Cochineal and carmine

Cochineal is a very old colorant. References go back as far as 5000 bc when Egyptian women used it to color their lips. It was introduced to Europe by Cortez who found it in Mexico. Production peaked around 1870 and then declined due to the introduction of synthetic colorants, but it is still a major commodity for Peru, Mexico, and the Canary Islands25,30 

Cochineal extract is obtained from the bodies of the female cochineal insects, particularly Dactylopius coccus Costa, by treating the dried bodies with ethanol. After removal of the solvent, the dried residue contains about 2-4% carminic acid, the main colored component. The cochineal insects grow on cactus and, 

Carmine is well entrenched in the food industry and probably will remain there because of its superior technological properties. It is, however, a very labor intensive industry because of the hand harvesting of the insects with a consequent high price. 

Carmine belongs to the anthraquinone class of compounds and several other chemically closely related compounds are also used as colorants.25 Kermes is a well known colorant in Europe. It is obtained from the insects, Kermes ilicis or Kermococcus vermilis, which grow on oak trees. It contains kermisic acid, the aglycone of carminic acid, and its isomer ceroalbolinic acid. Its properties are very similar to carmine. Lac is a red colorant obtained from the insect Laccifera lacca which is found on several families of trees in India and Malaysia. The lac insects are better known for their production of shellac. They contain a complex mixture of anthraquinones. Alkanet is a red pigment from the roots of Alkanna tinctoria Taush and Alchusa tinctoria Lom. All three have been cleared for food use in Europe but not in the US. 

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Apart from its use as a valuable mordant dyestuff for textiles, cochineal (EEC 120) is still used as a colourant in cosmetics, foods, aperitif and beverages (ref. 194) and is one of the several permitted natural colourants which includes for example p-carotene, betanidin from Beta vulgaris, curcumin from Curcuma tonga, certain anthocyanins and chlorophyll complexes to quote a few structures. Commercial interest in natural products such as cochineal and carminic acid has been reactivated by the increasing pressures to avoid synthetic azo colours, their association with potential carcinogenic attributes and the increasing popularity of green issues. Carminic acid is reputed to possess some anticancer activity (ref. 195,196) and is a distant structural relative of the antibiotics, carminomycin and carminomycinone. 

Cochineal Extract. Cochineal extract (Cl Natural Red 4, Cl No. 75470 EEC No. E 120) is the concentrated solution obtained after removing the alcohol from an aqueous-alcohoHc extract of cochineal, which is the dried bodies of the female insect Coccus cacti Dactylopius coccus costd) a variety of field louse. The coloring principle of the extract is beHeved to be carminic acid [1260-17-9] (40), an hydroxyanthraquinone linked to a glucose unit, comprising approximately 10% of cochineal and 2—4% of its extract. 

Cochineal pigments are extracted from dried bodies of female insects with water or with ethanol the result is a red solution that is concentrated in order to obtain the 2 to 5% carminic acid concentration customary for commercial cochineal. For carmine lakes, the minimum content of carminic acid is 50%. An industrial procedure applied in Spain uses ammonium hydroxide as the extracting agent and phosphoric acid as the acidifying agent. For analytical purposes the extraction is carried out with 2 N HCl at 100°C. The chemical synthesis of carminic acid has also been reported and is the subject of European and United States patents. ... 

Cochineal, carminic acid, and carmines are approved as food colorants in the EU under code E 120, and their purity criteria are regulated.The amount of E 120 permitted in food ranges from 50 to 500 mg/kg. Carminic acid and carmine are considered very good food colorants due to their high stability and tinctorial properties. Solutions of carminic acid are yellow to orange, while carmines show various stable brilliant red hues. - ... 

Analysis of Quinones from Cochineal Insects Carmine and... 

ANALYSIS OF QUINONES FROM COCHINEAL INSECTS CARMINE AND CARMINIC ACID... 

Carminic acid and carmine, cochineal E 120 Yes Female cochineal insect orange to red, pink to red ... 

