Patent GB-556580-A (GB)
Title: Manufacture of stilbene dyestuffs
IPC: C09B56/04
Filed: 1941-11-27
Abstract: 556,580. Dyes. GEIGY, J. R. AKT.-GES. Nov. 27, 1941, No. 15284. Convention date, Nov. 28, 1940. [Classes 2 (iii) and 15 (ii)] Stilbene dyes. In the production of stilbene dyes by alkaline condensation with aromatic amines of dinitrostilbenedisulphonic acid or dinitrodibenzyldisulphonic acid or conversion products of p-nitrotoluenesulphonic acid, all or part of the aromatic amine reactant is constituted by an aminodiaryltriazole carrying at least one sulphonic or carboxylic acid group but free from azo groups. The products may be treated in substance or on the fibre with oxidizing agents and/or, when metallizable groups are present, with agents yielding metal. Specified aminodiaryltriazole compounds are the 4<SP>1</SP>- and 61- sulphonic acids, 3<SP>1</SP>:8<SP>1</SP>-, 4<SP>1</SP>:8<SP>1</SP>-, 5<SP>1</SP>:7<SP>1</SP>- and 6<SP>1</SP>:8<SP>1</SP>-disulphonic acids and 3<SP>1</SP>:6<SP>1</SP>:8<SP>1</SP>-trisulphonic acids of 2-(4<SP>11</SP>-aminophenyl)-naphtho- 11:21:4:5-triazole, the 51:71-disulphonic acid of 2- (3<SP>11</SP> - aminophenyl) - naphtho-1<SP>1</SP>:2<SP>1</SP>:4:5- triazole, 2 - (4<SP>11</SP> - amino - 3<SP>11</SP>- sulphophenyl) - naphtho - 1<SP>1</SP>:2<SP>1</SP>:4:5-triazole-6<SP>1</SP>-sulphonic acid, 2-(4<SP>11</SP>- amino - 2<SP>11</SP> - sulphophenyl) - naphtho - 1<SP>1</SP>: 21:4:5-triazole and its 6<SP>1</SP>- sulphonic acid, the 2 - (3<SP>11</SP>- amino - 4<SP>11</SP> - chlorophenyl) - 5<SP>1</SP>:7<SP>1</SP>- disulphonic acid, 2-(4<SP>11</SP>-amino-2<SP>11</SP>-methozyphenyl) - 6<SP>1</SP> - sulphonic and 5':7-disulphonic acid, 2-(3<SP>11</SP>-amino-4<SP>11</SP>-methylphenyl)-5<SP>1</SP>:7<SP>1</SP>- disulphonic acid and 2-(4<SP>11</SP>-amino-3<SP>11</SP>-methyl- 6<SP>11</SP> -6 methoxyphenyl) - 6<SP>1</SP> - sulphonic acid derivatives of naphtho-1<SP>1</SP>:2<SP>1</SP>:4:5-triazole, the 2- (31- or 41-sulphophenyl), 2-(4<SP>1</SP>-methyl- or chloro-31-sulphophenyl), 2-(21:41-dimethyl - 6<SP>1</SP>-sulphophenyl), 2-(2<SP>1</SP>:5<SP>1</SP>-dimethyl- or dimethoxy-4<SP>1</SP>-sulphophenyl), 2-(3<SP>1</SP>-carboxyphenyl), 2-(4<SP>1</SP>-hydroxy-3<SP>1</SP>-carboxyphenyl) 2 - (2<SP>1</SP> -hydroxy - 3' - carboxy - 4<SP>1</SP> - sulphophenyl and 2-(4<SP>1</SP>-hydroxy-3<SP>1</SP>-carboxy-5<SP>1</SP>- methylphenyl) derivatives of 5-amino-1:3-benzotriazole, 5-amino-2:2<SP>1</SP>-(4<SP>1</SP>:8<SP>1</SP>-disulphonaphthyl - 1:3 - benzotriazole, 5-amino -2:1<SP>1</SP>- (41-sulphonaphthyl)-1:3-benzotriazole, 5-amino- 1 : 2<SP>1</SP> - (5<SP>1</SP>:7<SP>1</SP>- disulphonaphthyl - 1:3 - benzotriazole, 5-amino-1:2<SP>1</SP>-(6<SP>1</SP>-sulphonaphthyl)- 1:3 - benzotriazole, 5-amino-1:11(41- or 6'- sulphonaphthyl) - 1:3 - benzotriazole, the 1 - (21 - or 41 hydroxy - 3<SP>1</SP> - carboxyphenol), 1 - (4<SP>1</SP> sulphophenyl) and 1 - (3<SP>1</SP> - carboxyphenyl) derivatives of 5-amino-1:3-benzotriazole and 5-sulpho-l-(4<SP>1</SP>-aminophenyl) - 1:3 - benzotriazole. Examples relate to the alkaline condensation of (1) dinitrostilbenedisulphonic acid (1 or 2 mols.) with 2-(4<SP>11</SP>-aminophenyl)- naphtho - 1<SP>1</SP>:2<SP>1</SP>:4:5-triazole-5<SP>1</SP>:7<SP>1</SP>-disulphonic acid (1 mol.) followed by oxidation of the product with sodium hypochlorite ; '(2) dinitrostilbenedisulphonic acid ( 1 mol.) with 5-amino- 