Issue 10, 1980

Ring-opening of some radicals containing the cyclopropylmethyl system

Abstract

Mono- and bi-cyclic radicals containing the cyclopropylmethyl system are readily generated by interaction of the appropriate halides with triphenyl- or tributyl-stannane. Each radical studied underwent ring-opening by fission of the more substituted βγ-bond. In the case of the secondary radical (12b) the new double bond was formed preferentially in the trans-configuration. Rate constants, which cannot be determined with high accuracy by this method, lie in the range 1 × 107–3 × 108 s–1 at 25 °C. When generated by the flow method in the e.s.r. cavity α-hydroxycyclopropylmethyl radicals undergo β-fission followed by 1,5-hydrogen atom transfer to afford enoxyl radicals. The latter reaction occurs more slowly in water than in non-polar solvents. The rigid hydroxynortricyclyl radical (43) undergoes preferential fission of the less substituted βγ-bond, possibly because of the dipolar nature of the transition state.

Article information

Article type
Paper

J. Chem. Soc., Perkin Trans. 2, 1980, 1473-1482

Ring-opening of some radicals containing the cyclopropylmethyl system

A. L. J. Beckwith and G. Moad, J. Chem. Soc., Perkin Trans. 2, 1980, 1473 DOI: 10.1039/P29800001473

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