Patent GB-819174-A (GB)
Title: 1,2-metal complexes of monoazo dyestuffs of the benzene-azo-pyrazolone series
IPC: C09B45/14
Filed: 1956-04-09
Abstract: The invention comprises 1,2-metal complexes of monoazo dyestuffs which are free from sulphonic acid and non-complex forming carboxylic acid groups, at least one being of formula <FORM:0819174/IV (c)/1> where R1 is a benzene residue with Xo to N2, X is OH or COOH or a group convertible thereto during metallization, R2 is a benzene residue and R3 is alkyl or phenyl. R1 may carry a sulphonamido or sulphone group and R1 and R2 may contain groups such as alkyl, alkoxy, nitro or halogen groups.  Cobalt and chromium are preferred metals.  The dyestuffs are made by coupling diazotized appropriate anthranilic acids or o-aminophenols with the desired pyrazolone component and metallizing the product.  The metal-free dyestuffs may also be made by treating appropriate dyestuffs with the necessary sulphonyl chlorides.  The processes are effected in conventional fashion.  Specified pyrazolones are 1-(31- and 41-methyl-, -ethyl-, -propyl-, -benzene-, -p-methyl- and chlorobenzene - and o,p - dichlorobenzenesulphonyl - aminophenyl) - and 1 - (21 - chloro-41 - benzenesulphonylaminophenyl) - 3 - methyl- 5 - pyrazolones. Indicated as diazo components are anthranilic acid, 1-amino-2-phenol-4 - and - 5 - sulphonamides and sulphon-N-alkyl and -aryl derivatives thereof, 1-amino-5-chloro - 2 - phenol - 3 - and 1 - amino - 4-chloro - 2 - phenol - 5 - sulphonamides, 1-amino - 4 - and - 5 - nitro - 2 - phenols, 1-amino - 3 - nitro - 5 - methyl - 2 - phenol and 1-amino - 2 - phenyl - 4(5) - alkyl - or - aryl - sulphones.  Instead of o-hydroxy diazo components the corresponding o-ethers may be used with subsequent de-alkylating metallization (vide Specifications 681,653 and 740,589) and in place of the free anthranilic acid components, esters thereof may be used, the metallization then resulting in a saponification before complex formation.  The metal-yielding agents may be reacted with two different dyestuffs of the above group or with two dyestuffs one of which is of the above formula and the other is a known monoazo dyestuff complying with the above restrictions on sulphonic and carboxylic groups.  The dyestuffs dye resins, lacquers and plastic masses but are preferably used on material of animal origin, e.g. leather, silk and wool.  Synthetic polyamide and polyurethane fibres may also be dyed.  Wool is dyed from a neutral to weakly acid bath.  In examples illustrative of the preparation of the dyestuffs and their use in dyeing processes red, brown, yellow or blue tints being obtained, the components used are chosen from those listed above with the addition of 1-(31 - methyl - 51 - benzenesulphonylaminophenyl) - 3 - methyl - 5 - pyrazolone, 1 - amino-2 - phenol - 5 - sulphondimethylamide and -4-sulphomethylamide and 1 - amino - 2 - phenol-4-ethyl sulphone a dyestuff, not of the above formula, used in the preparation of a mixed dyestuff being 1-amino-5-nitro-2-phenol --> 1-methylsulphonylamino - 7 - naphthol. Specifications 304,298, [Class 2(iii)], 637,404, 706,370, 743,907, 746,944, 753,550, 758,016, 784,138 and 788,157 also are referred to.