Patent GB-771320-A (GB)
Title: Metalliferous azo-dyestuffs and process for making them
IPC: C09B45/14
Filed: 1954-05-20
Abstract: The invention comprises chromium or cobalt compounds which contain one atom of metal bound in complex union with 2 mols of different o - carboxy, o1 - oxy -, o, o1 - dioxy - or o - oxy, or o1 - amino - monoazo dyestuffs, one of which has a single free sulphonic acid group and another no sulphonic or carboxylic acid groups, and one of which, advantageously the latter, contains a sulphonic acid aryl ester group or especially a sulphone or sulphonamide group.  They may be made by metallizing appropriate mixtures of monoazo dyestuffs. The dyestuffs containing a sulphonic acid group may be of formula HO3S - R(OH) - N=N - R1OH where R and R1 are napthalene residues and especially of formula <FORM:0771320/IV(b)/1> where R1 is a naphthalene residue which may be halogenated. The dyestuffs free of acid groups may be of formula X - R2 - N=N - R1 where X is a sulphone or sulphonamide group and R2 is a phenolic and R1 a naphtholic residue.  The metal-free dyestuffs used as starting materials are made in conventional fashion and diazo compounds used in their preparation are advantageously those of o - oxy-anilines or - napthylamines which contain further substituents incapable of salt formation e.g. nitro, chlorine, methyl, methoxy, acetylamino and sulphonamido groups, the latter preferably being substituted. Specified diazo components used for dyestuffs containing a sulphonic acid group are 4 - and 5 - chloro -, 4, 6 - di - and 3, 4, 6 - tri - chlor-, 5-, 5 - and 6 - nitro -, 4 chloro - 5 - and - 6 - nitro -, 4 - nitro - 6 chloro - and - acetylamino -, 6 - nitro - 4 acetylamino - and 4, 6 dinitro - 2 - aminophenols, 1 - amino - 2 - naphthol, 2 - aminophenol - 4, and - 5 - sulphonic acid phenylamides, 4 - chloro - 2 - aminophenol 5 sulphonic acid phenyl-and N - ethyl - N - phenylamides, anthranilic acid and its 4 and 5-sulphonic acids, 2-aminophenol - 4 - and 5 - sulphonic acids, 4 - chloro- and - methyl - 2 - aminophenol-5 - and 6 - sulphonic acids, 4 - nitro - 2-aminophenyl - 6 - sulphonic acid - 6 - nitro 2 - aminophenol - 4 - sulphonic acid and preferably 2 - amino - 1 - naphthol - 4 - and - 8 - sulphonic acids, 6 - nitro -, bromo - and - methoxy - 1 - amino - 2 - naphthol - 4-sulphonic acids and especially 1 - amino - 2 - naphthol - 4 - sulphonic acid.  Indicated as coupling components for these diazo components are phenols e.g. p-cresol and p - tert, amyl phenol, b -keto - carboxylic acid esters and amides, e.g. acetoacetic acid anilide and 1 - acetoacetyl amino - 2 -, - 3 - and - 4 - chlorobenzenes, pyrazolones, e.g. 1 - n - octyl-, phenyl -, -(21-ethylphenyl) -, -(21-, 31- and 41- chloro and -methyl-phenyl) - (21, 51 - dichlorophenyl) - and - [napthyl - (11) - and - (21)] - 3 - methyl - 5 - pyrozolones 1, 3 - diphenyl - 5 - pyrazolone, 1 - phenyl - 5 - pyrazolone - 3 carboxylic acid phenylamide, oxyquinoline barbituric acids and especially naphthyl - amines and naphthols e.g. 6 - bromo, - methoxy - and -methyl - 2 - naphthols and naphthylamines, 2 - phenylaminonaphthalene, 2 - naphthylamine and its 1 - sulphonic acid, 1 - acetyl-, n - butyryl - benzyl - and -carbethoxy amino - 7 - naphthols, 5- and 7 - mono- and 5, 8- di-chloro-1 - naphthols, 4, 8 - and 5, 8 - dichloro - 2 2 - naphthols, 1- and 2- naphthols, 1 - phenyl - 3 - methyl - 5 - pyrazolone - 21-, -31- and -41- sulphonic acids, 21 - chloro - 1 - phenyl - 3 - methyl - 5 - pyrazolone - 41 - and - 51 - sulphonic acids, 21, 51 - dichloro - 1 - phenyl - 3 - methyl - 5 pyrazolone - 41 - sulphonic acid, 1 - [naphthyl-(11)] - 3 - methyl - 5 - pyrazolone - 41 -, -51 -, - 61-, -71- and - 81 - sulphonic acids, 1 - [naphthyl - (21)] 3 - methyl - 5 - pyrazolone - 21- and - 81 - sulphonic acids, 1 1 - acetoacetylamino - benzene - 4 - sulphonic acid, 2 - amino- and -oxy - naphthylaminobenzene - 4 - sulphonic acid, 2 - amino - and - oxy - naphthylene - 4 - , -5-, -6- and - 7 - sulphonic acids, 1 naphthol - 4-, - 5 - and - 8 - sulphonic acids and 2 - phenylaminonaphthalene - 31- and -41 - sulphonic acids.  Diazo compounds used in the preparation of the acid free dyestuffs may be made from amines already specified for diazo compounds which do not have a sulphonic acid group and the following specified amines: 4 - chloro - and - nitro-2 - aminophenol - 6 - sulphonamides, 6 - nitro - 2 - aminophenol - 4 - sulphonamide, 2 - aminophenol - 4 - and - 5 - sulphonic acid methyl -, phenyl - and - dimethyl - amides, 4 - chloro - 2 - aminophenol - 5 - sulphonic acid methyl-, ethyl -, isopropyl -, phenyl -, dimethyl-, diethyl - and N-methyl-N - phenyl - amides and corresponding compounds containing a methyl, ethyl and especially a phenyl and p - methyl - or - chloro - phenyl - sulphone group in place of the sulphonamide group.  Coupling components for use with these diazo compounds are those already specified which do not contain sulphonic acid groups and 1 - phenyl - 3 - methyl - 5 - pyrazolone - 31- sulphonic acid amide and methylamide, 2, 4 - dioxyquinoline, 5 - chloro - 8 - oxyquinolin, 2 - naphthoylamine - 4 -, - 5 - and - 6 - sulphonamide and amides and phenol esters of 1 - naphthol - 4-, -5- and - 8 - and 2 - naphthol - 4-, - 6 - and - 7 - sulphonic acids.  The mixture of dyestuffs to be metallized may be obtained by coupling 2 mols of a diazo compound with one mol of each of two different coupling components or the quantities of diazo compound and coupling components may be transferred.  Preferably the mixture contains at least one mol of dyestuff free of acid groups per mol of dyestuff containing a sulphonic acid group. Metallization is effected by conventional methods either by treating mixtures of metal-free azo dyestuffs with cobalt or preferably chromium yielding agents or by treating a metal-free dyestuff with a 1, 1 - metal complex of an appropriate dyestuff. The metal complexes dye silk, leather, wool and fibres of superpolyamides, superpolyurethanes and polyacrylonitrile from alkaline, neutral or weakly acid baths. Examples are provided illustrating the preparation of metal-complexes from certain of the above specified reactants, additional components listed being 2 - aminophenol - 4 - and 5 - sulphonamides and - 4 - sulphonic acid isopropylamide and 1 - carbomethoxy - 7 - naphthol, the metal complexes obtained being used to dye wool in blue, grey, yellow, red and green tints and nylon navy blue.