Patent GB-513109-A (GB)
Title: A manufacture of azo-dyestuffs and intermediate products
IPC: C09B39/00
Filed: 1938-02-09
Abstract: 513,109. Dyes' and intermediates ; dyeing. SOC. OF CHEMICAL INDUSTRY IN BASLE. Feb. 9, 1938, Nos. 4046 and 4047. Convention dates, Feb. 10, 1937, and Jan. 12, 1938. Sample furnished. [Classes 2 (iii) and 15 (ii)] Azo dyestuffs are manufactured by coupling a diazo compound with a coupling component which contains, united to the residue in which coupling takes place, a residue of the formula where R is the group -NCHO-, -NHSO-, -NHCOCH2O- or ##C-, X is hydrogen or an acyl group itself carrying at least one diazotizable amino group, and Y is an acyl group which also carries at least one diazotizable amino group ; or by reacting an azo dyestuff containing an amino group with an acid halide obtainable by treating with a halogenating agent a carboxylic acid of the general formula where x is an aroylamino group of the benzene series containing as a substituent in the nucleus a nitro group or other group convertible into an amino group and y is the same as x or is a nitro group or other group convertible into an amino group, and then treating the reaction product so as to convert into amino groups the groups so convertible. One method of carrying the invention into effect consists in reducing a dinitrobenzenecarboxylic acid to the corresponding nitroamino- or diamino-acid, condensing this with one or two molecular proportions of an acylating agent which contains a group convertible into a diazotizable amino group, converting the product into the corresponding acid chloride, condensing this with a coupling component or azo dyestuff containing an amino group, converting into amino groups the groups so convertible, and, if necessary, coupling the coupling component with a diazo compound. A second method consists in reacting a coupling component containing an amino group, e.g. an aminonaphtholsulphonic acid such as 1: 8 : 3: 6-, 1 : 8 : 4 : 6-, 2: 5 : 7- or 2 : 5 : 1 : 7-acids or 1 : 2-diamino-5-naphthol-7-sulphonic acid, or 1- (3<1> -aminophenyl)- 5 -pyrazolone - 3 -carboxylic acid, with an acylating agent or other agent capable of condensing with an amino group, which agent contains, for example, two nitro groups attached to a benzene nucleus, e.g. 3:5-dinitrobenzoyl chloride, 3:5-dinitrobenzene-1-sulphochloride or 2: 4-dinitrophenoxyacetyl chloride, or, when the coupling component contains two amino groups in o-position to one another, 2: 4-dinitrobenzaldehyde, reducing both nitro groups to amino groups, acylating one or both amino groups with an acylating agent containing a nitro group attached to an aromatic nucleus, e.g. m- or p-nitrobenzoyl chloride, p-nitrophenoxyacetyl chloride or m-nitrobenzenesul phochloride, or with corresponding compounds containing an acidylamino group in place of the nitro group, converting to amino groups the groups so convertible, and coupling the product with a diazo compound. The products have an affinity for vegetable fibres, and may be diazotized and developed on the fibre. In examples : (1) aniline is diazotized and coupled with 1- 3<1>- 5<1> - di - (4<11> - aminobenzoylamino) - benzoyl - amino} -8;naphthol-3 : 6-disulphonic acid (obtainable by condensing 1 : 8 : 3 : 6-acid with 3 5-dinitrobenzoyl chloride, reducing, condensing with p-nitrobenzoyl chloride and again reducing) ; the product dyes cotton bluish-red shades becoming brilliant red on diazotization and development with #-naphthol ; the coupling component may be replaced by the product obtained similarly from 2 : 5 : 7-acid, or bv the product obtained from 1-(4<1>-methyl-3<1>: 5<1>- diaminobenzenesulphonylamino) - 8 - naphthol - 3 : 6-disulphonic acid by reaction with pnitrobenzoyl chloride and reduction ; (2) 4- aminoazobenzene-4<1>-sulphonic acid is diazotized and coupled with 2- {3<1>-(4<11>-aminobenzoylamino)- 5<1>-aminobenzoylamino } - 5-naphthol-7. sulphonic acid (obtainable by condensing 2-(3<1>-amino-5<1>-nitrobenzoylamino)-5-naphthol- 7-sulphonic acid with p-nitrobenzoyl chloride and reducing, or by starting with 2-(3<1>-amino- 5<1>- acetylaminobenzoylamino) - 5 -naphthol - 7 - sulphonic acid and saponifying the acetylamino group before or after the reduction of the nitro group); the product dyes cotton bluish-red shades, becoming brilliant red on diazotization and development with #-naphthol ; the diazo component may be replaced by the dyestuff 1-amino-2:5-dichlorobenzene-4-sulphonic acid # 1 - amino - 2 - methoxynaphthalene - 6 - sulphonic acid, the product dyeing cotton blue-green shades which become green on diazotization and coupling with 1-phenyl-3-methyl-5-pyrazolone. A sample has been furnished under Sect. 2 (5) of the product obtained by reacting the dyestuff 2 - aminonaphthalene - 6 - sulphonic acid# (alkaline) 2 : 5 : 7-acid with 3-(4<1>-nitrobenzimide-chloride)-5-nitrobenzoyl chloride, and treating the product with sodium sulphide. The dyestuff may be diazotized on the fibre