Studies in Carbonium Ion Rearrangements

McKillop, Thomas Fulton Wilson (1968) Studies in Carbonium Ion Rearrangements. PhD thesis, University of Glasgow.

Abstract

Neoclovene, a product from acid-catalysed rearrangement of caryophyllene, has been synthesised in such a manner as to demonstrate the probable intermediacy of a specific carbonium ion in the formation of neoclovene from caryophyllene. These experiments also provide evidence for the relative configuration of neoclovene. Caryolan-1-ol, a second rearrangement product of caryophyllene, is found to yield at least ten products on dehydration with polyphosphoric acid. X-ray crystallography has been employed to determine the structure of one of the major products entitled pseudoclovene A and a synthesis of this olefin has been achieved. Mechanistic arguments are described to account for the formation of the known products. Extended Huckel Calculations have been performed for two simulated carbonium ion rearrangement reactions in the bicyclo(3,3,1)nonane series to examine the relative efficiencies of a double bond and a cyclopropane ring in stabilising a carbonium ion. The results obtained do not compare favourably with the available kinetic data and the possible reasons for this apparent anomaly are discussed.

• Item Type: Thesis (PhD)
• Qualification Level: Doctoral
• Keywords: Organic chemistry
• Date of Award: 1968
• Depositing User: Enlighten Team
• Unique ID: glathesis:1968-78485
• Copyright: Copyright of this thesis is held by the author.
• Date Deposited: 30 Jan 2020 15:15
• Last Modified: 30 Jan 2020 15:15
• URI: https://theses.gla.ac.uk/id/eprint/78485