Patent GB-626470-A (GB)
Title: Improvements in or relating to methine dyestuffs, their preparation and the sensitisation of photographic emulsions therewith
IPC: C09B23/02
Filed: 1946-06-17
Abstract: 3 - p - Carbethoxybenzyl - 5 - cyanmethyl - 1 : 2 : 4-oxodiazole is prepared by adding cyanacetyl chloride drop by drop to a solution of p - carbethoxyphenylacetamidoxime in ether, and boiling the product with acetic acid.  3 - (p - Tolyl) - 5 - cyanmethyl - 1 : 2 : 4 - oxodiazole is prepared by adding an ether solution of cyanacetyl chloride to an ether solution of p-toluamidoxime, and refluxing.  3 - (o - Methoxyphenyl) - 4 - acetonyl - 1 : 2 : 4 - oxodiazole is prepared by heating together ethyl acetoacetate and o-methoxybenzamidoxime.  3 - (p - Tolyl) - 5 - chloromethyl - 1 : 2 : 4 -oxodiazole is prepared by refluxing together monochloracetyl chloride and p-toluamidoxime in ether.  3 - (p - Tolyl) - 1 : 2 : 4 - oxodiazole - 5 - methylpyridinium chloride is prepared by heating 3 - (p - tolyl) - 5 - chloromethyl - 1 : 2 : 4 - oxodiazole with pyridine.  3 - (p - Tolyl) - 1 : 2 : 4 - oxodiazolyl - 5 - acetic acid ethyl ester is prepared by reacting p-toluamidoxime with malonic ester chloride.  3 - (p - Tolyl) - 5 - (p - nitrobenzoylmethyl) - 1 : 2 : 4-oxodiazole is prepared by condensing 3 - p - tolyl - 5 - acetonyl - 1 : 2 : 4 - oxodiazole with p-nitrobenzoyl chloride p  in ether in the presence of sodium alcoholate, and saponifying with ammonia.  3 - (p - Tolyl) - 1 : 2 : 4 - oxodiazolyl - 5 - pyruvic acid ethyl ester is prepared by condensing 3 - p - tolyl - 5 - methyl - 1 : 2 : 4 - oxodiazole with ethyl oxalate in ether in presence of sodium alcoholate.  Specification 344,409 is referred to.ALSO:<FORM:0626470/IV (c)/1> <FORM:0626470/IV (c)/2> <FORM:0626470/IV (c)/3> Methine or polymethine dyes of the formula of Fig. 1, wherein R is unsubstituted or substituted alkyl or aryl, Y is an electro-negative group such as cyan, pyridinium, or a group -CA-R1, wherein A is O or S and R1 unsubstituted or substituted alkyl, aryl or amino, or alkoxy or carbalkoxy, n is 2 or 3, L is an unsubstituted or substituted methine group, X and D are substituents activating a methylene group (e.g. X may be an electro-negative group and D a heterocyclic nucleus such as oxodiazole or benzthiazole or X may be a carbonyl group linked to D in such a way that X and D make part of a heterocyclic 5- or 6-membered ring such as pyrazolone, rhodanine, thiohydantoin, barbituric acid or thiobarbituric acid) are prepared by reacting a compound of formula <FORM:0626470/IV (c)/4> with a compound of formula C6H5.N(=L-L)n-1=L-NH-C6H5 or the corresponding hydrochloride.  By using one mole. of each reactant, compounds according to the formula of Fig. II are obtained, wherein R1 is H or alkyl, and such compounds can be reacted with compounds containing reactive methylene groups, e.g. compounds of formula A which may give rise to symmetrical dyes or heterocyclic nitrogen compounds having a reactive methyl group in a  or g  position to the nitrogen atom to give compounds of the formula of Fig. III, wherein E represents the non-metallic atoms for completing a 5- or 6-membered N-containing ring such as thiazoline, oxazole, selenazole, benzoxazole, benzthiazole, naphthoxazole, quinoline, or thiodiazole, R11 is unsubstituted or substituted alkyl, and m is 1 or 2.  The symmetrical dyes may be obtained directly in the first reaction by using excess of oxodiazole compound over 2 moles., or from compounds of the formula C2H5O-(L=L)n-1-CH (OC2H5)2.  