Patent GB-451970-A (GB)
Title: Manufacture of dyestuffs
IPC: C09B29/00
Filed: 1935-03-25
Abstract: Azo dyes of various colours are made by coupling with an amine of the benzene or naphthalene series, which may be substituted, a diazotized amine of the benzene series containing in p-position to the diazotizable amino group a nitro or an acylamino group, and in o-position a group --SO2R, where R is an alkyl or aralkyl group, which may be substituted; the conditions are so selected that the amino group in the coupling component determines the coupling. Specified diazo components are 1-amino-4-nitrobenzene-2-methyl- (or 2-ethyl or 2 - benzyl) - sulphone, the corresponding 1-amino-4-nitro-5-chloro- (or bromo or iodo) benzene-2-alkylsulphones, 1-amino-4-nitro-6-chloro- (or bromo or iodo) benzene-2-methyl-sulphone, 1 - amino - 4 : 6 - dinitrobenzene - 2 - methylsulphone, 2 - amino - 5 - acetylaminophenyl-ethyl (or -methyl or -benzyl) sulphone (or the corresponding benzoylamino or chloracetylamino compounds), 1-amino-4-nitrobenzene - 2 - benzylsulphonesulphonic acid, and 2 - amino - 5 - nitro - 6 - chlorophenylmethyl sulphone.  The products which contain a nitro group may be reduced to yield aminoazo dyes, which may then be acylated or alkylated or further diazotized and coupled.  When one (at least) of the components contains a sulphonic group, the products are useful as wool dyes and possibly for printing acetate silk; coupling components specified for use in this connection are b -naphthylamine, N-ethyl-b -naphthylamine and its sulphonic acids, 2-amino-8-naphthol-6-sulphonic acid and other aminonaphtholsulphonic acids, and N-ethyl-N-p-sulphobenzylaniline and other N-alkylanilinesulphonic acids.  When neither component contains a sulphonic group, products useful for dyeing acetate silk are obtained; coupling components specified in this connection are aniline, o- or m-toluidine, p-xylidine, p-cresidine, 2 : 5-dialkoxyanilines, naphthylamines, 1 : 5-aminonaphthol and its N-alkyl substitution products and other aminonaphthols, N-alkyl-N-oxyalkylamines of the benzene or naphthalene series, and esterified or etherified N-oxyalkylamines of the benzene or naphthalene series.  The dyes for acetate silk are preferably brought into a subdivided form by grinding with dispersing agents such as sulphite cellulose lye or the sulphonated residue from the manufacture of benzaldehyde; the pastes so obtained may be dried. Examples are given in which the following dyes are described: (1) 2 - amino - 5 - nitrophenylethyl sulphone --> N-ethyl-N-oxyethylaniline, N-dimethyl- or N-diethyl-aniline, aniline (as o -methanesulphonic acid), N-ethyl-N-cyanoethylaniline, N-ethyl-N-chlorethyl (or bromethyl) - aniline, N - ethyl - N - thiocyanoethylaniline, N - oxyethylaniline, N - methoxyethylaniline, N - acetoxyethylaniline, N - ethyl - N - acetoxyethylaniline, N - methoxyethyl - N - acetoxyethylaniline, N-diacetoxyethylaniline, m-phenylenediamine and its monoacetyl derivative, and m-toluylenediamine; (2) 2-amino-5-nitrophenylmethyl sulphone --> N-ethyl-N-methoxyethylaniline, N-dimethyl- or N-diethylaniline, or aniline (as o -methanesulphonic acid); (3) 2-amino-5-nitrophenylmethyl sulphone --> 2-methoxy-5-methyl-N-di(methoxyethyl)aniline or p 2-methoxy-5-methylaniline or its N-substitution products corresponding to the N-substitution products of aniline specified in example 1; 2-amino-5-nitrophenylethyl sulphone or 2-amino-5-nitrophenyloxyethyl sulphone may also be used as diazo component, as well as sulphones containing halogen atoms or additional nitro groups; (4) 2-amino-5-nitrophenylmethyl sulphone --> 2 - methoxy - 5 - methyl-N-methoxyethylaniline or 2 : 5-dimethylaniline or (example 5) 2-methoxy-5-methyl-N-di(oxyethyl)aniline or (example 6) 1-amino-5-naphthol; (7) 2-amino-5-nitrophenyl-benzyl (or -methyl or -ethyl) sulphone --> 2-amino-8-naphthol - 6 - sulphonic acid; (8) 2 - amino - 5-acetylaminophenyl-ethyl (or -methyl or -benzyl) sulphone, or the corresponding 5-benzoylamino or 5-chloracetylamino compounds, --> 2-amino-8-naphthol-6-sulphonic acid; the products of this example may be identical with those obtainable by reducing and acylating the products of example 7.  