Patent GB-627521-A (GB)
Title: Cyanine dyes and photographic emulsion containing same
IPC: C09B23/10
Filed: 1946-12-02
Abstract: P - (tert. - butyl) - phenoxyethyl p - toluenesulphonate is prepared by reacting together b -(p-p-tert.-butylphenoxy)-ethyl alcohol and p-toluenesulphonyl chloride in pyridine. P-(di-isobutyl) - phenoxyethyl p - toluenesulphonate, p - methylphenoxyethyl p - toluenesulphonate, p - cyclohexylphenoxyethyl p - toluenesulphonate, p - chlorophenoxyethyl p - toluenesulphonate, and p - phenylphenoxyethyl p - toluenesulphonate and corresponding arylthioalkyl and arylselenoalkyl p-toluenesulphonates are similarly prepared.  Arylthioalkyl and arylselenoalkyl alcohols are prepared by reacting thiophenols or selenophenols with chlorohydrin in the presence of sodium alcoholate.  2 - Methylbenzthiazole phenoxyethyl - p-toluenesulphonate is prepared by heating together 2-methylbenzthiazole and phenoxyethyl p-toluenesulphonate. 2-Methyl-5 : 6-methylenedioxybenzthiazole phenylthioethyl p-toluenesulphonate; the aryloxyalkyl, arylthioalkyl, and arylselenoalkyl, quaternary salts of 2-methylbenzoxazole, 2 - methyl - 6 - methoxybenzselenazole, 2 - methyl - 6 : 7 - benzbenzthiazole, 2 - methyl - 4 - phenylthiazole, 2 - methyl - 4-phenyloxazole, 2 - methyl - 4 - phenylselenazole, 2 - methylthiazoline, 2 - methylmercaptobenzthiazole, and 2 - phenylmercaptobenzthiazole; and the corresponding derivatives obtained by using the p-di-isobutylphenoxyethyl, p - methylphenoxyethyl, p-cyclohexylphenoxyethyl, p - chlorophenoxyethyl, and p-phenylphenoxyethyl p-toluenesulphonates and the corresponding sulphur and selenium compounds are similarly prepared.  The toluenesulphonates may be converted to the halides or perchlorates.ALSO:Cyanine dyes, such as cyanine, carbocyanine, dicarbocyanine, tricarbocyanine, tetracarbocyanine, pentacarbocyanine, hemicyanine, and styryl dyes, and dye bases, comprise two heterocyclic nitrogen nuclei, each of which contain one nitrogen atom only and one of which is either a five- or six-membered heterocyclic nucleus and the other is a five-membered heterocyclic nucleus, at least one of the nitrogen atoms in the heterocyclic nuclei having attached thereto an aryloxyalkyl, arylthioalkyl, or arylselenoalkyl group.  Dyes specified are obtained by refluxing together (1) 2-methyl-6 - methoxybenzselenazole phenoxyethyl p-toluenesulphonate, 2 - methylmercapto - 6-methylquinoline ethiodide (or 2 - iodo - 6-methylquinoline ethiodide), ethanol and triethylamine; (2) 2-(b -anilino-b -ethylvinyl)-6-phenylbenzoxazole ethiodide, 2 - methylbenzthiazole phenoxyethyl p - toluenesulphonate, and pyridine; (3) 2 - methyl - 5 : 6-methylenedioxybenzthiazole p - chlorophenoxyethyl p - toluenesulphonate, ethyl orthoformate, and pyridine; (4) 2 - methyl - 5 : 6-methylenedioxybenzthiazole p - (tert. - butyl)-phenoxyethyl p - toluenesulphonate, ethyl orthoformate, and pyridine; (5) 2 - methyl-5 : 6 - methylenedioxybenzthiazole - (p - diisobutyl) - phenoxyethyl p - toluenesulphonate, ethyl orthoformate, and pyridine; (6) 2-methyl - 5 : 6 - methylenedioxybenzthiazole p - methylphenoxyethyl p - toluenesulphonate, ethyl orthoformate, and pyridine; (7) 2-(b -anilinovinyl) - 4 - phenyl - 5 - methylthiazole ethiodide, 2 - methyl - 5 : 6 - methylenedioxybenzselenazole p - di - isobutylphenoxyethyl p - toluenesulphonate, pyridine, acetic anhydride, and triethylamine; (8) 2-methylbenthiazole phenylthioethyl p-toluenesulphonate, ethyl orthoformate, and pyridine; (9) 2-methyl - 5 : 6 - methylenedioxybenzthiazole p - methoxyphenoxyethyl p - toluenesulphonate, ethyl orthoformate, and pyridine; (10) 2 - methyl - 5 : 6 - methylenedioxybenzthiazole b  - naphthoxyethyl p - toluenesulphonate, ethyl orthoformate, and pyridine; (11) 2-(b  - acetanilidovinyl) - 5 : 6 - methylenedioxybenzthiazole ethiodide, 2 - methyl - 5 : 6-methylenedioxybenzthiazole phenylthioethyl p-toluenesulphonate, pyridine, and triethylamine; (12) 2-methyl-5 : 6-methylenedioxybenzthiazole phenylselenoethyl p-toluenesulphonate, ethyl orthoformate, and pyridine; (13) 2 - methyl - 6 : 7 - benzobenzthiazole phenoxypropyl p - toluenesulphonate, ethyl orthoformate, and pyridine; (14) 2-(4-acetanilidobutadienyl) - 5 : 6 - methylenedioxybenzthiazole ethiodide, 2 - methyl - 5 : 6-methylenedioxybenzthiazole phenylthioethyl p-toluenesulphonate, pyridine, and triethylamine; (15) 2-(6-acetanilidohexatrienyl)-5 : 6-methylenedioxybenzthiazole ethiodide, 2-methyl - 5 : 6 - methylenedioxybenzthiazole phenyloxyethyl p-toluenesulphonate, pyridine, and triethylamine. Ethyl orthoacetate, orthopropionate, and orthobenzoate may be used in place of ethyl orthoformate.