Patent GB-774150-A (GB)
Title: Improvements in or relating to metalliferous polyazo dyestuffs
Filed: 1955-01-21
Abstract: The invention comprises metalliferous polyazo dyestuffs having in the metal-free state the formula <FORM:0774150/IV(b)/1> where one R is the radicle of a diazo compound of an aminoazo dyestuff, obtained by coupling a diazo-mono- or -disazo compound containing a metallizable substituent o to the diazo group, in the 7-position of a 1-amino-8- naphthol-mono- or -disulphonic acid and the other R is the radicle of a diazo or diazomonoazo compound containing a metallizable substituent p to the diazo group the product containing from 2-5 sulphonic acid groups.  The compounds are made by coupling diazo-compounds of appropriate amines RNH2 in any order with resorcinol and treating the products with metal yielding agents or by first coupling one of the diazo-compounds with resorcinol, metallizing, coupling with the other diazo-compound and finally metallizing. Specified diazo components corresponding to those containing the naphthoasulphonic acid are derived from the following amines: 3-methoxy-4-amino-6-methyl-41-hydroxy 1, 11-azobenzene-31-carboxylic acid, 3-methoxy-4-amino-6-methyl-31-carboxy-41-hydroxy-1, 11-azo-benzene-51-sulphonic acid, 1-amino-3-carboxy-4-phenol-5-sulphonic acid --> 3-methylaniline --> 1-amino-2-methoxy-5-methyl-benzene, 4-amino-1, 11- azobenzene-3-mono-and 3, 41-id-sulphonic acids --> 1-amino-2-methoxy-5-methylbenzene and 1-amino-2-methoxynaphthalene - 6 - sulphonic acid, 2-(41 - amino)-phenyl-6-methylbenzthiazole-monosulphonic acid --> 1-amino-2-methoxy-benzene and its 5-methyl- and acetylamino derivatives, 2-(41-amino)-phenyl-6-methyl-benzthiazolemono- and -di-sulphonic acids --> 3-methylaniline --> 1-amino-2-methoxynaphthalene-6-sulphonic acid, 2-1-amino -2- methoxy -5- methylbenzene, 2-naphthylamine - 4, 8 - and 6, 8 - disulphonic acids --> 3 - methylaniline --> 1 - amino - 2 - methoxy - 5 - methylbenzene, 4 - amino - 41 - nitro - 1, 11 - stilbene-2, 21 - disulphonic acid --> - amino - 2 - methoxy - 5 - methylbenzene and 1 - amino - 2 - methoxynaphthalene - 6 - sulphonic acid, 1 - carboxy - 2 - aniline - 5 - sulphonic acid --> 1 - (41 - amino) - phenyl - 3 - methyl - 5 - pyrazolone --> 1 - amino - 2 - methoxy - 5 - methylbenzene, salicylic acid \sM 4, 41 - diamino - 1, 11 - diphenyl --> 1 - amino-2 - methoxy - 5 - methyl - benzene and 1 - amino - 2 - methoxynaphthalene - 6 - sulphonic acid, salicylic acid \sM 3, 31 - dimethoxy - 4, 41 - diamino - 1, 11 - diphenyl --> 1 - amino - 2 - methoxy - 5 - methylbenzene and 1 - amino - 2 - methoxynaphthalene - 6 - sulphonic acid, 3, 31 - dimethoxy - 4, 41 - diamino - 1, 11 - diphenyl, 1 - amino - 4 - (41 - amino) - benzoylamino benzene - 2 - carboxylic acid and 1 - amino - 4 - (31 - methyl - 41 - amino) - benzoyl - aminobenzene - 2 - carboxylic acid --> salicylic acid, salicylic acid \sM 1 - amino - 4 - (41 - amino) - benzoylaminobenzene --> 1 - amino - 2 - methoxy - 5 - methylbenzene and 1 - amino - 2 - methoxy - naphthalene - 6 - sulphonic acid and 1 - amino - 2 - naphthol - 4 - sulphonic acid \sM 3 - aminophenol --> 1 - amino - 2 - methoxy - 5 - methylbenzene.  