Patent GB-654690-A (GB)
Title: Improvements in cyanine dyes and photographic emulsions containing the same
IPC: C09B23/02
Filed: 1948-03-19
Abstract: An anhydro cyanine hydroxide or water soluble salt thereof of the general formula <FORM:0654690/IV (c)/1> wherein d and n each represent 0 or 1, m represents 0, 1 or 2, L represents a methine group (e.g. -CH= or -C(CH3)=), R represents a substituted or unsubstituted alkyl group, D represents a bivalent hydrocarbon radical, and Z and Z1 each represent the non-metallic atoms necessary to complete a 5 or 6-membered heterocyclic nucleus which may have a further ring or rings condensed therewith, is prepared by condensing a cyclammonium quaternary salt of the formula <FORM:0654690/IV (c)/2> wherein R1 is H or an alkyl group and X an acid anion, with a cyclammonium quaternary salt of the formula <FORM:0654690/IV (c)/3> wherein Q represents one of the groups -SR2, -CH=CR3-SR4, -CH=CH-NR5R6, or -CH=CH-CH=CH-NR7R8, wherein R2 represents an alkyl or aryl group, R3 and R4 alkyl groups, R5 and R7 H or alkyl or acyl groups, and R6 and R7 aryl groups.  The condensation may be effected in the presence of a basic condensing agent, e.g. pyridine or triethylamine.  Anhydro - 3 - b  - carboxyethyl - 5 : 51 - dichloro9 - methyl - 31 - b  - sulphoethylthiacarbocyanine hydroxide is prepared by heating together 3-b -carboxyethyl - 5 - chloro - 2 - thioacetylmethylenebenzthiazoline and methyl p-toluenesulphonate, adding 5 - chloro - 2 methylbenzthiazole - b  - sulphoethylbromide and pyridine, and refluxing.  Anhydro - 3 - b  - carboxyethyl - 5 : 51 - dichloro - 9 - ethyl - 31 - b  - sulphoethylthiacarbocyanine hydroxide, anhydro - 51 - chloro - 3 - ethyl - 31 - b  - sulphoethylthiacyanine hydroxide, anhydro - 5 - chloro - 11 - ethyl - 3 - b  - sulphoethylthia - 21 - cyanine hydroxide, anhydro-11-ethyl-3-b -sulphoethylthia-21-cyanine hydroxide, anhydro-1-ethyl-11 - p - sulphobenzyl - 2 : 41 - cyanine hydroxide, and anhydro - 3 - ethyl - 11 - p - sulphobenzylthia-41-cyanine hydroxide are similarly prepared.  A symmetrical anhydro cyanine hydroxide of the general formula is prepared by condensing a cyclammonium quaternary salt of the formula <FORM:0654690/IV (c)/4> with an ester of an orthocarboxylic acid or of a dithiocarboxylic acid, or with a b -arylamino-acrolein anil salt.  Anhydro - 5 : 51 - dichloro - 3 : 31 - di - b  - sulphoethylthiacarbocyanine pyridine salt is prepared by refluxing together 5-chloro-2-methyl-benzthiazole-b -sulphoethylbromide, ethyl orthoformate, and pyridine.  Anhydro-5 : 51-dichloro-9 - ethyl - 3 : 31 - di - b  - sulphoethylthiacarbocyanine hydroxide, anhydro - 5 : 51 - dichloro - 9 - methyl - 3 : 31 - di - b  - sulphoethylthiacarbocyanine hydroxide, anhydro-5 : 51-dichloro-3 : 31 di - p - sulphobenzylthiacarbocyanine hydroxide, anhydro - 3 - ethyl - 11 - p - sulphobenzylthia - 41 - carbocyanine hydroxide, anhydro-5 : 51-dichloro-3 : 31 - di - p - sulphobenzylthiadicarbocyanine hydroxide, and anhydro - 11 - ethyl - 61 - methoxy-5 - phenyl - 3 - b - sulphoethylthia - 21 - cyanine hydroxide are similarly prepared. Specifications 533,425, 546,705, 645,288, 647,542, 649,725 and 654,683 are referred to.