Patent GB-510091-A (GB)
Title: Manufacture of azo-dyestuff derivatives
IPC: C09B43/12
Filed: 1938-01-26
Abstract: 510,091. Dyes ; dyeing. SOC. OF CHEMICAL INDUSTRY IN BASLE. Jan. 26, 1938, Nos. 2514 and 2515. Convention dates, Jan. 26, 1937, and Jan. 7, 1938. [Classes 2 (iii) and 15 (ii)] Water-soluble aminoazo dyes of the 'kind defined below are treated in a medium consisting of a tertiary base with an organic acylating agent containing only one group having an acylating action and no hydroxy, sulphonic acid or carbonylic acid groups or groups reacting with a tertiary base to form quaternary ammonium compounds. The aminoazo dyes are those which contain carboxyhe or sulphonic acid groups and also primary amino groups the latter being in sufficient number to make the total of azo and primary amino groups at least three, subject to the further qualifications that (1) in the case of aminomonoazo dyes, two amino groups are attached to the same amyl nucleus, (2) disazo dyes are secondary and (3) polyazo dyes are those prepared by methods comprising diazotising an aminoazo compound and coupling. In examples (1) 1-aminonaphthalene-4-sulphonic acid or dehydrothiotoluidine-monosulphonic acid #1:3-diaminobenzene-4-sulphonic acid is treated with benzoyl, m-nitrobenzoyl, p-chlorbenzoyl or n-butyric acid chloride in pyridine ; (2) 2- aminonaphthalene-4.8-disulphonic acid #mtoluidine#m-toluidine is treated with benzoyl, 2:4-dichlorobenzoyl, 1-naphthoyl, phenoxyacetic acid or lauric acid chloride or acetic or propionic anhydride in pyridine; the first component in the above dye may be replaced by another aminonaphthalene sulphonic acid, e.g., 1-aminonaphthalene-3.6-disulphonic acid or 1:5-naphthylamine sulphonic acid, or by a benzene aminosulphonic acid, e.g., aniline-3- or - 4-sulphonic acid ; the middle component may be replaced by aniline (preferably in the form of w-methane sulphonic acid), 2-methoxy-5-toluidine, alpha-naphthylamine or its -6- or -7-sulphonic acid, 2-methoxy- or -ethoxy-1-naphthylamine, 1-amino-2-methoxy- or -ethoxynaphthelene-6- or -7-sulphonic acid ; the final component may be replaced .by one of the above middle components or by a diamine, e.g., m-phenylenediamine, m-toluylenediamine, 1:3-diaminobenzene -4- or -5- sulphonic acid, or 1:3-diamino- 4-nitro-benzene; (3) a trisazo dye obtained by diazotising one of the parent dyes in (2) and coupling with 1:3-diaminobenzene-4-sulphonic acid is treated with any of the acylating agents of (2) or with p- or m-nitrobenzoyl chloride, phenylacetic acid chloride, or butyric or benzoic anhydride in the presence of pyridine, dimethylaniline or tripropylamine ; the above end component may be replaced by 1:3-diaminobenzene or its -5-sulphonic acid, -2- or-4-methyl- 5-sulphonic acid, -4-phenoxy-4<1>-sulphonic acid, - 2-methoxy-5-sulphonic acid, -4-ethoxy-5-sulphonic acid, -4-nitro, -4-methyl or -4-chloro derivatives ; the middle components, in addition to those specified in (2), may be otoluidine, o-anisidine, p-xylidine, 2-ethoxy-5- toluidine, 2:5-dimethoxy- or -diethoxyaniline or monoacetyl-m-phenylenediamine; the initial component, in addition to those specified in (2), may be 2-aminonaphthalene-6-, -7- or -8- sulphonic acid, -3.6-, -6.8-, or -4.7-disulphonic acid or -3.6.8-trisulphonic acid, 1-aminonaphthalene-4-sulphonic acid, -4.7-disulphonic acid or -3.6.8.-trisulphonic acid, 1-amino-8-naphthol- 3.6-disulphonic acid (preferably in the form of an ester), aniline-2.4- or -2.5-disulphonic acid, -2- chloro-5-sulphonic acid or -4-nitro-2-sulphonic acid ; the first and second components may also be monoazo dyes, e.g., 4-aminoazobenzene-4<1>- or -3-sulphonic acid or -3.4<1>- disulphonic acid ; one of the products dyes cotton orange-brown capable of discharge ; (4) cotton is dyed yellowbrown with the first dye of (2). Other specified acylating agents are acetyl, anisoyl and benzene- or toluene-sulphonic chlorides, phosgene, isocyanates and mustard oil. 2-oxy-5-nitraniline #1:3-diaminobenzene-4-sulphonic acid is also specified as a suitable dye. The Specification as open to inspection under Sect. 91 comprises also treating any watersoluble azo dye containing at least one group, capable of acylation with an acylating agent, containing no substituent which would enhance the solubility in water, in the presence of a tertiary base. Additional acylating agents are maleic and cinnamic anhydrides, terephthalic acid dichloride and malonyl chloride. The group capable of acylation may be hydroxy or secondary amino as well as primary amino and additional dyes specified are sulphanilic acid # #-naphthol, p-aminoacetanilide # salicylic acid (saponified), and sulphanilic acid #alpha- or #-naphthylamine. Primary disazo dyes are also referred to. In additional examples (1) 4<1> - amino - 4 - oxy - 3 - methylazobenzene-5-carbonylic acid is treated with cinnamic acid chloride in pyridine ; (2) alpha-naphthylamine -2- naphthylamine-7-sulphonic acid is treated with benzoyl chloride or p-toluenesulphochloride and copper powder in pyridine ; (3) naphthionic acid # alpha-naphthylamine is treated as in (2) and benzoic anhydride may also be used ; (4) sulphanilic acid # alpha-naphthylamine is treated with acetic anhydride and copper powder in pyridine ; (5) p-toluenesulphonyl ester of 1- amino 8 - naphthol-3.6-disulphonic acid #2- methoxy-5-toluidine is treated with benzoyl or cinnamic acid chloride in pyridine and the product saponified ; it dyes viscose artificial silk yellow-red ; (9) salicylic acid #benzidine# m - phenylenediamine #dehydrothiotoluidine - disulphonic acid is treated with benzoyl chloride in pyridine ; (11) viscose artificial silk is dyed yellow-red with a dyestuff of (2). This subject-matter does not appear in the Specification as accepted.