is a plant species in the genus Rubia.The plant's roots contain several polyphenolic compounds like 1,3-Dihydroxyanthraquinone , 1,4-Dihydroxyanthraquinone , 1,2,4-Trihydroxyanthraquinone and 1,2-dihydroxyanthraquinone...
) and in various parts of Indian madder (Rubia cordifolia
Rubia cordifolia
Rubia cordifolia, often known as Common Madder or Indian Madder, is a species of flowering plant in the coffee family, Rubiaceae...
).
History
Madder has been cultivated as a dyestuffNatural dye
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 organic sources such as fungi and lichens....
since antiquity in central Asia
Asia
Asia is the world's largest and most populous continent, located primarily in the eastern and northern hemispheres. It covers 8.7% of the Earth's total surface area and with approximately 3.879 billion people, it hosts 60% of the world's current human population...
and Egypt
Egypt
Egypt , officially the Arab Republic of Egypt, Arabic: , is a country mainly in North Africa, with the Sinai Peninsula forming a land bridge in Southwest Asia. Egypt is thus a transcontinental country, and a major power in Africa, the Mediterranean Basin, the Middle East and the Muslim world...
, where it was grown as early as 1500 BC. Cloth dyed with madder root pigment was found in the tomb of the Pharaoh
Pharaoh
Pharaoh is a title used in many modern discussions of the ancient Egyptian rulers of all periods. The title originates in the term "pr-aa" which means "great house" and describes the royal palace...
Tutankhamun
Tutankhamun
Tutankhamun , Egyptian , ; approx. 1341 BC – 1323 BC) was an Egyptian pharaoh of the 18th dynasty , during the period of Egyptian history known as the New Kingdom...
and in the ruins of Pompeii
Pompeii
The city of Pompeii is a partially buried Roman town-city near modern Naples in the Italian region of Campania, in the territory of the comune of Pompei. Along with Herculaneum, Pompeii was destroyed and completely buried during a long catastrophic eruption of the volcano Mount Vesuvius spanning...
and ancient Corinth. In the Middle Ages, Charlemagne
Charlemagne
Charlemagne was King of the Franks from 768 and Emperor of the Romans from 800 to his death in 814. He expanded the Frankish kingdom into an empire that incorporated much of Western and Central Europe. During his reign, he conquered Italy and was crowned by Pope Leo III on 25 December 800...
encouraged madder cultivation. It grew well in the sandy soils of the Netherlands
Netherlands
The Netherlands is a constituent country of the Kingdom of the Netherlands, located mainly in North-West Europe and with several islands in the Caribbean. Mainland Netherlands borders the North Sea to the north and west, Belgium to the south, and Germany to the east, and shares maritime borders...
and became an important part of the local economy.
England
England is a country that is part of the United Kingdom. It shares land borders with Scotland to the north and Wales to the west; the Irish Sea is to the north west, the Celtic Sea to the south west, with the North Sea to the east and the English Channel to the south separating it from continental...
dye maker George Field had refined the technique to lake
Lake pigment
A lake pigment is a pigment manufactured by precipitating a dye with an inert binder, usually a metallic salt. The word lake is a homonym of lake as body of water and does not refer to it....
madder by treating it with alum
Alum
Alum is both a specific chemical compound and a class of chemical compounds. The specific compound is the hydrated potassium aluminium sulfate with the formula KAl2.12H2O. The wider class of compounds known as alums have the related empirical formula, AB2.12H2O.-Chemical properties:Alums are...
, and an alkali
Alkali
In chemistry, an alkali is a basic, ionic salt of an alkali metal or alkaline earth metal element. Some authors also define an alkali as a base that dissolves in water. A solution of a soluble base has a pH greater than 7. The adjective alkaline is commonly used in English as a synonym for base,...
, 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
Paint
Paint is any liquid, liquefiable, or mastic composition which after application to a substrate in a thin layer is converted to an opaque solid film. One may also consider the digital mimicry thereof...
