Patent GB-542731-A (GB)
Title: Process for the production of stilbene dyestuffs
IPC: C09B56/04
Filed: 1940-07-02
Abstract: 542,731. Stilbene and azo dyestuffs. GEIGY, AKT.-GES., J. R. July 2, 1940, No. 11148. Convention date, July 3, 1939. Addition to 532,970. Samples furnished. [Class 2 (iii)] Metalliferous stilbene dyestuffs are obtained by treating with metal yielding agents the products prepared by condensing dinitrostilbene disulphonic acid, dinitrodibenzyldisulphonic acid or the conversion product obtained by the action of caustic alkali on p-nitrotoluenesulphonic acid with an amino azo dyestuff having the following formula wherein X is a hydroxyl, alkoxy or carboxyl group or halogen, Y is a benzene nucleus which contains an amino group and is joined to the naphthalene nucleus by a second nitrogen atom, which may be part of a heterocyclic ring or by the bridges -N-N- or -N = C- which       |  |          |  form a heterocyclic ring with the assistance of a N, S or O atom and Z is COOH, SO  3 H or N but at least once COOH or SO 3 H. The benzene nuclei may contain further substituents. The amino azo dyestuffs may be prepared by coupling appropriate diazobenzene compounds and suitably substituted hydroxy naphthalenes. For making the diazo compounds, the following amines are mentioned 2 - amino - 1 - hydroxy - benzene - 4 - sulphonic acid, 4 - chlor - 2 - amino -1- hydroxybenzene-6-sulphoni.c acid, 4-chlor-2- amino - 1 - hydroxybenzene - 5 - sulphonic acid, 6 - chlor - 2 - amino - 1 - hydroxybenzene - 4 - sulphonic acid, 3 - amino - 2 - hydroxy - 5 - sulphobenzoic acid, 2 - amino - 4 - methoxybenzoic acid, 3 - amino - 4 - methoxy (or 4- hydroxy) benzoic acid, 4- (or 5-)nitro - amino - 1 - hydroxybenzene, 4 - chlor - 2 - amino - 1 - hydroxybenzene, 4 - methyl - 2 - amino - 1 - hydroxybenzene, 4 - chlor - 6 - nitro - 2 - amino - 1 - hydroxybenzene, 4 - methyl - 6 - nitro - 2 = amino - 1 - hydroxybenzene, 4 : 6 - dinitro - 2 - amino - 1 - hydroxybenzene, 5 - nitro - 2 - aminoanisol, 1 - amino - 2 - methoxy - 5 - methylbenzene and 2 : 5-dimethoxyaniline. Coupling components mentioned are : 3<SP>1</SP>- (or 4-) amino - C - phenyl - 1 : 2 - thiazolo - 5 - hydroxynaphthalene - 7 - sulphonic acid, 3<SP>1</SP> - amino - C - phenyl - 1 : 2 - thiazolo - 8 - hydroxynaphthalene - 6 - sulphonic acid, 3<SP>1</SP> - amino - C - phenyl - 2 : 1 - thiazolo - 8 - hydroxynaphthalene - -2:6- disulphonic acid, 3<SP>1</SP> - amino - C - phenyl - 1 (N) - 2 - oxazolo - 5 - hydroxynaphthalene - 7 - sulphonic acid, 3<SP>1</SP> - amino - C - - phenyl 1 : 2 - imidazolo - 5 - hydroxynaphthalene - 7 - sulphonic acid, 4<SP>1</SP> - aminophenyl - 5 - hydroxy - 7 - sulphonaphthyl - 1 : 2 - triazol, 3<SP>1</SP> - aminophenyl - 8 - hydroxy - 3 : 6 - disulphonaphthyl - 1 : 2 - triazol, 41 - aminophenyl - 2 - azimino - 5 - hydroxynaphthalene - 7 - sulphonic acid, 4<SP>1</SP> - aminophenyl - 2 - amino - 5 - hydroxynaphthalene - 7 - sulphonic acid, 6 - benzidinohydroxynaphthalene - 1 - sulphonic acid - 3, 6 - (4 - aminoanilino) - hydroxynaphthalene - 1 - sulphonic acid - 3, 31 - amino - 6<SP>1</SP> - methylphenyl - 5 - hydroxy - 7 - sulphona,phthyl - 1 : 2 - triazol, 4<SP>1</SP> - amino - 2<SP>1</SP> - chlorphenyl - 5 - hydroxy - 7 - sulphonaphthyl - 1 : 2 - triazol In examples : (1) the dyestuff prepared by coupling diazotized 4-nitro-2-amino-1-hydroxybenzene with 3<SP>1</SP> - amino - C - phenyl - 1 : 2 - N - - thiazolo - 5 - hydroxynaphthalene - 7 - sulphonic acid is condensed with sodium dinitrostilbenedisulphonate ; the product after being treated with copper sulphate dyes cotton brown shades ; (2) the dyestuff prepared by coupling. diazotized 4 - nitro - 2 - amino - 1 - hydroxybenzene with p-aminophenyl-5-hydroxy-7-sulphonaphthyl-1 : 2-triazol is condensed with sodium dinitrostilbenedisulphonate ; the product is coppered either in substance or on the fabric ; (3) sodium dinitrostilbenedisulphonate is condensed with a -mixture of the dyestuffs prepared by coupling diazotized m-aminobenzoic acid with saponified o-methoxyphenylaminomethylsulphonic acid and coupling diazotized 4-chlor-2-amino-1-hydroxybenzene with 3<SP>1</SP> - amino - C - phenyl - 1 : 2 - N - thiazolo - 5 - hydroxynaphthalerie-7-sulphonic acid ; the resulting dyestuff is coppered with ammoniacal copper sulphate ; (4) sodium dinitrostilbenedisulphonate is condensed with a mixture of dyestuffs prepared by coupling diazotized 2 - amino - 1 - hydroxybenzene - 4 - sulphonic acid with 2 : 5-dimethoxyaniline and by coupling diazotized 4-nitro-2-amino-1-hydroxybenzene with 3<SP>1</SP>-amino-C-phenyl-1 : 2-N-thiazolo - 5 - hydroxynaphthalene - 7 - sulphonic acid ; the product is coppered with ammoniacal copper sulphate. The colours of dyestuffs obtained by condensing one and two molecules of various aminoazo dyestuffs with dinitrostilbenedisulphonic acid are tabulated. The table includes dyestuffs obtained by condensing mixtures of aromatic amino compounds, e.g. dehydrothio-p-toluidinesulphonic acid and aminoazo dyestuffs with dinitrostilbenedisulphonic acid. Specifications 311,384, [Class 2 (iii)], and 348,283 are referred to. Samples have been furnished under Sect. 2 (5) of the Acts of dyestuffs prepared by condensing with the sodium salt of dinitrostilbenedisulphonic acid, aminoazo compounds obtained (a) by coupling diazotized 4-nitro-2-amino-1- hydroxybenzene with 6-benzidine-1-hydroxynaphthalene-3-sulphonic acid and (b) by coupling diazotized 4-chlor-2-amino-1-hydroxybenzene with 51-hydroxy-2-(3-aminophenyl) naphtho - 1<SP>1</SP> : 2<SP>1</SP> - oxazol) - 7<SP>1</SP> - sulphonic acid. The latter dyestuff is converted into the copper compound in substance. The coupling components containing oxazol and imidazol residues, used to prepare the above mentioned amino azo dyestuffs may be prepared according to the process of Specification 1675/05, [Class 2], from carboxylic acid anhydrides or chlorides and 1-amino-2: 5- dihydroxynaphthalene - 7 - sulphonic acid or 1 : 2 - diamino - 5 hydroxynaphthalene - 7 - sulphonic acid. The azimino and triazol coupling components may be prepared according to the known processes described in the U.S.A. Specification 916,161 and the French Specification 325,492 respectively.