Patent GB-640094-A (GB)
Title: Improvements in and relating to hemicyanine dyestuffs and photographic silver halideemulsions sensitised therewith
Inventor: DORMAEL ANDRE EMILE VAN
IPC: C09B23/01
Filed: 1947-03-14
Abstract: Hemicyanine dyes are prepared by reacting a primary aromatic diamine or salt thereof on an intermediate, such as a cyclammonium salt, which has a reactive group (e.g. an alkyl-, aralkyl-, or aryl-ether, -thioether, or -selenoether group or an amino or substituted amino group) linked by a vinyl or substituted vinyl group to the carbon atom in a - or g -position to the quaternary N-atom, or a 2-acyl-, 2-thioacyl-, 2-formyl- or 2-thioformyl-methylene heterocyclic N-containing base.  Dyes of the general formula of Fig. IV, wherein Q in NH2, Y represents the non-metallic atoms to complete a 5- or 6-membered heterocyclic ring, which may carry fused-on rings, A represents a divalent aromatic radical, which may be derived from benzene, naphthalene, diphenyl, diphenylmethane, diphenyl ether, benzophenone, diphenylamine, or stilbene, R is unsubstituted or substituted alkyl, alkylene, or aryl, L, L1, and L2 are unsubstituted or substituted methine groups, X is an acid residue, and n is 1 or 2 are prepared by reacting an excess of the primary aromatic diamine or salt thereof with the intermediate.  In examples, dyes are so prepared from (a) 2-b -acetanilidovinylbenzthiazole ethiodide and phenylenediamine by refluxing together in ethyl alcohol; (b) 2-formylmethylene-3-ethyl-2 : 3-dihydrobenzthiazole and benzidine by refluxing together in methyl alcohol with the introduction of HCl gas, and then treating with NaI; (c) 2-b -acetanilidovinylbenzoxazole ethiodide and p-phenylenediamine by refluxing together in ethyl alcohol; and (d) 2-b -methylmercapto: b -ethylvinylbenzthiazole dimethylsulphate and p-phenylenediamine by refluxing together in ethyl alcohol. Dyes of the general formula of Fig. IV, wherein Q is the formula of Fig. V, Y and Y1 represent the non-metallic atoms to complete the same 5- or 6-membered heterocyclic ring, which may carry fused-on rings, A is as before defined, R and R1 are <FORM:0640094/IV (c)/1> <FORM:0640094/IV (c)/2> identical and as before defined for R, L is an unsubstituted or substituted methine group, L, L1, and L2 are substituted or unsubstituted methine groups (L1 or L2 or both being substituted), X and X1 are acid residues, and n and m are both 1 or both 2 are prepared either by condensing an excess of the intermediate with the aromatic diamine or salt thereof, or by condensing the dyes of Formula IV, wherein Q is NH2 with the intermediates from which they were prepared. In examples, dyes are obtained by refluxing together in ethyl alcohol; (3) 2 - (b  - methyl - mercapto: b  - methylvinyl)-benzthiazole ethylmethylsulphate and p-phenylenediamine; (f) 2-(methylmercapto: b -ethylvinyl)-benzthiazole dimethylsulphate and p-phenylenediamine; and (g) the dye of (c), 2-methylbenzoxazole benzyl bromide, and ethyl orthoformate (followed by treatment with aqueous KI).  The diamine residue-NH-A-NH-or the group R or R1 may bear acid substituents, e.g. carboxylic or sulphonic acid groups.  Dyes of the general formula of Fig. IV, wherein the symbols are as before, but at least one of the pairs of related symbols Y, Y1, &c., are not identical and wherein L1 and L2 may both be unsubstituted methine groups are prepared by condensing the dyes of Formula IV, wherein Q is NH2 with intermediates similar to but not identical with the intermediates from which they were prepared.  In examples: (h) the dye of (a) is refluxed together with 2-(b -acetanilidovinyl) - benzoxazole methiodide in ethyl alcohol; (i) the dye of (b) is refluxed together with 2-(b -anilinovinyl)-thiazoline ethiodide in ethyl alcohol; (j) the dye of (c) is heated with 2 : 5 - dimethylbenzoxazole ethiodide and ethyl orthoformate; (k) the dye of (d) is refluxed together with 2-(b -acetanilidovinyl)-benzoxazole ethiodide in ethyl alcohol, followed by treatment with NaI solution; and (1) the dye of (a) is refluxed together with 2-(b -acetanilidovinyl)-quinoline ethiodide in ethyl alcohol.  According to the Provisional Specification, A may be a chemical bond.