. Over the following years, it was found that other metal salts, including those containing iron
Iron
Iron is a chemical element with the symbol Fe and atomic number 26. It is a metal in the first transition series. It is the most common element forming the planet Earth as a whole, forming much of Earth's outer and inner core. It is the fourth most common element in the Earth's crust...
, tin
Tin
Tin is a chemical element with the symbol Sn and atomic number 50. It is a main group metal in group 14 of the periodic table. Tin shows chemical similarity to both neighboring group 14 elements, germanium and lead and has two possible oxidation states, +2 and the slightly more stable +4...
, and chromium
Chromium
Chromium is a chemical element which has the symbol Cr and atomic number 24. It is the first element in Group 6. It is a steely-gray, lustrous, hard metal that takes a high polish and has a high melting point. It is also odorless, tasteless, and malleable...
, 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.
In 1826, the French
France
The French Republic , The French Republic , The French Republic , (commonly known as France , is a unitary semi-presidential republic in Western Europe with several overseas territories and islands located on other continents and in the Indian, Pacific, and Atlantic oceans. Metropolitan France...
chemist Pierre-Jean Robiquet found that madder root contained two colorants, the red alizarin and the more rapidly fading purpurin. The alizarin component became the first natural dye to be synthetically duplicated in 1868 when the German
Germany
Germany , officially the Federal Republic of Germany , is a federal parliamentary republic in Europe. The country consists of 16 states while the capital and largest city is Berlin. Germany covers an area of 357,021 km2 and has a largely temperate seasonal climate...
chemists Carl Graebe and Carl Liebermann, working for BASF
BASF
BASF SE is the largest chemical company in the world and is headquartered in Germany. BASF originally stood for Badische Anilin- und Soda-Fabrik . Today, the four letters are a registered trademark and the company is listed on the Frankfurt Stock Exchange, London Stock Exchange, and Zurich Stock...
, found a way to produce it from anthracene
Anthracene
Anthracene is a solid polycyclic aromatic hydrocarbon consisting of three fused benzene rings. It is a component of coal-tar. Anthracene is used in the production of the red dye alizarin and other dyes...
. About the same time, the English
England
England is a country that is part of the United Kingdom. It shares land borders with Scotland to the north and Wales to the west; the Irish Sea is to the north west, the Celtic Sea to the south west, with the North Sea to the east and the English Channel to the south separating it from continental...
dye chemist William Henry Perkin independently discovered the same synthesis, although the BASF group filed their patent before Perkin by only 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.
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 oxidation of anthraquinone-2-sulfonic acid with sodium nitrate
Sodium nitrate
Sodium nitrate is the chemical compound with the formula NaNO3. This salt, also known as Chile saltpeter or Peru saltpeter to distinguish it from ordinary saltpeter, potassium nitrate, is a white solid which is very soluble in water...
in concentrated sodium hydroxide. Alizarin itself has been in turn largely replaced today by the more light-resistant quinacridone
Quinacridone
Quinacridone is a red powder. It is an organic compound with the molecular formula C20H12N2O2. It is used as a pigment; analogs bearing this motif are known as quinacridones.-Quinacridones:...
pigments developed at DuPont
DuPont
E. I. du Pont de Nemours and Company , commonly referred to as DuPont, is an American chemical company that was founded in July 1802 as a gunpowder mill by Eleuthère Irénée du Pont. DuPont was the world's third largest chemical company based on market capitalization and ninth based on revenue in 2009...
in 1958.
