GB613458A - Improvements in and relating to the manufacture of meso-alkylmercapto substituted carbocyanine dyes and to photographic emulsions sensitized therewith - Google Patents

Abstract

Meso-alkylmercapto substituted symmetrical or unsymmetrical carbocyanine dyes of the general formula <FORM:0613458/IV (c)/1> wherein R and R1 are the same or different and are alkyl or aryl groups, R11 is an alkyl or aralkyl group, L is an unsubstituted or a substituted methine group, n and m are the same or different and 0 or 1, X is an anion, and Z and Z1 represent the non-metallic atoms to complete the same or different 5- or 6-membered heterocyclic nuclei, are prepared by condensing a quaternary salt of a heterocyclic nitrogen compound having an alkylmercapto, aralkylmercapto, or arylmercapto group in the 2- or 4-position to the quaternary nitrogen atom with a heterocyclic nitrogen quaternary salt of the general formula <FORM:0613458/IV (c)/2> R and R11 may be substituted alkyl, e.g. b -hydroxyethyl, b -ethoxyethyl, or b -carbomethoxyethyl. The condensation may be effected in presence of an acid-binding agent, e.g. pyridine, triethylamine, or an alkali metal carbonate. 31 - Ethyl - 3 - methyl - 9 - methylmercapto - 4 : 5 : 41 : 51 - dibenzselenathiacarbocyanine bromide is prepared by refluxing together 2-methylmercapto - b - naphthaselenazole metho-p - toluenesulphonate, 2 - (21 - ethylmercapto)-propenyl - b - naphthathiazole etho - p - toluene-sulphonate, and pyridine, and adding aqueous KBr to an aqueous solution of the product. 3 - 31 - Diethyl - 9 - methylmercapto - 4 : 5 : 41 : 51 - dibenzselenathiacarbocyanine bromide, 9-decylmercapto - 31 - ethyl - 3 - methyl - 4 : 5 : 41 : 51 - dibenzselenathiacarbocyanine perchlorate, 11 : 3 - diethyl - 9 - methylmercaptothia - 21 - carbocyanine perchlorate, 3 : 31 - diethyl - 9 - methylmercaptooxathiacarbocyanine iodide, 3-ethyl - 31 - phenyl - 9 - methylmercaptothiacarbocyanine iodide, 3 - 11 - diethyl - 9 - methymercaptothia - 41 - pyridocarbocyanine iodide, 3 : 31 - diethyl - 9 - methylmercapto 4-1 - phenylthiazolocarbocyanine iodide, 3 : 31 - diethyl - 41 - methyl - 9 - methylmercaptooxathiazolocarbo cyanine iodide, 3 : 31 - diethyl - 9 - methyl mercaptothiaselenacarbocyanine iodide, 3 : 31 - diethyl - 9 - methylmercaptoselenacarbocyanine iodide, 3 : 31 - dimethyl - 9 - ethylmercaptothiacarbocyanine iodide, 9 - benzylmercapto - 3 - (b - ethoxyethyl) - 31 - methylthiaselenacarbocyanine bromide, and 3 - allyl - 31 - ethyl - 9 - methylmercaptothiacarbocyanine bromide are similarly prepared. Specifications 472,227, 549,203 and 610,566, are referred to.