Patent GB-489335-A (GB)
Title: Improvements in or relating to the manufacture and use of dyestuffs suitable for sensitising photographic emulsions
IPC: C09B23/01
Filed: 1937-01-22
Abstract: Dyes are made by condensing a 5 - membered heterocyclic ring compound of the type <FORM:0489335/IV/1> where R may be alkyl, aryl or aralky, Y=O or S and Z=H2 or a group corresponding to either of the following formulae: (A) <FORM:0489335/IV/2> where R, R1 and R2=alkyl, aryl or aralkyl, Y=O or S and D=the remainder of a heterocyclic nucleus, (cf. Specification 487,051), or (B) <FORM:0489335/IV/3> where R1=alkyl, aryl or aralkyl and N may be contained in a heterocyclic ring or part of a non-cyclic chain or part of an amino group external to a carbocyclic ring which forms part of the chain and n=O or a positive integer, (cf. Specification 426,718), or (C) A-CH= which represents the residue of an aldehyde of the general formula A-CH=O in which A is a monovalent grouping, with an alkyl salt to convert the thione or selenone grouping into a reactive group and condensing the resulting compound with one of the following types of compounds: (a) a 5-membered ring compound containing the system <FORM:0489335/IV/4> (b) a heterocyclic nitrogen compound having a reactive CH3 group or external =CH2 group or reactive NH2 or =NH group in the a - or g -position to one only of the nitrogen atoms, (c) a compound containing the grouping <FORM:0489335/IV/5> where R1, R2 and R3=alkyl, aryl or aralkyl or R1 and R2 may be part of the same arylene ring, (d) carbocyclic compounds containing a -CH2CO- group, (e) acids or esters of the type COOR-CH2-(CX=CH)n-COOR where X=H or a monovalent substituent, R=H or an alkyl or similar group and n=O or 1, (f) anhydrides of acids of the general formula CH3-(CX)2n-1=CH-COOH where X=H or a monovalent group and n=1 or 2, (g) ammonia or amidines or hydrazines or diamines or their salts. When the 5-membered ring compounds containing the system <FORM:0489335/IV/6> which are condensed with the quaternary salt of the compounds <FORM:0489335/IV/7> correspond to the general formula <FORM:0489335/IV/8> the resulting product conforms to the same general formula as the starting material and so may be treated with an alkyl salt and condensed with any of the compounds (a)-(g) above. When this second condensation is with a compound <FORM:0489335/IV/9> the product will once more conform to the general formula of the starting material, and by proceeding in this way the condensation may be repeated as often as desired; the final product may be further condensed with any of the other types of compound (b) to (g) above. Examples of 5-membered ring compounds of the first formula above are 4-keto-2-thio (or seleno) tetrahydrothiazoles, -oxazoles or -selenazoles or their N-alkyl, aralkyl or aryl derivatives.  The dyes are sensitizers for photographic silver halide emulsions.  In examples; (1) (a) 1-methylthiolbenzoxazole and methyl p-toluene sulphonate are fused together and then boiled with N-ethyl rhodanic acid in pyridine; (b) the product is again heated with methyl p-toluene sulphonate, treated with malonic acid in pyridine and the dye precipitated with potassium iodide (equations and formulae given); similar dyes may be prepared starting from 1-methylthiolbenzthiazole and 1- wacetanilidovinylbenzthiazole; (2) the product of (1) (a) is fused with 1-methylbenzthiazole and methyl p-toluenesulphonate and then refluxed with pyridine; the dye is precipitated with potassium bromide; the product of 1 (a) is refluxed with 1-methylbenzoxazole and ethyl p-toluenesulphonate in alcohol in presence of sodium acetate; similar dyes may be prepared from compounds made according to (1) (a) from N-alkylrhodanic acids and quaternary salts of methyl thiol heterocyclic nitrogen compounds (e.g. benzoxazole, benzthiazole, quinoline and quinazoline) condensed with quinaldine, lepidine, 1-methylbenzselenazole or quinaldine; (3) (a) 1-methyl 4 : 5-methylenedioxybenzthiazole and methyl-p-toluene sulphonate are fused together, boiled with diphenylformamidine and acetic anhydride and the product condensed with N-ethylrhodanic acid in pyridine; (b) the product obtained is fused with methyl p-toluene sulphonate and condensed with malonic acid in pyridine; (4) (a) 1-methylbenzthiazole and methyl p-toluenesulphonate are fused together, condensed with diphenylformamidine in acetic anhydride and the product refluxed with N-ethylrhodanic acid in pyridine; (b) the product obtained is fused with 1-methylbenzthiazole and methyl p-toluene sulphonate and then refluxed with pyridine; (5) the product of (4) (a) is fused with 