Structure and properties
Alizarin is one of ten dihydroxyanthraquinoneDihydroxyanthraquinone
A dihydroxyanthraquinone is any of several isomeric organic compounds with formula , formally derived from an anthraquinone by replacing two hydrogen atoms by hydroxyl groups. Dihyroxyantraquinones have been studied since the early 1900s, and include some compounds of historical and current...
isomers. Its molecular structure can be viewed as being derived from anthraquinone
Anthraquinone
Anthraquinone, also called anthracenedione or dioxoanthracene is an aromatic organic compound with formula . Several isomers are possible, each of which can be viewed as a quinone derivative...
by replacement of two neighboring
Vicinal
Vicinal may refer to:* Vicinal , stands for any two functional groups bonded to two adjacent atoms.* Vicinal , a word where all letters have alphabetic neighbors....
hydrogen
Hydrogen
Hydrogen is the chemical element with atomic number 1. It is represented by the symbol H. With an average atomic weight of , hydrogen is the lightest and most abundant chemical element, constituting roughly 75% of the Universe's chemical elemental mass. Stars in the main sequence are mainly...
atoms (H) by hydroxyl
Hydroxyl
A hydroxyl is a chemical group containing an oxygen atom covalently bonded with a hydrogen atom. In inorganic chemistry, the hydroxyl group is known as the hydroxide ion, and scientists and reference works generally use these different terms though they refer to the same chemical structure in...
groups (-OH).
It is soluble in hexane and chloroform, and can be obtained from the latter as red-purple crystals, m.p. 277–278 °C.
Alizarin changes color depending on the pH of the solution it is in, thereby making it a pH indicator.
Applications
Alizarin Red is used in a biochemical assay to determine, quantitatively by colorimetryColorimetry
Colorimetry is "the science and technology used to quantify and describe physically the human color perception."It is similar to spectrophotometry, but is distinguished by its interest in reducing spectra to the physical correlates of color perception, most often the CIE 1931 XYZ color space...
, 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.
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. The process of staining calcium with alizarin works best when conducted in basic solution.
In clinical practice, it is used to stain synovial fluid
Synovial fluid
Synovial fluid is a viscous, non-Newtonian fluid found in the cavities of synovial joints. With its yolk-like consistency , the principal role of synovial fluid is to reduce friction between the articular cartilage of synovial joints during movement.-Overview:The inner membrane of synovial joints...
to assess for basic calcium phosphate
Calcium phosphate
Calcium phosphate is the name given to a family of minerals containing calcium ions together with orthophosphates , metaphosphates or pyrophosphates and occasionally hydrogen or hydroxide ions ....
crystals. 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.
In geology, it is used as a stain to indicate the calcium carbonate
Calcium carbonate
Calcium carbonate is a chemical compound with the formula CaCO3. It is a common substance found in rocks in all parts of the world, and is the main component of shells of marine organisms, snails, coal balls, pearls, and eggshells. Calcium carbonate is the active ingredient in agricultural lime,...
minerals, calcite
Calcite
Calcite is a carbonate mineral and the most stable polymorph of calcium carbonate . The other polymorphs are the minerals aragonite and vaterite. Aragonite will change to calcite at 380-470°C, and vaterite is even less stable.-Properties:...
and aragonite
Aragonite
Aragonite is a carbonate mineral, one of the two common, naturally occurring, crystal forms of calcium carbonate, CaCO3...
.
See also
- Alizarine inkAlizarine inkAlizarine ink was created in 1855 by Professor Leonhardi of Dresden, Germany, by adding Alazarin dye to conventional iron gall ink...
- AnilineAnilineAniline, phenylamine or aminobenzene is an organic compound with the formula C6H5NH2. Consisting of a phenyl group attached to an amino group, aniline is the prototypical aromatic amine. Being a precursor to many industrial chemicals, its main use is in the manufacture of precursors to polyurethane...
- 1,2,4-Trihydroxyanthraquinone or purpurin, another red dye that occurs in madder root.
- HydroxyanthraquinoneHydroxyanthraquinoneA hydroxyanthraquinone is any of several organic compounds with formula C14H9O2, which can be viewed as derivatives of an anthraquinone through replacement of one hydrogen atom by an hydroxyl group ....
- DihydroxyanthraquinoneDihydroxyanthraquinoneA dihydroxyanthraquinone is any of several isomeric organic compounds with formula , formally derived from an anthraquinone by replacing two hydrogen atoms by hydroxyl groups. Dihyroxyantraquinones have been studied since the early 1900s, and include some compounds of historical and current...
- List of dyes
- List of colors (compact)