GB562566A - Improvements in or relating to cyclic quaternary ammonium dyestuff intermediates - Google Patents

Abstract

Dye intermediates are prepared by condensing a compound of formula R1S-CH­CH-CH(XR1)2, where the groups R1 are alkyl groups and the groups X both O or both S, with a quaternary salt of a heterocyclic nitrogen base which contains a reactive methylene group in the a - or g -position to the quaternary nitrogen atom in acid conditions. The quaternary salt is preferably an alkyl quaternary salt, and the reactive methylene group may be a methyl or mono-substituted methyl group. The reactants may be heated together in the presence of a solvent therefor and of a compound capable of reacting with mercaptan or alcohol split off during the reaction, e.g. lower fatty anhydrides such as acetic anhydride, which serve both purposes. The intermediates have the formula <FORM:0562566/IV/1> wherein R2 is H or an alkyl or aralkyl group and R3 an alkyl or aralkyl group or a substituted alkyl group (e.g. hydroxylalkyl) or an unsaturated aliphatic group (e.g. allyl). R1, R2 (if not H), and R3 are preferably lower alkyl groups (e.g. methyl or ethyl). A represents an acid radical, e.g. chloride, bromide, iodide, alkyl sulphate, p-toluenesulphonate, or perchlorate, and n is 0 or 1. D stands for the residue of a heterocyclic nitrogen compound, e.g. substituted and unsubstituted thiazoles, thiazolines, oxazole, oxazolines, selenazoles, selenazolines, pyridine, quinoline, lepidine, indolenine, diazines (e.g. pyrimidine and the diazines described in Specification 425,609), thiodiazoles, or quinazoline, or the corresponding substituted and unsubstituted polycyclic compounds, e.g. benzthiazoles, naphthathiazoles, and anthrathiazoles and the corresponding polycyclic oxazoles and selenazoles. The heterocyclic compounds may contain substituents in the benzene nuclei, e.g. alkyl, aryl, amino, hydroxy, or alkoxy groups or halogen atoms. 1-o (-Ethylthiobutadienyl)-benzthiazole methiodide is prepared by fusing together 1-methylbenzthiazole and methyl p-toluenesulphonate, refluxing with a mixture of acetic anhydride and either b -ethylthioacrolein diethyl mercaptal or b -ethylthioacrolein diethyl acetal, and pouring into hot potassium solution. 1 : 3 : 3 - Trimethyl - 2 - (o - ethylthiobutadienyl) - indolenium perchlorate, 1 - (o - ethylthiobutadienyl) - benzselenazole ethiodide, 1 - (o - ethylthiobutadienyl) - benzoxazole ethyl p - toluenesulphonate, 4 - (o - ethylthiobutadienyl) - quinoline methyl perchlorate, 2 - (o - ethylthiobutadienyl) - quinoline methyl perchlorate, 1 - (o - ethylthiobutadienyl) - 4 - chlorobenzthiazole methiodide, and 2 - (o - ethylthiobutadienyl) - benzthiazole b - acetoxyethyl iodide are similarly prepared. Specifications 562,565 and 562,567 also are referred to.