Patent GB-977968-A (GB)
Title: Improvements in or relating to disazo and polyazo dyestuffs derived from 1-naphthal-4,6-di-sulphonic acid
Inventor: WEHRLI WALTER
IPC: C09B62/012
Filed: 1961-04-07
Abstract: The invention comprises dyes of formula <FORM:0977968/C4-C5/1> where D is a mono- or di-nuclear aryl radicle, D1 is a benzene or naphthalene radicle, D2 and D4 are benzene, naphthalene, acylacetylamino or pyrazolone radicles, D3 is a benzene, naphthalene, diphenyl, stilbene, acylacetylamino or pyrazolone radical, X is a simple link between the groups D-D or a bridge member, preferably -N = N-, <FORM:0977968/C4-C5/2> <FORM:0977968/C4-C5/3> or <FORM:0977968/C4-C5/4> between these groups, Z being halogen, or an hydroxy, thiol or amino group which may be substituted, Y is a bridge member between the groups D-D, preferably -NH-CO-, -CO-NH-, -NH-CO-NH-, HN-OC-CO-NH, -HN-OC-CH = CH-CO-NH-, -HN-OC-CC1 = CH-CO-NH-, <FORM:0977968/C4-C5/5> or <FORM:0977968/C4-C5/6> Z being halogen, or a hydroxy, thiol or amine group which may be substituted and each of m, u, p and q may be 1 or 2.  The invention includes copper and nickel complexes of metallizable dyes of the above formula. The dyes may be made by coupling a compound of formula B-N = N-D-R1, where D is as above, R1 is a diazonium group and B is a radicle of the benzene, naphthalene, pyrazolone or acylacetyl-amino series, which may itself contain an azo group, or groups, with 1-naphthol-4,6-disulphonic acid or by converting a compound of formula <FORM:0977968/C4-C5/7> where D is as above and R is NO2 into an azo or azoxy compound or when R is diazonium group coupling with an appropriate coupling component, which may contain an azo group, or groups, and, if the coupling component has one remaining diazotizable amino group, this group is diazotized and the product coupled with an appropriate component, or when R is a primary or secondary amino group 2 mols. of the aminoazo compounds are condensed with 1 mol. of a dihalide of a divalent acid or with cyanuric chloride or one of its condensation products.  Representative of indicated compounds where R is NO2 are e.g. 1-amino-4-nitrobenzene - 2 - carboxylic acid, 1 - amino - 5-nitro - 2 - phenol, 1 - amino - 2 - carboxymethoxy - 5 - nitrobenzene, 2 - amino - 4 - chloro-5 - nitrophenol, 2 - amino - 4 - nitro - 6 - sulpho-1 - phenol and 1 - (41 - nitrobenzoyl) - amino-4 - aminobenzene - 3 - carboxylic acid --> 4,6-disulpho - 1 - naphthol. Representative of acid dihalides specified are phosgene, oxalyl, fumaryl and iso- and tere-phthalic acid dichlorides and dibromides. Instead of condensing with an acid dihalide the aminoazo dye may be condensed with a monocarboxylic acid chloride of the benzene series which contains a substituent convertible into an amino group e.g. 3-nitro-4-methylbenzoic acid.  The products thus obtained are reduced, diazotized and coupled with appropriate components e.g. salicylic acid, cresotic acid, 1-naphthol, 2-naphthol-7-sulphonic acid, 1-naphthol-4,6-disulphonic acid, 1,8 - dihydroxynaphthalene-3,6 - disulphonic acid, 1 - naphthol - 3,6,8 - trisulphonic acid, 1 - phenyl - 4 - methyl - 5 - pyrazolone - 31 - sulphonic acid, 1 - (31 - carboxyphenyl) - 3 - methyl - 5 - pyrazolone, 2-amino - benzoylamine -, chloracetylamino - and crotonylamino - 5 - naphthol - 7 - sulphonic acid, 1 - amino - 8 - naphthol - 2,4 - disulphuric acid, 1 - acetoacetylamino - 4 - methoxybenzene and barbituric acid.  Other final components specified include e.g. <FORM:0977968/C4-C5/8> and <FORM:0977968/C4-C5/9> Instead of a final component an intermediate may be used e.g. aniline, 3-amino-4-methoxy-1-methylbenzene, 3 - amino - 1 - sulphoacetyl-aminobenzene, 1 - naphthylamine, and 1-amino - 2 - ethoxynaphthalene - 6 - sulphonic acid, and the product diazotized and coupled with a final component e.g. one of those indicated above.  Metallizable compounds may be metallized in conventional fashion, on the fibre, or in substance.  Compounds in which R is a diazo group may be obtained by diazotizing appropriate amines or by tetrazotizing one mol. of an appropriate diamine and coupling with one mol. of 1-naphthol-4,6-disulphonic acid.  Indicated diamines include 4,41-diamino-3,31 - dimethoxy -, - dicarboxy -, - dicarboxy-methoxy and - dihydroxy -1,1 - diphenyl. The dyes colour cotton and regenerated cellulose in a variety of colours.  Cellulose acetate and triacetate wool, silk, nylon, acrylic, and polyethylene terephthalate fibres are reserved. Numerous examples are provided of the preparation of the dyes, and their metal derivatives, and the use of both metal-free and metallized dyes in the colouring of cotton and regenerated cellulose.