Patent GB-744666-A (GB)
Title: Manufacture of cupriferous trisazo-dyestuffs
IPC: C09B31/20
Filed: 1952-10-31
Abstract: The invention comprises cupriferous azodyestuffs of formula <FORM:0744666/IV(c)/1> where X is the residue of a hydroxyl or carboxyl group vicinal to the azo group and bound in complex union with the copper atom: Y is a methyl or carboxyl group; R1 is a residue of the benzene series; R2 is a benzene or naphthalene residue bound in para-position to the azo linkages and R3 is an aromatic residue the group -O-Cu-O- being bound to the residues R2 and R3 in positions vicinal to the azo linkage. They may be made by coppering dyestuffs of formula <FORM:0744666/IV(c)/2> where X is a hydroxyl, alkoxy or carboxy group vicinal to the azo group; R1 and Y are as above; R2 is a benzene or naphthalene residue bound in para-position to the azo-linkages and containing a hydroxy or alkoxy group in ortho-position to the -N=N-R3 group and R3 is an aromatic residue bound to the azo linkage in a position vicinal to the hydroxyl group. Advantageously R1 contains a sulphonic acid group and in ortho-position to the azo-linkage a hydroxyl, methoxy or carboxyl group, R2 is a residue of formula <FORM:0744666/IV(c)/3> where n is 1 or 2 and the SO3H group is in a b -position and R3 is the residue of an amino-oxynaphthalene sulphonic acid bound to the azo-linkage in a position vicinal to the hydroxyl group, especially an acyl - or acyl - amino - oxynaphthalene mono - or di - sulphonic acid.  The starting tris-azo dyestuffs may be made by coupling a diazotized amine of formula X-R1-NH2 with a pyrazolone of formula <FORM:0744666/IV(c)/4> diazotizing the resulting amino-monoazodyestuff and coupling with a middle component of formula <FORM:0744666/IV(c)/5> (in which O-alkyl may be replaced by another metallisable group) and coupling the diazo compound of the resulting aminodisazo-dyestuff with an appropriate end component of formula H-R3-OH.  Advantageously initial components are chosen which contain in addition to the metallisable group, a group imparting solubility, especially a sulphonic acid group. Specified initial components are: -4 - amino, 2 - carboxy, 2 - amino - 4 - sulphonamido, 2 - amino - 4 - sulpho -, 2 - amino - 4 - sulpho - 6 carboxy -, 2 - amino - 4, 6 - disulpho - and 2 - amino - 4 - chloro - 6 - sulpho - 1 - oxybenzene, 1 - amino - 2 - methoxy - and - carboxy - benzene and their 5 - sulphonic acids, 1 - amino - 2 - carboxy - 4 - sulpho - benzene and 5 - ethoxy - 2 - carboxy - 1 - amino benzene.  Specified pyrazolones are:-1 - [411 - aminostilbene - (41)] - 5 - pyrazolone - 3 - carboxylic acid - 21:211 - disulphonic acid and especially 1 - [411 - aminostilbene - (41)] - 3 - methyl - 5 - pyrazolone-21:211 - disulphonic acid. Specified middle components are 1 - amino - 2 - methoxy - 5 - methylbenzene, 1 - amino - 2, 5 - dimethoxy - and diethoxy - benzene, 1 - amino - 2 - methoxy - 5 - ethoxybenzene, and 1 - 2 - ethoxy - 5 - methoxybenzene, and 1 - amino - 2 - oxy - 5 - methylbenzene, 1 - amino - 2 - methoxy - and ethoxy - naphthalene and 1 - amino - 2 - methoxy - and - ethoxy - naphthalene - 6 - and - 7 - sulphonic acids.  Specified end components are 2 - oxynaphthalene and the - 6 - and - 3, 6 - sulphonic acids thereof, 1 - oxynaphthalene - 4 -, - 3, 6 - or -3, 8 - sulphonic acids, 1, 8 - dioxy - naphthalene -3, 6 - disulphonic acid, 1 - amino - 5 - oxynaphthalene7 - sulphonic acid, 1 - amino - 8 - oxynaphthalene - 4 - sulphonic acid, 2 - amino - 5 - oxynaphthalene - 7 - sulphonic acid, 2 - amino - 8 oxynaphthalene - 6 - sulphonic acid, 2 - amino - 6 - oxynaphthalene - 8 - sulphonic acid, 1 - amino - 8 - oxynaphthalene - 2, 4-, -3, 6- or -4, 6- disulphonic acid, 1 - acetylamino - 8 - oxynaphthalene - 3, 6-disulphonic acid, 1 - benzoylamino - 8 - oxynaphthalene - 4 - and - 3, 6 - sulphonic acids, 2 - acetyl - and -benzoyl - amino - 6 - oxynaphthalene - 8 - sulphonic acid, 2 - acetyl-, -benzoyl-, -(41 - chlorobenzoyl)-, -phenyl, -(21 or 41 - methoxyphenyl)-, and -(31 or 41 - carboxy - methoxyphenyl) - amino - 5 - oxynaphthalene - 7 -sulphonic acid, 2 - (41 - methylphenyl)-, -(41 - chlorophenyl) - and - phenyl - amino - 5 - oxynaphthalene - 7, 31 - disulphonic acid and 2 - phenyl - amino - 5 - oxynaphthalene - 7, 41 - disulphonic acid.  Coupling with pyrazolone is preferably effected in weakly alkaline media, with the middle component in weakly acid to neutral media and the final component is preferably coupled in the presence of pyridine.  So that the cupriferous dyestuffs may be sufficiently soluble it is generally necessary that they contain 4-6 sulphonic acid groups.  Coppering, during which dealkoxylation may be necessary, is effected with divalent copper salts or a copper tetrammine complex as in Specification 644,883.  Dyestuffs in which R2 is a naphthalene residue containing an alkoxy group vicinal to the azo-linkage connecting R2 and R3 are advantageously coppered with copper sulphate in the presence of an alkali acetate whereas the corresponding benzene dyestuffs are advantageously treated with copper tetrammine sulphates.  The dyestuffs dye wool, silk, cotton, linen, artificial silk and regenerated cellulose in grey to olive-green tints. Examples are provided illustrating the use of certain of the above specified components in the preparation of copperized dyestuffs additional end components used being 1 -acetyl-amino - 4 - sulpho-, 2 - phenyl - amino - 6 - sulpho - 31 - carboxy - and 2 - phenylamino -6, 31 - disulpho - 8 - oxynaphthalene.