抄録
Bromination of butylsulfonylacetone (I) in glacial acetic acid yielded a monobromo compound, m.p. 119° (from alcohol), when the reaction mixture was allowed to stand for about 0.5-1.0 hour after discoloration of bromine. No depression of the melting point was observed on admixture with 1-butylsulfonyl-3-bromopropanone (II), obtained by the dry hydrogen bromide decomposition of the diazoketone (VIII) formed from butylsulfonylacetic chloride (VII) and diazomethane. The oily substance formed by the reduction of (II) with zinc dust in glacial acetic acid gives the same 2, 4-dinitrophenylhydrazone as that of m.p. 140° of (I). Condensation of (II) and thiourea gave 2-amino-4-butyl-sulfonylmethylthiazole (III). 1-Butylmercapto-3-chloro-2-propanone obtained from butylmercaptoacetic chloride (IX) through diazoketone (X) gave 2-amino-4-butylmercapto-methylthiazole (XII) by condensation with thiourea, and its acetate (XIII), m.p. 85°, is different from that of the isomer, m.p. 96-98°. Admixture of (IV), obtained by the oxidation of (XIII), with the acetate of (III) showed no depression, but the admixture with the isomer of the same melting point, m.p. 138°, i.e. 2-acetamino-4-methyl-5-butylsulfonylthiazole, showed depression. Reaction of 2-amino-5-bromothiazole (XIV) and alkylmercaptane, under the same conditions as those in the case of 2-amino-4-methyl-5-bromothiazole, gave the objective 5-alkylmercapto (XVI) and 5-alkylsulfonyl (XVII) derivatives, but these could not be detected by the method from butylmercapto-acetaldehyde diethyl acetal.
