Patent GB-738309-A (GB)
Title: Manufacture of metalliferous azo-dyestuffs of the stilbene series
IPC: C09B56/04
Filed: 1952-12-12
Abstract: The invention comprises metalliferous azodyestuffs of formula <FORM:0738309/IV (c)/1> where Me is an atom of copper or nickel bound in complex union, U is O or <FORM:0738309/IV (c)/2> bound through -O-to Me, R1 is H or an alkyl or aryl radicle, R2 is H or an alkyl radicle, R3 is a benzene or naphthalene residue in which -U-Me, -N=N- and -Z- respectively occupy 2-, 1- and 4-positions, Z is an azo or azoxy linkage and R4 is the residue of an azo component or a triazole residue formed by oxidizing an ortho-amino-azo group. They may be made by treating the appropriate unmetallized dyestuff with agents yielding copper or nickel.  The unmetallized dyestuffs may be made by condensing a compound of formula <FORM:0738309/IV (c)/3> with an amino-azo dyestuff of formula <FORM:0738309/IV (c)/4> where U is an alkoxy, hydroxy or carboxylic group, advantageously in the presence of aqueous alkali hydroxide, the resulting group Z being either an azo or an azoxy group, the amino-azo dyestuffs being made by coupling a diazo compound of an amine of formula <FORM:0738309/IV (c)/5> where X is a substituent convertible to an amino group, e.g. a nitro or acylamino group, in an alkaline medium with a 2-amino-8-oxynaphthalene - 6 - sulphuric acid and converting X to NH2.  Amines indicated for <FORM:0738309/IV (c)/6> are 5 - nitro - or - acylamino - 2 - amino - 1 - oxy-, -carboxy- or -alkoxy-benzenes which may contain alkyl, e.g. methyl or ethyl or alkoxy groups or halogen, especially chlorine, atoms, those specified being: 5-nitro-2-amino1-oxy-, -methoxy-, -carboxy-, and 1,4-dimethoxy-benzene, 5-nitro-4-chloro-, -methyl- or methoxy - 1 - oxybenzene, 5 - acetylamino - 2 - amino - 1 - oxy - or - carboxy - benzene and 5 - nitro - 4 - methyl - 2 - amino - 1 - methoxybenzene. N - substituted 2 - amino - 8 - oxynaphthalene - 6 - sulphonic acids specified are 2 - phenylamino - 8 - oxynaphthalene - 6 - sulphonic acid, its -31- or -41-carboxylic or sulphonic acids and -31-sulphonamide, 2-di-(b -oxyethylamino)- and -(41 - carboxymethoxyphenylamino) - 8 - oxynaphthalene - 6 - sulphonic acid and 2-[41-811-oxynapthyl-[211]-aminophenyl] - 6 - methylbenzthiazole - X,611 - disulphonic acid. 2-Amino-8-oxynaphthalene-6-sulphonic acid may also be used. R4 is advantageously -N=N-R5, where R5 is the residue of an oxybenzene ortho carboxylic acid bound to the azo linkage in para position relative to the hydroxy group or R5 may be an alkoxy- (e.g. methoxy- or ethoxy-) benzene residue or R4 may be <FORM:0738309/IV (c)/7> where R7 is an aromatic ring containing at most 2 fixed rings and fixed on to the triazole ring at the positions indicated.  R3 is advantageously a naphthalene residue. Alternatively the unmetallized dyestuffs may be made by coupling a 2-amino-8-oxynaphthalene-6-sulphonic acid of formula <FORM:0738309/IV (c)/8> with a diazo compound of an amino-azo- or -azoxy dyestuff of formula <FORM:0738309/IV (c)/9> which may be made by reacting a stilbene of formula <FORM:0738309/IV (c)/100> with a p-diaminobenzene which contains a hydroxyl, alkoxy or carboxy group in an appropriate position, e.g. 2,5-diamino-benzene-1-carboxylic acid, or the above naphthol is coupled in alkaline medium with the diazo compound of an amino-azo dyestuff obtained by coupling a middle component of the benzene or naphthalene series containing an alkoxy or carboxy group in ortho position to the amino group, in an acid medium with a diazotized amino-stilbene of formula <FORM:0738309/IV (c)/111> specified middle components for the condensation being p 1-amino-2-methoxybenzene and 5-methyl and methoxy derivatives thereof, 1-amino-2,5-diethoxybenzene, 1-aminobenzene-2-carboxylic acid and 1-amino-2-methoxy- or -2-ethoxy-naphthalene-6- or -7-sulphonic acids and the amino-stilbenes may be made by reducing the corresponding nitro-compound.  Conventional means are used for metallizing.  Copper compounds are preferred.  Coppering may be effected as in Specification 644,883.  Advantageously coppered products are obtained in which copper is present only in the residue of the amino-azo dyestuff, this being effected by coppering in acid media, or by coppering in alkaline media using the appropriate quantities of reagents, any copper entering the ortho-oxycarboxy-grouping being removed by acid treatment. Metallization may be effected on the fibre or in substance.  The dyestuffs dye wool, leather, linen, cotton, artificial silk and regenerated cellulose.  Green-olive, yellow-brown or brown tints are obtained.  Examples are provided showing the preparation and use of copper and nickel dyestuffs from certain of the above specified reagents, R7 being typified as a naphthalene-4-sulphonic acid attached to the triazole ring in the 1- and 2-positions and additional naphthols used are 2-(N-methylphenylamino)- and -dimethylamino-8-oxynaphthalene-6-sulphonic acid.