NPE Effects in Bimolecular Elimination

Christine D. Chalk; James McKenna; Leslie B. Sims; Ian H. Williams

doi:10.1021/ja00392a005

NPE Effects in Bimolecular Elimination

Christine D. Chalk, James McKenna, Leslie B. Sims, Ian H. Williams

Department of Chemistry

University of Sheffield

Research output: Contribution to journal › Article › peer-review

Abstract

A force field for the transition states of E2 reactions between hydroxide and alkoxide bases and simple chloroalkanes has been developed by calibration against typical experimental kinetic isotope effects observed in such reactions and forms the basis of calculations of NPE effects. No allowances are made for steric effects associated with alkylation in the substrate or base. With this model force field only slight NPE contributions to relative reactivity are observed from homology among substrates (ethyl vs. isomeric propyl chlorides) or among alkoxide bases. A more substantial difference is observed in a comparison of hydroxide and methoxide ion promoted eliminations from ethyl chloride.

Original language	English
Pages (from-to)	281-284
Number of pages	4
Journal	Journal of the American Chemical Society
Volume	103
Issue number	2
DOIs	https://doi.org/10.1021/ja00392a005
Publication status	Published - 1 Jan 1981

ASJC Scopus subject areas

Catalysis
General Chemistry
Biochemistry
Colloid and Surface Chemistry

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10.1021/ja00392a005

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AB - A force field for the transition states of E2 reactions between hydroxide and alkoxide bases and simple chloroalkanes has been developed by calibration against typical experimental kinetic isotope effects observed in such reactions and forms the basis of calculations of NPE effects. No allowances are made for steric effects associated with alkylation in the substrate or base. With this model force field only slight NPE contributions to relative reactivity are observed from homology among substrates (ethyl vs. isomeric propyl chlorides) or among alkoxide bases. A more substantial difference is observed in a comparison of hydroxide and methoxide ion promoted eliminations from ethyl chloride.

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NPE Effects in Bimolecular Elimination

Abstract

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