and developed with #-naphthol. The Specification as open to inspection under Sect. 91 comprises generally the introduction, into azo dyestuffs or intermediates containing an.amino group, of externally united aryl residues which contain two amino groups of which at least one contains as a substituent an acyl residue containing at least one diazotizable amino group. Additional starting materials specified are amines of the benzene series such as aniline and its o-, m- and p-sulphonic acids, naphthylamines and their sulphonic acids, diamines such as o-, m- and p-phenylenediamines, 1 : 8-naphthylenediamine and its sulphonic acid, also 4:4<1>-diaminostilbene-2 : 2<1>- disulphonic acid, dehydrothiotoluidinemono- and -disulphonic acids, dehydrothioxylidinedisulphonic acid and sulphonic acids of primuline base. Reference is made to the use, in the preparation of the coupling component of (1) above, of minstead of p-nitrobenzoyl chloride, of 2 : 5 : 1 : 7-acid, 1:8: 4-acid or 1-(3'-aminophenyl)-5-pyrazolone-3-carboxylic acid, in place of 1 : 8 : 3 : 6-acid and of 2 : 4-dinitrophenoxyacetyl chloride in place of 3 : 5-dinitrobenzoyl chloride, and of the use, in the preparation of the coupling component of (2) above, of mnitrobenzoyl chloride or p-nitrophenoxyacetyl chloride in place of p-nitrobenzoyl chloride and of 2 : 8 : 6-acid, 1:8: 4-acid or 1-(3<1>-aminophenyl)-5-pyrazolone-3-carboxylic acid in place of 2 : 5 : 7-acid ; also to the use, as diazo components in (1) and (2) above, of o-toluidine, m-xylidine, o-anisidine, p-chloraniline or #- naphthylamine, and in (2) the use, as diazo component, of aniline and, as coupling components, of the products obtained from 2-(3<1>- amino - 5<1> - nitrobenzoylamino) - 5 - naphthol - 7-sulphonic acid or 2-(3<1>:5<1>-diaminobenzoylamino)-5-naphthol-7-sulphonic acid by reaction with m-nitrobenzoyl chloride and reduction. In further examples : (a) 4 : 4<1>-diaminostilbene- 2 : 2<1>-disulphonic acid is reacted with 3-acetylamino-5-nitrobenzoyl chloride, and the product is reduced, condensed with p-nitrobenzoyl. chloride, reduced and saponified ; cotton is impregnated with the product, which is then diazotized and coupled with #-naphthol (redorange shades), #-hydroxynaphthoic acid (red) or 1-phenyl-3-methyl-5-pyrazolone (yellow) ; (b) 2 : 4-diaminophenyl-1 : 2naphthimidazole-5- hydroxy-7-sulphonic acid (obtainable from 1 : 2-diaminonaphthalene-5 : 7-disulphonic acid and 2 4-dinitrobenzaldehyde) is condensed with 3-nitrobenzenesulphochloride and the product is reduced ; (c) dehydrothiotoluidinedisulphonic acid is reacted with 2:4-dinitrophenoxyacetyl chloride and the product is reduced, condensed with m-nitrobenzoylchloride and reduced ; (d) sulphanilic acid is diazotized and coupled with the compound of the formula the product may be diazotized on the fibre and developed with 1-phenyl-3-methyl-5-pyrazolone, yielding yellow shades ; (e) sulphanilic acid is diazotized and coupled with the product obtained from 1- {3<1> - (3<11> - amino - 5<11> - nitrobenzoylamino) - phenyl} - 5 - pyrazolone - 3 - carboxylic acid by condensation with p-nitrobenzoyl chloride and reduction ; the product may be diazotized on the fibre and developed with 1-phenyl-3-methyl-5-pyrazolone, yielding yellow shades ; (f) the dyestuff 1 : 8 : 3 : 6-acid p-toluenesulphonic ester#1-amino-2 : 5-hydroquinone diethyl ether is diazotized, coupled with one of the first two coupling components of (1) above, and saponified to remove the p-toluenesulphohic residue ; the product dyes cotton blue shades, becoming green on diazotization and development with 1-phenyl-3-methyl- 5-pyrazolone : (g) the dyestuff 2-aminonaphthalene-5-sulphonic acid #1-amino-2-methoxynaphthalene-6-sulphonic acid is diazotized and coupled with the first coupling component of (2) above ; the product dyes cotton blue shades becoming green on diazotization and development with 1-phenyl-3-methyl-5-pyrazolone ; the initial diazo component may be replaced by 1-amino-2 : 5-dichlorobenzene-4-sulphonic acid (blue-green shades becoming green on development) ; (h) the diazo dyestuff p-aminoazobenzenesulphonic acid # 1-amino-2-methoxynaphthalene-6-sulphonic acid is diazotized and coupling with the first coupling component of (2) above (blue-green shades which on development are converted into becoming green shades capable of discharge) ; (i) the dyestuff 1 : 8 : 3 : 6- acid p-toluenesulphonic ester#1-amino-2 5- hydroquionediethyl ether# a mixture of 1- amino-naphthalene-6-6- and 7-sulphonic acids is diazotized, coupled with one of the first two coupling components of (1) above and saponified (blue shades becoming green on development) ; (j) cotton is dyed with the second product of (g) from a bath containing Glauber's salt and benzylated and sulphonated Á-heptadecylbenzimidazole, and the dyestuff is diazotized on the fibre and developed with 1-phenyl-3- methyl-5-pyrazolone to a green shade. This subject-matter does not appear in the Specification as accepted.