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The E2C mechanism in elimination reactions. IX. Re-examination of the olefin-like transition-state

Muir, D.M. and Parker, A.J. (1983) The E2C mechanism in elimination reactions. IX. Re-examination of the olefin-like transition-state. Australian Journal of Chemistry, 36 (9). pp. 1667-1673.

Link to Published Version: http://dx.doi.org/10.1071/CH9831667
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Abstract

The kinetics and product olefins arising from E2C-like elimination reactions of secondary bromides and tosylates having various alkyl and conjugating substituents at Cα and Cβ are re-examined in the light of the theoretical Pross-Shaik valence-bond model and the apparent lack of a β-phenyl effect. Comparison of the effect of substituents at Cα and Cβ shows that whilst there are differences in reactivity and products of E2C reactions there is also a large degree of double-bond character in the transition state. There is a good correlation between the kinetics of E2C reactions and the double-bond stabilization energy arising from both alkyl and conjugating substituents. Contributing valence-bond structures, giving asymmetry and partial charge at Cα and Cβ appear to vary in importance according to leaving group and substituent type.

Item Type: Journal Article
Murdoch Affiliation(s): School of Mathematical and Physical Sciences
Publisher: Commonwealth Scientific and Industrial Research Organization Publishing
Copyright: © 1983 CSIRO
URI: http://researchrepository.murdoch.edu.au/id/eprint/31617
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