Patent GB-573831-A (GB)
Title: Manufacture of new sulphur dyestuffs
IPC: C09B49/12
Filed: 1943-11-19
Abstract: Sulphur dyes are made by the interaction, with heating if desired, of an organic dyestuff or pigment of the anthraquinone, indigo, thioindigo, phthalocyanine, thiazole, indophenol, acridine, azine, perylene tetracarboxylic imide, dibenzpyrenequinone, azo or sulphur class and the aluminium chloride-sulphur monochloride complex of constitution AlCl32S2Cl2.  Sulphur monochloride or other diluents such as completely halogenated aliphatic compounds, e.g. carbon tetrachloride or hexachlorethane, sulphur - containing compounds, e.g. sulphur dioxide, sulphuryl chloride and sulphur dichloride, or selenium monochloride, or aluminium chloride or equivalent condensing agents such as zinc, ferric or cupric chloride may be employed with the above complex.  The crude reaction products may be purified by extraction with alkali, if necessary, with subsequent oxidation.  The dyes may be vatted with sodium sulphide solutions, e.g. with sodium sulphide melted in its own water of crystallization and may be employed to dye cotton and acetate or viscose rayon, the dyeings being oxidized on the fibre as by aeration or treatment with sodium perborate or acetic acid and sodium bichromate.  Wool, silk and nylon fibres may also be dyed with the products.  In the examples, the complex prepared by heating one mol. of aluminium chloride with a slight excess over two mols. of sulphur monochloride, is reacted with the following dyestuffs or pigments under varying conditions: copper phthalocyanine (alone or in presence of zinc, ferric or cupric chlorides), indigo, dithio-b -isoindigo and 4.41 - dimethyl -6.61 - dichlorothio - indigo (all in presence of carbon tetrachloride), 6.61-diethoxy-thioindigo (in presence of sulphuryl chloride), 2.1.21.11-naphthioindigo (in presence of liquid sulphur dioxide), N-phenylindophenol, carbazole-indophenol, 3.8-diamino-4.7-dimethyl-acridine, 2-methyl-3-amino-6-hydroxy-phenazine, the tetrakisazo dye 2-naphthylamine-6.8-disulphonic acid --> aniline --> m-toluidine (phosgenated), the trisazo dye salicylic acid \sM benzidine --> (alkaline) H-acid (acid) \sM 2.5-dichloroaniline, Pontamine black, the disazo dyes sodium 4-aminoazobenzene-4-sulphonate --> benzoyl-p-aminobenzoyl-J-acid and H-acid --> cresidine (phosgenated), Lithosol claret, Pontachrome fast red, 1-aminonaphthalene-2-sulphonic acid --> 2.3-hydroxynaphthoic acid, m-chloroaniline --> 2.3-hydroxynaphthoic acid o-toluidide, 3.31-diamino-azoxybenzene \sQ 2.3-hydroxynaphthoic acid anilide (2 mols.), indanthrone, Ponsol red violet, anthraquinone-1.2.5.6-di-(C-phenylthiazole), dibenzanthrone, iso - dibenzanthrone, 3.4.8.9 - dibenzenpyrenequinone - (5.10), 1.8 - di - p - toluidino - anthraquinone, quinizarin, safranine, metal - free phthalocyanine, p.p1-di-(6-methylbenzthiazyl)-azobenzene, perylene - 3.4.9.10 - tetracarboxy - N.N1-diphenyldi-imide (in presence of cupric chloride) and the product of the oxidation of Primuline base with sodium hypochlorite in presence of ethylene glycol monoethyl ether.  Specifications 217,936, [Class 2 (iii)], 342,466, 366,472 and 435,342 are referred to.  The Specification as open to inspection under Sect. 91 comprises also the interaction of organic dyestuffs or pigments in general or of aromatic or aromatic-heterocyclic compounds, being dyestuff or pigment intermediates, with any complex of aluminium chloride and sulphur monochloride.  In additional examples, sulphur dyes are made by treating rhodamine, dehydrothio-p-toluidine or Primuline base with the complex AlCl3.2S2Cl2. Additional starting materials specified are benzene, toluene, naphthalene, anthracene, acenaphthene, benzpyrenequinone, carbazole, quinoline, acridine and phenazine.  The starting materials may be substituted by groups such as nitro, nitroso, amino, chloro, sulpho, carboxy, hydroxy or cyano groups. Sulphur dichloride or other agents which liberate sulphur monochloride under the influence of aluminium chloride may be used in place of sulphur monochloride in the preparation of the complex. This subject-matter does not appear in the Specification as accepted.