Patent GB-781286-A (GB)
Title: Manufacture of new cobaltiferous azo-dyestuffs
IPC: C09B45/20
Filed: 1953-10-23
Abstract: The invention comprises cobalt complexes which contain one atom of metal per two mols. of at least one sulphonic and carboxylic acid group free dyestuff of formula R-N = N-A-NH2, where R is a hydroxybenzene residue attached to the azo group o to the OH group, and A is a naphthalene residue which is attached to the azo group in adjacent position to the amino group, the dyestuff molecule containing a sulphone group having more than one carbon atom and/or at least one acid amide group, preferably a sulphonamide group, R containing at the most one sulphonamide group.  The dyestuffs are made in conventional fashion by metallizing appropriate monoazo dyestuffs made from the required phenols and naphthylamines.  Two sulphonamide groups may be present in A either separately or in one substituent, e.g. -SO2NH aryl SO2NH2.  If two sulphonamide groups are present one of them is preferably substituted.  Preferably sulphonamide groups are present and R contains a nitro group. Dyestuffs of formula: <FORM:0781286/IV (b)/1> where one Y is H and the other a sulphonamide group are especially preferred.  Specified diazo components are 2-aminophenol-4- and 5-ethyl, n- and iso-propyl, n-butyl and benzyl sulphones, 2 - aminophenol - 4 - nitro - and chloro - 6-phenyl, 4 - and 6 - nitro - 6 - and 4 - benzyl and 6 - nitro - 4 - ethyl - and benzyl sulphones, 3 - and 4 - amino - 4 - and 3 - hydroxy, 3-amino - 4 - hydroxy - 41 - methyl -, chloro - and methoxy - and 4 - amino - 3 - hydroxy - 41-methyl - 1,11 - diphenyl sulphones, 2 - aminophenol - 4 - carboxylic acid amide, and especially 2 - aminophenol - 4 - and 5 - sulphonamides and their corresponding methyl, ethyl, isopropyl, n-, sec. and tert. butyl, b -hydroxy- and chloro-ethyl, benzyl, cyclohexyl, phenyl, p-chlorophenyl or tolyl amides and the corresponding dimethyl diethyl, dibutyl, N-methyl- and ethylphenyl amides, 4-nitro- and chloro-2-aminophenol - 6 -; 4 - chloro - and methoxy - 2 - aminophenol - 5 - and 6 - chloro - and nitro - 2 - aminophenol - 4 - sulphonamides, 4-nitro-, chloro - and methoxy -, 5 - nitro -, 4-chloro - and methyl - 5 - nitro -, 4 - nitro - 6-chloro - and acetylamino -, 4,6 - dichloro -, and dinitro - 6 - nitro - 4 - acetylamino - 1 - methyl - and chloro - and 4 - methoxy - 5 - chloro - 2-aminophenols.  Specified naphthylamines are 2-naphthylamine - 4 -, 5 -, 6 - and 7 - sulphonamides, 6 - sulphonic acid methyl, isopropyl- and phenylamides and 6-ethyl- and phenylsulphones, 1 - naphthylamine - 4 - and 5 - sulphonamides and sulphonic acid methyl amides, 6 - bromo -, methoxy - and methyl - 2 - naphthylamine and especially 2-naphthylamine or its 1-sulphuric acid (which loses the acid group on coupling), vide Specification 756,148.  The dyestuffs may be metallized in admixture with other o-hydroxy-o1-amino-, hydroxy- and carboxy-monoazo dyestuffs.  Preferably the additional dyestuffs are of formula HO-R-N = N-R1 where OH is oto -N = N- and R is a benzene residue free of SO3H and COOH groups and R1 is the residue of an azo-component free of SO3H and COOH groups attached to -N = N- oto an OH or NH2 group. Particularly preferred mixed dyestuffs are obtained from a dyestuff of the preferred nitrobenzene series indicated above and a dyestuff of formula: <FORM:0781286/IV (b)/2> Specified diazo components for the additional dyestuffs are 6-acetylamino-4-nitro-, 4- and 5-nitro -, 4,6 - dinitro - and dichloro -, 4 - nitro-6 - chloro -, 6 - nitro - 4 - methyl - and acetylamino - 2 - aminophenol, 2 - aminophenol - 4- and 5-methyl sulphones and the other sulphones and sulphonamides listed above. Specified coupling components for the additional dyestuffs are 5 - chloro - and 5,8 - dichloro - 1 - naphthol, 2 - naphthol, 6 - methoxy - and bromo - 2 - naphthol, 1 - acetyl -, n - butyryl, benzoyl - carbomethoxy - and carboethoxyamino - 7 - naphthol, 4 - methyl -, tert. amyl and acetylaminophenol and preferably 1-phenyl- and (21 -, 31 - and 41 - chlorophenyl) - 3-methyl - - pyrazolones, 1 - phenyl - 5 - pyrazolone-3-carboxylic acid amides, acetoacetic acid anilide, 1 - acetoacetylamino - 21 -, 31 - and 41-chlorobenzene and the above mentioned naphthylamines. The dyestuffs dye animal materials such as silk, leather and wool and superpolyamide and urethane fibres from weakly alkaline to weakly acid baths.  In examples which illustrate the preparation of the dyestuffs and their use in dyeing wool and nylon in grey and green shades the components used are chosen from those specified above with the addition of the following azo components: 2-naphthylamine - 6 - sulphonic acid anilide - 31 - sulphonamide, 6 - sulphonic acid dimethylamide and 6 - methyl sulphone, 1 - naphthylamine - 3-sulphonic acid methylamide and 4-methyl-2-acetylamino- and 4-tert. amyl-phenols.  Specification 326,226, [Class 2(iii)], also is referred to.