Cochineal and lac dye can be studied by HPLC with spectrophotometric and NI ESI MS detection. [34] In cochineal, carminic acid appears as a dominant colouring agent. In lac dye extracts, the signal at m/z 536 corresponding to a quasi-molecular ion of laccaic acid A is observed as the dominant one. [19]... 

Fig. 2.32. Chromatograms obtained at 420 and 500 nm for pure cochineal (a) and for cochineal adulterated by erythrosin (b), at a concentration of 0.35 X10-3 kg per kg cochineal, and by trans-fi-carotene (c) at a concentration of 6X10-3 kg per kg cochineal. Cochineal pigments dcH, dcIH, dcIV and dcVII, unknown pigments of D. coccus Costa ca, carminic acid fl, flavokermesic acid and ka, kermesic acid. marks the peak of the added colourant. Reprinted with permission from M. Gonzalez et al. [72].

Porphyrophora polonica L. (Polish cochineal) contains small amounts of the kermes dyes kermesic acid and flavokerme-sic acid besides the cochineal dye carminic acid. These secondary components cannot be identified unless they have previously been concentrated. 

Armenian cochineal may have been an important article of commerce in earlier times (10). Masschelein-Kleiner and Maes (75) identified carminic acid on ten samples of Egyptian textiles from the 5th to the 7th century A.D., but not kermesic acid. This result applies only to Armenian cochineal and not to any other of the dyes known in antiquity. The authors also found Armenian cochineal on various Nubian and Hebrew textiles. 

The story of cochineal is beautifully told by Amy Butler Greenfield in her book A Perfect Red, published in 2005. Cochineal was the dye which the Aztecs had discovered, and it is produced by the scale insect Dactylopius coccus that feeds only on the prickly pear cactus. The red molecule of cochineal is carminic acid881 and it constitutes 10% of their... 

The major pigment of cochineal is polyhydroxyanthraquinone C-glycoside, car-minic acid (Formula 9.16), which may be present at up to 20% dry weight of the mature insects. Cochineal extract or carminic acid are rarely used as coloring materials for food, but are usually offered in the form of their lake. Aluminum complexes (lakes) can be prepared with ratios of cochineal and aluminum varying from 8 1 to 2 1, having corresponding shades from pale yellow to violet. 

The colourant principle of cochineal is carminic acid (30) which is used as carmine in the form of its aluminium and other metallic chelates (calcium-aluminium) in much the same way that alizarin was formerly employed as a mordant dye by chelation of the 1,2-dihydroxy system. 

When Hernan Cortez arrived in Mexico in 1518, he was intrigued by the beautifully colored Aztec fabrics he saw there. The source of the dye appeared to be seeds on the surface of certain cactus plants, but closer scrutiny revealed that they were not seeds at all. They were little bugs. Today, we know these insects as cochineal and the dye they yield as carmine. Montezuma, the Aztec king, was so fond of wearing robes made of carmine-dyed fabric that he imposed a tax upon his subjects to be paid in dried cochineal insects. 

Even if alizarin had served its time as a dyestuff for textiles, natural cochineal still finds broad application as a colourant for foodstuffs. Given the high expenditure required for isolation of the natural product, a ftiUy synthetic preparation of nature-identical kermesic and carminic acids can be attractive if one takes into account that higher prices can be realised for food colourants than for textile dyes. In this connection, the first total synthesis of carminic acid has been described by John Tyman and Pietro AUevi. [62,63]... 

E120 Cochineal, carminic acid and carmines E160C Paprika extract, capsanthin, capsorubin ... 

Carlyle (2001) also notes a number of terminological forms listed by English colourmen for cochineal lakes such as carmine, crimson lake, crimson lake extra, extra carmine lake, and crimson lake extra fine. Further, combinations of vermilion (q.v.) and carmine were given names such as carmine vermilion and Florentine and Chinese lake. 

Carmin is the alumina lake of cochineal and is approved as food dye and in cosmetic and pharmaceutical applications. 

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