Patent GB-649725-A (GB)
Title: Process for the manufacture of 2-methyl-5-phenylbenzthiazole, methine dyes and sensitized photographic emulsions
IPC: C07D277/64
Filed: 1947-11-24
Abstract: 2 : 21 - Dinitro - 4 : 41 - diphenyl - diphenyl-disulphide is prepared by adding aqueous sodium disulphide to a boiling methanol solution of 4-bromo-3-nitrodiphenyl and refluxing. 2-Methyl-5-phenylbenzthiazole is prepared by adding zinc dust to a glacial acetic acid suspension of 2 : 21 - dinitro - 4 : 41 - diphenyl - dipheny disulphide, adding acetic anhydride, and heating. 2 - b  - Acetanilidovinyl - 5 - phenylbenzthiazole ethiodide is prepared by refluxing together 2 - methyl - 5 - phenylbenzthiazole ethiodide, diphenylformamidine, and acetic anhydride, 2-b -Acetanilidovinyl-4-phenylbenzthiazole ethiodide is similarly prepared.ALSO:Dyes of the general formula <FORM:0649725/IV (c)/1> wherein d is 1 to 4, n is 1 or 2, L is a substituted or unsubstituted methine group, R and R1 are alkyl, X is an anion, and Z represents the residue of a 5- or 6-membered ring, which may have fused-on benzene rings (e.g. thiazole or 4-methyl-, 4-phenyl-, or 4 : 5-diphenyl-thiazole; benzthiazole or 4- or 5-phenyl-, 5-, 6-, or 7-chloro-, 5-bromo-, 5- or 6-methyl-, 4- or 6-methoxy, or 5-dimethylamino-benzthiazole; a -or b -naphthathiazole; selenazole or 4-methyl-or 4-phenyl-selenazole; benzselenazole or 5-chlorobenzselenazole; benzoxazole or 5-phenyl-, 5-chloro-, or 5-methoxy-benzoxazole; or quinoline or 6-chloro- or 6-methoxy-quinoline) are prepared by the usual methods from quaternary salts of 2-methyl-5-phenylbenzthiazole, e.g. by condensing with a cyclammonium quaternary salt of general formula <FORM:0649725/IV (c)/2> wherein X is Cl, Br, I, a thioether group, or a group of the formula R2R2N-(L=L)d-1, or of the formula R4S-L=L, wherein R2 is aryl, R3 is H, alkyl, or aryl, and R4 alkyl. Monomethine cyanine dyes are prepared using cyclammonium quaternary salts of the above general formula such that X is Cl, Br, I, or a thioether group.  11 : 3-Diethyl-61-methoxy-5 - phenylthia-21-cyanine-p-toluenesulphonate is prepared by refluxing together 2-methyl-5-phenylbenzthiazole ethyl - p - toluenesulphonate and 6 - methoxy - 2 - phenylmercaptoquinoline ethyl-p-toluenesulphonate in ethyl alcohol containing triethylamine. 11-Ethyl-61-methoxy-3-methyl - 5 - phenylthia - 21 - cyanine p-toluenesulphonate, 3 - 2 - carboxyethyl - 11 - ethyl - 61 - methoxy - 5 - phenylthia - 21 - cyanine iodide, 3 : 31 - diethyl - 5 - phenylthiacyanine iodide, and 31 - ethyl - 3 - methyl - 5 - phenyloxathiacyanine iodide are similarly prepared.  Trimethine cyanine dyes are prepared using cyclammonium quaternary salts of the above general formula such that X1 is R2R3N-CH= CH or R4S-L=L, or, in the case of symmetrical dyes, by condensing a quaternary salt of 2-methyl-5-phenylbenzthiazole with an orthocarboxylic ester (e.g. triethyl, tri-n-propyl, and tri-n-butyl orthoformate; triethyl orthoacetate, orthopropionate, orthophenylacetate, and orthobenzoate; trimethyl ortho-n-valerate and ortho-p-toluate; and methyldiethyl ortho-n-caproate and ortho-iso-caproate). 