Patent GB-578014-A (GB)
Title: Manufacture of new azo-dyestuffs
IPC: C09B43/16
Filed: 1943-03-26
Abstract: Azo dyes of the general formula <FORM:0578014/IV/1> wherein R represents a residue carrying a ketoenolic grouping, K represents a residue of a heterocyclic compound comprising a 6-membered ring of 3 or 4 carbon atoms and 3 or 2 nitrogen atoms, with not more than 2 nitrogen atoms adjacent to one another, at least 2 and not more than 3 of the C atoms carrying replaceable halogen atoms, B represents -CO- or a residue of the type represented by K, and <FORM:0578014/IV/2> represents the residue of a yellow aminoazo dyestuff carrying at least one metal-complex-forming grouping, are obtained by (a) reaction of 4 : 41-diaminostilbene-2 : 21-disulphonic acid (1 mol.) with a heterocyclic compound as above (2 mols.) and reaction of the product with a compound (1 mol.) of the general formula <FORM:0578014/IV/3> and then with a yellow aminoazo dyestuff as above (1 mol.) which may or may not be of this last general formula, any residual replaceable halogen atoms in the product being replaced, if desired, e.g. by reaction with aniline, N - methylaniline, methylamine or ethanolamine; (b) reaction of 4-amino-41-nitrostilbene-2 : 21-disulphonic acid (1 mol.) with the heterocyclic compound (1 mol.) and with a compound (1 mol.) of the general formula <FORM:0578014/IV/4> followed by reduction of the nitro group and reaction of the resulting aminoazo product (1 mol.) with phosgene or a heterocyclic compound as above (1 mol.) and with the yellow aminoazo dyestuff (1 mol.) which may be of the general formula given in (a) or of the type of the first-obtained aminoazo product or a derivative of salicylic acid; (c) reaction of 4-amino-41-nitrostilbene-2 : 21-disulphonic acid (1 mol.) with phosgene or a heterocyclic compound as above (1 mol.) and the yellow aminoazo dyestuff (1 mol.), followed by reduction of the nitro group and condensation of the product (1 mol.) with a heterocyclic compound as above (1 mol.) and with a compound (1 mol.) of the general formula <FORM:0578014/IV/5> (d) reaction of 4-amino-41-nitrostilbene-2 : 21-disulphonic acid or 4 : 41-diaminostilbene-2 : 21-disulphonic acid (1 mol.) with phosgene or a heterocyclic compound as above (1 mol.) and with 1 : 4-diaminobenzene-3-carboxylic acid (1 or 2 mols.), diazotising or tetrazotising the product and coupling with a keto-enolic component, reducing any nitro group present and condensing the product as in (c) with a compound of the general formula <FORM:0578014/IV/6> Specified compounds of this general formula are those obtainable by reducing the nitro group in the products obtained by coupling diazotised 5-nitro-2-aminobenzoic acid with acetoacetic acid esters and arylamides, pyrazolones, barbituric acid, benzoylacetone or 2 : 4-dihydroxyquinoline.  Specified heterocyclic compounds as above are cyanuryl chloride or bromide, 1-phenyl- or methyl - 3 : 5 - dichloro - 2 : 4 : 6 - triazine, 2 : 4-dichloroquinazoline and 2 : 4 : 6-tribromopyrimidine.  Specified yellow aminoazo dyestuffs in addition to those of the last-mentioned general formula are 4-amino-41-hydroxy-azobenzene-31-carboxylic acid and its 2-, 21- and 51-methyl derivatives, the reduced m- or p-nitrobenzoyl derivatives of these, the condensation product from 4 : 41-diaminostilbene-2 : 21-disulphonic acid (1 mol.), a cyanuryl halide (1 mol.), aniline (1 mol.) and 4-amino-2-methyl-5-methoxy-41-hydroxy-azobenzene-31 -sulphonic acid (1 mol.) and 5-(41-aminobenzoyl) amino-2-aminobenzoic acid --> 3-methyl-5-pyrazolone.  Numerous examples are given.  The products dye textiles consisting of or containing cellulose, e.g. mixtures of cotton and artificial fibres of regenerated cellulose or regenerated cellulose matted with inorganic pigments, or mixtures of wool and such artificial fibres, in yellow shades which may be treated with metal (e.g. copper) salts during or after dyeing.  In some cases, the metal compounds of the dyestuffs may be prepared in substance, e.g. by the action of copper sulphate and excess of ammonia, and may be applied in the manner of substantive dyestuffs.