Patent GB-877307-A (GB)
Title: Improvements relating to monoazo dyestuffs containing haloacylamino groups and their use
Filed: 1959-04-22
Abstract: Acids of formula ClCH2-CO-NH-CH2-A-X-COOH where A is an aryl radical and X is a direct link or an organic p  acyclic bridge member are made by condensing acids of formula H - A - X - COOH with N-methylol-o -chloroacetamide.  Indicated as bridge members are low molecular aliphatic radicals which may contain hetero atoms in the chain thus the starting acids may be e.g. aryl-acetic or -propionic acids, aryloxy-acetic acids and arylthio-acetic acids.  The aryl residue is preferably benzenic and contains nucleophilic substituents e.g. methyl groups, or substituents bound to the aryl residue via O, S or amide N atoms. Functional derivatives of the acids e.g. the acid halides, are described and used as dyestuff intermediates (see Group IV(c)). In examples which illustrate the preparation of acid chlorides X is a direct link, -OCH2-and a xenyl residue, and A is a benzene residue containing alkyl or alkoxy substituents.ALSO:The invention comprises dyes of formula:-  F-(NH-CO-X-A-CH2-NHCO-CH2Cl)n where F is the residue of a dye derived from an #s-diazobenzene sulphonic acid and a coupling component, A is an aryl residue, X is a direct link or an organic acylic bridge member and n is 1 or 2, in the latter case the acylamino group must be in both azo and diazo portions of F.  The dyes are made by conventional diazotization and coupling processes or by acylating appropriate aminoazo dyes with a functional reactive derivative of a carboxylic acid of formula:-  Cl CH2-CO-NH-CH2-A-X-COOH. They may also be made by treating a dye of formula:-  F-(NH-CO-X-A-H)n with N-methylolo -chloro-acetamide. Indicated as bridge members for X are low molecular aliphatic radicals which may contain hetero atoms.  Indicated aromatic carboxylic acids containing are aryl-acetic and -propionic acids, aryloxy acetic acids and arylthio acetic acids.  The aryl residues are preferably monocyclic, others indicated being diphenyl, diphenyl ether, diphenyl ketone, aroylamino phenyl and naphthyl radicals.  The aryl residues of the acylating agents, preferably contain nucleophilic substituents, e.g. methyl groups or groups joined to the aryl residue by means of an ether oxygen or sulphur atom or an amide nitrogen atom.  Preferred diazo components are 2-aniline-1-sulphonic acid or low molar homologues thereof e.g. 5-methyl-2-aniline-1-sulphonic acid.  Indicated azo components are hydroxy- and amino-benzenes, naphthalenes and pyrazoles, preferred being naphthol- and aminonaphthol sulphonic acids, especially those containing an a  hydroxy group with a sulphonic acid group in a meta position thereto e.g. 1- or 2-amino- 8-naphthol-6-sulphonic acid and 1- and 2-amino- 8-naphthol-3, 6-disulphonic acids.  The dyes are used to colour wool and other polypeptide fibres in yellow, blue, red or brown shades.  Weakly acidic aqueous dye-baths are used for dyeing wool.  Examples are provided of the preparation of the dyes by the methods outlined above, and their use in dyeing processes, representative of the diazo moieties are:-aniline-1-sulphonic acid, 2-amino-5-methyl- and -carbethoxyamino-benzene-1-sulphonic acid, 4-amino-diphenyl-ether- 3-sulphonic acid, 2-amino- 5-(41-methyl-31- chloroacetylaminomethyl - benzoylamino)-benzene- 1-sulphonic acid and 2-amino- 4-(31, 41-dimethyl- 61-chloroacetylaminomethylphenoxy -acetylamino)-benzene- 1-sulphonic acid and representative of the coupling component moieties are:-2-amino- 8-naphthol- 6-sulphonic acid and its N-ethyl- 21-methylphenylamide, 1-benzoylamino- 8-naphthol-3, 6-disulphonic acid, 1-(21-chloro- 61-methylphenyl) - 3-methyl- 5-aminopyrazole, 1-(21, 51-dichloro- 41-sulphophenyl)- 3-methyl- 5-pyrazolone, 1-(31-chlorophenyl)- 3-methyl- 5-pyrazolone, 2-(41-methyl-31-chloroacetylaminomethylbenzoylamino) - 5-napthol-7-sulphonic acid and 1-[411-methyl- 311-chloroacetylaminomethylxenyl- (41)- carbonyl-amino]- 8-naphthol- 3, 6-disulphonic acid.