Dyes of formula I may be obtained by condensing hemioxonoles with the oxodiazole bases, and dyes of formula III by condensing with the oxodiazole bases quaternary cyclammonium salts having in a - or g -position to the quaternary N atom a reactive group, e.g. halogen, alkylmercapto, arylamino or acylarylamino, which may be at the end of a polymethine chain, or by reacting a mixture of the oxodiazole base and a quaternary cyclammonium salt with an orthoester.  5 - (b  - Anilino - a  - acetylvinyl) - 3 - p - tolyl-1 : 2 : 4-oxodiazole is prepared by reacting 3-(p-tolyl)-5-acetonyl-1 : 2 : 4-oxodiazole with diphenylformamidine.  A dye may be prepared by reacting this intermediate with 2-methylbenzthiazole ethobromide in presence of triethylamine and alcohol, or alternatively by reacting 2-b -anilinovinylbenzthiazole ethiodide with 3-(p-tolyl)-5-acetonyl-1 : 2 : 4-oxodiazole.  Dyes may also be prepared by reacting 3-(p-carbethoxybenzyl)-5-cyanmethyl-1 : 2 : 4-oxodiazole and 2 - b  - (anilinovinyl) - benzthiazole ethiodide in the presence of triethylamine, acetic anhydride and alcohol; by reacting 2-b -anilinovinyl - 5 - methyl - 1 : 3 : 4 - thiodiazole benzylbromide (obtained by heating 2 : 5-dimethyl-1 : 3 : 4-thiodiazole with benzylbromide and then with diphenylformamidine) with 3-(p-tolyl) - 5 - cyanmethyl - 1 : 2 : 4 - oxodiazole; by reacting 2-b -anilinovinylbenzoxazole p-carboxy-benzylbromide and 3 - (p - tolyl) - 5 - acetonyl-1 : 2 : 4-oxodiazole; by reacting 3-(o-methoxyphenyl) - 5 - acetonyl - 1 : 2 : 4 - oxodiazole with 2 - b  - anilinovinylbenzthiazole ethiodide; by reacting 3-(p-tolyl)-5-cyanmethyl-1 : 2 : 4 oxodiazole with 5-(o -anilino-a -cyanobutadienyl)-3-p-tolyl-1 : 2 : 4-oxodiazole (obtained by reacting 3 -(p - tolyl) - 5 - cyanmethyl - 1 : 2 : 4 - oxodiazole with b -anilinoacroleinanil hydrochloride in presence of triethylamine); by refluxing 3-(p-tolyl)-5-acetonyl-1 : 2 : 4-oxodiazole and glutacondialdehydedianil hydrochloride in presence of triethylamine; by reacting 3-(p-tolyl)-5-(61-anilino-11-cyan-11 : 31 : 51-hexatrienyl)-: 2 : 4-oxodiazole with 3 - (p - tolyl) - 5 - cyanmethyl-1 : 2 : 4-oxodiazole in presence of piperidine, pyridine and alcohol; by reacting 2-(41-acetanilido-11 : 31-butadienyl)-benzthiazole ethiodide and 3 - (p - tolyl) - 5 - cyanmethyl - 1 : 2 : 4 - oxodiazole in presence of triethylamine and alcohol (alternatively by reacting 3 - (p - tolyl) - 5 - (41-anilino-11-cyan-11 : 31-butadienyl)-1 : 2 : 4-oxodiazole with 2-methylbenzthiazole ethiodide); by reacting 2-b -anilinovinylbenzthiazole ethiodide with 3-(p-tolyl)-1 : 2 : 4-oxodiazolyl-5-methylpyridinium chloride in presence of triethylamine, acetic anhydride and alcohol; and by reacting 2-b -anilinovinylbenzthiazole ethiodide and 3-(p-tolyl)-1 : 2 : 4-oxodiazolyl-5-acetic acid ethyl ester in presence of triethylamine, acetic anhydride and alcohol.  3 - (p - Tolyl) - 5 - (61 - anilino - 11 - acetyl-11 : 31 : 51-hexatrienyl)-1 : 2 : 4-oxodiazole i prepared by reacting 3-(p-tolyl)-5-acetonyl-1 : 2 : 4-oxodiazole with glutacondialdehydedianil hydrochloride in presence of triethylamine at room temperature.  3 - (p - Tolyl) - 5 - (61-anilino-11-cyan-11 : 31 : 51-hexatrienyl)-1 : 2 : 4-oxodiazole is similarly prepared. Samples have been furnished under Sect. 2(5) of dyes prepared by boiling together in absolute alcohol containing acetic anhydride and triethylamine: (1) 3-(p-tolyl)-5-(p-nitrobenzoyl-methyl)-1 : 2 : 4-oxodiazole and 2-b -anilinovinyl-benzthiazole ethiodide and (2) 3-(p-tolyl)-1 : 2 : 4-oxodiazolyl-pyruvic acid ethyl ester and 2-b -anilinovinylbenzthiazole ethiodide, and (3) by boiling together in absolute alcohol containing sodium alcoholate 3-(p-tolyl)-5-(41-anilino-11-cyano - 11 : 31 - butadienyl) - 1 : 2 : 4 - oxodiazole and 1-phenyl-3-methyl-5-pyrazolone.  Specification 344,409 is referred to.