Patent GB-932022-A (GB)
Title: New tetrazapolymethine dyes
Inventor: BAUMANN HANS
IPC: C09B35/04
Filed: 1961-05-16
Abstract: The invention comprises dyes of the general formula <FORM:0932022/IV(a)/1> in which R1 and R2 denote alkyl radicals with 1 to 4 carbon and/or aralkyl radicals, A denotes a p-phenylene or 1:4-naphthylene radical which may contain further radicals but is free from sulphonic acid groups, X denotes one of the divalent radicals: <FORM:0932022/IV(a)/2> Y denotes the equivalent of an anion, B denotes the radical of an amine or an aliphatic or heterocyclic enamine or enol capable of coupling and free from sulphonic acid groups, R4 denotes a hydrogen atom, an alkyl group with 1 to 4 carbon atoms or an aryl group and R6 denotes a hydrogen atom, an alkyl group with 1 to 4 carbon atoms or an aryl group which may be substituted and in which R5 and R6 together may form a carbocyclic ring and wherein B denotes the radical of an aliphatic or heterocyclic enamine or enol when X denotes the divalent radical <FORM:0932022/IV(a)/3> and a process for the production of tetrazapolymethine dyes wherein a salt of an amino azo compound of the general formula <FORM:0932022/IV(a)/4> in which R11 is a hydrogen atom, an alkyl with 1 to 4 carbon atoms or an aralkyl radical, R21 is a hydrogen atom, an alkyl radical with 1 to 4 carbon atoms or an aralkyl radical, A is a p-phenylene or 1,4-naphthylene radical which is free from sulphonic acid groups but may contain other radicals, X is one of the divalent radicals <FORM:0932022/IV(a)/5> or <FORM:0932022/IV(a)/6> Z is the equivalent of an anion, R4 is a hydrogen atom, an alkyl radical with 1 to 4 carbon atoms, an aryl or carboxyl group, R5 is a hydrogen atom, an alkyl group with 1 to 4 carbon atoms or an aryl radical and R6 is a hydrogen atom, an alkyl group with 1 to 4 carbon atoms or an aryl radical which may be substituted and in which R5 and R6 together may form a carbocyclic ring is diazotized and the diazonium compound is coupled with an amine or an aliphatic or heterocyclic enamine or enol free from sulphonic acid groups and capable of coupling and, when R21 stands for a hydrogen atom, the coupling product is converted into the corresponding quaternary salt by treatment with an alkylating agent. Starting materials of the triazole series may be obtained by coupling diazotized 3-amino-1,2,4-triazole or its alkyl, aryl or carboxyl derivatives substituted in the 5-position with amino benzenes or aminonaphthalenes which couple in p-position to the amino group and which may be substituted with e.g. alkyl, alkoxy, or acylamino groups or halogen.  Starting materials of the imidazole series may be obtained by coupling p-nitro- or p-acetylaminobenzenes or-amino-naphthalenes with imidazole or its derivatives substituted in the 4- and/or 5-positions by alkyl and/or aryl radicals, treating the coupling product with alkylating agents and converting the nitro or acetylamino group into an amino group by reduction or hydrolysis. Coupling components specified include such compounds as acetoacetic phenylamide, 1-diethylamino-3-methyl benzene, 1-amino-naphthalene, 1-phenyl-3-methylpyrazolone-(5), 1-phenyl-3-methylpyrazole, 2,4-dihydroxy quinoline, 4-hydroxyindazole, 1,3,3-trimethyl-2-methylene indoline, 1-methyl-2-phenylindole and 2-methylindoline.  Alkylating agents specified include such compounds as ethyl bromide, benzyl chloride, toluene sulphonic methyl ester and diethyl sulphate. Many anions are specified for Y and Z chloride and tetrachlorozincate being preferred.  Examples are furnished.  The dyes are suitable for dyeing and printing leather and textile materials of wool, silk, cellulose, cellulose acetate, synthetic linear polyamides such as poly S -caprolactam and polyhexamethylene diammonium adipate, synthetic linear polyesters such as polyethylene terephthalate, polyacrylonitrile, poly-1, 1-dicyanoethylene copolymers of acrylonitrile and/or 1,1-dicyanoethylene with other polymerizable compounds such as vinyl chloride and vinyl acetate.