Patent GB-633873-A (GB)
Title: Improvements in the manufacture of methin dyes containing an isoquinoline nucleus and in photographic emulsions containing them
IPC: G03C1/83
Filed: 1947-04-19
Abstract: Methine dyes containing an isoquinoline nucleus are prepared by condensing a 1 methyl isoquinoline alkyl quaternary salt of the formula <FORM:0633873/IV (c)/1> wherein R is an alkyl or substituted alkyl group and X is an anion with (a) a cyclammonium alkyl quaternary salt having in the a-position a b -arylaminovinyl group (including a b -alkyl-, b -substituted alkyl-, or b -acylarylaminovinyl group); (b) chloroform, bromoform, iodoform, chloral hydrate, or a chloral alcoholate; (c) a compound of the formula <FORM:0633873/IV (c)/2> wherein R4 is H, alkyl, substituted alkyl, or aryl, R5 is aryl, R6 is alkyl or substituted alkyl, and Q represents the atoms to complete a 5-membered heterocyclic ring; (d) a 1-alkylmercaptoisoquinoline alkyl quaternary salt; or (e) a pyrrole aldehyde of formula <FORM:0633873/IV (c)/3> wherein R7 and R8 are alkyl or substituted alkyl and R9 alkyl, substituted alkyl, or aryl. 31 - Ethyl - 2 - methyl - 1 - isoquinooxacarbocyanine iodide is prepared by refluxing together 1 - methylisoquinoline methiodide, 2 - (b -acetanilidovinyl)-benzoxazole ethiodide, pyridine, and triethylamine.  31 - Ethyl - 2 - methyl - 1 - isoquinothiacarbocyanine iodide, 2 : 3 - diethyl - 1 - isoquinothiacarbocyanine iodide, 2 - methyl - 31-n-propyl-1-isoquinooxacarbocyanine iodide, 31 - n - butyl - 2 - methyl - 1 - isoquinooxacarbocyanine iodide, 31 - isobutyl - 2 - ethyl - 1 - isoquinoselenacarbocyanine iodide, 31 - ethyl - 2 - methyl - 41 - phenyl - 1 - isoquinothiazolocarbocyanine iodide, and 31-ethyl-2-methyl-1-isoquino-41 : 51-benzthiacarbocyanine iodide are similarly prepared.  2 : 21 - Dimethyl - 1 : 11 - isoquinocarbocyanine iodide is prepared by refluxing together 1-methylisoquinoline methiodide, iodoform, and alcoholic KOH.  2 : 21-Diethyl-1 : 11-isoquinocarbocyanine iodide, 2 : 21 - di - n - propyl - 1 : 11 - isoquinocarbocyanine iodide, 2 : 21 - di - n - butyl - 1 : 11-isoquinocarbocyanine iodide, and 2 : 21-di-b  - ethoxyethyl - 1 : 11 - isoquinocarbocyanine iodide are similarly prepared.  3 - Ethyl - 5 - [(2 - ethyl - 1 - isoquinolylidene) - ethylidene]-rhodanine is prepared by refluxing together 1-methylisoquinoline ethiodide, 5-acetanilidomethylene-3-ethylrhodanine, ethyl alcohol, and triethylamine. 3-Ethyl-5-[(2-methyl-1-isoquinolylidene)-ethylidene]-rhodanine, 3-phenyl-5 - [(2 - n - propyl - 1 - isoquinolylidene) - ethylidene] - rhodanine, 3 - b  - hydroxyethyl - 5 - [(2 - n - butyl - 1 - isoquinolylidene) - ethylidene] - rhodanine, 3 - ethyl - 5 - [(2 - ethyl - 1 - isoquinolylidene) - ethylidene] - 2 - thio - 2 : 4 - oxazoledione, 5 - [(2 - ethyl - 1 - isoquinolylidene) - ethylidene] - 1 : 3 - diphenyl - 2 - thiohydantoin, 4 - [(2 - ethyl - 1 - isoquinolylidene) - ethylidene] - 3 - methyl - 1 - phenyl - 5 - pyrazolone, 4 - [(2 - methyl - 1 - isoquinolylidene) - ethylidene] - 3 - methyl - 1 - sulphophenyl-5-pyrazolone, and 3-carboxymethyl-5-[(2 - ethyl - 1 - isoquinolylidene) - ethylidene] - rhodanine are similarly prepared.  2 : 21 - Dimethyl - 1 : 11 - isoquinocyanine perchlorate is prepared by heating together 2 - methyl - 1 - thioisoquinolone and methyl - p-toluenesulphonate adding 1-methylisoquinoline methiodide, ethyl alcohol, and triethylamine, refluxing, and treating a methyl alcohol solution of the iodide produced with hot aqueous sodium perchlorate.  2 - Ethyl - 21 - methyl - 1 : 11-isoquinocyanine iodide and perchlorate, 2 : 21 - di - n - propyl - 1 : 11 - isoquinocyanine iodide and perchlorate, 2 : 21-di-n-butyl-1 : 11-isoquinocyanine iodide, 2 : 21-di-b -ethoxyethyl-1 : 11-quinocyanine iodide and perchlorate, and 2 : 21 - di - b  - hydroxyethyl - 1 : 11 - isoquinocyanine iodide and perchlorate are similarly prepared.  2 : 21 : 51 - Trimethyl - 11 - phenyl - 1 - isoquino - 31 - pyrrolocarbocyanine iodide is prepared by refluxing together 1-methylisoquinoline methiodide, 2 : 5-dimethyl - 1 - phenyl - 3 - pyrrolecarboxaldehyde, ethyl alcohol, and piperidine.  1 - Ethyl - 21 : 51 - dimethyl - 11 - phenyl - 1 - isoquino - 31 - pyrrolocarbocyanine perchlorate, 11 - lauryl - 2 : 21 : 51 - trimethyl - 1 - isoquino - 31 - pyrrolocarbocyanine perchlorate, 11 : 2 - diethyl - 21 : 51 - dimethyl - 1 - isoquino - 31 - pyrrolocarbocyanine perchlorate, 2 - b  - hydroxyethyl - 11 - lauryl - 21 : 51 - dimethyl - 1 - isoquino - 31 - pyrrolocarbocyanine perchlorate, and 2 - b  - ethoxyethyl - 11 - ethyl - 21 : 51 - dimethyl - 1 - isoquino - 31 - pyrrolocarbocyanine perchlorate are similarly prepared.  Specifications 529,440 and 633,874, [Group IV (b)], are referred to.