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A nonelectrocyclic path from the cyclobutene cation radical to the 1,3-butadiene cation radical

✍ Scribed by Dennis J. Bellville; Ronald Chelsky; Nathan L. Bauld

Publisher
John Wiley and Sons
Year
1982
Tongue
English
Weight
289 KB
Volume
3
Category
Article
ISSN
0192-8651

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✦ Synopsis

Abstract

The conversion of the cyclobutene cation radical to the 1,3‐butadiene cation radical has been studied using MINDO/3 and ab initio SCF MO methods. Not only smooth electrocyclic but also stepwise, non‐electrocyclic routes were considered. Both calculational methods agree that the preferred reaction path is a novel nonelectrocyclic one proceeding through an intermediate β€œcyclopropylcarbinyl cation radical.” The quantitative agreement in the activation parameters calculated by the two methods is excellent. The proposed intermediate also provides an attractive explanation for the mass spectrometric fragmentation patterns of the cyclobutene and butadiene cation radicals.

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