Patent GB-604687-A (GB)
Title: Trinuclear cyanine dyes
IPC: C09B23/12
Filed: 1945-08-23
Abstract: A trinuclear cyanine dye base which may have the formula <FORM:0604687/IV(b)/1> wherein A represents the atoms necessary to complete a ring of the usual cyanine dye type, R is alkyl, alkylene, alkoxy, alkoxyalkyl, acetoxyalkyl, aryl or aralkyl group, R1 and R2 are each H or alkyl, and n is 1, 2 or 3, is prepared by reacting a methylene bis-azole with a cyanine dye intermediate under the influence of heat in the presence of a basic condensing agent. The corresponding dyes are formed by reaction with alkyl or aryl esters. The methylene bis-azole may contain an indolenine, oxazole, pyridine, quinoline, thiazole, thiazoline, tellurazole, or selenazole ring, and the cyanine dye intermediate may contain a benzthiazole, benzoxalole, indolenine, naphthoxazole, oxazole, pyridine, quinoline, thiazole, or thiazoline ring and an alkyl (methyl, ethyl, or propyl) or aryl (phenyl or naphthyl) mercapto or anilido or substituted anilido (acetanilido or 4-chloroacetanilido) reactive group.  3 : 31 - Diethyl - 2 : 21 - dibenzthiazolyl - 311 - ethyl - 211 - (ethylidene) benzthiazolylidenemethane di-iodide is prepared by refluxing together methylene bis-benzthiazole, 2-(b -acetanilidovinyl)-benzthiazole ethiodide, and triethylamine in pyridine, heating the dye base obtained with dimethyl sulphate in chlorobenzene, and adding aqueous potassium iodide solution to an alcohol solution of the product.  3 : 31-Diethyl-2 : 21-dibenzoxazolyl - 311 - ethyl - 311 - (ethylidene) benz thiazolylidene methane di-iodide, 2 : 21-dibenzthiazolyl - 311 - ethyl - 211 - (b  - ethylethylidene) benzthiazolylidenemethane, 2 : 21 - dibenzthia - zolyl - 311 - ethyl - 611 - methyl - 211 - (b  - ethyl - ethylidene) benzthiazolylidenemethane and 2 : 21-benzthiazolyl - 311 - ethyl - 211 - (D 2-butenylidene) benzthiazolylidenemethane are similarly prepared.  Methylene bis-benzoxazole is prepared by dry distillation of a mixture of o-aminophenol and diethyl malonate.  A sample has been furnished under Sect. 2 (5) of a dye made by refluxing together 2-methylmercaptobenzthiazole methiodide, methylenebis-benzthiazole and triethylamine.  Specifications 408,272, [Group XX], 408,273, 527,627, 537,961, 546,527, 549,202 and 549,203 are referred to.ALSO:A trinuclear cyanine dye base which may have the formula <FORM:0604687/IV (c)/1> wherein A represents the atoms necessary to complete a ring of the usual cyanine dye type, R is alkyl, alkylene, alkoxy, alkoxyalkyl, acetoxyalkyl, aryl or aralkyl group, R1 and R2 are each H or alkyl, and n is 1, 2 or 3, is prepared by reacting a methylene bis-azole with a cyanine dye intermediate under the influence of heat in the presence of a basic condensing agent. The corresponding dyes are formed by reaction with alkyl or aryl esters. The methyllene bis-azole may contain an indolenine, oxazole, pyridine, quinoline, thiazole, thiazoline, tellurazole, or selenazole ring, and the cyanine dye intermediate may contain a benzthiazole, benzoxozole, indolenine, naphthoxazole, oxazole, pyridine, quinoline, thiazole, or thiazoline ring and an alkyl (methyl, ethyl, or propyl) or aryl (phenyl or naphthyl) mercapto or anilido or substituted anilido (acetanilido or 4-chloroacetanilido) reactive group.  3 : 31 - Diethyl - 2 : 21 - dibenzthiazolyl - 311\h - ethyl - 211 - (ethylidene) benzthiazolylidenemethane di-iodide is prepared by refluxing together methylene bis-benzthiazole, 2-(b -acetanilido-vinyl)-benzthiazole ethiodide, and triethylamine in pyridine, heating the dye base obtained with dimethyl sulphate in chlorobenzene, and adding aqueous potassium iodide solution to an alcohol solution of the product.  3 : 31-Diethyl-2 : 21-dibenzoxazolyl - 311 - ethyl - 211 - (ethylidene) benz thiazolylidene methane di-iodide, 2 : 21-dibenzthiazolyl - 311 - ethyl - 211 - (b  - ethylethylidene) benzthiazolylidenemethane, 2 : 21 - dibenzthia - zolyl - 311 - ethyl - 611 - methyl - 211 - (b  - ethyl - ethylidene) benzthiazolylidenemethane and 2 : 21-benzthiazolyl - 311 - ethyl - 211 - (D 2 - butenylidene) benzthiazolylidenemethane are similarly prepared.  A sample has been furnished under Sect. 2 (5) of a dye made by refluxing together 2-methylmercaptobenzthiazole methiodide, methylenebis-benzthiazole and triethylamine.  Specifications 408,272, [Group XX], 408,273, 527,627, 537,961, 546,527, 549,202 and 549,203 are referred to.