Synthesis of sulfur compounds by the aid of vinyl ethers and acetylene communication 10. Synthesis and certain reactions of ethyl vinyl sulfide

Abstract

1. Conditions have been found for the synthesis of ethyl vinyl sulfide in 60% yield. 2. It has been shown that ethanethiol and hydrogen sulfide add to ethyl vinyl sulfide, in the air and in presence of traces of oxygen, in the direction contrary to that required by Markovnikov's rule; but, in presence of hydroquinone or of the acid catalyst SO2, addition of the thiol proceeds in accordance with the rule. 3. It has been shown that polymerization of ethyl vinyl sulfide does not occur in presence of the ionic catalysts FeCl3 and SnCl2, but occurs in presence of 2,2′-azobis(2-methylpropionitrile), under the action of sunlight, and when kept for a long time. 4. The reaction of ethyl vinyl sulfide with mercuric chloride in alcoholic and aqueous solutions leads to the formation of a mercurated salt of ethanethiol, but in ethereal solution the product is an unstable complex salt, which is decomposed by water and alcohol. 5. It has been shown that ethyl vinyl sulfide, although the sulfur analog of ethyl vinyl ether, has a considerably greater tendency to undergo addition reactions that are contrary to Markovnikov's rule and have a free-radical character.