Patent GB-766535-A (GB)
Title: Manufacture of new chromiferous azo-dyestuffs
IPC: C09B45/16
Filed: 1952-12-15
Abstract: Compounds of formula <FORM:0766535/IV(b)/1> where R1 is a benzene residue with NH2 o to OH and bound to the sulphonamide group in the 4, 5 or 6 position, the NH2 group being in the 2 position and X is a benzene residue containing a substituent of formula: <FORM:0766535/IV(b)/2> where Z1 and Z2 are H atoms or alkyl or oxyalkyl groups containing up to 6 carbon atoms, may be made, for example, by treating an amine X-NH2 with 1-chloro-2-nitrobenzene-4-sulphonic acid chloride, treating the resulting sulphonamide with an alkali or alkaline earth metal hydroxide to give the corresponding 1-oxy-compound and converting the nitro group in the latter to an amino group.  Instead of 1-chloro - 2 - nitrobenzene - 4 - sulphonyl chloride, 1,2-benzoxazolone-5-sulphonyl chloride may be used and after the resulting sulphonamide formation the oxazolone ring is hydrolysed. The products are dyestuff intermediates, vide Group IV (c).  In Example (1) 1-chloro-2-nitrobenzene-4-sulphonyl chloride is reacted with 1-aminobenzene-3-sulphonic acid amide to yield 1-chloro-2-nitrobenzene-4-sulphonic acid phenylamide-31-sulphonic acid amide the chlorine atom of which is replaced by a hydroxyl group on treatment with an appropriate hydroxide and the nitro group of the resulting compound reduced to an amino group to yield 2 - amino - 1 - phenol - 4 - sulphonic acid phenylamide - 31 - sulphonic acid amide, and 1,2-benzoxazolone - 5 - sulphonic acid chloride is reacted with 1-aminobenzene-3-sulphonic and amide to yield the corresponding -N-phenylamide-31-sulphonic acid amide which is hydrolysed with an alkali metal hydroxide to yield 2 - amino - 1 - phenol - 4 - sulphonic acid phenylamide-3-sulphonic acid amide.  Specifications 637,404 and 709,495, [both in Group IV (c)], are referred to.ALSO:The invention comprises complex chromium compounds which contain one or two ortho : ortho1-dioxy-monoazo-dyestuffs which are free of sulphonic and carboxylic acid groups and at least one of which corresponds to the formula <FORM:0766535/IV(b)/1> where R1 is a benzene residue bound to the azo linkage in ortho-position to the hydroxyl group, and bound to the <FORM:0766535/IV(b)/2> group in the 4, 5 or 6 position, the azo linkage being in the 2 position, R2 is the residue of the keto-methylene compound bound to the azo linkage in a position vicinal to the keto-group and X is a benzene residue which contains the group <FORM:0766535/IV(b)/3> where Z1 and Z2 are hydrogen atoms or alkyl or oxyalkyl residues containing at most 6 carbon atoms.  They may be made by coupling the appropriate keto-methylene and ortho-oxy-diazo-compounds, the latter being obtained by diazotizing an amine of formula <FORM:0766535/IV(b)/4> The benzene residue of the #s-aminophenol may contain further substituents incapable of salt formation, e.g. halogen atoms or a nitro group.  Advantageously the residue X contains the group -So2-NH2 and optionally further substituents such as a chlorine atom or a methyl group.  Amines specified are 2-amino-1-oxy-4-nitro-or-chloro-or-6-chloro-benzene-4-sulphonic acid phenylamide-31-sulphonic acid amide, 2-amino-1 oxy-6-nitro-benzene-4-sulphonic acid-phenylamide-41-sulphonic acid amide, 2-amino-1-oxybenzene-4- or -5-sulphonic acid - phenylamide - 31 - sulphonic acid - methyl-, -oxyethyl, -isopropyl-and-n-butylamides, 2-amino-1-oxy-4-chlorobenzene-5-sulphonic acid phenylamide-31-sulphonic acid amide and especially 2-amino-1-oxybenzene-4- or -5-sulphonic acid phenylamide-21-, -31- or -41-sulphonic acid amides.  Specified keto-methylene compounds are acetoacetic acid amide, methyl-amide, n-butylamide, phenylamide, dimethylamide, 21-, -31- or -41-chlorophenylamide, benzoylacetic acid amide and phenylamide, barbituric acid, 2, 4-dioxy-quinoline, 3-methyl or -phenyl - 5 - pyrazolone, 1 - n - butyl - , -phenyl-and-(21-, -31- or -41-chlorophenyl)-3-methyl-5-pyrazolone, 5 - pyrazolone - 3 - carboxylic acid amide and methyl-, ethyl-, isopropyl-, n-butyl-, -21-, -31- or -41-chlorophenyl-, phenyl- and -31- methyl-phenylamide, 1-phenyl-5-pyrazolone-3-carboxylic acid amide, and 21-, -31- or -41-chlorophenyl-, methyl-, isopropyl- and phenyl-amides.  By treatment with appropriate quantities of reagents compounds containing 1 atom of chromium with one or two molecules of dyestuff may be obtained. 1, 2-complexes are also obtained by chroming in weakly acid to alkaline medium with chromium compounds of aliphatic- or aromatic orthooxy-carboxylic acids which contain chromium in complex union.  Preferred are complexes derived from two molecules of the same dyestuffs.  The dyestuffs dye plastic masses, resins, lacquers and especially animal materials, e.g. silk, leather and particularly wool, superpolyamides or superpolymethanes.  Dyeings in yellow to red tints are obtained.  Examples are provided of the use of certain of the above specified components in the preparation of dyestuffs.  Specifications 637,404 and 709,495 are referred to.