Patent GB-587481-A (GB)
Title: Cyanines and related compounds and photographic emulsions sensitised therewith
IPC: C09B23/02
Filed: 1944-07-17
Abstract: Unsymmetrical cyanine dyes are prepared by condensing, as first component, a quaternary salt of a heterocyclic nitrogen compound having in the a - or g -position to the nitrogen atom of the quaternary salt a reactive halogen atom, or a reactive alkylmercapto, aralkylmercapto, alkylmercaptovinyl, aralkylmercaptovinyl, alkylmercaptobutadienyl, aralkylmercaptobutadienyl, alkoxylbutadienyl, N - arylaminovinyl, N - arylacylaminovinyl, N - arylaminobutadienyl, or N-arylacylaminobutadienyl group with, as second component, a compound containing a reactive methyl, cyanomethyl, or methylene group, which is a heterocyclic nitrogen compound containing a methyl or cyanomethyl group in the a - or g - position to a quaternary or tertiary (according as the group is methyl or cyanomethyl respectively) nitrogen atom, or a cyclic or acylic compound containing a reactive methylene group adjacent to a carboxyl or <FORM:0587481/IV/1> group, at least one of which heterocyclic nitrogen compounds is 1 : 5-phenanthroline bearing in the a -position to the 1-nitrogen any one of the specified reactive substituents (except methylene) and optionally further substituents elsewhere, e.g. methyl, phenyl, ethyl, or carboxy groups or halogen atoms.  The vinyl or butadienyl radical may contain simple substituents such as alkyl. The first component may be 2-methylmercapto-1 : 5-phenanthroline methyl p-toluenesulphonate, 2 - d  - acetanilidobutadienyl - (1 : 31) - 6 - methyl - 1 : 5 - phenanthroline ethiodide, 2-methylmercaptoquinoline methiodide, 2 - b - acetanilidovinyl-1 : 3 : 3-trimethylindolenine iodide, 2 - b  - acetanilidovinylbenzthiazole ethiodide, 2 - methylmercapto - 1 : 5 - phenanthroline ethyl p-toluenesulphonate, 2-methylmercapto - 21 : 1 - naphthathiazole ethiodide, 2 - methylmercaptobenzthiazole ethyl p-toluenesulphonate, 2 - ethoxybutadienyl - (1 : 3) - benzthiazole ethiodide, 4 - b  - acetanilido vinylquinoline ethiodide, 2 - b  - acetanilidido-vinylbenzoxazole ethiodide, 2 - b  - ethylmercaptovinyl - 6 - phenylbenzoxazole methyl p - toluenesulphonate, 2 - b  - acetanilidido vinyl - 1 : 5 - phenanthroline ethiodide, 2 - d  - acetanilididobutadienyl - (11 : 31) - benzthiazole ethiodide, 2 - a - acetanilididovinylbutadienyl-(11 : 31)-6-methyl-1 : 5-phenanthroline methiodide, 2 - b  - acetanilidovinyl - 6 - methyl - 1 : 5 - phenanthroline ethiodide, 2 - b  - methylmercapto - b  - methylvinylmercaptobenzthiazole ethyl p - toluenesulphonate, 2 - iodo - 1 : 5 - phenanthroline ethiodide, 2 - (d  - methyl - d  - ethylmercaptobutadienyl - (1 : 3) - 6 - methyl - 1 : 5 - phenanthroline ethiodide, or 2-(a -methyl-d -ethylmercaptobutadienyl-(1 : 3) - 1 : 3 : 3-trimethylindolenine chloride.  