Carbonium Ion Intermediates from Allylcarbinyl and Cyclopropylcarbinyl Derivatives

Citation

Kover, Warner Bruce (1964) Carbonium Ion Intermediates from Allylcarbinyl and Cyclopropylcarbinyl Derivatives. Dissertation (Ph.D.), California Institute of Technology. doi:10.7907/3Q9Z-7H69. https://resolver.caltech.edu/CaltechETD:etd-09252002-143022

Abstract

NOTE: Text or symbols not renderable in plain ASCII are indicated by [...]. Abstract is included in .pdf document. The products of the amine-nitrous acid reaction of ([alpha]-methylallyl)-carbinylamine were determined. The deamination of dideutero-([beta]-methylallyl)-carbinylamine was found to yield apparently unrearranged dideutero-([beta]-methylallyl)-carbinol and 1-methylcyclobutanol with > 97% of the deuterium in the 3-position. The deamination of dideutero-([alpha]-methylallyl)-carbinylamine was found to yield methylallylcarbinol with 78% of the deuterium in the [alpha]-methylene position and (2-methylcyclopropyl)-carbinol with 66% of the deuterium on the cyclopropyl ring. The deamination of dideutero-(2-methylcyclopropyl)-carbinylamine was found to yield methylallylcarbinol with 74% of the deuterium in the vinyl methylene position and (2-methylcyclopropyl)-carbinol with 85% of the deuterium on the carbinyl carbon. These results are discussed in terms of various intermediates. It is concluded that the experimental evidence appears to require interpretation in terms of the equilibrating nonclassical bicyclobutonium and homoallylic carbonium ions.

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