Patent GB-426564-A (GB)
Title: Process for the manufacture of water-insoluble azodyestuffs
Filed: 1933-10-05
Abstract: Azo dyes; azo dyes, forming on the material; lakes.--Azo dyes are produced in substances, on a substratum or on the fibre by coupling an arylamide of 3-hydroxydiphenylene-sulphide 2-carboxylic acid or of 3-hydroxydiphenylene-oxide-2-carboxylic acid (which are obtainable by the process of Specification 426,403) with a diazotized primary aromatic or heterocyclic amine, the components being free from groups inducing solubility in water.  The dyeings range mainly from yellowish dark brown to black.  The following examples are specified. (1) Cotton yarn is treated for \ba1/2\be hour at 40--50 DEG  C. in an aqueous bath containing the 2<1>-methoxy-4<1>-chloranilide of 3-hydroxydiphenylene-oxide-2-carboxylic acid, alcohol, caustic soda and turkey red oil, is thereafter squeezed and developed for \ba1/2\be hour in an aqueous solution of diazotized 1-amino-2-methyl-4-nitrobenzene and is finally rinsed, soaped at the boil, rinsed and dried to obtain a dark brown dyeing; a table is given showing the colours of the dyeings with other diazo components viz., 2 : 5-dichloraniline, 1-amino-2-nitro-4-chloro-benzene, 1-amino-2-methoxy-4-nitrobenzene, 4-nitraniline, 1-amino-2-methyl-5-nitrobenzene, 4-aminodiphenylamine, 4-amino-2 : 3<1>-dimethylazobenzene and 1-amino-2-chloro-5-methoxy-4-benzoylaminobenzene; a further table shows the colours of the dyeings with the use as coupling component of the corresponding 2<1> : 5<1>-dimethoxy-4<1>-chloranilide and as diazo components of 2-aminocarbazole, 2-aminodiphenylene oxide and 3-aminodiphenylene sulphide.  (2) The dyestuffs 2-nitraniline --> the 2<1>-toluidide or the 4<1>-chloranilide of 3-hydroxydiphenyleneoxide-2-carboxylic acid are prepared in substance, the coupling in the first case being in caustic soda containing sodium acetate and in the second case in aqueous pyridine. (3) Cotton yarn is impregnated for \ba1/2\be hour at 40--50 DEG  C. in an aqueous bath containing the 2<1>-methoxy-4<1>-chloranilide of 3-hydroxydiphenylene-sulphide-2-carboxylic acid, alcohol and caustic soda and is thereafter squeezed and developed for \ba1/2\be hour in an aqueous solution of diazotized 1-amino-2-nitro-4-chlorobenzene to obtain a yellowish blackish brown dyeing; a table is given showing the colours of the dyeings with other diazo components, viz., 3-chloraniline, 2-, 3- or 4-nitraniline, 1-amino-2-nitro-4-methylbenzene, 1-amino-2-methyl-4 (or 5)-nitrobenzene, 1-amino-2-methoxy-4-nitrobenzene, 1-amino-2-methyl-3 (or 5)-chlorobenzene, 2-aminodiphenylsulphone, 1-aminoanthraquinone, 1 - amino - 2 - chlor-5-methoxy-4-benzoylaminobenzene and 4-amino-2 : 3 (or 3 : 2<1>) dimethylazobenzene; a further table shows the colours of the dyeings with the use as coupling component of the corresponding 2<1>-anisidide and as diazo components of 2-aminocarbazole, 2-aminodiphenylene oxide and 3-aminodiphenylene sulphide.  (4) The dyestuff 1-amino-2-nitro-4-methylbenzene --> the 2<1>-anisidide of 3-hydroxydiphenylene-sulphide-2-carboxylic acid is prepared in substance.  The Specification as open to inspection under Sect. 91 comprises also the use of other specified coupling components, viz. the anilide, 2<1>-toluidide, 2<1>- and 4<1>-anisidides, 2<1>-methyl-4<1>-chloranilide, 2<1> - methyl - 4<1> - anisidide, 2<1> : 5<1>-dimethoxyanilide, 2<1> : 4<1>-dimethoxy-5<1>-chloranilide and 1<1>-naphthylamide of 3-hydroxydiphenylene-oxide-2-carboxylic acid, and the anilide, 2<1> - toluidide, 2<1> - phenetidide, 3<1>-nitranilide, 4<1>-chloranilide, 3<1> : 4<1>-dichloranilide, 2<1> - methyl - 4<1> - chloranilide, 2<1> - methyl - 4<1> - methoxyanilide, 2<1> : 5<1> - dimethoxyanilide, 3<1> : 6<1> - dimethoxy - 4<1> - chloranilide, 2<1> : 4<1>-dimethoxy - 5<1> - chloranilide, 1<1> - naphthylamide, 1-aminocarbazole derivative, dianisidide and 2-amino-6-ethoxybenzothiazole derivative of 3-hydroxydiphenylene-sulphide-2-carboxylic acid, and the use of other specified diazo components, viz. 1-amino-2-methyl-4-chlorobenzene, 1-amino-2-methoxy-5-chlorobenzene, 1-amino-2 - methoxybenzene - 5 - sulphodiethylamide, 1-amino-2-methoxy-5-methyl-4-benzoylamino-benzene, 1 - amino - 2 - methoxy - 4 - methyl - 5 - benzoylaminobenzene, 4 - amino - 3 - methoxy diphenylamine, 1-amino-2-chlor-5-w-trifluoromethylbenzene, 4-amino-2 : 5-dimethoxy-4<1>-nitroazobenzene, 1 - amino - 2 : 4 - dimethyl-5-benzoylaminobenzene, 4 - chloro - 2 - amino-diphenyl ether, 4 - amino - 2 : 4<1> - dimethyl-5-methoxy - 2<1> - nitroazobenzene, 1 - amino - 2 : 5-dimethoxy (or diethoxy) -4-benzoylaminobenzene, 1 - amino - 2 - methoxy - 5 - nitrobenze, 1 - amino - 2 - methoxy - 5 - w - trifluoromethylbenzene, 2-chloraniline and 4-aminodiphenyl amine-4<1> : 1<11>-azo-2<11>-methyl-4<11>-amino-5<11> -methoxybenzene.  This subject-matter does not appear in the Specification as accepted.