Patent GB-592267-A (GB)
Title: Improvements in the manufacture of polymethin dyes and in photographic emulsions containing the same
IPC: G03C1/18
Filed: 1944-08-28
Abstract: Cyanine dyes of the general formula <FORM:0592267/IV/1> wherein R and R1 each represent a methyl or an ethyl group, R2 represents an alkyl group or an aryl group of the benzene or naphthalene series, R3 represents H or a methyl or an ethyl group, Q represents H, an alkoxy group, or an aryloxy group of the benzene or naphthalene series, Z and Z1 each represent the non-metallic atoms to complete a benzthiazole, benzoxazole, benzolenazole, a - or b -naphthathiazole, or a - or b -naphthoxazole nucleus, and X represents an anion are prepared (a) by condensing with an orthoester, a benzthiazole, benzoxazole, benzselenazole, a - or b -naphthathiazole, or a - or b -naphthoxazole quaternary salt having in the a -position to the quaternary nitrogen atom an alkoxymethyl or aryloxymethyl group of the benzene or naphthalene series, (b) by condensing a benzthiazole, benzoxazole, benzselenazole, a - or b -naphthathiazole, or a - or b -naphthoxazole quaternary salt having in the a - or g -position to the quaternary nitrogen atom a b -arylaminovinyl (including an acylated b -arylaminovinyl) group with a benzthiazole, benzoxazole, benzselenazole, a - or b -naphthathiazole, or a - or b -naphthoxazole quaternary salt having in the a -position to the quaternary nitrogen atom an alkoxymethyl group or an aryloxymethyl group of the benzene or naphthalene series, or (c) condensing a benzthiazoline, benzoxazoline, benzselenazoline, a -or b -naphthathiazoline, or a - or b -naphthoxazoline having in the a -position to the nuclear nitrogen atom an acylated alkoxymethylene or aryloxymethylene group with a quaternary salt of a heterocyclic nitrogen base having a methyl group in the a - or g -position to the quaternary nitrogen atom.  8 : 10-Di-(p-methoxyphenoxy)-3 : 31-dimethyloxacarbocyanine perchlorate is prepared by heating together 2 - (p - methoxyphenoxymethyl) - benzoxazole and methyl p-toluenesulphonate, adding dry pyridine and ethyl orthoformate and refluxing, and adding hot aqueous sodium perchlorate.  3 : 31 - Dimethyl - 8 : 10 - diphenoxy-5 : 51-diphenyloxacarbocyanine perchlorate, 8 : 10-diethoxy - 3 : 31 - dimethyloxacarbocyanine per - chlorate, 3 : 31 - dimethyl - 8 : 10 - di - (m - toloxy) - thicarbocyanine bromide, 8 : 10 - di - (p - chloro - phenoxy) - 3 : 31 - dimethylthiacarbocyanine p-toluenesulphonate, 3 : 31 - dimethyl - 8 : 10 - di - (b -naphthoxy) - thiacarbocyanine iodide, 8 : 10 - di - ethoxy - 3 : 31 - dimethylthiacarbocyanine iodide, 3 : 31-dimethyl-8 : 10-diphenoxy-4 : 5 : 41 : 51 dibenzoxacarbocyanine iodide, 3 : 31 - dimethyl - 8 : 10-diphenoxy-6 : 7 : p  61 : 71-dibenzoxacarbocyanine methylsulphate, 3 : 31-dimethyl-8 : 10-diphenoxyselenacarbocyanine bromide, 3 : 31-dimethyl-8 : 10-diphenoxy-6 : 6 : 61 : 71-dibenzthiacarbocyanine bromide, and 3 : 31 - dimethyl-8 : 10-diphenoxy-4 : 5 : 41 : 51-dibenzthiacarbocyanine bromide are similarly prepared. 31-Ethyl-3-methyl-8-phenoxythiacarbocyanine iodide is prepared by heating together 2-phenoxymethylbenzthiazole and methyl p-toluenesulphonate, and adding dry pyridine, 2-(b -acetanilidovinyl)-benzthiazole ethiodide, and triethylamine, and refluxing.  