Patent GB-525237-A (GB)
Title: Manufacture of phthalocyanines containing alkyl- or aralkylsulphonium groups
IPC: C09B47/20
Filed: 1939-02-20
Abstract: 525,237. Dyes ; dyeing. COFFEY, S., HADDOCK, N. H., JACKSON, J. R. F., and IMPERIAL CHEMICAL INDUSTRIES, Ltd. Feb. 20, 1939, No. 5642. [Classes 2 (iii) and 15 (ii)] Water-soluble sulphonium derivatives of phthalocyanines are made by interacting alkyl sulphates or sulphites, containing not more than 4 carbon atoms in the alkyl group, with alkyl- or aralkyl-thiol phthalocyanines. The latter may contain other substituents, e.g., pyridyl, and can be made by heating an alkyl- or aralkyl-thiol phthalic acid or anhydride with a metal salt in the presence of urea. Compounds of elements of the fifth group, e.g. molybdates, vanadates and phosphates, and boric acid may be added if desired. The starting materials may also be applied in admixture with other aromatic compounds containg two carboxylic groups in o-position to each other, whereby phthalocyanines containing less than four thiol substituents are obtained. The copper phthalocyanines used as parent materials may also be made by heating alkyl- or aralkyl-thiol-1:2- dihalogenobenzenes with cuprous cyanide in presence of organic nitrogen bases, e.g., quinoline. The sulphonium derivatives are direct dyes for cotton and viscose artificial silk, dyeing in green shades which change to blue when treated with aqueous sodium hypochlorite or other suitable oxidizing agents. Examples describe the treatment with dimethylsulphate of (1) copper tetra-4-methylthiol phthalocyanine, made by boiling 3:4-dibromo- 1-methylthiol benzene with cuprous cyanide in pyridine and nitrobenzene, or by heating 4- methylthiol phthalic acid with urea, cuprous chloride and ammonium molybdate, (2) copper tetra-3-methylthiol phthalocyanine, made by heating 3-methylthiolphthalic anhydride with urea and cuprous chloride, (3) nickel or cobalt tetra-4-methylthiol phthalocyanines, made by heating 4-methylthiol phthalic acid with urea and nickelous or cobaltous chloride, (4) copper tetra-4-benzylthiolphthalocyanine, made from 4-benzylthiolphthalic anhydride, urea and cuprous chloride, (5) copper di- and tri-4- methylthiolphthalocyanines, (6) copper di-4- methylthiol-di-4-pyridyl phthalocyanine, made by heating a mixture of 4-methylthiol phthalic anhydride and 4-pyridylphthalimide with urea and cuprous chloride, (7) metal free tetra-4- methylthiol phthalocyanine, made by removing by treatment with sulphuric acid, the magnesium from magnesium tetra-4-methylthiol phthalocyanine, which is itself made by heating 4-methylthiol phthalic anhydride with urea and magnesium chloride, and (8) copper tetra-4-ethylthiolphthalocyanine, made from 4-ethylthiol phthalic anhydride, cuprous chloride and urea ; also (9) the treatment with diethylsulphate of copper tetra-4-methylthiol phthalocyanine, and (10) the treatment with dimethylsulphite of copper tri-4-methylthiol phthalocyanine. 3:4 Dibromo-1-methylthiolbenzene is made by reacting diazotized 3:4-dibromaniline with potassium ethyl xanthate, hydrolysing the reresulting xanthic ester, and methylating the dibromothiolbenzene obtained. 4-Methylthiolphthalic acid is made by methylating 4-thiolphthalic acid. 3-Methylthiolphthalic anhydride is made by reacting diazotized 3-aminophthalic acid with potassium ethyl xanthate, hydrolysing the xanthic ester, methylating the resulting 3- thiolphthalic acid and treating the product with acetic anhydride. 4-Benzylthiolphthalic anhydride is made by reacting benzyl chloride with 4-thiolphthalic acid and treating the product with acetic anhydride. 4-Ethylthiolphthalic anhydride is made by treating 4-thiolphthalic acid with diethyl sulphate and treating the product with acetic anhydride.