REARRANGEMENT OF CARBONIUM IONS AND FREE RADICALS IN THE BICYCLO(3.1.0)HEXYL SYSTEM.
Abstract
The objective of the research was the characterization of carbonium ion and free radical intermediates in the bicyclo(3.1.0)hexyl system and carbene intermediates in the bicyclo(3.1.0)hexylidene system. Electrophilic additions of hydrogen chloride and the conjugate acid of methanol to bicyclo(3.1.0)hexene-2 demonstrate that the trishomocyclopropenyl carbonium ion is not a detectable product determining intermediate and that the addition reactions proceed via a 2-bicyclo(3.1.0)hexyl intermediate. Two bivalent intermediates were generated by sodium methoxide induced decomposition of the p-toluenesulfonylhydrozon es of bicyclo(3.1.0)hexanone and 2-bicyclo(3.1.0)hexanone. Free radical addition of methanethiol to bicyclo(3.1.0)hexene-2 yields thiomethoxybicyclohexanes and thiomethoxymethylcyclopentenes. Free radical chlorination, using t-butyl hypochlorite, and chloroformyllation, using oxalyl chloride, generate exclusively 2- and 3-bicyclo(3.1.0)hexyl radical intermediates, which behave in a completely analogous fashion to the thiomethoxy radicals generated in methanethiol addition. (Author)
Document Details
- Document Type
- Technical Report
- Publication Date
- Sep 30, 1966
- Accession Number
- AD0655139
Entities
People
- Peter K. Freeman
Organizations
- University of Idaho