A table is given also in which the following dyes are described: (a) 2 - amino - 5 - nitrophenylmethyl sulphone --> N-ethyl-N-oxyethylaniline, N-ethyl-N-ethoxy-ethylaniline, 2-methoxy-5-methyl-N-butyl-N-methoxyethylaniline, N - methyl - N - methoxyethylaniline, 2 : 5 - dimethoxy - N - di(methoxyethyl)aniline, N-methyl-N-acetoxyethylaniline, N-di(oxyethyl)aniline, 2-methoxy-5-methyl-N-oxyethyl-N-methoxyethylaniline, 2-methoxy-5 - methyl - N - methoxyethyl - N - dioxypropylaniline '1-methylamino-5-naphthol, 1-allylamino-5-naphthol, 1-oxyethylamino-5-naphthol, 2 - methoxy - 5 - methyl - N - ethylaniline, N - allyl - N - methoxyethylaniline, N - allyl - N - ethylaniline, 2-amino 8-naphthol-6-sulphonic acid, 2-phenylamino-8-naphthol-6-sulphonic acid, and 1-amino-5-naphthol-7-sulphonic acid; (b) 2-amino-5-nitrophenylethyl sulphone --> N-di(oxyethyl)aniline and 2-amino-8-naphthol-6-sulphonic acid; (c) 2-amino-5-nitrophenylbenzyl sulphone --> N-di(oxyethyl)-aniline; (d) 2-amino-5-nitro-6-chlorophenylmethyl sulphone --> N di(oxyethyl)aniline, 2 - methoxy - 5 - methyl - N - methoxyethyl - N - dioxypropylaniline, and 1-amino-5-naphthol; (e) 2 - amino - 5 - acetylaminophenylmethyl sulphone --> 2-aminonaphthalene-6-sulphonic acid, 2-amino-8-naphthol-6-sulphonic acid, and N - ethyl - N - p - sulphobenzylaniline; (f) 2-amino-5-acetylaminophenylbenzyl sulphone --> 2-aminonaphthalene-6-sulphonic acid and N-ethyl-N-p-sulphobenzylaniline; (g) 2-amino-5 - benzoylaminophenylmethyl sulphone --> 2-amino-8-naphthol-6-sulphonic acid.  In examples of the use of the dyes: (1) wool is dyed in an aqueous bath containing sodium sulphate, sulphuric acid, and the dye 2-amino-5-acetylaminophenylethyl sulphone --> 2-amino-8-naphthol-6-sulphonic acid; (2) acetate silk is dyed in a soapy aqueous bath in which the dye 2-amino-5-nitrophenylmethyl sulphone --> N-ethyl-N-methoxyethylaniline is emulsified with the aid of a dispersing agent such as turkey red oil, sulphite cellulose lye, or the sulphonated residue from the manufacture of benzaldehyde.  1 - Amino - 4 - nitrobenzene - 2 - benzylsulphone sulphonic acid is obtainable by treating 1-amino-4-nitrobenzene-2-benzylsulphone with sulphuric acid containing sulphuric anhydride.  2 - Amino - 5 - acetylaminophenyl - ethyl (or -methyl or -benzyl) sulphone and the corresponding N-benzoyl or N-chloracetyl compounds are made by reducing the corresponding 2-amino-5-nitrophenyl-alkyl (or -aralkyl) sulphone and treating the diamino compound with an appropriate acylating agent.  N - Ethyl - N - cyanoethylaniline is obtainable from N-ethyl-N-o -bromethylaniline and potassium cyanide.  N - Ethyl - N - thiocyanoethylaniline is obtainable from N-ethyl-N-o -bromethylaniline and potassium sulphocyanide. N-Di(acetoxyethyl)aniline is obtainable by heating N-di(oxyethyl)aniline with acetic anhydride and sodium acetate.  The other esterified or etherified oxyalkylarylamines specified above are obtainable as described in British Specification 422,843 or French Specification 758,079.  The Specification as open to inspection under Sect. 91 mentions, as diazo components, 1 - amino - 4 - nitrobenze - 2 - oxyethyl (or -2-oxybenzyl or 2-carboxymethyl or 2-carboxymethylestermethyl) sulphone and the corresponding 5-chloro-, 5-bromo-, or 5-iodo compounds.  This subject-matter does not appear in the Specification as accepted.