Patent GB-743907-A (GB)
Title: Manufacture of new metallisable monoazo-dyestuffs and complex metal compounds thereof
IPC: C09B45/14
Filed: 1952-12-01
Abstract: Amines for use as diazo components in the preparation of dyestuffs, containing no sulphonic or carboxylic acid groups and corresponding to the formula <FORM:0743907/IV(a)/1> where R is an aromatic residue of the benzene series and R1 is a benzene residue in which OH and NH2 are in the o position, may be made by the methods illustrated below in connection with specific compounds. 1-Chloro-2-nitrobenzene-4-sulphonyl chloride is treated with benzene and aluminium chloride to yield 1-chloro-2-nitrobenzene - 4 - phenylsulphone which is hydrolysed with caustic soda to the corresponding 1 - oxy - compound the nitro group of which is subsequently reduced with sodium sulphide or hydrogen and nickel to yield 4-oxy-3-amino-1,11-diphenyl sulphone. Benzoxazolone is treated with chloro-sulphonic acid to yield the corresponding sulphochloride which is converted to the sulphone by treatment with benzene and aluminium chloride the sulphone on treatment with caustic soda yielding 4-amino-3-oxy-1,11-diphenylsulphone.  2 - Nitro - 1 - chlorobenzene-4-sulphinic acid is condensed with benzyl chloride to yield 2-nitro-1-chlorobenzene-4-benzyl sulphone which is hydrolysed to the corresponding phenol the nitro group of which is reduced to yield 2 - amino - 1 - oxybenzene - 4 - benzyl sulphone.  The preparation of the following azo components is also described. 5-Pyrazolone-3-carboxylic acid ethyl ester heated with n-butylamine yields 5 - pyrazolone - 3 - carboxylic acid n-butylamide also obtainable by treating 5-pyrazolone - 3 - carboxylic acid with phosphorus trichloride and simultaneously or subsequently with n-butylamine to convert the carboxylic chloride thus produced.ALSO:The invention comprises dyestuffs free of sulphuric and carboxylic acid groups and of formula <FORM:0743907/IV(c)/1> where R is an aromatic residue of the benzene series including a benzyl residue, A is the residue of an azo component bound to -N=N- in a position vicinal to a hydroxyl group and R1 is a benzene residue in which the hydroxyl group and -N=N- are in the ortho position.  The dyestuffs may be metallized e.g. with iron, nickel, aluminium, copper and especially cobalt or chromium compounds.  The dyestuffs may be made by the alkaline coupling of a diazo-compound of an appropriate sulphone substituted amine free of sulphuric and carboxylic acid groups with the desired azo component.  The amines may contain in R11 and/or advantageously in R1 substituents such as halogen atoms e.g. chlorine, alkyl groups e.g. methyl, alkoxy groups e.g. methoxy, nitro groups, -CO-alkyl groups or acylamino groups e.g. acetylamino. Specified amines are 2-amino-1 - oxy - 4 - nitrobenzene - 6 - phenyl - and -benzyl-sulphone and 2-amino-1-oxy-4 -chlorobenzene-5 or -6-phenyl sulphone, 3 -amino-4-oxydiphenyl sulphone, 4-amino-3 -oxydiphenyl sulphone, 2-amino-1-oxybenzene-4- or -5-benzyl sulphone, 3-amino-4 -oxy-41-methyl- 3-amino-4-oxy-41-methoxy-, 4-amino-3-oxy-41-methyl- and 3-amino-4 -oxy-41-chloro-1, 11-diphenyl sulphone.  Specified azo components are 4-methyl-, -chloro-, -methoxy-, 3, 4-dimethyl-, 4-t-amyl-, 4 -acetylamino-1-oxybenzene, 4-methyl-2 -acetylamino-1-oxybenzene, resorcinol, b -naphthol, 2, 6-dioxy-, 2,oxy-6-bromio- and -6-methoxynaphthalene, 2-oxynachthalene -4-, -6- or -7-sulphonamide, 1-oxy-4-methyl-, -5-chloro- and -5, 8-dichloro-naphthalene, 1 -oxynaphthalene-3-, -4- or -5- sulphonamide, 1-oxy -4- methylnaphthalene -8- sulphonamide, 1-acetylamino-, 1-n-butyrylamino- and 1-benzoylamino-7-oxynaphthalene or 7-oxynaphthyl-(1)-carbamic acid methyl or ethyl ester, 3-methyl-, 3-phenyl-, 1-n-butyl -3-methyl- and 1-phenyl-3-methyl-5-pyrazolone, 1-phenyl-3-methyl-5-pyrazolone-31- or -41sulphonamide, 5-pyrazolone-3-carboxylic acid amide or 3-carboxylic and methyl-, ethyl-, isopropyl-, sec butyl-, t-butyl or n-butyl-amide, or 3-carboxylic acid phenyl- or tolyl-amide, 1-phenyl-5- pyrazolone-3 -carboxylic acid amide or methylamide, barbituric acid, 2, 4-dioxyquinoline, acetoacetic acid amide or methyl-, n-butyl-, phenyl-, dimethyl- or d  chlorophenylamide, 1-acetoacetylaminobenzene-2-, -3- or -4-sulphonamide, and benzoylacetic acid amide.  Azo components containing sulphonamide groups are preferred.  Chroming may be effected in conventional fashion to give products containing about one atom of chromium per mol of dyestuff an especially valuable compounds are also obtained which contain one atom of chromium or cobalt per 2 mols of dyestuff. Mixed dyestuffs may be used in the latter instance at least one dyestuff corresponding to the above general formula. The dyestuffs may be used for dyeing plastic masses, resins, waxes and lacquers and especially for dyeing or printing animal fibres such as silk, leather and particularly wool and also for dyeing synthetic materials comprising superpolyamides and superpolyurethanes.  Tints obtained vary from yellow to red or grey.  Examples and a table are provided showing the use of certain of the above specified components in the preparation of dyestuffs and a chromium complex of a mixture of dyestuffs derived from 3-amino -4-oxy 1, 11-diphenyl sulphone and 5-pyrazolone-3-carboxylic acid-n-butylamide and 2-amino-1-oxybenzene-4-sulphonic acid methylamide and 1-(41-chloro)-phenyl-3 -methyl-5 pyrazolone is also prepared. Specification 637,404 is referred to.