Patent GB-772019-A (GB)
Title: Chromium- and cobalt-containing azo dyestuffs of the benzene-azo-2-hydroxynaphthalene-3-carboxylic acid series
IPC: C09B29/20
Filed: 1954-06-29
Abstract: The invention comprises chromium- or cobalt-containing dyestuffs which in their metal-free state are of formula <FORM:0772019/IV(b)/1> where R1 is H, lower alkyl, lower hydroxyalkyl, lower alkoxyalkyl, aralkyl cycloalkyl, phenyl or substituted phenyl, R2 is H, lower alkyl or with R1 and N is the residue of a heterocyclic amine, X is o to - N = N - is metallizable substituent and R is phenyl or substituted phenyl and, when R1 and R2 together contain more than 3 carbon atoms, must bear a sulphonamide, N - substituted - sulphonamide or alkylsulphonyl group.  The term "lower" denotes a group containing 1-6 carbon atoms.  Preferably R contains a sulphonamide N - substituted sulphonamide or akylsulphonyl group R1 is H, lower alkyl or phenyl and H2 is H. he dyestuffs are made by coupling preferably in an alkaline medium, a diazo compound of an appropriate amine with the required - napthol - 3 - carboxylic acid amide and metallizing the product in known fashion generally to yield 1, 2 complexes. Hydroxy methoxy carboxy and carboxymethoxy groups are specified metallizable groups. Preferred amines are 2 - amino - 1 - hydroxy or - methoxy - benzenes which may contain lower alkyl lower alkoxy, aryl- or substituted - acylamino, nitro, halogen, sulphonamide, N - substituted - sulphonamid and alkylsulponyl groups Anthranilic acid optionally bearing an alkylsulphonyl, sulphonamide or N - substituted - sulphonamide group is a specified 2 - aminobenzene - 1 - carboxylic acid.  The N - substituents of the naphthol - carboxylic acid amides may be further substituted e.g. the alkyl radicals may contain hydroxy or methoxy groups and the phenyl group may contain lower alkyl, sulphonamide, alkylsulphonyl or alkoxy groups or halogen atoms. Heterocyclic residues for - N R1 R2 may be derived from morpholine, pyrrolidine or piperidine.  The dyestuffs dye wool from a neutral bath and silk from a weakly acid bath in red, brown, violet, blue and green shades and also dye leather and synthetic nitrogenous fibres such as polyamide fibres.  The invention also comprises 1, 2-metal complex dyestuffs obtained when one or more of the above metal-free dyestuffs is metallized together with one or more dyestuffs of the fomula R1 - N = N - R11 - OH where R1 is phenyl or substituted phenyl containing a hydroxy or carboxy group o to the azo group but otherwise free of water-solubilising groups, R11-OH is a naphthol or phenol residue free of water-solubilising groups with the OH group o to - N = N - or for a pyrazolone free of water-solubilising groups or acylacetic acid arylamide free of water solubilising groups, the fraction of the dyestuff or dyestuffs carrying a water-solubilising group being at least 50 mol, per cent. Specified water-solubilising groups are SO3H, COOH, alkylsulphonyl, sulphonamide N - lower alkyl, cycloalkyl, aralkyl, aryl or acyl substituted sulphonamide groups. Lower alkyl, aryl, nitro, acylamino and halogen substituents are specified as not influencing water-solubility.  In examples cobalt or chromium-containing dyestuffs are made and their use in dying nitrogenous fibres is illustrated, in the preparation of water-soluble dyestuffs the following diazo components are used 2 - amino - 1 - phenol - 4 - sulphonic acid amide, methyl -, 21 - methoxy- andhydroxy - ethyl-, phenyl - and 31 - bromo - 21-, 31- and 41 chloro, 21, 41 - dichloro -, 21 - and 31 - methyl - and 21- and 41 methoxy - and 41 - ethoxy - phenyl-amides, 2 - amino - 1 - methoxybenzene - 4 - sulphonic acid (41 - methoxy) - phenylamide, 2 - amino - 1 - phenol - 4 - chloro - 5 - sulphonic acid amide and methylamide, 2-amino - 1 - phenol - 5 - sulphonic acid amide and methyl- and 21 - methoxy - and-methyl- and 21-31 and 41 - chloro - phenylamides, 2 - amino - 4 - chloro- and - methylsulphonyl - 1 - phenol and 2-amino-1 - carboxy - benzene - 5 - sulphonic acid phenylamide, together with the following coupling components 2 - naphthol - 3 - carboxylic acid amide and methyl-, isopropyl-, amyl-, 21 - methoxy- and - hydroxy - ethyl, 31 - methoxy- and - hydroxypropyl-, phenyl- and 41 - chloro - 21-methyl31- sulphonamido - and - methylsulphonyl-and 21 - carboxy-phenyl-, cyclohexyl-, benzel-, 21 - phenylethyl -, N - methyl - N - phenyl - and diethyl - amides and morpholide piperidide and pyrolidide, water-insoluble dyestuffs, metallizable in admixture with certain of the above water-soluble dyestuffs being made from the following diazo components 2 - amino - 4 - chloro - 1 - phenol and its 5 - nitro-derivative, 2-amino - 4 - nitro - 6 - chloro - 1 - phenol, 1 - aminobenzene - 2 - carboxylic acid, 2 - 2 - amino - 4 - methyl - 1 - phenol and 2 - amino - 4 - nitro - 1 - phenol, together with the following coupling components b  - naphthol, 1 acetylamino - 7 - naphthol, 2 - naphthol - 3 - carboxylic acid amide, 2 - acetylamino - 4 - methyl - and - tert butyl - 1 - phenol, acetoacetylaminobenzene, 1 - acetoacetyl - aminonaphthalene and 1 - phenyl - 3 - methyl - 5 - pyrazolone.  Specification 637,404 and 693,245 are referred to.