Patent GB-938029-A (GB)
Title: Improvement in the production of diaza polymethine dyes
Inventor: HUENIG SIEGFRIED
IPC: C09B27/00
Filed: 1961-08-31
Abstract: The invention comprises quaternary diazasulphones, to be used for the preparation of diazapolymethine dyes (see Group IV(c)), of the general formula <FORM:0938029/IV(a)/1> in which R is an alkyl, cycloalkyl, aralkyl or aryl radical, X is a divalent atom or divalent radical which forms with moiety <FORM:0938029/IV(a)/2> a 5 or 6 membered heterocyclic ring, R1 is an alkyl or aryl radical, substituted if desired, Z\s8 is the equivalent of an anion and n is zero or one and a process for the production of quaternary diazosulphones to be used for the production of said dyes wherein a sulphonyl hydrazone of the general formula <FORM:0938029/IV(a)/3> or a salt thereof of the general formula <FORM:0938029/IV(a)/4> in which R is an alkyl, cycloalkyl, aralkyl or aryl radical, X is a divalent atom or a divalent radical which forms with the moiety <FORM:0938029/IV(a)/5> or <FORM:0938029/IV(a)/6> a 5 or 6 membered heterocyclic ring, C1 is an alkyl or aryl radical, substituted if desired, ? is the equivalent of an anion and n is zero or 1, is treated with an oxidizing agent in the presence of an acid. Sulphonyl hydrazones specified include methane, chlormethane, ethane-(sulphuric ester), benzene, 4-toluene, 2,5-dichlorbenzene, 2- and 3-nitrobenzene-sulphonyl hydrazones of N-alkyl, N-aralkyl-and N-aryl-benzy-thiazolones-(2); N-alkyl and N-aralkyl and N-arylthiazolones-(2); and pyridones-(4); N-alkylpyridones-(2); N-alkylquinolones-(2) and-(4); N-alkyl-3,3-dimethylindolinones-(2); N1N1 - dialkylbenzimidazolones; N-alkyl-1,2,4-triazolones-(3; N-alkyl-1,2,4-thiadiazolones -(3) and -1,3,5-thiadiazolones-(2). These heterocyclic ring systems may be further substituted by radicals such as halogen atoms, alkyl, alkoxy, aryl, alkylsulphonyl, arylsulphonyl, carboxylic ester, nitro, substituted or unsubstituted, amino, sulphonic acid amide and for carboxylic acid amide groups. The salts of such compounds may be employed.  Oxidizing agents specified include lead tetra acetate, lead dioxide, hydrogen peroxide preferably in connection with ferrous salts, chromates, dichromates, bromine nitric acid, potassium hexacyanoferrate -(III) or ferric chloride.  Many alkylating agents are specified.  Examples are furnished. Specification 781,426 is referred to.ALSO:In a process for the production of diaza polymethine dyes a sulphonyl hydrazine of the general formula <FORM:0938029/IV(a)/1> is reacted with an oxidizing agent and an alkylating agent and the reaction product is coupled with a compound which is capable of coupling or a sulphonyl hydrazone of the general formula <FORM:0938029/IV(a)/2> or a salt thereof of the general formula <FORM:0938029/IV(a)/3> is treated with an oxidizing agent in the presence of an acid and the reaction product is coupled with a compound which is capable of coupling, R in the above-mentioned general formulae being an alkyl, cycloalkyl, aralkyl or aryl radical, X is a divalent atom or radical which forms with the moiety <f/4> or <FORM:0938029/IV(a)/4> a 5 or 6 membered heterocyclic ring, R1 is an alkyl or aryl radical, substituted if desired, Z\s8 the equivalent of an anion and n zero or one.  The compounds capable of coupling employed in the process are those used as coupling components in the chemistry of azo dyes.  The quaternary diazo sulphones are obtained by reacting the sulphonyl hydrazones of the formula <FORM:0938029/IV(a)/5> or their salts of the formula <FORM:0938029/IV(a)/6> with oxidizing agents in the presence of strong acids (see Group IV(b)).  The coupling reaction may take place in presence of organic diluents and at elevated temperature. Sulphonyl hydrazones specified include methane, chloromethane ethane (-sulphuric ester), benzene, 4-toluene, 2,5-dichlorobenzene, 2- and 3-nitrobenzene-sulphonylhydrazones of N-alkyl, N-aralkyl and N-aryl-benzthiazolones-(2); N-alkyl-4,5,6,7-tetrahydrobenzene-thiazolones-2; N-alkyl, N-aralkyl and N-aryl-thiazolones-(2) and pyridones (4); N-alkylpyridones-(2); N-alkylquinolones-(2) and -(4); N-alkyl-3,3-dimethylindolinones-(2); N,N1-dialkyl-benzimidazolones; N-alkyl-1,2,4-triazolones-(3); N-alkyl-1,2,4-thiadiazolones-(3) and -1,3,5-thiadiazolones-(2).  The heterocyclic ring systems may be further substituted by such radicals as halogen, alkyl, alkoxy, aryl, alkylsulphonyl, arylsulphonyl, carboxylic ester, nitro and substituted or unsubstituted amino-, sulphonic acid amide and/or carboxylic acid amide groups.  The salts of such compounds may be used, e.g. the perchlorates, tetrafluoroborates, chlorides, bromides, benzenesulphonates or dihydrogenphosphates.  Oxidizing agents specified include lead tetra-acetate, lead dioxide, hydrogen peroxide, preferably in combination with ferrous salts, potassium or sodium chromates or dichromates, bromine, nitric acid, potassium ferricyanide and ferric chloride.  Many alkylating and aralkylating agents are specified. Coupling components specified include hydroxybenzenes, naphthols, acetoacetic ester and arylamides, acetyl acetone, cyanoacetic ester, malonic dinitrile, 1,3-dihydroxybenzenes, aminobenzenes, 1-methyl-2-phenylindole, tetramethyl indoline, 2,4-dihydroxy quinoline, 3-hydroxy thionaphthene, barbituric acid and 1-phenyl-3-methyl pyrazolone.  The dyes colour tanned cotton, wool, polyacrylonitrile and copolymers containing polyacrylonitrile and acrylonitrile.  The coupling may take place on the fibre. Specification 871,426 is referred to.