The second component may be lepidine ethiodide, 2-methyl benzselenazole ethiodide, acetylacetone, oxazole-2 : 4-dione, 2-cyclohexenyl-(1)-benz thiazole ethyl p-toluenesulphonate, 1-phenyl-3-methyl - 5 - pyrazolene, barbituric acid, 2-methyl-6-phenyl-1 : 5-phenanthroline ethiodide, 2 : 6-dimethyl-1 : 5-phenanthroline ethiodide, 2-methylthiazoline ethiodide, 2-cyanomethyl - 6 - methyl - 1 : 5 - phenanthroline, lepidine benzyl chloride, 2 : 6-dimethyl-1 : 5-phenanthroline methiodide, 2 : 3 : 3-trimethylindolenine ethiodide, 2-methyl-4-furylthiazole ethiodide, 2-methyl-6-phenyl-1 : 5-phenanthroline-8-carboxylate ethosulphate, rhodanine, N-ethylrhodanine, or N-phenylrhodanine. The condensation may be effected in presence of an acid-binding agent such as sodium ethylate, sodium acetate, sodium carbonate, triethylamine, triethanolamine, or N-methylpiperidine.  A solvent such as ethanol may be added, or pyridine may be used both as acid-binding agent and diluent.  (1 : 6-Dimethyl-1 : 5-phenanthroline-2) (1-ethylquinoline - 4) - trimethinecyanine iodide is obtained by heating together 4-b -anilinovinylquinoline ethiodide, acetic anhydride, and triethylamine, diluting the cooled melt with ethanol, adding 2 : 6-dimethyl-1 : 5-phenanthroline methiodide, and then adding triethylamine.  (1 : 6-Dimethyl-1 : 5-phenanthroline - )(1 - ethylbenzoxazole - 2) - trimethinecyanine iodide, (1-ethyl-6-methyl-1 : 5-phenanthroline - 2)(1 - ethyl - 3 : 3 - dimethylindolenine - 2) - trimethinecyanine iodide, (1 - ethyl - 6 - methyl - 1 : 5 - phenanthroline - 2) (1 - ethyl - 21 : 11 - naphthathiazole - 2) - monomethine cyanine iodide, (1-methyl-1 : 5-phenanthroline-2) (1 - ethylquinoline - 5) - monomethinecyanine iodide, (1 : 6-dimethyl-1 : 5-phenanthroline-2) (1 - ethylbenzthiazole - 2) - trimethinecyanine iodide, (1 - ethyl - 6 - methyl - 1 : 5 - phenanthroline - 2) (1 - ethylbenzthiazole - 2) - mono - methyltrimethinecyanine iodide, (1 - ethyl - 6 - methyl - 1 : 5 - phenanthroline - 2) (1 - methyl - 6 - phenyl benzoxazole - 2) - trimethinecyanine iodide, (1 - ethyl - 1 : 5 - phenanthroline - 2) (1 - ethylbenzthiazole - 2) - pentamethinecyanine iodide, (1 : 6 - dimethyl - 1 : 5 - phenanthroline - 2) (1 - ethyl - 5 - furylthiazole - 2) - pentamethinecyanine iodide, 1 - cyano - 1 - (61 - methylphenanthrolyl21) - 3 - (111 - ethylbenzthiazolylidene - 211) propene-(1), 1 - ethyl - 2 - b b  - diacetylallylidene-6 - methyl - 1 : 2 - dihydro - 1 : 5 - phenanthroline, 1 - ethyl - 6 - methyl - 2 - phenanthrolyideneethylidene rhodanine, (1-ethyl-6-methyl-1 : 5-phenanthroline - 2) (1 - ethylquinoline - 2) - monomethinecyanine iodide, (1 - ethyl - 6 - methyl - 1 : 5 - phenanthroline - 2) (1 - ethylbenzthiazole - 2) - monomethinecyanine iodide, (1 - methyl - 1 : 5-phenanthroline - 2) (1 - ethylbenzselenazole - 2) - monomethinecyanine iodide, (1 - methyl - 1 : 5 - phenanthroline - 2) (1 - ethyl - 5 - furylthiazole - 2) - monomethinecyanine iodide, (1 - methyl - 1 : 5-phenanthroline - 2) (1 - ethylthiazoline - 2) - monomethinecyanine iodide, (1 - ethyl - 1 : 5-phenanthroline - 2) (1 - ethyl - 4 - furylthiazole -2)-monomethinecyanine iodide, (1 - ethyl - 6 - methyl-1 : 5 - phenanthroline - 2) (1 - ethyl - 1 : 5 - phenanthroline - 2) - monomethinecyanine iodide, (1 - ethyl- 1 : 5 - phenanthroline - 2) (1 - ethyl - 21 : 11 - naphthathiazole - 2) - monomethinecyanine iodide, (1 : 6 - dimethyl - 1 : 5 - phenanthroline - 2) (1 : 3 : 