Synthesis of sulfur-containing substances based on vinyl ethers and acetylene 16. Concerning the mobility of the ?-alkoxy groups in ethyl alkyl and aryl sulfides

Abstract

1. The reaction conditions for vinyl alkyl ethers and mercaptans were refined, allowing one to prepare predominately the addition products which were contrary to the Markovnikov rule, A series of 1-alkoxy-2-alkyl(aryl)-mercaptoethanes was obtained in good yield. 2. It was shown that the alkoxy group in 1-alkoxy-2-alkyl(aryl)mercaptoethanes may be readily replaced by chlorine. A series of 1-chloro-2-alkyl(aryl)mercaptoethanes was synthesized by the following reaction sequence: $$C_4 H_9 OCH = CH_2 \xrightarrow{{RSH}}C_4 H_9 OCH_2 CH_2 SR\xrightarrow{{HCI}}ClCH_2 CH_2 SR.$$ 3. It was suggested that the reaction proceeds through formation of an ethylene sulfonium ion which permits one to understand the dependence of the ease of substitution of the alkoxy group on the structure of the other parts of the original sulfide, found in this work.