SYNTHESIS OF CF3-CONTAINING SULFUR HETEROCYCLES - THE FIRST STABLE 2-THIETANOL DERIVATIVE

摘要

The reaction of a,P-unsaturated CF3-containing ketones R(1)R(2)C=CHCOCF3 1-4 with ammonium hydrosulfide was investigated. The structure of the enones was shown to influence the reaction path, and the corresponding six-membered sulfur heterocycles bearing trifluoromethyl groups, 5-8, or mercaptan, 9, were obtained. The reaction of 3-adamantylidene-1,1,1-trifluoropropan-2-one,3, results in the corresponding four-membered heterocycle 8, which has a stable 2-thietanol fragment. The oxidation of sulfides 5-8 by hydrogen peroxide yields sulfones 10-12 or 1,3-sultine 13 (in the case of 8). Product stereochemistry and reaction mechanism are discussed. [References: 28]