Patent GB-546710-A (GB)
Title: Manufacture of new azo-dyestuffs
IPC: C09B43/16
Filed: 1940-07-29
Abstract: 546,710. Dyes. SOC. OF CHEMICAL INDUSTRY IN BASLE. July 29, 1940, Nos. 12268 and 12269. Convention dates, July 12, 1939, and June 14, 1940. [Classes 2 (iii) and 15 (ii)] Yellow dyeing azo dyestuffs having pronounced affinity for natural or regenerated cellulose and of the general formula K(R)n, wherein K represents the residue remaining after exchange of at least two halogen atoms of a heterocyclic compound containing at least two and at most three exchangeable halogen atoms, n represents 2 or 3, R represents the residue of a colourless or yellow amino compound remaining after exchange of a hydrogen atom of the NH 2  group by means of one of the said halogen atoms, at least two of the amino compounds being yellow aminoazo compounds of which (a) at least one contains one of the groups -CO.NH- or -O.CH 2 .CO.NH- and at most two azo groups and (b) at least one contains an o-hydroxycarboxylic acid grouping on a benzene nucleus, and in which the aryl residues which are combined with two azo groups, or with one azo group and one of the -CO.NH- or -O.CH 2 .CO.NH- groups, or with the amino groups of the aminoazo compounds, are of the benzene series, are obtained by causing the halogen-containing heterocyclic compound to react with the two appropriate aminoazo compounds and, if desired, exchanging a remaining halogen atom for the residue of a colourless or yellow amino compound, the reactions being performed in any desired order, and the components being so chosen that the finished dyestuff contains one or more sulphonic acid groups. Alternatively, the azo groups may be formed by diazotization and coupling after causing the halogen-containing heterocyclic compound to react with the appropriate intermediate compounds. The fastness to light and to washing of dyeings with the products is improved by treatment in the dyebath or in a subsequent operation with salts of metals, especially copper. Specified halogen-containing heterocyclic compounds are cyanuryl chloride, 2:4:6-tribromopyrimidine, 2-phenyl 4:6-dichloro 1:3:5-triazine, 2:6-dichloro-4-methylpyrimidine and 2:4-dichloroquinazoline. Specified products of which the formulae are given are the dyestuffs obtainable by condensing (I) cyanuryl chloride (1 mol.) with 2 mols. of the product obtained by reducing the nitro group in the product of the action of 4-nitrobenzoyl chloride on 3- amino-5-sulpho-2-hydroxybenzoic acid # 3- aminotoluene, and with 1 mol. of 4-amino-4'- hydroxyazo-benzene-3<SP>1</SP>-carboxylic acid, (II) cyanuryl chloride (1 mol.) with 1 mol. of 2-4<SP>1</SP>- aminophenoxyacetyl)-aminonaphthalene-4:8-disulphonic acid # cresidine and with 2 mols. of 4-amino-4<SP>1</SP>-hydroxy-azo -benzene-31-carboxylic acid, (III) and (IV) cyanuryl chloride (1 mol.) with 1 mol. of the product obtained by reducing the nitro group in the product of the action of 4-nitrobenzoyl chloride on the product of reduction of the nitro group of (III) 2-nitro-5- aminobenzoic acid or (IV) 5-nitro-2-aminobenzoic acid # 1-(2<SP>1</SP>-chloro-4<SP>1</SP>-sulpho) phenyl- 3-methyl-5-pyrazolone, with 1 mol. of the product obtained by reducing the nitro group in the product of the action of 4-nitrobenzoyl chloride on the monoazo compound 5-amino-3- sulpho-2-hydroxybenzoic acid # cresidine, and with 1 mol. of aniline, (V) cyanuryl chloride (1 mol.) with 1 mol. of the product obtained by