Patent GB-793086-A (GB)
Title: Improvements in or relating to copperable polyazo dyestuffs
IPC: C09B35/46
Filed: 1956-06-01
Abstract: The invention comprises dyestuffs of formula <FORM:0793086/IV (b)/1> where y and z are OH or COOH, R is H or an alkyl, cycloalkyl, aralkyl or aryl group which may contain substituents, <FORM:0793086/IV (b)/2> is the residue of a compound capable of coupling in the position adjacent to an enolizable keto group, and nucleus I may contain substituents, and mixtures of two or more of the above polyazo dyestuffs.  They may be made by coupling 1 mol. of a tetrazo compound of an appropriate diphenyl with 1 mol. of the benzene-azonaphthalene dyestuff and keto-methylene end components.  The first coupling is preferably performed in a soda-alkaline medium and the final coupling in the presence of a tertiaryorganic base.  Indicated keto-methylenes are 5-pyrazolones, acylacetic acid amides, arylamides and alkylamides, malonic and barbituric acid derivatives, acetyl- and benzoyl-acetone and 4-hydroxy-1-alkyl- and 2,4-dihydroxyquinolines, preferred being 3-methyl-, 1-phenyl-and -(31- and 41-chloro, -nitro and -methyl sulphonyl and 21, 51-dichloro)-phenyl-3-methyl-5-pyrazolones, 1 - phenyl - 3 - methyl - 5 - pyrazolone-31- and-41-sulphonic acid amides, and particularly acetoacetylaminobenzene which may contain halogen, amino, nitro, alkylsulphonyl, sulphonic acid, sulphonamide, carboxylic acid and azo groups as nuclear substituents, 1- and 2-acetoacetylamino-naphthalenes and their mono- and di-sulphonic acids, 1-aceto acetylamino-hexane, -octane, -2-ethylhexane and -2,2-dimethylethane.  The keto-enol component may be a mixture of such compounds and mixtures of 5-pyrazolone and acetoacetic acid aryl amides are instanced.  The dyestuffs dye cotton and fibres of regenerated cellulose in violet shades which are displaced towards grey or black on after-coppering.  Examples are provided of the preparation of the dyestuffs and their use in dyeing processes, the dyestuffs being (1) acetoacetylaminobenzene \sM 4,41-diamino-1,11 - diphenyl - 3,31 - dicarboxylic acid --> 2 - phenylamino - 5 - naphthol - 7 - sulphonic acid \sM 2-aminophenol-4-sulphonamide; (2) 2-acetoacetylaminonaphthalene - 6 - sulphonic acid \sM 4,41-diamino-1,11-diphenyl-3,31-dicarboxylic acid --> 2-phenylamino-5-naphthol-7-sulphonic acid \sM 2-amino-4-nitrophenol; (3) mixed 1-acetoacetylaminonaphthalene-6-and -7-sulphonic acids \sM 4,41-diamino-3,31-dihydroxy-1,11-diphenyl --> 2-phenylamino-5-naphthol-7-sulphonic acid \sM 2-amino-4-nitrophenol; (48) mixed acetoacetylaminobenzene and 1-phenyl-3-methyl-5-pyrazolone, or certain of their derivatives, \sM 4,41-diamino-1,11 - diphenyl - 3,31 - dicarboxylic acid --> 2-phenylamino - 5 - naphthol - 7 - sulphonic acid \sM 2 - aminophenol - 4 - sulphonamide; and in (49) the acetoacetylaminobenzene of (48) is replaced by an acetoacetylaminonaphthalene sulphonic acid such as 2-acetoacetylamino-6-sulphonic acid, and a Table is also provided listing examples of products the values (additional to those indicated above) for R being H, methyl, butyl, cyclohexyl, benzyl, chlorophenyl and tolyl, the phenyl residue of the azo dyestuff end component additionally being derived from 2 - amino - 4 - methylsulphonyl -, - 5 - nitro -, -4-chloro-6-nitro- and -4-nitro-6-carboxy-1-phenols, 2 - aminophenol - 5 - sulphonamide, -4-sulphonic acid methyl-, 21-hydroxyethyl- and 31-methoxypropyl amides, 2-aminophenol-4-sulphonic acid and its 4-nitro-derivative, 2-amino-6-carboxy-phenol-4-sulphonic acid, 2-amino - 5 - nitrobenzene - 1 - carboxylic acid, 2 - amino - 1 - carboxybenzene - 4 - sulphonic acid and additional keto-enol components are 1 - acetoacetylamino - 3 - sulphonamido -, - 2 - methoxy- and -chloro-, -2,5-diethoxy-, -2,5-dimethoxy-4-chloro-, -4-methoxy-, -hydroxy- and -acetyl- and -benzoyl-amino-benzenes, 1-acetoacetylamino - 2 - methoxy - benzene - #c - monosulphonic acid, 1-acetoacetylaminobenzene-2-and -4-carboxylic and sulphonic acids, 1-acetoacetylaminobenzene - 4 - carboxylic acid - (41 - hydroxy - 31 - carboxy) - phenylamide, 1 - acetoacetylaminodiphenylamino-3-sulphonic acid, 1-aceto- and -benzoylacetylaminobenzene-3-sulphonamides, 2 - acetoacetylaminonaphthalene-5-, -6- and -7-sulphonic acids, 1-acetoacetylaminonaphthalene - 5 - sulphonic acid, 2 - benzoylacetylaminonaphthalene - 6 - sulphonic acid, 5 - acetoacetylamino - 1,2,3,4 - tetrahydroxynaphthalene, 1 - phenyl - 3 - methyl - 5 - pyrazolone - 31 - sulphonamide, 1 - naphthyl-(21) - 3 - methyl - 5 - pyrazolone - 61 - sulphonic acid, 4 - acetoacetylamino - 1,11 - azobenzene - 41-mono- and 3,41-di-sulphonic acids and mixtures of acetoacetylaminobenzene and its 3-sulphonic acid and 1-acetoacetylamino-4-chlorobenzene and 1-acetoacetylaminonaphthalene-5-sulphonic acid.