Studies of Cyclopropylcarbinyl-Allylcarbinyl Free Radicals

Citation

Rosen, Allan Joseph (1964) Studies of Cyclopropylcarbinyl-Allylcarbinyl Free Radicals. Dissertation (Ph.D.), California Institute of Technology. doi:10.7907/A61A-Z940. https://resolver.caltech.edu/CaltechETD:etd-10012002-153114

Abstract

NOTE: Text or symbols not renderable in plain ASCII are indicated by [...]. Abstract is included in .pdf document. The di-t-butyl peroxide-initiated decarbonylations of cyclopropylacetaldehyde and dimethylcyclopropylacetaldehyde in the presence of benzyl mercaptan have been carried out and the chain-transfer constants of neopentane, n-butane, 2,3-dimethylbutane, methylcyclopropane, and isopropylcyclopropane with styrene at 79.1[degrees] have been determined in an attempt to ascertain the nature and number of the intermediates involved in interconversions of certain cyclopropylcarbinyl and allylcarbinyl derivatives in free-radical reactions. These interconversions are shown to be reversible. It is concluded that the nonclassical homoallyl radical and the classical allylcarbinyl radical are the intermediates involved in the free-radical interconversion of the cyclopropylcarbinyl and allylcarbinyl skeletons. No evidence is found for the existence of a nonclassical dimethylhomoallyl radical; the classical dimethylcyclopropylcarbinyl and ([gamma, gamma]-dimethylallyl)-carbinyl radicals are probably the only intermediates involved in the free-radical interconversion of the dimethylcyclopropylcarbinyl and ([gamma, gamma]-dimethylallyl)-carbinyl skeletons.

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