1-methylbenzthiazole and ethyl p-toluenesulphonate; similar dyes are prepared by condensing quinaldine methiodide and 5-acetanilidomethenyl-N-methylrhodanic acid in pyridine and condensing the product with 1-methylbenzthiazole or quinaldine and ethyl p-toluene sulphonate in pyridine; other compounds made according to (4) (a) and 5 (a) may be condensed as above with 1-methylbenzthiazole, 1-methylbenzoxazole, quinaldine, lepidine, 1-methylbenzselenazole or 1-ethylbenzoxazole; (6) (a) 1-methylbenzthiazole and methyl p-toluene sulphonate are fused together and the product boiled with N-ethylrhodanic acid and acetic anhydride in pyridine; (b) the compound obtained is fused with methyl p-toluene sulphonate and refluxed with N-ethylrhodanic acid in pyridine; (c) the product obtained according to (b) is fused with methyl p-toluene sulphonate and then refluxed with N-ethylrhodanic acid in pyridine; (7) the product from 1-methylthiolbenzthiazole methyl p-toluene sulphonate and N-ethylrhodanic acid according to (1) (a)) is fused with ethyl p-toluene sulphonate and then condensed with N-ethylrhodanic acid; (8) the product of (1) (a) is fused with methyl p-toluene sulphonate and boiled with N-ethylrhodanic acid in pyridine; similar products made according to (1) (a) are condensed with N-ethylrhodanic acid; (9) the compound made according to (3) (a) from N-ethylrhodanic acid and 1-o -acetanilidovinylbenzthiazole methyl p-toluene sulphonate is fused with ethyl p-toluene sulphonate and condensed with N-ethylrhodanic acid; other similar products made according to (3) (a) and the product from quinaldine methiodide and 5-o -acetanilidomethenyl-N-methylrhodanic acid are similarly condensed; (10) the product of (9) is fused with methyl p-toluene sulphonate and condensed with N-ethylrhodanic acid; (11) the product from 1-o -acetanilidovinylbenzthiazole methyl p-toluene sulphonate and N-ethylrhodanic acid (made according to (3) (a)) is fused with methyl p-toluenesulphonate and condensed with 1-phenyl-3-methyl-5-pyrazolone; (11) (a) the product from quinaldine ethiodide and 5 - o  - acetanilidomethenyl - N - ethylrhodanic acid and the product from 1-methylthiolbenzthiazole methyl p-toluene sulphonate and N-methylrhodanic acid (made according to (1) (a) are condensed as in (11); (12) the product from 1-methythiolbenzthiazole methyl-p-toluene sulphonate and N-ethylrhodanic acid (made as in (1) (a) and (12) (a) the product from 1-o -acetanilidovinylbenzthiazole methyl p-toluene sulphonate and N-ethylrhodanic acid (made as in (3) (a)) are fused with methyl p-toluene sulphonate and condensed with hydrazine hydrochloride in pyridine; (13) the product from N-methylrhodanic acid and p-dimethylaminobenzaldehyde is fused with ethyl p-toluene sulphonate and 1-methylbenzthiazole; (14) the starting product of (12) is fused with 1-amino-benzthiazole and ethyl p-toluene sulphonate; (14) (a) the product of (4) (a) is condensed as in (14) and the dye precipitated with potassium iodide; (15) the starting product of (12) is fused with methyl p-toluene sulphonate and refluxed with ammonium nitrate in pyridine; or (16) fused with ethyl-p-toluene sulphonate and condensed with indene; or (17) fused with ethyl-p-toluene sulphonate and condensed with glutaconic acid; or (18) fused with methyl p-toluenesulphonate and condensed with thiohydantoin; or (21) fused with methyl p-toluenesulphonate and condensed with crotonic anhydride; (19) and (20) the product from 1-o -acetanilidovinylbenzthiazole and 2-thio-3-methyl- or ethyl-4-ketotetrahydrooxazole (made according to (3) (a)) is fused with 1-methylbenzthiazole and ethyl p-toluenesulphonate and then refluxed with pyridine.  Samples have been furnished under Sect. 2 (5) of dyes prepared as follows: (1)-(3) 2-thio-3 - ethyl - 4 - keto - 5 - (- methyl di - hydrobenzthiazolylidene) - tetrahydrothiazole (from 1 - methythiolbenzthiazole - methyl-p-toluene sulphonate and N-ethylrhodanic acid) is heated with methyl p-toluene sulphonate and condensed in pyridine with (1) 1 : 3-indandione; (2) p-phenylenediamine and (3) benzamidine hydrochloride; (4) N-methylrhodanic acid is fused with 1-methylbenzthiazole and methyl p-toluene sulphonate and the product boiled with pyridine; (5) the compound obtained according to example 6 using lepidine, methyl-p-toluene sulphonate, N-methylrhodanic acid and acetic anhydride (formula given) is fused with 1-methylbenzthiazole and methyl p-toluenesulphonate and the product boiled with pyridine. Specifications 424,559, 425,609, 428,359, 431,141, 431,186, 431,187, 432,628, 438,420, 447,038, 461,668, 461,688, and 485,110 also are referred to.