11-Butyl-3-ethyl - 5 - phenylthia - 41 - carbocyanine iodide is prepared by refluxing together 2-b -acetanilido-vinyl-5-phenylbenzthiazole ethiodide, lepidine n-butiodide, and pyridine.  3 : 31-Diethyl-51-phenylselenathiacarbocyanine iodide and 3 : 31-diethyl - 4 : 51 - diphenylthiacarbocyanine iodide are similarly prepared.  3 : 31-Diethyl-5 : 51-diphenylthiacarbocyanine bromide is prepared by refluxing together 2 - methyl - 5 - phenylbenzthiazole ethyl-p-toluenesulphonate, ethyl orthoformate, and pyridine, and treating the hot solution with hot aqueous potassium bromide.  3 : 31 - Diethyl - 9 - methyl - 5 : 51 - diphenylthiacarbocyanine bromide, 3 : 31 : 9-triethyl-5 : 51-diphenylthiacarbocyanine iodide, and 9-ethyl-3 : 31-dimethyl - 5 : 51 - diphenylthiacarbocyanine iodide are similarly prepared.  Dyes may also be prepared from intermediates such as 2-(2-methylmercapto - 1 - butenyl) - benzthiazole methyl - p - toluenesulphonate, 2 - (1 - methyl - 2 - methylmercapto - 1 - butenyl) - benzthiazole methyl - p - toluenesulphonate, 2 - (methylmercaptopropenyl) - 3 : 4 - trimethylenebenzthiazolium - p - toluenesulphonate, 5 - chloro - 2 - (2 - methylmercapto - 1 - butenyl) - benzselenazole methyl - p - toluenesulphonate, 2 - (2 - methylmercaptostyryl) - b  - naphthathiazole ethiodide, 5-chloro-2-(b -cyclopropyl:b -methylmercaptovinyl) - benzthiazole methyl-p - toluenesulphonate, 2 - (b  - cyclobutyl : b  - methylmercaptovinyl) - benzthiazole methyl - p-toluenesulphonate and 2-(b -cyclohexyl : b -methylmercaptovinyl) - benzthiazole methyl - p-toluenesulphonate. Pentamethine cyanine dyes are prepared using cyclammonium quaternary salts of the above general formula such that X1 is a R5R6N-CH=CH-CH=CH group (R5 being H, alkyl, or acyl, and R6 being aryl), or, in the case of symmetrical dyes, by condensing a quaternary salt of 2-methyl-5-phenylbenzthiazole with a b -arylaminoacrolein anil salt.  11 : 3 - Diethyl - 5 - phenylthia - 41 - dicarbocyanine iodide is prepared by refluxing together 2-methyl-5-phenylbenzthiazole ethyl-p-toluenesulphonate, 4-(4-acetanilido-1 : 3-butadienyl)-quinoline ethiodide, ethyl alcohol, and triethylamine.  3 : 31 - Diethyl - 5 : 51 - diphenylthiadicarbocyanine iodide is prepared by refluxing together 2 - methyl - 5 - phenylbenzthiazole ethyl - p - toluenesulphonate, b  - anilinoacrolein anil hydrochloride, ethyl alcohol, and triethylamine, and treating a hot methanol solution of the dye with hot aqueous potassium iodide.  Heptamethine cyanine dyes are prepared using cyclammonium quaternary salts of the above general formula such that X1 is a R7R8-L=L-K=K-L=L group, R7 being H, alkyl, or acyl and R8 being aryl, or, in the case of symmetrical dyes, by condensing a quaternary salt of 2-methyl-5-phenylbenzthiazole with a glutaconic aldehyde dianilide salt.  3 : 31 - Diethyl - 5 : 51 - diphenylthiatricarbocyanine ethylsulphate is prepared by reacting together 2-methyl-5-phenylbenzthiazole diethyl sulphate and glutaconic aldehyde dianilide hydrochloride in ethyl alcohol containing piperidine.  