The Chemistry of Dyestuff. Dyestuffs. XXIII. Oxyketone Dyestuffs.

A Manual for Students of Chemistry and Dyeing
M. Fort, M.Sc. (Leeds) Late Lecturer in Dyeing in the Bradford Technical College and L. L. Lloyd, Ph.D. (Bern) Lecturer in Organic and Technical Chemistry in the Bradford Technical College
Cambridge: at the University Press 1919
(First edition 1917, reprinted 1919)
The dyestuffs of this series belong to the mordant class and are mainly used in conjunction with a metallic mordant.

One of the simplest dyes of this series is Alizarin Yellow C, which is gallacetophenone. It is prepared by heating acetic acid with pyrogallol in presence of zinc chloride.

Alizarin Yellow A is the corresponding trioxy benzophenone. This dyes redder shades than the above compound.

Dyestuffs are obtained by careful oxidation of oxybenzoic acids. Galloflavin W (B.) is obtained by oxidation of gallic acid in alcoholic potash solution with air, followed by treatment of the product with acid.

The simplest of the diketo-dyes of this series is Alizarin Black WR, SW, SWR, etc. (B.) is 1.2-dioxy-5.8-naphthoquinone, and is prepared from crude diuitronaphthalene (1.5 and 1.8-) by heating with a solution of sulphur sesquioxide in sulphuric acid solution, followed by hydrolysis of the 1.2-amino-oxy-α-naphthoquinone-imine by boiling with dilute acid. The insoluble Naphthazarin is converted into a water-soluble product by addition of sodium bisulphite.

One of the oldest and best known members of this series is Alizarin which is present in madder root, which contains from two to four per cent, as a glucoside. It is a good example of those colouring matters which dye only with the aid of a mordant, and which yield various colours with different mordants (polygenetic dyes). The use of a mordant is obligatory, alizarin itself having no affinity for vegetable fibres, and only imparting a fugitive orange brown colour to animal fibres. Its compound with alumina is red, with stannous oxide orange, with chromic oxide brownish violet, with ferrous oxide blackish violet, with ferric oxide brownish black. These colours when produced on textile fibres are fast to light, washing, and milling, etc., the fastness however varying somewhat with the mordant used.

In 1869 Perkin, and also Graebe and Liebermann, produced alizarin from anthraquinone by sulphonation with fuming sulphuric acid, followed by caustic fusion in presence of an oxidising agent. In. the manufacture of alizarin it is only necessary to obtain anthraquinoneβ-sulphonic acid, since this compound on heating with caustic soda gives alizarin.

Nascent hydrogen is obtained during the reaction; this reduces the alizarin to a leuco compound and also causes a poor yield of the dyestuff. The oxidising agent is added to prevent nascent hydrogen from being formed, thus obtaining a good yield of the dyestuff.

Alizarin P (B. A.), VI (B.), IE (By.), No. I (M.), etc., is obtained when anthraquinone-β-sulphonic acid is heated with alkali, etc. It is however usually obtained along with other oxy derivatives of anthraquinone. During the sulphonation of anthraquinone small quantities of disulphonic acid are also obtained, these giving trioxy anthraquinones by alkali fusion.

By further sulphonation of anthraquinone a mixture of 2.6and 2. 7-anthraquinone sulphonic acids is obtained These compounds may be separated by crystallisation of their sodium salts. They give, on fusing with alkali, Flavopurpurin or Alizarin YCA (B.A.), CH, RG (B.), VG, XG (By.), etc. [-] and Anthra- or Iso-purpurin or Alizarin SO (B.A.), SX, GD (B.), RF, WR (By.), etc.

Purpurin (B.A.) (B.), or 1.2.4-trioxyanthraquinone is obtained by oxidation of alizarin in sulphuric acid solution by manganese dioxide.

Alizarin Bordeaux B (By.), etc., is obtained by Oxidation of alizarin with strong fuming sulphuric acid, giving a sulphuric ester which is hydrolysed by strong sulphuric acid (80%). The aluminium lake is bordeaux and the chrome lake violet blue.

Alizarin Cyanin R, 2R, NS, WRR (By.), etc., is obtained by oxidation of alizarin bordeaux with manganese dioxide similarly to the oxidation of alizarin to purpurin. This dyestuff gives a violet aluminium lake and a blue chrome lake.

