GB756874A - Improvements relating to heavy metal complexes of azo dyestuffs and their use - Google Patents

Abstract

Ethanolamine chromosalicylate is prepared in solution by dissolving salicyclic acid in hot aqueous ethanolamine, heating and adding a solution of chromic fluoride followed by an aqueous ethanolamine solution which is added until an alkaline reaction to brilliant yellow is obtained. Reference has been directed by the Comptroller to Specification 637,404, [Group IV (c)].ALSO:The invention comprises dyestuffs, of formula:-<FORM:0756874/IV(c)/1> where M1 is chromium or cobalt; M2 is an alkali metal or ammonium cation; D1 is a co-ordinated dyestuff of formula:- <FORM:0756874/IV(c)/2> and D2 is a co-ordinated dyestuff containing no acid water solubilizing groups of formula:- <FORM:0756874/IV(c)/3> where A is a radical of an azo component of the benzene, naphthalene, 5-pyrazole or acetoacetic acid phenyl amide series coupled in ortho position to the phenolic or enolic hydroxy group; X is a nitro or alkyl sulphone group having 1 to 4 carbon atoms in the alkyl group, and Y is hydrogen or o non-salt-forming substituent, such as a nitro or acetylamino group. In a preferred dyestuff D2 is the same as D1. The dyestuffs are made by reacting the first dyestuffs (D1) alone, or mixed with the second dyestuff (D2), with agents giving chromium or cobalt so that two dyestuff molecules are bound in complex union with one metal atom. Preferably the same diazo component, i.e. 4-nitro-2-amino-1-hydroxyzenzene is used for both ryestuffs and may be coupled with a mixture of 3.4-dimethyl - 1 - hydroxybenzene and the azo component corresponding to A, the resultant dyestuff mixture being metallized. Specified azo components A are 4 - hydroxy - 1 - methyl - or - 1:2 - dimethyl - benzene, 4 - hydroxy - 3 - acetylamina - 1 - methylbenzene, 2 - naphthol, 1 - acetylamino - or - carbom-ethoxyamino - 7 - naphthol, 6 - methoxy - 2 - naphthol, 1 - phenyl - 3 - methyl - 5 - pyrazolone, 1 - (21 - or 31 - or 41 - chlorophenyl) - 3 - methyl - 5 - pyrazolone, and acetoacetic acid anilide or -21-, -31- or -41- chloranilide. The metallization is carried out in known manner, approximately equal amounts of the dyestuffs are used, and the reaction is carried out in aqueous solution or suspension or in organic solution, e.g. in ethyl or isopropyl alcohol, ethylene glycol monomethyl or monoethyl ether, formamide or N-dimethyl formamide. Specified metallizing compounds are chromic fluoride, chromic acetate, chromic formate, cobalt chloride, cobalt sulphate, cobalt nitrate and the alkali salts of chromosalicylic acid. The metallized dyestuffs dye wool, silk, superpolyamide, superpolyurethane and casein fibres in brown shades In examples and a Table, 4 - nitro - 2 - amino - hydroxybenzene --> 3:4 - dimethyl - 1 - hydroxybenzene is metallized alone or mixed with the following dyes: 2 - amino - 1 - hydroxybenzene - 4 -methylsulphone --> 2 - naphthol or 1 - (31-chlorophenyl) - 3 - methyl - 5 - pyrazolone or acetoacetic acid phenylamide or acetoacetic acid - 21 - chlorophenyl amide; 4 - nitro - 2 - amino - 1 - phenol --> 4 - methyl - 2 - carbomethoxyamino - or -carboethoxyamino - or - carbomethoxyethoxyamino - 1 - phenol or 1 - phenol - 3 - methyl - 5 - pyrazolone or 2 - naphthol or 1 - carbomethoxyamino - 7 - naphthol; 4:6 - dinitro - 2 - amino - 1 - hydroxybenzene --> 1 - phenyl - 3 - methyl - 5 - pyrazolone; 4 - nitro - 6 - acetylamino - or - methyl - or - chloro - 2 - amino - 1 - phenol --> 3:4 - dimethyl - 1 - phenol and 2 - amino - 1 - phenol - 4 - ethylsulphone --> 1 - (31 - chlorophenyl) - 3 - methyl - 5 - pyrazolone. Reference has been directed by the Comptroller to Specification 637,404.