Patent GB-787646-A (GB)
Title: Metallisable azo dyestuffs derived from quinoline
Inventor: ANDREW HERBERT FRANCIS
IPC: C09B45/00
Filed: 1954-11-03
Abstract: The invention comprises dyestuffs of formula Q1-N=N-D-N=N-Q2 where D is a residue of a tetrazotized primary aromatic diamine which may contain substituents and Q1 and Q2 are residues of coupling components at least one being of formula <FORM:0787646/IV (b)/1> where A is O or NH, R is OH, or an alkoxy or amino group, M is a water-solubilizing group removable by metallization and the quinoline nucleus may contain substituents in positions other than the 5-position.  Water-solubilizing groups mentioned are -SO3H, -PO3H2 and -B.X.Y where B is CO or SO2, X is a bridging group such as -CH2- -CHCl-, -C6H4-, -C4H2O- and -C6H4CH2- and Y is -COOH, -SO3H or a quat. ammonium group of the form -N(tert.)anion.  The dyestuffs are made by sulphating, phosphating or acylating, by methods described in Specifications 761,776, 785,038 and 786,567, the corresponding dyestuffs where M is H.  The starting dyestuffs may be made by coupling a diazo compound of a primary aromatic diamine with two mol. proportions of appropriate coupling components. Compounds in which Q1 and Q2 are identical may also be made by diazotizing a nitro derivative of a primary aromatic diamine, coupling with an appropriate coupling components, and either reducing the product to an azoxy or azo compound with e.g. alkaline glucose, or reducing to an amine and linking two mols. of the dyestuff, for example, with phosgene.  The solubilizing group may be introduced before or after reduction of the nitro group. Dyestuffs where only Q1 is of the above formula are made by diazotizing a nitro derivative of an aromatic amine and coupling with the quinoline component, sulphating, phosphating, or acylating the product, reducing the nitro group to amino, diazotizing and coupling with a component to introduce Q2. Specified diamines are benzidine, 4,41-diaminoazobenzene, -benzanilide, -diphenylurea, -dibenzanilide and -diphenylmethane and 1,5-diaminonaphthalene, although preferred are diamines which contain a metallizable group oto the amino group such as 3,31,dicarboxy-, dihydroxy-, bis-carboxymethoxy- and dimethoxy - 4,41 - diaminodiphenyl, 31,4 - diamino-3,41 - dimethoxybenzanilide and 4,41 - diaminodiphenylurea- and -diaminoazobenzene-3,31-dicarboxylic acids.  Specified quinoline coupling components are 6,8-dihydroxy-, 6-hydroxy- and -methoxy-8-amino- and 6-methoxy-8-hydroxyquinolines. Indicated as other coupling components are phenols, naphthols, hydroxyindazoles, acetoacetarylides and pyrazolones.  The dyestuffs dye cellulosic fibres, those containing -SO3H or -PO3H2 groups being after-coppered by an acidic process and those containing -B.X.Y being after-coppered by an alkaline process.  Examples are provided of the preparation of the dyestuffs from certain of the above specified components by the methods outlined above and their use in dyeing cellulosic fibres by after-coppering processes in red, yellow and blue shades, 4,41-diaminodiphenylamine being an additional diamine, the acylating agents being sulphur trioxide or phosphorus pentoxide in triethylamine and m-sulphobenzoyl and -furoyl and m-chloromethylbenzoyl chlorides and the other coupling components used are 6-hydroxyindazole and 1-phenyl-3-methyl-5-pyrazolone. Examples are also provided in which 5-nitro-2-aminophenol is diazotized and coupled with one mol. proportion of a quinoline component, sulphated, and the product reduced to an amine which is diazotized and coupled with 2-acetylamino- or -amino-4-hydroxybenzthiazole, 8-hydroxyquinoline and its 6-hydroxy-, -chloro- and -amino- and 7-sulpho - derivatives, 8 - amino - 6 - hydroxyquinoline and salicylaldoxime.