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The Resolution of 2,3 Benzcycloheptanol: The Stereochemistry of Additions to Asymmetric Olefinic Compounds.

Withey, Donald Sidney. (1967) The Resolution of 2,3 Benzcycloheptanol: The Stereochemistry of Additions to Asymmetric Olefinic Compounds. Doctoral thesis, University of Surrey (United Kingdom)..

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Abstract

In Part I, the resolution of (+-)-2,3-Benzcycloheptanol is described, and the tendency of the hydrogen phthalate of this carbinol to undergo hydrolysis by an alkyl-oxygen fission mechanism is established. The ease with which this alkyl-oxygen fission occurred was found to be intermediate between that observed with the carbinols l-phenylethanol and 1,2,3,4-tetrahydro-l-naphthol. This was in harmony with the published ethanolysis rates of the chlorides corresponding to these three carbinols, and the possible reasons for this behaviour are discussed. In Part II, various aspects of the partial asymmetric syntheses resulting when optically active olefinic carbinols are brominated or hydrogenated are considered. An apparent exception to the general pattern of behaviour was the bromination of l-phenylallyl alcohol. A re-examination of this reaction suggested that there was no anomaly, and the conflicting results are discussed. The hydrogenation of 3-methylpent-3-en-2-ol to 3-methylpentan-2-ols of known absolute configuration is discussed and the existing theory for the dissymmetric nature of this catalytic hydrogenation is discussed. A modification to this theory is proposed and supporting evidence is presented. As an extension to the well established dissymmetric additions to a,B-unsaturated asymmetric carbinols, a study of the reactions of some B,y-analogues was attempted. These were all unsuccessful. 1-(4'-Methoxy-l'-naphthyl)but-3-en-l-ol gave an unstable dibromo-derivative. 2-Methylpent-l-en-4-ol gave an unstable dibromo-ketone and trans-4-Methylhex-4-en-2-ol could not be prepared with sufficient purity for hydrogenation experiments.

Item Type: Thesis (Doctoral)
Divisions : Theses
Authors :
NameEmailORCID
Withey, Donald Sidney.
Date : 1967
Contributors :
ContributionNameEmailORCID
http://www.loc.gov/loc.terms/relators/THS
Additional Information : Thesis (Ph.D.)--University of Surrey (United Kingdom), 1967.
Depositing User : EPrints Services
Date Deposited : 22 Jun 2018 15:16
Last Modified : 06 Nov 2018 16:54
URI: http://epubs.surrey.ac.uk/id/eprint/848414

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