The 4 - mono - and 3, 6 - or 4, 6 - disulphonic acids are preferred 1 - amino - 8 - naphthol - sulphonic acids.  Coupling of the above diazo components with the naphthol sulphonic acids may be effected in weakly alkaline solution, advantageously when using a 1 - amino - 2 - alkoxynaphthalene - 6 - sulphonic acid with the addition of an agent such as pyridine, the diazotization of the intermediates generally being effected by the indirect method.  Specified amines for the preparation of the diazo compounds corresponding to the second R are 1 - hydroxy - and - methoxy - 2 - aminobenzene - 4 - sulphonic acids and their amides, 2 - amino - 4 - nitrophenol and its 6 - nitro - and - sulpho - derivatives, anthranilic acid, 2 - amino - 6 - chlorophenol - 4 - sulphonic acid, 1 - methoxy - 2 - amino - 5 - nitrobenzene and its - 4 - sulphonic acid, 1 - amino - 2 - naphthol - 4 - sulphonic acid, 1 - amino-2 - methoxynaphthalene - 6 - sulphonic acid, 3 - methoxy - 4 - amino - 6 - methyl - 41 - hydroxy - 1, 11 - azobenzene - 31 - carboxylic acid, 3 - methoxy - 4 - amino - 6 - methyl - 31 - carboxy - 41 - hydroxy - 1, 11 - azobenzene - 51 - sulphonic acid, 3 - methoxy - 4 - amino - 6 - methyl - 1, 11 - azobenzene - 31 - and - 41 - sulphonic acid and 3 - amino - 4 - hydroxy - 1, 11 - azobenzene - 31 - sulphonic acid.  The first coupling with resorcinol may take place in acetic acid, neutral or weakly alkaline solution the second coupling generally requiring in addition to an alkaline agent such as ammonia or sodium carbonate, a diazo stabilizer such as naphthalene - 2 - sulphonic acid and, in some cases, an agent such as pyridine. Metallization may be effected in known fashion most advantageously by heating the aqueous dyestuff paste with metal-yielding agents in the presence of alkali metal salts of lowmolecular aliphatic carboxylic acids.  Specified metals are nickel and copper the latter being preferred.  The dyestuffs may be after-coppered.  Colour shades obtained vary between blue, olive, khaki, brown and grey.  Examples are provided of the preparation of the dyestuffs and their use in dyeing cotton and regenerated cellulose additional specified components corresponding to the first diazo component being salicylic acid \sM 1, 4 - diaminobenzene --> 1 - amino - 2 - methoxynaphthalene - 6 - sulphonic acid, 2 - (41 - amino) - phenyl - 6 - methylbenzthiazole monosulphonic acid --> 1 - amino - 2 - hydroxy - 5 - methylbenzene, 2 - (41 - amino) - phenyl - 6 - methylbenzthiazole 1 31 - sulphonic acid --> 1 - methoxy - 2 - amino - 4 - methylbenzene, 1 - amino - 4 - phenol - 3 - carboxylic acid --> 1 - amino - 2 - methoxy - 5 - methylbenzene, 1 - amino - 3 - carboxy - 2 - phenol - 5 - sulphonic acid --> 1 - amino - 2 methoxy - 5 - methylbenzene, 1 - amino - 2 - phenol - 5 - sulphonic acid --> 1 - (41 - amino) - phenyl - 3 - methyl - 5 - pyrazolone --> 1 - amino - 2 - methoxy - 5 - methyl - benzene and 1 - naphthylamine - 4, 8 - disulphonic acid --> 3 - methylaniline --> 1 - amino - 2 - methoxy - 5 - methylbenzene and additional components corresponding to the second diazo component are derived from 1 - methoxy - 2 - amino - 6 - chlorobenzene - and 2 - amino - 6 - nitrophenol - 4 - sulphonic acids.