The chemistry of cyano-acetylenes. Part VIII. Claisen, amino-Claisen, and thio-Claisen rearrangements in the reactions of cyano-acetylenes with allyl alcohol, prop-2-ynol, allyl amines, and prop-2-enethiol

Abstract

The Claisen rearrangement was observed in the reaction of (diethylamino) propiolonitrile with allyl alcohol in the presence of boron trifluoride etherate at room temperature. No amino-Claisen rearrangement occurred in the reactions of propiolonitrile, chloropropiolonitrile, or (diethylamino) propiolonitrile with allylamine or diallylamine.

The thio-Claisen rearrangement occurred in the reactions of chloropropiolonitrile and (diethylamino)propiolonitrile with prop-2-enethiol at room temperature. Some mechanisms are discussed.