Patent GB-557549-A (GB)
Title: Improvements in or relating to dyestuffs
IPC: C09B23/10
Filed: 1942-04-23
Abstract: 557,549. Dyes. KENDALL, J. D. April 23, 1942, No. 5436. Samples furnished. [Class 2 (iii)] [Also in Group XX] Dyes are produced by condensing a dye intermediate of formula (where X and Y each represent O or S, R' is H or a hydrocarbon group, R 2  is a hydrocarbon group and R 3  an alkyl group) with an alkyl or aralkyl quaternary salt of a heterocyclic nitrogen compound of the thiazole, selenazole or quinoline series having, in the α- or γ-position to the quaternary nitrogen atom, an external reactive methylene group (including an external methyl group or mono-alkyl-substituted methyl group). One molecular proportion of the dye intermediate may be used with at least 2 molecular proportions of the quaternary salt and the reaction effected in the absence of any condensing agent or in the presence of only a small quantity of a base giving a tri-nuclear dye, or the reagents may be used in substantially equimolecular proportions, and the reaction effected in the presence of a strong base in a quantity in excess of that necessary to react with acid bye-products of the reaction, giving a di-nuclear dye. The di-nuclear dyes may be converted to tri-nuclear dyes by conversion to quaternary salts by treatment with an alkyl or aralkyl salt and condensing with a .molecular equivalent of the same class as and the same as or different from the second reagent. Quaternary salts of the appropriately substituted thiazoles, selenazoles, and their polycyclic homologues (e.g. of the benzene, naphthalene, acenaphthene, or anthracene series), thiazolines, selenazolines, quinoline, α- and #-naphthaquinolines, and lepidines may be used. The polycyclic compounds may be substituted in the carbocyclic rings with one or more groups, e.g. alkyl, aryl, amino, hydroxy, alkoxy, or methylene-dioxy groups, or by halogen atoms. The groups R, and R 2  may be methyl, ethyl, propyl, benzyl, naphthylmethyl, phenyl, naphthyl, allyl, or cinnamyl groups, and may be substituted by amino, hydroxy, or alkoxy groups or by halogen atoms. The group attached to the N atom of the quaternary salt is preferably an alkyl or hydroxy alkyl group. In exampe 1, a dye is prepared by reacting 2 - thio - 3 - ethyl - 4 - keto - 5 - (γ - ethylthiocrotonylidene) - tetrahydrothiazole or 2 - thio - 3 - ethyl - 4 - keto - 5 - (γ - ethoxycrotonylidene) - tetrahydrothiazole with 1-methylbenzthiazole ethiodide in ethyl alcohol in the presence of diethylamine or triethylamine. In examples 2 and 3, dyes are prepared by reacting 2 - thio - 3 - ethyl - 4 - keto - 5 - (y - ethylthiocrotonlidene) - tetrahydrothiazole with lepidine ethiodide or with p-toluquinaldine ethiodide. In examples 4 and 7, 2-thio-3-methyl- 4 - keto - 5 - (y-ethylthiocrotonylidene) - tetrahydrothiazole or 2 - thio - 3 - ethyl - 4 - keto - 5- (y - ethylcrotonylidene) - tetrahydrothiazole is reacted with 1-methylbenzthiazole ethiodide in ethyl alcohol in the presence of a large excess of diethylamine to give di-nuclear dyes. In example 5, a dye is prepared by reacting 2 - thio - 3 - methyl - 4 - keto - 5 - (y - ethylthiocrotonylidene) - tetrahydro-oxazole and 1- methylbenzthiazole ethiodide in ethyl alcohol in the presence of triethylamine. In example 6, a dye is prepared by reacting 2-thio-3-methyl- 4 - keto - 5 - (y - ethyl - y - ethylthioallylidene) - tetrahydrothiazole with 1-methylbenzthiazole ethiodide in the presence of diethylamine. The dyes sensitize gelatino-silver iodobromide emulsions in the red and far-red regions of the spectrum. Sensitizing data are given. Samples have been furnished under Sect. 2 (5) of dyes obtained by condensing (a) 1-methyl-4- chlorobenzthiazole methyl - p - toluenesulphonate, (b) 1-methylbenzselenazole methyl-ptoluenesulphonate, (c) 1-methyl-5-dimethylaminobenzthiazole methyl - p - toluenesulphonate, and (d) 6-acetylaminoquinaldine methyl-p-toluenesulphonate with 2-thio-3-ethyl- 4 - keto - 5 - (y - ethylthiocrotonylidene) - tetrahydrothiazole, (b), (e), and (d) being converted to the corresponding iodides. Specification 557,550 is referred to.