Solvolytic Studies in the Bicyclononane Field

[摘要] Cis- and trans-3-allylcyclohexanol have been synthesised and the kinetics and products of buffered acetolysis of the corresponding tosylates investigated. No double bond participation was observed either in the solvolysis products or in the kinetic behaviour. Exo- and endo-2-bicyclo(3,3,1)nonanol,exo- and endo-6-bicyclo(3,2,2)nonanol and exo- and endo-2-bicyclo(4,2,1)nonanol have been synthesised (the latter two in insufficient epimeric purity for study) and the kinetics and products of buffered acetolysis of the corresponding tosylates have been studied. Interesting kinetic behaviour has been uncovered here and explanations for this are outlined in the text. An exciting non-classical/classical ion interplay has been observed and with the evidence obtained to date, it appears that in this series of isomeric bicyclononyl p-toluenesulphonates, which represents three Wagner/Meerwein related pairs of tosylates, the extent of neighbouring carbon-carbon bond participation and non-classical behaviour varies greatly throughout this series. Thermodynamic parameters are extensively employed as supporting evidence for the proposed intermediacy of a flexible 'twin-twist boat' conformation in the solvolysis of endo-2-bicyclo(3,3,1)nonyl tosylate, and proposals are outlined for future experiments designed to provide more information on the nature of this intermediate.

[发布机构] University:University of Glasgow

[关键词] Organic chemistry