Patent GB-904096-A (GB)
Title: New metalliferous monoazo-heterocyclic-dyestuffs and their manufacture and use
IPC: C09B62/02
Filed: 1960-05-26
Abstract: The invention comprises complex heavy metal compounds of dyes of formula <FORM:0904096/IV (b)/1> where R is a benzene residue bound to the azo link in o-position to OH, X is H or a heterocyclic ring which has no dye character, is bound to R via a nitrogen bridge and has at least one Hlg atom which, in the presence of an acid-binding agent, enables the dye to form a chemical bond with the OH groups of polyhydroxylated fibrous material, and Y is an acyl residue or a heterocyclic ring which has no dye character and at least one labille Hlg atom, as defined above, and which metal complexes must have at least one heterocyclic ring as defined above.  1,2-Complexes of chromium or cobalt are preferred.  Copper and nickel complexes are also mentioned.  The dyes may be used by treating corresponding complexes in which X is NH2 or H and Y is H or an acyl residue with an appropriate halo-heterocyclic compound and, if desired, also with a reactive organic mercapto or hydroxy compound or with ammonia or an at most secondary amine.  The dyes may also be made by metalising the corresponding metal-free dyes and by oxidative metallisation of corresponding dyes in which the residue of the diazo component contains no hydroxy group ortho to the azo link.  Preferred are dyes of formulae <FORM:0904096/IV (b)/2> <FORM:0904096/IV (b)/3> where T is the heterocyclic ring, advantageously a monochloro-1,3,5-triazine residue and R1 is the residue of an organic sulphonic or carboxylic acid containing not more than 7 carbon atoms, or a heterocyclic ring as defined.  Particularly preferred are 1,2-complexes of chromium or cobalt in which R is the residue of an amino-phenol sulphonic acid. Indicated further substituents for R are alkoxy, alkyl, cyano, halogen, acylamino, nitro, sulphonic acid, sulphonamide and sulphone groups.  Aryl residues include those of carboxylic, carbamic and sulphonic acids.  Representative of indicated acyl groups are formyl, caproyl, carbethoxy, benzoyl, toluenesulphonyl and (Me)2NSO2. Representative of haloheterocyclic reactants are a ,g -dichloroquinoline, 1,4-dichlorophthalazine, methyldichloropyrimidine, 2,4-dichloroquinazoline, trichloro- or tribromo- and tetrachloro-pyrimidines, trihalo-1,3,5-triazines or compounds of formula <FORM:0904096/IV (b)/4> where A is an alkyl, aryl, etherified hydroxy, mercapto or primary or secondary amino group, pyrimidines and triazines and primary amino groups being preferred.  Examples of compounds from which A may be derived are methanol, phenol, thiophenol, ethyl-, methoxypropyl-, cyclohexyl-, dimethyl- and chloroethyl-amines, aniline, ethanolamine, piperidine, aminocarbonic acid ester, hydrazine, ammonia and aniline mono- or disulphonic acids.  The dyes colour polyhydroxylated materials, e.g. regenerated cellulose, cellulose, linen and cotton.  Preferably they are used in conjunction with a treatment by an acid-binding agent. Grey or violet tints are obtained.  They may also be used in conventional fashion for dyeing nitrogenous fibres, e.g. polyamide, polyurethane, silk, leather and wool.  Examples are provided of the preparation of the dyes and their use in colouring processes. Specifications 797,946, 837,124, 838,339 and 888,960 are referred to.