Elimination and addition reactions. Part 44. Eliminative fission of cycloalkanols

Abstract

Activation parameters for the fission of cyclopropanols and cyclobutanols with phenyl groups α or phenylthio or phenylsulphonyl groups β to the hydroxy group have been obtained. The results show very large differences in reactivity between cyclopropanols and cyclobutanols; such differences are also found in energy profiles for the opening of cycloalkoxide ions obtained by using MINDO3. The results are entirely compatible with other three-membered/four-membered ring comparisons and the role of strain in these systems is discussed. Attempts to extend the well established enforced catalysis of cycloalkanol ring fission to electrophiles other than Brønsted acids have failed.