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.
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Translated fromIzvestiya Akademii Nauk. Seriya Khimicheskaya, No. 4, pp. 620–623, April, 1995.
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Ermolaeva, L.V., Appolonova, S.A., Plemenkov, V.V. et al. Theoretical study of bimolecular elimination (E2) reactions. Possibility ofsyn E2 elimination in the series of 2-R-2-R'-1-halocyclopropanes. Russ Chem Bull 44, 599–602 (1995). https://doi.org/10.1007/BF00698486
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DOI: https://doi.org/10.1007/BF00698486