Patent GB-649674-A (GB)
Title: Manufacture of copperable disazo and polyazo dyestuffs
IPC: C09B35/00
Filed: 1948-09-14
Abstract: Diamines of the general formula <FORM:0649674/IV (b)/1> where R means hydrogen, halogen, or a methy or hydroxy group are prepared by methods such as those of Specification 341,970, e.g. by the reaction of a 3-nitro-4-acyloxybenzoyl halide with 2 : 5-diamino-benzoic acid to give a 3 - nitro - 4 - acyloxybenzoylamino compound, which is then reduced, and partially hydrolysed to remove the acyl group, or the hydrolysis may take place during benzoylation or reduction.  Instead of nitroacyloxybenzoyl chlorides there may be used nitro-hydroxybenzoyl chlorides, e.g. 3-nitro-4-hydroxy-benzoyl chloride, prepared from the corresponding acid by treatment with thionyl chloride.ALSO:Copperable diazo and polyazo dyestuffs are made by coupling 1 mol. of a tetrazo compound of a diamine of the general formula <FORM:0649674/IV (c)/1> wherein R means hydrogen, halogen, a methyl or alkoxy group, in any desired order, with 1 mol. of a derivative of a b -ketocarboxylic acid capable of coupling and with either 1 mol. of a different or identical b -ketocarboxylic acid derivative or with a naphthol-sulphonic acid coupling in a position adjacent to the hydroxyl group which may contain further substituents and also azo groups.  Coppering may be carried out in the dyebath or in a fresh bath.  The following examples describe the coupling of 1 mol. of tetrazotized 1-(31-amino-41-hydroxybenzoylamino) - 4 - aminobenzene - 3 - carboxylic acid with (1) two mols. of 1-(41-aminophenyl)-3-methyl - 5 - pyrazolone, 1 - phenyl - 3 - methyl - 5 - pyrazolone, 3 - methyl - 5 - pyrazolone, 1 - (21- or 41-chlorophenyl)-3-methyl-5-pyrazolone, or 1-phenyl-3-methyl-5-pyrazolone-31- or 41-sulphonamide; (2) 1 mol. of 2-methoxyacetoacetic acid anilide-monosulphonic acid and 1 mol. of 4-aminoacetoacetic acid anilide; (3) 1 mol. of 1-phenyl-3-methyl-5-pyrazolone and 1 mol. of 2-(31- or 41-aminobenzoyl-amino)-6-hydroxynaphthalene-8-sulphonic acid, 2-(31-amino - 41 - chlorobenzoylamino) - 6 - hydroxynaphthalene-8-sulphonic acid, or 2-acetyl- or benzoyl - amino - 6 - hydroxynaphthalene - 8 - sulphonic acid; (4) 1 mol. of 2-phenyl-amino-5-hydroxynaphthalene - 7 - sulphonic acid and 1 mol. of 4-amino-acetoacetic acid anilide, or acetoacetic acid anilide, or 4-acetylaminoacetic acid anilide; (5) 1 mol. of 1-(41-aminophenyl)-3-methyl-5-pyrazolone and 1 mol. of hydroxynaphthalene-4-sulphonic acid or 2-hydroxynaphthalene - 7 - sulphonic acid; (6) 1 mol. of 2-(41-hydroxy-31-carboxyphenylamino) - 5 - hydroxy - naphthalene - 7 - sulphonic acid, 2 - (31 - carboxyphenylamino) - 8 - hydroxynaphthalene - 6 - sulphonic acid and 1 mol. of 2-methoxyacetoacetic acid anilide; (8) 1 mol. of 4-acetylamino-acetoacetic acid anilide, 3-methyl-5-pyrazolone, or 1-(41-chlorophenyl)-3-methyl-5-pyrazolone and 1 mol. of 2-hydroxy-naphthalene-4-sulphonic acid.  In example (7), 1 mol. of 1-(31-amino-41-hydroxybenzoyl-amino)-4-amino benzene 3-carboxylic acid, 1 - (31 - amino - 41 - hydroxy - 5 - methoxy benzoyl - amino) - 4 - aminobenzene - 3 - carboxylic acid, or 1 - (31 - amino - 41 - hydroxy - 61 - chlorobenzoyl - amino) - 4 - aminobenzene - 3-carboxylic acid is coupled with 1 mol. of 1 - (41 - aminophenyl) - 3 - methyl - 5 - pyrazolone and 1 mol. of 1-acetylamino-8-hydroxynaphthalene-4-sulphonic acid.  In example (9) cotton is dyed a yellowish-brown shade from a bath containing a dye prepared as in (1), sodium carbonate, and sodium sulphate, followed by treatment in a bath containing copper sulphate and acetic acid.  A list of other starting materials is given, including as naphthol sulphonic acids containing azo groups 1 - (41 - hydroxy - 31 - carboxyphenylazo - (11)) - 2 - amino - 5 - hydroxynaphthalene - 7 - sulphonic acid, and 1-(41-nitro-21-carboxy-phenylazo - (11)) - 2 - amino - 5 - hydroxynaphthalene - 7-sulphonic acid.  A table summarises forty other examples employing a diamine of the general formula given with various first and second coupling components.  The Specification as open to inspection under Sect. 91 comprises also the use as starting materials of diamines of the above formula in which the hydroxy group is acylated, the acyl group being removed by hydrolysis of the completed dyestuff molecule. This subject-matter does not appear in the Specification as accepted.