GB517396A - Process for the manufacture of wool dyestuffs of the anthraquinone series - Google Patents

Abstract

517,396. Dyes. I.G. FARBENINDUSTRIE AKT.-GES. July 26, 1938, Nos. 22233 and 22234. Convention dates May 6, 1937, and July 26, 1937. [Class 2 (iii)] Blue wool dyestuffs are prepared by reacting 1-amino-4-halogenanthraquinones with monoaminobenzene sulphonic acid aryl esters or aryl amides, followed by sulphonation, or by reacting 1-amino-4-halogenanthraquinone-2- sulphonic acids with monoaminobenzene sulphonic acid aryl esters or arylamides. The reaction is preferably carried out in presence of copper acetate or chloride and in presence of alkali or alkaline earth metal salts of weak acids, e.g. sodium acetate, carbonate or bicarbonate, and fuming sulphuric acid or chlorsulphonic acid may be used as sulphonation agents. An indifferent solvent or excess of the aminoaryl sulphonic acid derivative may be used. In examples, (1) 1-amino-2-methyl-4- bromo- or chloro-anthraquinone is condensed with m-sulphanilic acid methylanilide, anilide or p-toluidide followed by sulphonation ; (2) 1-amino-2.4-dibromoanthraquinone is condensed with m-sulphanilic acid methylanilide, followed by sulphonation ; (3) 1-amino-2.4- dibromo-6-chloranthraquinone is condensed with with 1 - amino - 4 - chlor (or methyl) - benzene - 3 - sulphomethylanilide, followed by sulphonation ; (4) 1 - amino - 2.4 - dibromo - 6 - sulphodimethylamido (or sulphomethylanilido) - anthraquinone is reacted with m- .sulphanilic 'acid methylanilide, followed by sulphonation ;. (5) 1 - amino - 2.4 - dibromoanthraquinone is reacted with p-sulphanilic acid methylanilide, followed by sulphonation ; (6) 1 - amino - 2 - methyl - 4 - bromoanthraquinone is reacted with m-sulphanilic acid phenyl-, p-cresyl-, or p-chlorphenyl-ester followed by sulphonation; (7) 1-amino-4-. bromoanthraquinone - 2 - sulphonic acid is reacted with m-sulphanilic acid methylanilide or m-sulphanilic acid phenyl ester; (8) 1- amino-4-bromoanthraquinone - 2 - sulphonic acid is reacted with 4-methylaniline-3-sulphophenylester, 4 - methylaniline - 3 - sulpho - p<1> - chlorphenylester or 4 - methylaniline - 3 - sulphomethylanilide; (9) 1 - amino - 4 - bromoanthraquinone - 2 - sulphonic acid is reacted with 4-methylaniline-3-sulphonic acid- 2<1>-carbomethoxy (or carboethoxy)-phenylester or with 4-methylaniline-3-sulpho-o<1>-carboxyphenylester followed by esterification with dimethyl or diethyl sulphate ; the corresponding carboxymethylanilide derivatives may replace the carboxyphenylester derivatives. m-Sulphanilic acid methylanilide is obtained by condensing m-nitrobenzene sulphochloride with methylaniline and reducing the nitro group. p-Sulphanilic acid methylanilide is obtained by condensing methylaniline with N-acetyl-p- .sulphanilic acid chloride, followed by saponification of the acetyl group. m-Sulphanilic acid phenyl ester is obtained by condensing m-nitrobenzene sulphochloride with phenol and reducing the nitro group. 1 - Amino - 2.4 - dibromo - 6 - chloranthraquinone is obtained by dibrominating 1-amino- 6-chloroanthraquinone. 1 - Amino - 2.4 - dibromo - 6 - sulphodimethylamido (or sulphomethylanilido) - anthraquinone is obtained by reacting 1-nitroanthraquinone-6- sulphochloride with dimethylamine (or methylaniline), followed by reduction of the nitro group and dibromination. 1 - Amino - 4 - chlorbenzene - 3 - sulphomethylanilide is obtained by condensing 1-amino-4- chlorbenzene-3-sulphochloride with methyl aniline. 4 - Methylaniline - 3 - sulphophenylester is obtained by condensing 1 - nitro - 4 - methylbenzene - 3 - sulphochloride . with phenol and reduction of the group. 4-Methylaniline-3-sulphonic acid-2<1>-carbo - methoxy-phenylester is obtained by condensing 1-nitro-4-methylbenzene-3-sulphochloride with methyl salicylate, and subsequent reduction. The Specification as open to inspection under Sect. 91 also refers to the use of pyridone anthrones and pyrimidone anthrones as starting materials, and in further examples describes (1) the reaction of 4-bromo-N-methyl-anthrapyridone with m-sulphanilic acid methylanilide, followed by sulphonation, and' (2) the'reaction of 1-amino-4-methylbenzene-3-sulphomethylanilide with 1 - methylamino - 4 - bromoanthraquinone, followed by reaction of the product with ammonium chloride and urea in phenol to form a pyrimidone ring, and sulphonation. This subject-matter does not appear in the Specification as accepted.