3 : 31-Diethyl-10-phenoxyoxathiacarbocyanine perchlorate is similarly prepared.  31-Ethyl-3 : 9-dimethyl-8-phenoxythiacarbocyanine iodide is prepared by refluxing together 2-(acetylphenoxymethylene)-3 - methylbenzthiazoline, 2 - methylbenzthiazole etho-p-toluenesulphonate, and acetic anhydride, and adding hot aqueous potassium iodide.  b -(m-Toloxy)-ethylidenerhodanine, 3-ethyl-5-(3 - ethyl - 2 - benzthiazolylidane) - b  - (m - toloxy) - ethylidene - 2 - thio - 2 : 4 - oxazoledione, 3 - ethyl - 5 - (3 - methyl - 2 - benzoxazolylidene) - b  - (p - chloro - phenoxy) - ethylidenerhodanine, 3 - ethyl - 5 - (5 - chloro-3-methyl-2-benzoxazolylidene) -b -phenoxyethylidene-2-thio-2 : 4-oxazoledione, and 5 - (4 - ethyl-2-benzthiazolylidene)-b -methoxyethylidene) -3-phenylrhodanine are similarly prepared.  2 - (p - Methoxyphenoxymethyl) - benzoxazole is prepared by heating together 2-(p-methoxyphenoxyacetylamino)-phenol and phosphorus pentoxide and pouring into aqueous sodium carbonate.  2 - Phenoxymethyl - 5 - phenylbenz - oxazole, 5 - chloro - 2 - phenoxymethylbenzoxazole, 2 - (p-chlorophenoxymethyl)-benzoxazole, 2-phen - oxymethyl-b -naphthoxazole, 2-phenoxymethyl-a -naphthoxazole, and 2-ethoxymethylbenzoxazole are similarly prepared. 2-(p-Methoxyphenoxyacetylamino)-phenol is prepared by adding p-methoxyphenoxyacetyl chloride slowly to a solution of o-aminophenol in pyridine and pouring into aqueous sodium carbonate. p-Methoxyphenoxyacetyl chloride is prepared by heating together p-methoxyphenoxyacetic acid and thionyl chloride. 2-Ethoxyacetylaminophenol is prepared by adding ethoxyacetyl chloride slowly to a solution of o-aminophenol in pyridine and pouring into aqueous sodium carbonate.  m-Toloxymethylbenzthiazole is prepared by adding a solution of m-toloxyacetyl chloride in dry benzene to a suspension of zinc o-aminophenylmercaptide and zinc chloride in dry benzene, and refluxing.  2-Ethoxymethylbenzthiazole, 2 - (b  - naphthoxymethyl) - benzthiazole, p - chlorophenoxymethylbenzthiazole, 2 - phenoxy - methylbenzthiazole, and 2 - phenoxymethylbenz - selenazole are similarly prepared.  2-Phenoxymethyl-a -naphthathiazole is prepared by adding phosphorus pentasulphide to a heated solution of phenoxyacetyl-b -naphthylamine in dry pyridine and oxidizing the phenoxythioacetyl-b -naphthylamine obtained with aqueous potassium ferricyanide.  Phenoxythioacetyl-a -naphthylamine and 2 - phenoxymethyl - b  - naphtha - thiazole are similarly obtained.  Phenoxyacetyl-a -naphthylamine is prepared by heating together a -naphthylamine and phenoxyacetyl chloride. Phenoxyacetyl-b -naphthylamine is similarly obtained.  2 - (b  - Acetanilido - a  - phenoxyvinylbenzthiazole methiodide is prepared by heating together 2-phenoxymethylbenzthiazole methiodide and diphenylformamidine.  2 - (Acetylphenoxymethylene)-3-methylbenzthia - zoline is prepared by heating together 2-phenoxymethylbenzthiazole and methyl p-toluenesulphonate, adding acetic anhydride and triethylamine, and refluxing.  According to the Provisional Specification, R and R1 may represent alkyl groups having from one to four carbon atoms and R3 may represent H or an alkyl or cycloalkyl group.