In a process for the preparation of a chlorozincate salt of a benzothiazolium azo compound by treating a benzothiazole azo compound with a dialkylsulfate having of from 1 to 4 carbon atoms, in an aqueous medium at a temperature of from about 10.degree. to 80.degree. C., the improvement which comprises carrying out the alkylation with the use of 1.8 to 2.5 mols of the dialkylsulfate calculated on the starting azo compound, and in the presence of an acid acceptor consisting essentially of a zinc compound capable of binding an acid, at a pH not exceeding 7, and separating the tetrachlorozincate salt of the benzothiazolium azo compound formed by adding an alkali metal chloride.