Patent GB-904876-A (GB)
Title: New dyestuffs containing carboxylic acid groups and their production
Inventor: BRAUN WILLY
IPC: C07C205/56
Filed: 1960-07-13
Abstract: The invention comprises dyes of formula <FORM:0904876/IV (b)/1> where F is a dye residue containing at least one aromatic ring, A is a direct link or CO, SO2, CH2CO and CH2SO2 connected to an aryl ring of the dye residue, Y is a direct link or -C(H)Z2 or -CH(Z2)-CH(Z3)-, Z2 is H or with Z1 or Z3 is a direct link, Z1 and Z3 are H or form direct links with Z2, V is a tertiary or quat. amino group with up to 10 C atoms which may be part of a heterocyclic ring, and n is 1-4. The dyes are made by treating dyes or intermediates containing a group of formula -A-CH (Z1)-Y-COOH with formaldehyde, or a compound which supplies formaldehyde, in the presence of a secondary or tertiary amine and, if necessary, forming the dye from the intermediate.  Preferred dyes are those of the anthraquinone, azo or phthalocyanine series, others indicated being oxazines, azomethines or triarylmethanes. Specified residues for -A-CH(Z1)-Y- are -CH2, -CH2.CH2-, -CH2.CH2.CH2-, -CH=CH-, -CH=CH-CH2-, -CH2-CH=CH-, -CO-CH2, -SO2CH2, -CH2 COCH2-, -CH2SO2CH2-, -COCH2CH2-, -COCH=CH-, -SO2CH2CH2 and SO2 CH\cCCH.  Benzene and naphthalene are indicated as aromatic rings.  Substituents, e.g. methyl and halogen may be present in the aromatic rings.  Phenyl rings may be attached to the remainder of the dye residue via an azo, carbon-amide or sulphonamide bridge. Representative of specified dyes used as starting materials are the reaction products of 1-chlor-, 1,8-dichlor-4,5-dihydroxy-, 1-methylamino-4-brom- and 1-amino-2-sulpho-or -carboxy-4-brom-anthraquinones and 4-brom- N-methylanthrapyridone with aryl amines such as 4-aminophenyl and 3-aminobenzoyl-acetic acid and 4-aminophenyl-propionic acid, the reaction products of the acid chlorides of 1-amino-2-carboxy- or 1,4-diamino-2-sulpho-anthraquinones with amines such as g -(4-aminophenyl)-acetoacetic acid and b -(3-aminobenzoyl) acrylic acid, reaction products of copper, phthalocyanine sulphonyl chlorides with amines as above, 4-aminocinnamic acid, g -(3-aminophenyl)- butyric acid or b (3-amino-2-methylbenzoyl)-acrylic acid --> 1-naphthol and its 3,6-disulphonic acid, 2-naphthol-3-carboxylic or acetoacetic acid arylides, pyrazolones or amino-phenols or -naphthols, and toluidine, benzidine, 1-naphthylamine, aniline-3-sulphonic acid, 4-aminodiphenyl, 4,41-diaminodiphenyl- 3,31-disulphonic acid or aniline-4-carboxylic acid --> 2-hydroxybenzoylacetic acid, b -(1-hydroxy-4-naphthoyl)-propionic acid or b -(1-hydroxy-4-naphthoyl) acrylic acid.  Representative of secondary or tertiary amines specified are dimethyl- and N-methyl-cyclohexyl- and benzyl-amines, N-methylaniline, piperidine, morpholine, triethylamine, triethanolanine and quinoline.  Quaternary ammonium compounds are obtained when the reaction is effected in an acidic medium, by appropriate treatment of the free tertiary bases with inorganic or organic acids or, by treating products obtained from secondary amines, with alkylating agents.  The dyes colour textile materials, e.g. silk, wool, cellulose acetate, polyamides, polyesters and polyacrylonitrile and leather and paper.  Some of the dyes are used in the washproof dyeing of native and regenerated cellulose. Examples are provided of the preparation of the dyes and their use in colouring a number of materials in a variety of shades.