Patent GB-838791-A (GB)
Title: Improvements relating to cobalt and chromium complexes of metallisable monoazo dyestuffs and their use
IPC: C09B45/14
Filed: 1956-07-13
Abstract: Compounds containing N-acyl-N-alkyl- or -cycloalkyl-amino groups are specified and are used as diazo and azo components in the preparation of azo dyestuffs (see Group IV (c)).  They are prepared by known methods.  Compounds specified include 4-N-methylsulphonyl-N - methylamino - 2 - acetylaminophenol, 4 - N - cyclohexyl - N - acetyl - 2 - aminophenol, and 2 - amino - 4 - N - methylsulphonyl - N - methylamino-phenol.  In examples: (1) 1-N-acetyl-or -carbomethoxy- or -methylsulphonyl- or -propionyl-N-methylamino-7-naphthols are prepared by acylating 1-aminonaphthalene-7-sulphonic acid with p-toluene-sulphonyl chloride, reacting the sulphonylamino compound with dimethyl sulphate, saponifying with sulphuric acid to give 1-methylaminonaphthalene-7-sulphonic acid, treating this in molten alkali to give 1-methylamino-7-naphthol which is N-acylated in known manner; (2) 2-N-methylsulphonyl-N-methylamino-7-naphthol is prepared by converting 2-naphthol-7-sulphonic acid by the Bucherer reaction into 2-methylaminonaphthalene-7-sulphonic acid, fusing this with alkali to give the naphthol and acylating with methyl sulphochloride; (3) acetoacetic acid-(21-, 31-or 41-N-acetyl-N-methyl-amino)-anilides are obtained by reacting the corresponding acetylmethylamino-anilines with diketene.  Reference has been directed by the Comptroller to Specifications 637,404, 667,168, 692,073 and 736,034.ALSO:The invention comprises complex chromium or cobalt compounds of monoazo dyes of formula <FORM:0838791/IV(c)/1> wherein A is a benzene radical, B is the radical of an azo component, X is a metallizable group or a group convertible thereto under metallizing conditions ortho to -N=N-, Y is a hydroxyl or amino group ortho to -N=N-, R is an alkyl or cycloalkyl group, "acyl" is an organic acyl radical, n is 1 or 2 and A and B are free from sulphonic acid groups or carboxyl groups not taking part in the complex formation.  They are prepared by diazotizing a suitably substituted aniline coupling with a suitable azo component and treating the monoazo dye with a chromium or cobalt compound.  Specified azo components include amino- or hydroxy-benzenes, acylacetanilides, pyrazolones, naphthols and naphthylamines.  The "acyl" group may be acetyl, benzoyl, furoyl, methyl or ethyl or b -chloroethylsulphonyl, benzenesulphonyl or carbomethoxy.  The radicals A and B may be further substituted, for example by halogen atoms, or alkyl, alkoxy, nitro, acylamino, sulphonamido and sulphone groups.  The metallization is effected by known processes and complexes of mixtures of the dyes may be prepared.  The complexes give yellow, red, brown, orange, olive to grey shades on nitrogenous fibres and may be used to colour lacquers or acetylcellulose spinning solutions.  In examples: (1) the monoazo dye 4-nitro-2-aminophenol -\sY 1 - N - acetyl - N - methyl - amino - 7 - naphthol is prepared and treated with sodium chromosalicylate to give the chromium complex; the monoazo dye 4-chloro-2-aminophenol -\sY 2-N - methylsulphonyl - N - methyl - amino - 7 - naphthol is prepared and treated with cobalt acetate and tartaric acid to give the cobalt complex, and many similar chromium and cobalt complexes are specified; (2) the mixture of monoazo dyes prepared by diazotizing a mixture of 6-nitro-2-amino-4-tert.-amylphenol and 6-nitro-2-amino-p-cresol and coupling with 1 - (41 - N - acetyl - N - methyl - amino) - phenyl - 3 - methyl - 5 - pyrazolone is treated with ammonium chromosalicylate to give the mixed chromium complex. Specification 813,186 is referred to.  Reference has been directed by the Comptroller to Specifications 637,404, 667,168, 692,073 and 736,034.