5-Arylmercapto-及び5-Arylsulfone-thiazole誘導体の合成 (第1報)

抄録

Condensation of vinyl acetate and p-nitrophenylsulfenyl chloride gives α-chloro-β-(p-nitrophenylmercapto)-ethyl acetate (I), m.p. 65°, which, by halogenation, gives α, β-dichloro-β-(p-nitrophenylmercapto)-ethyl acetate (II), m.p. 82-83°. Refluxing (II) with equivalent quantity of thiourea in absolute alcohol results in the formation of 2-amino-5-(p-nitrophenylmercapto)-thiazole (III), m.p. 172-174°. Oxidation of (I) with permanganate gives 2-chloro-β-(p-nitrophenylsulfone)-ethyl acetate (IV), m.p. 112-113°, which, similar to (I), condenses to 2-amino-5-(p-nitrophenylsulfone)-thiazole (V), m.p. 225°. (I) and (IV) respectively give p-nitrophenylmercapto-acetal, oil, and p-nitrophenylsulfone-acetal, m.p. 85°, when dissolved in alcohol containing 5% hydrochloric acid at a room temperature. These acetals are easily hydrolysed to their corresponding aldehydes with hot conc. hydrochloric acid in acetic acid solution to give respectively p-nitrophenylmercapto-acetaldehyde, oil (thiosemicarbazone, m.p. 189°) and p-nitrophenylsulfone-acetaldehyde, m.p. 104°, (semicarbazone, m.p. 211° (decomp.); thiosemicarbazone, m.p. 215°).