Water-soluble phthalocyanines containing quaternary or ternary salt groups and synthesis thereof

摘要

Water-soluble phthalocyanine derivatives, of the general formula R(CH2X)n, wherein R is a substituted or unsubstituted metal or metal-free phthalocyanine nucleus, X is a quaternary ammonium, ternary sulphonium or isothiouronium group, and n is a number greater than 1, are manufactured by treating a phthalocyanine containing at least two chloro- or bromo-methyl groups by methods known to be capable of replacing the chlorine or bromine atoms of chloro- or bromo-methyl groups by quaternary ammonium, ternary sulphonium or isothiouronium groups, e.g. (1) by heating with a tertiary nitrogenous base, or (2) by treatment with an alkali metal derivative of a mercaptan of the formula RSH (wherein R is a substituted or unsubstituted alkyl, cycloalkyl, aralkyl or aryl radicle) and treatment of the resulting sulphide with an ester such as is known to convert sulphides into ternary sulphonium salts, or (3) by treatment with a thiourea containing at least one hydrogen atom directly attached to nitrogen. The products dye cotton and other textile materials in blue or green shades from aqueous solutions, the preparation of which is in some cases advantageously assisted by the addition of suitable surface-tension reducing agents, e.g. condensation products of b -naphthol and ethylene oxide. In examples: (1) copper tri-(chloromethyl)-phthalocyanine is suspended in b -ethoxyethanol and heated with a solution of sodium methyl mercaptide in ethyl alcohol, and the resulting copper tri-(methylmercaptomethyl)-phthalocyanine is heated with dimethyl sulphate; (2) copper tri-(chloromethyl)-phthalocyanine is heated with tetramethylthiourea; (3) with pyridine; (4) with tetramethylthiourea in the presence of water; (5) with thiourea and water; (6) with N-methylthiourea and water; (7) with N : N1-dimethylthiourea and water; (8) with N : N : N1-trimethylthiourea; (9) with triethylamine in the presence of benzyl alcohol; (10) with N : N-dimethylcyclohexylamine and benzyl alcohol; and (11) with b -diethylaminoethanol; (12) copper tri - (methylmercaptomethyl) - phthalo - cyanine, made as in (1), is heated with methyl p-toluenesulphonate; (13) copper tetra-(chloromethyl)-phthalocyanine is treated as in (1); (14) copper di-(chloromethyl)-phthalocyanine is treated as in (4); (15) a mixture of copper penta- and hexa-(chloromethyl)-phthalocyanines is suspended in b -ethoxyethanol and heated with benzyl mercaptan in the presence of a solution of sodium in b -ethoxyethanol, and the resulting benzylmercapto derivative is heated with dimethyl sulphate; (16) the benzyl mercaptan in (15) is replaced by p-thiocresol; (17) copper tetra-(chloromethyl)-tetra-4-benzoylphthalocyanine is treated as in (1); (18) copper octa-(chloromethyl)-tetra-4-phenylphthalocyanine is treated as in (4); (19) copper tetra - (chloromethyl) - tetra - 4 - phenyl - phthalocyanine is heated with pyridine; (20) a mixture of nickel p di- and tri-(chloromethyl)-phthalocyanines is treated as in (1); (21) copper tri - (chloromethyl) - phthalocyanines is treated as in (1); (21) copper tri-(bromomethyl)-phthalocyanine is treated as in (3); (22) metal-free tri - (chloromethyl) - phthalo - cyanine is similarly treated; (23) the benzyl mercaptan in (15) is replaced by cyclohexyl mercaptan; and (24) by butyl mercaptan. Additional starting materials specified are, on the one hand, copper tri-(chloromethyl)-octa-3 : 6-chlorophthalocyanine, and, on the other hand, triethylamine, thiophenol and N-phenylthiourea. Specification 586,340 is referred to.