Indigo vat

Table 12.38 Summary of advantages and disadvantages of the three most important types of reducing agent for indigo, vat or sulphur dyeing [239]...

Indigoid soluble dyes, 7 373t Indigo vat dye, 9 181 Indirect-arc furnaces, 12 297—298 Indirect coal liquefaction, 6 858-867 Indirect cooler evaporators, 21 537 Indirect extrusion, copper, 7 693 Indirect food additives, 12 29, 34 categories of, 12 31 Indirect-gap semiconductors, 14 837 ... 

Ethylene/chlorotrifluoroethylene copolymer Vat blue 1. See D8iC Blue No. 6 Indigo Vat blue 4. See Indanthrone Vat blue 6. See D8iC Blue No. 9 Indanthrene blue... 

This is another class used in the dyeing of cotton. Vat dyes are water insoluble but can be easily reduced to give an aqueous alkaline solution of the leuco form of the dye with which the cotton fabric is treated. Once the leuco dye has penetrated the fibers, it is oxidized, often with air, to reform the vat dye, which is now locked inside the fiber. For an example, see structure 8 (Fig. 5), Cl Vat Blue 1, also known as indigo. Vat dyes are not used in detergents. 

Textile dyes were, until the nineteenth century invention of aniline dyes, derived from biological sources plants or animals, eg, insects or, as in the case of the highly prized classical dyestuff Tyrian purple, a shellfish. Some of these natural dyes are so-caUed vat dyes, eg, indigo and Tyrian purple, in which a chemical modification after binding to the fiber results in the intended color. Some others are direct dyes, eg, walnut sheU and safflower, that can be apphed directly to the fiber. The majority, however, are mordant dyes a metal salt precipitated onto the fiber facUitates the binding of the dyestuff Aluminum, iron, and tin salts ate the most common historical mordants. The color of the dyed textile depends on the mordant used for example, cochineal is crimson when mordanted with aluminum, purple with iron, and scarlet with tin (see Dyes AND DYE INTERMEDIATES). 

Addition of sodium dithionite to formaldehyde yields the sodium salt of hydroxymethanesulfinic acid [79-25-4] H0CH2S02Na, which retains the useful reducing character of the sodium dithionite although somewhat attenuated in reactivity. The most important organic chemistry of sodium dithionite involves its use in reducing dyes, eg, anthraquinone vat dyes, sulfur dyes, and indigo, to their soluble leuco forms (see Dyes, anthraquinone). Dithionite can reduce various chromophores that are not reduced by sulfite. Dithionite can be used for the reduction of aldehydes and ketones to alcohols (348). Quantitative studies have been made of the reduction potential of dithionite as a function of pH and the concentration of other salts (349,350). 

Indigo is the most important vat dye, dating back to ancient times and produced on an industrial scale since 1880. To replace the indigo dyes, the indanthrone (21) class of dyes was developed. Indanthrone has superior characteristics as a vat dye and became a key material for further development of anthraquinoid vat dyes. There exist a variety of anthraquinone vat dyes differing in the chromophoric system. The color-structure relationship of vat dyes have been rationalized by the Pariser-Parr-Pople molecular orbital (PPP MO) method. Some examples of commercialized anthraquinoid vat dyes are shown in Scheme 6.14... 

A question which has intrigued colour chemists for years is why indigo, a relatively small molecule, absorbs at such long wavelengths. The colour of indigo depends crucially on its environment. It is known that, in the vapour phase, the only situation in which it approaches a monomolecular state, indigo is red. In solution, indigo exhibits pronounced positive solvatochromism in non-polar solvents it is violet, while in polar solvents it is blue. In the solid state, and when applied to fabric as a vat dye, it is... 

Vat Dyes. Vat dyes are insoluble in water. Indigo, for example, an ancient blue dye, is probably the best-known example of an ancient vat dye others include woad and Tyrian purple. Since the process of dyeing requires that the dye be in solution, dyeing with a vat dye (or vat dyeing, as the process is known) is possible only after the vat dye has been made soluble by a relatively long and somewhat complicated chemical procedure. The terms vat dye and vat dyeing are probably derived from the large tanks or "vats", in which the process was carried out in ancient times. 

Vat dyes (the best known are Tyrian purple, indigo and woad) are insoluble in water. Before dyeing, they must be reduced into water-soluble leucoforms. After impregnation of the textile, dyestuffs are again oxidized into colour forms. As far as their extraction is concerned, aprotic solvents are usually recommended, e.g. pyridine, dimethylformamide or dimethylsulfoxide. 

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