Patent GB-758637-A (GB)
Title: Manufacture of new metalliferous azo-dyestuffs
IPC: C09B45/14
Filed: 1952-12-22
Abstract: The invention comprises complex cobalt or chromium compounds which contain one or two monoazo-dyestuffs free of sulphonic acid groups and containing a single carboxylic acid group not bound in a position vicinal to a hydroxyl or amino group, and at least one of which dyestuffs is of formula <FORM:0758637/IV(c)/1> where R1 is a benzene residue bound to the azo linkage in ortho-position to the hydroxyl group, R2 is a residue of an azo component bound to the azo linkage in a position vicinal to a hydroxyl group or a naphthylamine residue bound to the azo linkage in a position vicinal to the amino groups, n is in integer not greater than 7, m is 1 or 2 and X is an aryl residue containing the carboxylic acid group.  Cobalt or chromium-containing dyestuffs derived from one molecule of a dyestuff of the above formula and one molecule of any monazo-dyestuff free of sulphonic acid groups are also obtained.  They may be made by treating one or two dyestuffs of the above formula, or one dyestuff of the above formula together with another monazo dyestuff free of sulphonic acid groups, with agents yielding cobalt or chromium advantageously so that the dyestuff contains one atom of metal in complex union with two monazo-dyestuff molecules, this being effected either by the use of appropriate quantities of reagents or by metallizing in a weakly acid to alkaline medium.  Preferred metallizing agents are cobalt complex compounds and particularly chromium complex compounds of aliphatic or aromatic orthooxycarboxylic acids.  Divalent cobalt compounds may also be used.  Dyestuffs of the above formula may be made by coupling an appropriate naphthylamine or hydroxyl-containing component with a diazotized amine free of sulphonic acid groups of formula <FORM:0758637/IV(c)/2> where R1, X, n and m are as above.  With oxy-compounds as azo components coupling in an alkaline medium is preferred. R1 containing the amino group in the 2-position and the hydroxyl group in the 1position is preferably bound to the -SO2-group in the 4-, 5- or 6-position.  It may contain further substituents such as alkyl, nitro, alkoxy or acylamino groups or a halogen atom. X may be naphthalene or advantageously a benzene residue which in addition to the catalyst group may contain groups such as methyl or methoxy groups or a chlorine atom.  Specified amines are 2-amio-1-oxybenzene-4-sulphonic acid -N-21-naphthylamide-31-carboxylic acid, 2-amino-1-oxy-6-chloro- and - nitro - benzene - 4 - sulphonic acid and phenylamide-21- carboxylic acid, 2-amino-1-oxybenzene-4-or -5-sulphonic acid N-methyl-phenylamide-21-carboxylic acid or phenylamide-21-, -31- or -41-carboxylic acid, 2-amino-4-chloro-1-oxybenzene-5- or -6-suphonic acid phenylamide-21-carboxylic acid, 3-amino-4- oxydiphenylsulphone-21-carboxylic acid and 4-amino-3-oxydiphenylsulphone-21- or -41-carboxylic acids.  Specified azo-components are 2-naphthylamine and the 6-sulphonic acid amide thereof, 4-methyl-, 3, 4-dimethyl, 4-tert.-amyl- and 4-acetylamino-1-oxybenzene, 4-methyl-2-acetylamino-1-oxybenzene, resorcinol, b -naphthol, 2, 6-dioxynaphthalene, 2-oxy-6-bromo-, methoxy- or -sulphonanilido-naphthalene, 2-oxynaphthalene-6- or -7-phenylsulphonate, 1-oxy-4-methylnaphthalene, 1-oxo-5-chloro- or 5, 8-dichloronaphthalene, 1-oxynaphthalene -3-, -4-or 5-sulphonic acid isopropylamide, 1-acetyl-, n-butyrl- or -benzoyl-amino-7-oxynaphthalene, 7-oxynaphthyl-(1)-carbaomic acid methyl, ethyl or phenyl esters, 3-methyl- or -phenyl-5-pyrazolone, 1-n-butyl-, -phenyl- or -(21-, -31 or -41-chloro-)-phenyl-3-methyl-5-pyrazolone, 5-pyrazolone-3-carboxylic acid amide and -3-carboxylic acid N - methyl-, -ethyl-, isopropyl-, -butyl-, -21-, -31- or -41-chlorophenyl-, -phenyl- or -paramethylphenylamide, 1-phenyl-5-pyrazolone-3-carboxylic acid amide and 3-carboxylic acid methyl-isopropyl-phenyl- or p-chlorophenyl-amide, barbituric acid, 2, 4-dioxyquinoline, ethyl and phenyl acetoacetate, acetoacetic acid amide and -N-methyl-, -butyl-, -phenyl-, dimethyl- and -21-, -31- and -41-chlorophenylamides and benzoyl-acetic acid amide and phenylamide.  In the production of mixed dyestuffs from one dyestuff of the above formula and any other monoazo dyestuff free of sulphonic acids it is preferred that the latter is also free of carboxylic acid groups.  The other monazo-dyestuff may be an o, o1-dioxy- or o-oxy-o1-carboxy-monoazo-dyestuf of the benzene-azo-benzene, benzene-azo-naphthalene, benzene-azo-pyrazolone or benzene-azo-acylaceticacid amide series, those mentioned being made from the above specified coupling components and diazo compounds of the following amines: 4-chloro-, -nitro-, -methyl-, 4, 6-dichloro- and -dinitro-2-amino-1-oxybenzene, 4-nitro- and -chloro-6-acetylamino- and 6-nitro- and -chloro-4-acetylamino - 2 - amino - 1 - oxybenzene, 4-chloro-5- and -6-nitro-2-amino-1-oxybenzene, 2-amino-1-oxybenzene-4- or -5-sulphonic acid amide and N-methyl-, -ethyl-, isopropyl-, -octyl-, -cyclohexyl-, -phenyl-, p-chlorophenyl-, -dimethyl- and -methyl-phenyl-amides, 2-amino-1-oxybenzene-4- or -5- methylsulphone, 3-amino-4-oxy- and 4-amino - 3 -oxy-diphenylsulphone, 5- nitro-amino-1-oxybenzene, 2-aminobenzene-1-carboxylic acid and its 5-sulphonic and amide, -sulphonic acid methyl- and phenyl-amides, -methylsulphone and -phenylsulphonate.  The metallized dyestuffs are used for dyeing plastic materials, waxes, resins and lacquers and especially superpolyamides and superpolyurethanes and particularly animal materials such as silk, leather and especially wool.  Weakly alkaline to weakly acid, particularly the latter, dyebaths are used. Dyeings are obtained in grey or yellow to red tints. Examples are provided illustrating the use of certain of the above specified reagents in the preparation of dyestuffs, additional diazo components used being obtained from 2-amino-1-oxybenzene-4-sulphonic acid N-ethyl-phenyl-amide-21-carboxylic acid and -4-sulphonic acid 41-ethoxyphenylamide-21-carboxylic acid. Specification 637,404 is referred to.