reducing the nitro group in the product of the action of 4-nitrobenzoyl chloride on anthranilic acid # 1-(41-amino)phenyl-5-pyrazolone-3- carboxylic acid, with 1 mol. of the product obtained by reducing the nitro group in the product of the action of 4-nitrobenzoyl chloride on 5-amino-3-sulpho-2-hydroxybenzoic acid # cresidine, and with 1 mol. of aniline, (VI) cyanuryl chloride (1 mol.) with 1 mol. of the product obtained by reducing the nitro group in the product of the action of 4-nitrobenzoyl chloride on the product of reduction of the nitro group of 4-nitroaniline-2- sulphonic acid # 1-(4<SP>1</SP>-hydroxy-3<SP>1</SP>-carboxy)phenyl-3-methyl- 5-pyrazolone, with 1 mol. of 4-amino-51- methyl-4<SP>1</SP>-hydroxy-azo-benzene -31-carboxylic acid and with 1 mol. of 4-amino-azo-benzene- 41-sulphonic acid, (VII) cyanuryl chloride (1 mol.) with 1 mol. of the product obtained by reducing the nitro group in the product of the action of 4-nitrohenzoyl chloride on 5-amino-3-sulpho-2-hydroxybenzoic acid, diazotizing and coupling with aniline (1 mol.), with 1 mol. of 4-amino-azo-benzene-4<SP>1</SP>-sulphonic acid and with 1 mol. of aniline, (VIII) cyanuryl chloride (1 mol.) with 1 mol. of the product obtained by reducing the nitro group in the product of the action of 4-nitrobenzoyl chloride on 5-amino-3-sulpho-2-hydroxybenzoic acid # aniline, diazotizing and coupling with 1-(4<SP>1</SP>- amino)phenyl-3-methyl-5-pyrazolone (1 mol.), with 1 mol. of 4-amino-4<SP>1</SP>-hydroxy-azo-benzene- 3<SP>1</SP>-carboxylic acid and with 1 mol. of aniline, (IX) 2:4-dichloroquinazoline (1 mol.) with 1 mol. of 2-(3<SP>1</SP>-aminobenzoyl)aminonaphthalene- 4:8-disulphonic acid # 3-aminotoluene and with 1 mol. of the product obtained by reducing the nitro group in the product of the action of 4-nitrobenzoyl chloride on 5-amino-3-sulpho-2- hydroxybenzoic acid # cresidine, (X) 2-phenyl- 4:6-dichloro-1:3:5-triazine (1 mol.) with 1 mol. of 2-(4<SP>1</SP>-aminobenzoyl)aminonaphthalene-4:8- disulphonic acid # 3-aminotoluene and with 1 mol. of the product obtained by reducing the nitro group in the product of the action of 4-nitrobenzoyl chloride or 5-amino-4-sulpho- 2-hydroxybenzoic acid # cresidine, (XI) 2:6- dichloro-4-methylpyrimidine (1 mol.) with 1 mol. of 4-amino-4<SP>1</SP>-hydroxy-azo-benzene-3<SP>1</SP>- carboxylic acid and with 1 mol. of the final component in IX, (XII) cyanuryl chloride (1 mol.) with 1 mol. of anthranilic acid # 1-(4<SP>1</SP>- amino-2:2<SP>1</SP>-disulpho) stilbenyl-3-methyl-5- pyrazolone, with 1 mol. of the product obtained by reducing the nitro group in the product of the action of 3-nitrobenzoyl chloride on 5- amino-3-sulpho-2-hydroxybenzoic acid # cresidine, and with 1 mol. of aniline, (XIII) 1:4- diaminobenzene (1 mol.) with the condensation product (2 mols.) from cyanuryl chloride (1 mol.) with 1 mol. of the product obtained by reducing the nitro group in the product of the action of 4-nitrobenzoyl chloride on 2-aminonaphthalene-4:8-disulphonic acid # cresidine and with 1 mol. of 4-amino-4<SP>1</SP>-hydroxy-azobenzene-31-carboxylic acid. Numerous detailed examples are given of the production of these and similar dyestuffs. Specifications 209,723, [Class 15 (ii)], and 315,451, [Class 2 (iii)], are referred to. The Specification as open to inspection under Sect. 91 comprises also dichlorophthalazine as a halogen-containing heterocyclic compound. This subject-matter does not appear in the Specification as accepted.