Kermes red

Kermisic Acid. Many accounts claim that kermisic acid [476-35-7] (Cl Natural Red 3 Cl 75460) is the oldest dyestuff ever recorded (23). The name kermes is derived from an Armenian word meaning Httle worm for which the later Latin equivalent was vermiculus, the basis of the Knglish word Vermillion. The dye was obtained from an oriental shield louse, K. ilicis which infest the holm o5kQuercus ilex and the shmb oak. coccifera. The dye produces a brilliant scarlet color with an alum mordant. Although expensive, it was cheaper than its rival Tyrian Purple. It was in great demand until the sixteenth century when it was displaced by carminic acid. 

Karmesinbeeren, /.pi. kermea berries, kermes. karmesin-farblg, a. crimson-colored. -rot a. crimson-red, crimson. 

Scharlach, m. scarlet scarlet fever scarlet runner, -beeren,/./>/. kermes berries, kermea. scharlachen, scharlachfarben, a. scarlet. Scharlach-farbe,/. scarlet color or dye. -fieber, n. scarlet fever, scarlatina, scharlachrot, a. scarlet, bright red. Scharlach-rot, n. scarlet cochineal. -wurm, m. cochineal insect. 

Oaks and especially Quercus coccifera are host plants for Kermes ilicis, producing the red kermes pigment. In Asia, the Laccifer lacca insects that grow on trees like Schleichera oleosa, Ziziphus mauritiana, and Butea monsperma are the sources of the red lac dye. - ... 

Quite a variety of red dyes of both vegetable and animal origin were used in antiquity, although only a few of them ever attained practical importance. Among these were madder, of vegetable origin, probably the most widely used and in its heyday also the most important red dye, and kermes and cochineal, both derived from the bodies of insects. 

It has been recognised for centuries that certain natural dyes, including alizarin, kermes, cochineal and fustic, now known to contain o-dihydroxy phenolic or anthraquinonoid residues in their structures, can be fixed on natural fibres using oxides or salts of transition metals as mordants. Although mordanted wool dyed with alizarin showed excellent fastness, reproducibility of shade was difficult to achieve because of the variable composition of the raw materials available. The famous Turkey red, in which alizarin was applied to aluminium-mordanted wool in the presence of calcium salts, formed a metallised complex the nature of which remains in considerable doubt. 

The appreciation of color and the use of colorants dates back to antiquity. The art of making colored candy is shown in paintings in Egyptian tombs as far back as 1500 bc. Pliny the Elder described the use of artificial colorants in wine in 1500 bc. Spices and condiments were colored at least 500 years ago. The use of colorants in cosmetics is better documented than colorants in foods. Archaeologists have pointed out that Egyptian women used green copper ores as eye shadow as early as 5000 bc. Henna was used to redden hair and feet, carmine to redden lips, faces were colored yellow with saffron and kohl, an arsenic compound, was used to darken eyebrows. More recently, in Britain, in the twelfth century, sugar was colored red with kermes and madder and purple with Tyrian purple. 

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. 

Hernan Cortes, who had arrived in America in 1518, did not fail to recognize the commercial value of cochineal. Indeed, the dried insects became the first product exported from the New World to the Old, and Europeans couldn t get enough of that vibrant, beautiful scarlet color. France s famed Gobelin tapestries were tinted with cochineal. There was such demand for the dye that by the sixteenth century Spain was importing half a million pounds of cochineal annually. That s an impressive amount, especially considering that it takes seventy thousand hand-gathered insects to make a pound of the dye. Cochineal red became so popular that it drove kermes into obscurity, and cochineal is still used today. 

The red insect dyes from Dactylopius coccus COSTA (American cochineal), Kermococcus vermilio PLANCHON (kermes), and Kerria lacca KERR (lac dye) can also be readily distinguished by thin-layer chromatographic comparison. 

Kermococcus vermilio PLANCHON (Kermes vermilio (PLANCH.) TARG.) formerly Kermes ilicis L. (10) (Coccidae) (C.I. Natural Red 3)... 

Kermes belongs to the oldest red textile dyes (70), and it was traded by Phoenician merchants as early as 1500 B.C. (10). 

Figure 9. TLC comparison of the red insect dyes in the Karabagh carpets, figures 7 and 8, after dissolving the dye extracts in different organic solvents. 1 and 2, extracts of the Karabagh carpet (figure 7) 1, soluble in ether 2, soluble in ethyl acetate + methanol 3 and 4, extracts of the Karabagh carpet (figure 8) 3, soluble in ether 4, soluble in ethyl acetate + methanol 5 and 6, extracts of Armenian cochineal S, soluble in ether 6, soluble in ethyl acetate + methanol 7, Polish cochineal 8, American cochineal 9, kermes 10, laccaic acids (XXVIII - XXXII) 11, erythrolaccin (XXXIII) 12, deoxyerythrolaccin (XXXTV).

Figure 12. Identification of the insect dyes in the Sicilian coronation robe (figure 10) and in the Tunicella (figure 11) by TLC comparison. Solvent butanone-2 - formic acid (7 3) 1-3, extracts of the three samples of dyeings of the coronation robe 1, red silk 2, lining material, filling threads 3, lining material, warp threads 4, red silk from the border material of the Tunicella 5, kermes 6, Polish cochineal 7, American cochineal 8, laccaic acids from lac dye.

The thin-layer chromatogram shows at first sight that the red samples of the coronation robe and of the Tunicella have been dyed with kermes (Kermococcus vermilio PLANCHON). As the comparison shows, not only the green spot of kermesic acid, but also the red spot of flavokermesic acid is clearly visible. 

As the acetic acid is added you will begin to see a red-brown solid form and fall to the bottom. This is the Kermes Mineral. Allow the solids to settle, then decant the clear liquid from the top and save it aside. This liquid contains mostly sodium acetate which can be recovered for use in the acetate work. Its previous association with antimony makes it even more valuable. 

The still moist Kermes is washed several times with rainwater by covering it with ten to twenty times its volume of water and letting it settle, then decant and repeat. Place the wet solid into a dish to dry. The resulting red-brown powder, the Kermes, is now cleansed of many impurities that are associated with antimony ores including the alumina and silica matrix. Chemically, the powder represents a complex mixture of antimony trisulfide and antimony trioxide. 

Other alkalis will also work to dissolve the stibnite, such as potassium hydroxide, even liquid ammonia. By altering the concentrations, and order of mixing the acid and alkali solutions, the powder can be made to take on shades of canary yellow to brilliant orange to crimson red as the particle size varies. Kermes is much easier to calcine to a light oxide powder because of its greater purity. 

Dyeings with the red insect dyes cochineal (C.I. Natural Red 4), kermes (C.I. Natural Red 3), and lac dye (C.I. Natural Red 25) bleed an orange shade. After shaking with ethyl acetate and pentanol (1 1), the dye solutions can be used for TLC comparisons. 

In the case of lac dye, clearly the separation of the laccaic acids A, B, C, D, and E (39-42) can be seen, and in the case of kermes, the separation into kermesic acid (green spot) and flavokermesic acid (red spot) can be seen. References 39-42 describe the determination of the constitutions of the laccaic acids A-E and indicate their constitutions. 

Figure 3. TLC of hydroxyanthraquinones from red insect dyes. I, cochineal 2, lac dye and 3, Kermes vermilio.

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