3-trimethylindolenine - 2) - trimethinecyanine iodide, (1-ethyl-6-methyl-1 : 5-phenanthroline-2) (1 : 3 : 3-trimethylindolenine-2)-trimethinecyanine iodide, (1-methyl-1 : 5-phenanthroline-2) (1-ethylbenzselenazole-2)-trimethinecyanine iodide, (1 - methyl - phenanthrolylideneethylidene) - N - ethylrhodanine, (1 - ethyl - 6 - methyl - 1 : 5 - phenanthroline) (1 - ethylbenzthiazole - 2) - d  - methylpentamethinecyanine iodide, and (1 - ethyl - 6 - methyl - 1 : 5 - phenanthroline - 2) (1 : 3 : 3-trimethylindolenine-2)-b -methylpentamethinecyanine iodide are similarly prepared.  1 - Methyl - 2 - phenanthrolone is prepared by oxidising 1 : phenanthroline methosulphate with caustic soda and potassium ferricyanide.  1-Ethyl-2-phenanthrolone is similarly prepared.  1 - Methyl - 2 - thiophenanthrolone is prepared by treating 1-methyl-2-phenanthrolone with P2S5. 1-Ethyl-2-thiophenanthrolone is similarly prepared. 2-Methylmercapto-1 : 5-phenanthroline methyl-p-toluenesulphonate is prepared by heating 1-methyl-2-thiophenanthrolone with methyl p-toluenesulphonate.  2-Methylmercapto-1 : 5-phenanthroline ethyl p-toluenesulphonate is similarly prepared.  2-Methyl-4-furylthiazole ethiodide is prepared by brominating furyl methyl ketone, condensing with thioacetamide, and treating with ethyl iodide.  2 - Cyanomethyl - 6 - methyl - 1 : 5 - phenanthroline is obtained by heating the oxime of 6-methyl-2-phenanthrolylpyruvic acid.  2 - b  - Ethylmercaptovinyl - 6 - phenylbenzoxazole methyl p-toluenesulphonate is prepared by reacting 2-methyl-6-phenylbenzoxazole with methyl p-toluenesulphonate and condensing the quaternary salt with ethyl trithio - orthoformate.  2 - d  - Acetylanilidobutadienyl-(11 : 31) - 6 - methyl-1 : 5-phenanthroline methiodide is prepared by heating 2 : 6-dimethyl-1 : 5-phenanthroline methiodide with b -anilinoacrolein hydrochloride in acetic anhydride.  The corresponding ethiodide is similarly prepared.  2 - b  - Anilinovinyl - 6 - methyl - 1 : 5 - phenanthroline ethiodide is prepared by condensing 2 : 6-dimethyl - 1 : 5 - phenanthroline with diphenylformamidine.  2 - b  - Acetanilidovinyl - 6 - methyl - 1 : 5 - phenanthroline ethiodide is prepared by heating 2-b -anilinovinyl-6-methyl-1 : 5-phenanthroline ethiodide with acetic anhydride containing a little triethylamine.  2 - b  - Ethylmercaptovinyl - 1 : 5 - phenanthroline methiodide is prepared by heating 2-methyl-1 : 5-phenanthroline methyl p-toluenesulphonate with ethyl trithio-orthoformate in acetic anhydride.  2 - (d  - Methyl - d  - ethylmercapto - butadienyl - (11 : 3) - 6 - methyl - 1 : 5 - phenanthroline ethiodide is prepared by treating 1-ethyl-2-b b -diacetylallylidene-6-methyl-1 : 2-dihydro-1 : 5-phenanthroline in methanol and ethyl mercaptan with dry gaseous HCl and treating the product in aqueous solution with potassium iodide. 2 - b  - Methylmercapto - b  - methylvinylmercaptobenzthiazole ethyl p-toluenesulphonate is prepared by reacting 1 - ethyl - 2 - thioacetylmethylene benzthiazolone with methyl p-toluenesulphonate. 2 - Iodo-1 : 5-phenanthroline ethiodide is prepared by heating 2-chloro-1 : 5-phenanthroline with ethyl iodide in a sealed tube.