Chemistry of acetylenic ethers. XXIII. Some reactions of acetylenic thioethers

Abstract

Abstract From acetylenic thioethers, Grignard or lithium derivatives can be obtained, which react with carbonyl compounds to yield the expected carbinols. The reactions with carbon dioxide and ethyl chlorocarbonate also are normal. By oxidative “dimerisations” of the thioethers the diacetylenic bis‐thioethers are obtained. Hydration of acetylenic thioethers is much less easy then for oxygen ethers. Piperidine is added in an anti‐Markownikow way as is also the case for thiols and thiol acids. Rearrangement of carbinols derived from acetylenic thioethers by acids yields the expected thiol esters. This is a method for the preparation of α,β‐unsaturated thioesters. Partial reduction of the carbinols and hydrolysis of the products yields α,β‐unsaturated aldehydes.