ISSN:
1573-9171
Keywords:
AM1 method
;
transition states
;
nucleophilic elimination (E2) reaction
;
halocyclopropanes
Source:
Springer Online Journal Archives 1860-2000
Topics:
Chemistry and Pharmacology
Notes:
Abstract Reactions of the methoxide ion with substituted halocyclopropanes, which result in E2 elimination, have been studied by the semiempirical quantum-chemical AM1 method. The transition states corresponding totrans andcis routes have been localized. The energetic predominance of thetrans route over thecis route is reduced by 2.6 kcal mol−1 on going from 1-chloropropane to chlorocyclopropane because of the features of cyclopropane geometry. It has been demonstrated that, in the gas phase,cis elimination may predominate overtrans elimination for a particular stereoisomer of 2-cyano-2-methyl-1-halocyclopropanes due to weakening of orbital interactions and Coulomb repulsion between the cyano group and the MeO− anion in thetrans E2 transition state.
Type of Medium:
Electronic Resource
URL:
http://dx.doi.org/10.1007/BF00698486
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