Patent GB-755113-A (GB)
Title: New cobaltiferous azo-dyestuffs and process for making them
IPC: C09B45/20
Filed: 1954-02-05
Abstract: The invention comprises cobalt complexes of dyestuffs free of sulphonic and carboxylic acid groups of formula R-N = N-A-NH-Y where R is a residue of a diazo component of the benzene series bound to the azo link vicinal to a hydroxy group, Y is an alkyl or advantageously aryl residue which may contain substituents, and A is a naphthalene residue which is bound to the azo link vicinal to the -NH-Y- group.  Preferred are compounds containing one atom of cobalt to two mocules of monoazo-dyestuff especially those of the above formula where R is a nitrobenzene residue.  Y is a benzene residue and the naphthalene residue is bound to the azo link in the 1- and the -NH-Y group in the 2-position and in which at least one of the aromatic residues R, A and Y contain a sulphone or sulphonamide group which may contain substituents, particularly preferred cobalt components being obtained from dyestuffs of formula <FORM:0755113/IV(c)/1> where one Y is a sulphonamide group and the other H.  The cobalt dyestuffs are obtained from the unmetallized dyestuffs in the usual way by treating with a cobalt-yielding agent. Mixtures of two different dyestuffs of the above formula or of one dyestuff of the above formula and an o : o1-dioxy-monoazodyestuff free of sulphonic and carboxylic acid groups.  Preferred o : o1-dioxy-monoazodyestuffs are those of the benzen-azoacylacetic acid amide series especially where substituted by sulphone or sulphonamide groups.  All the unmetallized dyestuffs are made by conventional methods. Diazo-components may be made from the following specified amines: -2-amino -1- phenol -4- or -5- methyl, -ethyl, -n-propyl, -isopropyl, -n-butyl or -benzyl sulphones, 4-chloro -2- amino 1-phenol -6- methyl and 6 chloro -2- amino -1-phenol -4- methyl sulphones, 2-amino -1-oxy -4- chlorobenzene -6- phenyl sulphone 3-amino -4- oxy-diphenyl sulphone which may contain a sulphonamide substituent, 4-amino-3-oxydiphenyl sulphone, 3-amino-4-oxy-4-methyl, -chloro- and -methoxy-1, 11, diphenyl sulphone, 4-amino -3- oxy -41-methyl-1, 11-diphenyl sulphone 6-nitro -2-amino -1- phenol -4- sulphonic acid -N-phenylamide -41- methyl sulphone, 2-amino -1- phenol -4- and -5- sulphonic acid amide and the corresponding -methyl-, -ethyl-, -isopropyl- -n-butyl-, -sec butyltert butyl-, oxyethyl- -benzyl-, cyclohexyl- and -phenylamide and the corresponding -dimethyl-, -diethyl-, -dibutyl-, -N- methyl -N- b -oxyethyl-, -N- methyl phenyl- and -N- ethylphenyl amides, 4-chloro -2- amino -1- phenol -5- and -6- sulphonic acid amide 6-chloro -2- amino -1- phenol -4- sulphonic acid amide, 4-methoxy -2- amino -1- phenol -5- suphonic acid amide, 4-nitro -2- amino -1- phenol -6- methoxy sulphone, 6-nitro -2- amino -1- phenol -4- methyl sulphone, 2-amino -1- oxy -6- nitrobenzene -4- phenyl and -benzyl sulphones and -4- nitrobenzene -6- phenyl and benzyl sulphones, 6-nitro -2- amino -1- phenol -4- sulphonic acid amide, 4-nitro -2- amino -1- phenol -6- sulphonic acid amide and -alkyl-, -oxyalkyl-, -N- alkyl -N- oxyalkyl- and -phenyl amides of the last two sulphonamides, 4-nitro-, -chloro- and -methoxy-, 5-nitro-, 4, 6-dichloro- and -dinitro-, 4-methoxy -5-chloro-, 4-chloro -5- nitro-, 4-nitro -6- chloro- or -acetylamino-, 6-nitro -4- chloro- or -acetylamino -2- amino -1- phenol and 3-amino -4- oxyacetophenone.  Specified coupling components are 1-phenylamino-naphthalene -4- methyl sulphone -sulphonic acid amide and -sulphonic acid methyl and phenyl-amides, 1-benzylaminonaphthalene -4- sulphonic acid amide, 2-methyl-, -oxyethyl- and phenyl-aminonapthalene, 2-phenylaminonapthalene, -6- methyl sulphone, -sulphonic acid amide and isopropylamide, 2-phenylaminonaphthalene -21-, -31- and -41- sulphonic acid amide and -21- and -41- methyl- or -ethyl sulphone, 2-phenylaminonaphthalene - 6 - sulphonic acid isopropylamide -21-, -31- and -41- sulphonic acid amid and -31- sulphonic acid methylamide, 2 - phenylaminonaphthalene-6-sulphonic acid m and p-sulphonamidophenylamide and 2 - sulphonamidophenylaminonophthalene-6-sulphonic acid phenylamide. Other d  : d -dihydroxy monoazo dyestuffs for use in mixtures may be obtained from the above specified diazo components and coupling components such as naphthols, 5-pyrazolones and acetoacetic acid arylides.  The dyestuffs are used in dyeing silk, leather, wool and superpolyamides or -urethanes.  Dyeing may be effected from weakly alkaline to weakly acid baths.  Examples and Tables are provided of the use of certain of the above specified components in the preparation of cobalt dyestuffs which dye wool in green shades coupling components used in the d  : d 1dihydroxy azo dyestuffs being acetoacetic acid anilide and d -chloranilide, 1-(4-chlorophenyl)-3-methyl-5-pyrazolone and 2-oxy-8-acetylaminonaphthalene.