2 - (41 - sulphophenyl) - 1:3 - benzotriazole (1 mol.) and oxidation as in (1); (3) dinitrostilbenedisulphonic acid (1 mol.) with 5-amino-1- (3<SP>1</SP> - carboxyphenyl) - 1:3 - benzotriazole (1.2 mols. approx. or 2 mols.), followed by oxidation by passing chlorine into the alkaline solution; (4) dinitrostilbenedisulphonic acid (1 mol.) with 5-amino-2-(3<SP>1</SP>-carboxyphenyl)- 1:3-benzotriazole (1 mol.) ; (5) dinitrostilbenedisulphonic acid (1 mol.) with 1 mol. each of the 61-sulphonic and 51:71-disulphonic acids of 2- (4<SP>11</SP> - aminophenyl) - naphtho - 1<SP>1</SP>:2<SP>1</SP>:4:5- triazole, and oxidation as in (1); (6) dinitrostilbenedisulphonic acid (1 mol.) with 1 mol. approx. each of 2-(4"-aminophenyl) - naphtho- 1<SP>1</SP>:2<SP>1</SP>:4:5 - triazole - 6<SP>1</SP> - sulphonic acid and 3 - aminobenzoic acid # 2:5 - dimethoxyaniline, and oxidation as in (1) ; (7) dinitrostilbenedisulphonic acid (1 mol.) with 1 mol. each of the product of saponification of 4-aminoacetanilide # salicyclic acid and 5-amino-2- (41 - hydroxy - 3<SP>1</SP> - carboxyphenyl) - 1:3 - benzotriazole ; the brown-orange dyeings of the product on cotton become red-brown, of improved fastness to washing and water, on after-treatment with copper salts ; (8) dinitrostilbenedisulphonic acid (1. mol.) with 2- aminophenol - 4 - sulphonic acid# 2:5 - di - methoxyaniline (approx. 0.5 or 0.85 mol.) and 2 - (4<SP>11</SP> - aminophenyl) - naphtho - 1':2<SP>1</SP>:4:5 - triazole - 5<SP>1</SP>:7<SP>1</SP> - disulphonic acid (1 mol.) followed by coppering of the product in substance; (9) dinitrostilbenedisulphonic acid (1 mol.) with the copper compound (1 mol.) of 2 - aminophenol - 4 - sulphonic acid# 2:5 - dimethoxyaniline and 5-amino-2-(41-hydroxy- 3<SP>1</SP> - carboxyphenyl)-1:3-benzotriazole (approx. 0.65 mol.). Tables are also given showing (a) the shades of the direct and after-coppered dyeings on cotton obtainable with the products of condensation of dinitrostilbenedisulphonic acid (1 mol.) with 1 or 2 mols. of various aminodiaryltriazole compounds, (b) the shades of the direct and in some cases the after-coppered dyeings on cotton obtainable with the products of condensation of dinitrostilbenedisulphonic acid (1 mol.) with 1 mol. each of various aminodiaryltriazole compounds and various aromatic amines or aminoazo compounds, and (c) the shades of the dyeings on cotton with the copper complex compounds obtainable by coppering in substance metallisable condensation products of the type used in (b). 2 - (3<SP>1</SP> - or 4 - Aminophenyl) - naphtho - 1<SP>1</SP>:2<SP>1</SP>:4:5 - triazolesulphonic acids and their substitution products are obtained by reducing the nitro group in the products of oxidation of the corresponding nitrophenyl-azo-naphthylamine compounds. 5 - Amino - 2 - (sulpho or carboxy - phenyl or sulpho - naphthyl) - 1:3 - - benzotriazoles and their substitution products are obtained by oxidation of the corresponding sulpho- or carboxy - phenyl - or sulpho - naphthyl - azo - m-phenylenediamines with ammoniacal copper sulphate. 5 - Amino - 1:21 - (5<SP>1</SP>:7<SP>1</SP> - disulphonaphthyl) - 1:3-benzotriazole is obtained by hydrolysis of the acetylamino group in diazotized 2-amino-4- acetylaminophenyl - 2<SP>1</SP> - naphthylamine - 51: 7<SP>1</SP> - disulphonic acid and other of the above compounds of this type are obtained analogously.