Solvolytic Studies in the Bicyclononane Field

Penrose, Alexander Ballingall (1969) Solvolytic Studies in the Bicyclononane Field. PhD thesis, University of Glasgow.

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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.

Item Type: Thesis (PhD)
Qualification Level: Doctoral
Keywords: Organic chemistry
Date of Award: 1969
Depositing User: Enlighten Team
Unique ID: glathesis:1969-78525
Copyright: Copyright of this thesis is held by the author.
Date Deposited: 30 Jan 2020 15:12
Last Modified: 30 Jan 2020 15:12

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