Merocyanine dyes of the general formula <FORM:0649725/IV (c)/3> wherein m is 1, are prepared by condensing a quaternary salt of 2-methyl-5-phenylbenzthiazole with an arylaminomethylene compound of the general formula <FORM:0649725/IV (c)/4> wherein R10 is H or acyl and R11 is aryl, or by condensing the quaternary salt with an orthocarboxylic ester and a compound of the general formula <FORM:0649725/IV (c)/5> 5 - [(3 - Ethyl - 5 - phenyl - 2(3) - benzthiazolylidene) - ethylidene] - 3 - laurylrhodanine is prepared by refluxing together 2-methyl-5-phenylbenzthiazole ethiodide and 5 - acetanilidomethylene-3-laurylrhodanine in ethyl alcohol containing triethylamine.  3 - Phenyl - 3 - [(3 - ethyl - 5 - phenyl - 2(3) - benzthiazolylidene) - ethylidene]-rhodanine and the corresponding 3-methyl and 3-b -hydroxyethyl dyes, 3-ethyl-5-[(3 - ethyl - 5 - phenyl - 2(3) - benzthiazolylidene) - ethylidene] - 2 - thio - 2 : 4 - (3 : 5) - oxazoledione, 3 - ethyl - 5 - [(3 - ethyl - 5 - phenyl - 2(3) - benzthiaxolylidene) - ethylidene] - 1 - phenyl - 2 - thio - hydantoin, 1 - phenyl - 3 - methyl - 4 - [(3 - ethyl - 5 - phenyl - 2(3) - benzthiazolylidene) - ethylidene] - 5 - pyrazolone, 1 - benzthiazolyl - 3 - methyl - 4 - [(3 - ethyl - 5 - phenyl - 2(3) - benzthiazolylidene) - ethylidene] - 5 - pyrazolone, 2 - diphenylamino - 5 - [(3 - ethyl - 5 - phenyl - 2(3) - benzthiazolylidene)-ethylidene]-4(5)-thiazolone, and 2-ethylphenylamino - 5 - [(3 - ethyl - 5- phenyl - 2(3) - benzthiazolylidene) - ethylidene] - 4(4) - thiazolone are similarly prepared.  3-Ethyl-5-[(3-ethyl-5-phenyl - 2(3) - benzthiazolylidene) - isopropylidene] - 2 - thio - 2 : 4(3 : 5) - oxazoledione is prepared by refluxing together 2-methyl-5-phenylbenzthiazole ethyl - p - toluenesulphonate, 3 - ethyl - 2 - thio - 2 : 4(3 : 5) - oxazoledione, and ethyl orthoacetate in ethyl alcohol containing triethylamine.  The corresponding dyes from rhodanine, 3-ethylrhodanine, 3-phenylrhodanine, 3 - ethyl - 1 - phenyl - 2 - thiohydantoin, and 1 : 3-diphenyl-2-thiohydantoin are similarly prepared.  The corresponding dyes from 3-ethyl - 1 - phenyl - 2 - thiohydantoin and 1 : 3 - diethyl-2-thiobarbituric acid may also be prepared by reaction with 2-b -acetanilidovinyl-5-phenylbenzthiazole ethiodide.  Merocyanine dyes of the above general formula, wherein m is 2, are prepared by reacting the corresponding simple merocyanine dye with an alkyl ester and then condensing with a 5- or 6-membered heterocyclic ketomethylene compound.  2-(3-Ethyl-4-oxo-2-thiono - 5 - thiazolidylidene) - 5 - [(3 - ethyl - 5 - phenyl - 2(3) - benzthiazolylidene) - ethylidene] - 3 - lauryl - 4 - thiazolidone is prepared by refluxing together the reaction product of 5-[(3-ethyl-5-phenyl - 2(3) - benzthiazolylidene) - ethylidene] - 3 - laurylrhodanine and methyl - p - toluenesulphonate with 3-ethylrhodanine in alcohol containing triethylamine.  The corresponding dyes from 3-phenylrhodanine, 3-ethyl-2-thio-2 : 4(3 : 5) - oxazoledione, 1 : 3 - diphenyl - 2 - thiohydantion, and 3-ethyl-1-phenyl-2-thiohydantoin are similarly prepared. Specifications 533,238, 585,666 and 647,542 are referred to.