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

Abstract

Activation parameters for the fission of cyclopropanols and cyclobutanols with phenyl groups a or phenylthio or phenylsulphonyl groups j3 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 MIND03. 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 Brsnsted acids have failed.

BIS-DESULFOGLUCOSINOLATES: A NEW CLASS OF BOLAFORMS

“…In a first attempt, the corresponding ditosylates (obtained from the diols in 75% yield) were heated at 155 C in DMSO, in the presence of sodium carbonate as described by Stirling et al [20] However, the purification of dialdehydes proved tedious due to the presence of side-products and the overall yields could never exceed 40%. Thus, 1,8-octanedial 1 and 1,12-dodecanedial 2 were synthesized from commercially available 1,8-octanediol and 1,12-dodecanediol, respectively.…”