Studies in the Bicycl (3.2.2)Nonane System

Flood, William Wilson (1971) Studies in the Bicycl (3.2.2)Nonane System. PhD thesis, University of Glasgow.

Abstract

Studies in the Bicyclo(3.2.2)nonane System. Synthetic studies on the bicyclo(3.2.2)nonane system were undertaken with the aim of preparing compounds suitable for conformational and solvolytic studies on this system. Electrolytic decarboxylation of maleic anhydride adducts was used in the preparation of many of these compounds. In the conformational studies, it has been found that the three carbon bridge in bicyclo(3.2.2)nona-6,8-diene was extremely mobile, the bridge interconverting rapidly between equivalent conformations. Using n. m. r. spectroscopy at low temperatures, attempts to determine the activation energy of this process were unsuccessful, as were attempts on bicyclo(3.2.2)nona-6,8-dien-3-one and bicyclo(3.2.2)nona-6,8-dien-2-one, each of which was also found to have an extremely mobile three carbon bridge. I. R. and n. m. r. studies on ten alcohols and some of their derivatives yielded much information on the conformational preferences of the three carbon bridge in each of these compounds. In the solvolytic studies, the acetolysis of the tosylates of six of the above alcohols was investigated. The rate of acetolysis of each tosylate was measured. In the series having the tosylate group substituted at C-3, the rate studies showed that, in the unsaturated tosylates, there was no acceleration of ionisation caused by anchimeric assistance of the double bond. In the series in which the tosylate group was substituted at the C-2 position, the rate studies showed that endo-bicyclo(3.2.2)non-6-en-2-yl tosylate underwent acetolysis slightly faster than bicyclo(3.2.2)nonan-2-yl tosylate. In the series with the tosylate at C-3, the products of acetolysis showed that the only solvolysis processes were elimination or direct substitution of tosylate by acetate. In the series with the tosylate at C-2, the solvolysis processes were found to be rather more complex. Tosylates of exo-bicyclo(3.2.2)non-6-en-2-ol and bicyclo(3.2.2)nona-6,8-dien-2-ol did not form under the usual reaction conditions. Under these conditions, it was shown unambiguously that exo-bicyclo(3.2.2)non-6-en-2-ol underwent the unexpected rearrangement to bicyclo(3.2.2)non-6-en-1-ol. Evidence for bicyclo(3.2.2)nona-6,8-dien-2-ol undergoing rearrangement to bicyclo(3.2.2)nona-6,8-dien-1-ol, under similar conditions, was also obtained.

• Item Type: Thesis (PhD)
• Qualification Level: Doctoral
• Keywords: Organic chemistry
• Date of Award: 1971
• Depositing User: Enlighten Team
• Unique ID: glathesis:1971-78559
• Copyright: Copyright of this thesis is held by the author.
• Date Deposited: 30 Jan 2020 15:10
• Last Modified: 30 Jan 2020 15:10
• URI: https://theses.gla.ac.uk/id/eprint/78559