Patent GB-517769-A (GB)
Title: Dyes and photographic silver halide emulsions containing the same
IPC: G03C1/14
Filed: 1938-06-07
Abstract: 517,769. Sensitizing dyes. KODAK, Ltd. June 7, 1938, No. 16964. Convention date, June 4, 1937. Drawings to Specification. [Classes 2 (iii) and 15 (ii)] [Also in Group XX] Photographic silver halide emulsions are sensitized by means of dyes of the general formula where A=O or S, (L)n=an open chain in which L represents a methenyl group, n = 1, 3 or 5, P =H or an aliphatic radical while Q=an aliphatic radical or P and Q together represent the non-metallic atoms necessary to complete a cyclic basic nucleus other than a pyrrol nucleus and Z =the non-metallic atoms necessary to complete a heterocyclic nucleus. The term aliphatic includes un-saturated and substituted radicals. A list of radicals and basic nuclei which P and Q may represent and a list of 5- and 6-membered heterocyclic nuclei exempli- Z fying the residue =C-C =A are given in the Specification. The dyes may be made by reacting a basic primary or secondary non-aromatic amine other than pyrrol with a compound of the formula prepared by acylating the product obtained by first reacting a compound of the formula with a heterocyclic compound of the formula The acylation may also take place during the condensation. In the examples (n =1 ) (1) and (2) 5 - acetanilidomethylene - 3 - phenyl- or 3 - ethylrhodanine is condensed with piperidine in ethyl alcohol ; the starting material is made by heating 3-phenyl- or 3-ethylrhodanine with diphenylformamidine in kerosene and refluxing the 5 - anilinomethylene - 3 - phenyl - or 3 - ethyl rhodanine thus obtained with acetic anhydride in presence of triethylamine, (3) 5 - acetanilidomethylene - 3 - ethyl - 2 - thio - 2:4 - oxazoledione is condensed with morpholine in ethyl alcohol; the starting material is made from 3 - ethyl - 2 - thio - 2:4 - oxazoledione as in (1), (n=3) (4)-(6) 5 - (alpha-acetanilidoallylidene)- 3-ethylrhodanine is condensed as above with piperidine, morpholine, or diethylamine ; the starting material is made by refluxing 3-ethylrhodanine, #-anilinoacroleinanil hydrochloride and acetic anhydride, (7)-(11) the following are condensed with piperidine: 5-(alpha-acetanilido- - allylidene) - 2 - diphenylamino - 4 - thiazolone, 5 - (alpha - acetanilidoallylidene) - 3 - ethyl - 2 - thio - 2:4 - oxazoledione, 4 - (alphaacetanilidoallylidene)- 1 - benzothiazyl - 3 - methyl - 5 - pyrazolone, 5 - (alpha - acetanilidoallylidene) - 3 - ethyl - 1 - phenyl - 2 - thiohydantoin, 4 - (#- acetanilidoallylidene) - 3 - methyl - 1 - phenyl - 5 - pyrazo - lone ; these compounds may be made from the corresponding heterocyclic compound, #-anilinoacrolein anil hydrochloride and acetic anhydride (n =5 ) (12)-(14) 5 - (5 - acetanilido - # <2>,<4> - pentadienylidene - 3 - ethylrhodanine is condensed with-piperidine, morpholine or diethylamine ; the starting material is made by condensing 3-ethylrhodanine with glutaconic aldehyde dianilide hydrochloride in presence of alcohol and triethylamine and acetylating. Some of the dyes may be alkylated by treating with an alkylating agent, e.g. dialkyl sulphates or alkyl-p-toluene sulphonates in presence of powdered alkali and methyl alcohol. The dyes may also be used for light filters and for dyeing textiles, e.g. those from cellulose acetate yarn. Sensitizing data and spectrogramsfor certain of the dyes are given. Specifications 394,537, 428,222 and 470,725 are referred to.