1.5-dinitroanthraquinone similarly to 1.5-dinitromiphthalene gives on .treatment with a solution of sulphur sesquioxide an oxy-imido compound which, on hydrolysis with ordinary sulphuric acid, gives the hexahydroxyanthraquinone shown above.

By increasing the number of oxy groups in anthraquinone, the polygenetic nature of the resulting dyes becomes gradually diminished.

Nearly all of the above dyestuffs of the anthraquinone series are converted into acid mordant dyes by sulphonation with fuming sulphuric acid.

Alizarin Red S (By.), WS (M.), etc., Alizarin Powder SA, Alizarin Carmine (B.A.) is the product obtained when alizarin is sulphonated with fuming sulphuric acid at 170°C.

Erweco Alizarin Acid Red BS (W.) is a mixture of the sodium salts of alizarin 5and 8-monosulphonic acids. It is obtained by sulphonation of alizarin with fuming sulphuric acid in presence of mercury. Alizarin 3.5and alizarin 3.8-disulphonic acids are obtained, which, on hydrolysis, give monosulphonic acids.

Anthracene Brown (R.H.), (B.A.), W, WR (B.G., etc.), or Alizarin Brown R, W, H (M.), etc., or 1.2.3-trioxyanthraquinone is obtained by condensation of benzoic and gallic acids in sulphuric acid solution. It is always associated with some or rufigallol, which is also known as Anthracene Brown SW (B.) or Alizarin Brown R, S (M.), etc.

Alizarine Orange AO, AOP (B.A.), A, W, SW (B.), N (M.), etc., is obtained by the action of nitric acid upon alizarin in suspension in nitrobenzol, acetic acid, ligroin, or sulphuric acid, to which boric acid is added.

If the alizarin is benzoylated before nitration, the nitro group enters the alpha position, and on hydrolysis and reduction with sodium sulphide gives Alizarin Garnet (M.).

Alizarin Blue S, SW (B.), (By.), etc., is the sodium bisulphite compound of Alizarin Blue ABI (B.A.), X, R, WX (B.), F (M.), GG, XA, WA (By.), etc,

It is obtained by the action of glycerin, nitroalizarin, and amidoalizurin in sulphuric acid solution, viz., by the application of Skraup's reaction to nitro derivatives of the anthraquinone dyes.

Alizarin Green S (M.) is a similar substance obtained from α-amidoalizarin, Alizarin Green X (B.) and Alizarin Indigo Blue (B.) are corresponding compounds obtained from 3-nitro-Alizarin Bordeaux, and treatment of this compound with sulphuric acid at 200°C. finally converting into bisulphite compounds, while Alizarin Black P (M.) is obtained from 3-nitroflavopurpurin.

On account of the insolubility of these dyes they are marketed as 20 % pastes. Soluble powders are obtained by formation of an addition product with two molecules of sodium bisulphite.

Most of the following derivatives of aminoanthraquiuones are after-chrome mordant dyes; they may, however, be applied also as simple acid colours.

Alizarin Irisol D, R (By.), etc., is obtained by heating p-toluidine with quinizarin (1.4-dioxy anthraquinone) followed by sulphonation.

Anthraquinone Violet (B.) is obtained from 1.5diamidoanthraquinone by heating with p-toluidine followed by sulphonation of the product thus obtained.

Alizarin Sky Blue B (By.) is obtained by condensation of p-toluidine with dibrom-α-amidoanthraquinone followed by sulphonation.

Alizarin Saphirol B (By.) is obtained by sulphonation of 1.5-dioxyanthraquinone (Anthrarufin) followed by nitration and reduction.

Various brands of this dye are used in dyeing mode shades on wool, which are very fast so long as chlorides (NaCl) are absent.

Alizarin Cyanin Green E, G (By.), etc., is obtained by sulphonation of the product produced by heating quinizarin with p-toluidine.

Acid Alizarin Green G (M.) results when dinitroanthrachrysone disulphonic acid is reduced in alkaline solution with sodium sulphide.

- See also "The Present Condition of the Chemistry of Anthraquinone," by R. K. Schmidt, Jour. Soc. Chem. Ind. 1914, p. 1039.

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