Patent GB-774916-A (GB)
Title: New trisazo-dyestuffs and process for making them
IPC: C09B45/28
Filed: 1954-10-07
Abstract: The invention comprises dyestuffs of formula <FORM:0774916/IV(b)/1> where R1 is the residue of a phenol o-carboxylic acid or a heterocyclic residue containing a 5 - membered hetero-ring having at least 2 hetero-atoms of which at least one is an exclusively cyclically bound N atom, and R3 is a residue containing a total of 3 benzene nuclei of which the end benzene nucleus contains o OH and COOH groups and 2 of the 3 benzene nuclei are bound together by an azo link, and in which the SO3H group is bound to a b -C atom in I. They are made by decoppering the corresponding coppered complex. Decoppering is effected in known manner, e.g. with salts of hydrosulphuric acid or with hydrochloric acid or alkali metal cyanides.  The copper complexes are made by treating a compound of formula <FORM:0774916/IV(b)/2> where R1 and R3 are as above and n is 1 or 2 with copper-yielding agents under conditious such that the alkyl group is eliminated and the o-aminoazo grouping is oxidized to a triazole ring e..g. by heating with about 4 atomic proportions of copper in the form of a tetramine complex per mol of dyestuff. The o - alkoxy, o1 - hydroxy dyestuffs are made by coupling an appropriate diazotized 2 - alkoxy - 1 - naphthylamine in alkaline solution with an appropriate J-acid derivative the alkoxynaphthylamine and J-acid derivative being made in conventional fashion.  The component corresponding to R1 is preferably free from OH groups which impart a capacity for coupling to the component.  Components corresponding to R1 are 4 - aminophenol - 2 - carboxylic acid, 5 - and 6 - aminoindazoles, 6 - and 7 - amino, 2 - methyl - 6 - amino - and 2 - (41-amino - phenyl) - benzimidazoles, 4,6,1 and 7 - aminobenztriazoles, 6 - aminobenzthiazole, sulphonated 2 - methyl - 41 - aminonaptho - 11, 21 : 4, 5 - imidazole and 5 - amino - 1,2,4 - triazole - 3 - carboxylic acid.  Although two of the benzene nuclei of R3 are connected by an azo link the third may be connected by a bridging member such as CONH or a direct link.  The nuclei of R3 may contain substituents such as halogen, alkyl and alkoxy groups, and advantageously the diazotized NH2 group, the bonds between the nuclei and the OH group of the end nucleus are all in p-position relatively to one another.  Thus R3 may be derived from X-R4-N = N-R5 where X is a diazotized amino group, R4 is a diphenyl residue bound in the 4 and 41 positions to X and N2, and R5 is a residue of a phenol o - carboxylic acid bound to N2 in p-position relative to OH.  These compounds are made in known manner from appropriate diphenyls e.g. 3,31 -dimethyl -, - dichloro - and - dimethyloxy - 4,41 - diaminodiphenyl and 4,41 - diaminodiphenyl and coupling components such as 5 - and 6 - methyl - and 6 - chloro - phenol - 2 carboxylic acid and especially salicylic acid.  The dyestuffs dye materials of animal origin e.g. wool, silk and leather, and especially cellulose-containing materials such as cotton, linen, artificial silk and regenerated cellulose.  They may be coppered in known fashion on the fibre or in the dyebath, particularly when the dyestuffs contain no additional sulphonic acid groups to those shown in the above formula and especially by the process of Specification 455,274 [Group IV].  The products may be after-treated with formaldehyde condensation products as in Specification 619,969.  In examples illustrating the preparation of the dyestuffs and their use in dyeing vegetable fibres in olive green tints by an after-coppering process certain of the above specified reactants are used additional corresponding to R1 being 7-aminoindazole and 5 - aminobenzimidazole, additional corresponding to R1 being 1 - amino - 4 - (41 - aminobenzoylamino) - benzene and 1,4 - phenylene diamine and to R5 being 2 carboxy - 4 - benzoylaminophenol the o - alkoxynaphthylamines being 2 - methoxy and - ethoxy - 1 - naphthylamine - 6 - sulphonic acids.