REARRANGEMENT OF CARBONIUM IONS AND FREE RADICALS IN THE BICYCLO(3.1.0)HEXYL SYSTEM.
Rept. from Sep 62-30 Sep 66,
IDAHO UNIV MOSCOW DEPT OF CHEMISTRY
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The objective of the research was the characterization of carbonium ion and free radical intermediates in the bicyclo3.1.0hexyl system and carbene intermediates in the bicyclo3.1.0hexylidene system. Electrophilic additions of hydrogen chloride and the conjugate acid of methanol to bicyclo3.1.0hexene-2 demonstrate that the trishomocyclopropenyl carbonium ion is not a detectable product determining intermediate and that the addition reactions proceed via a 2-bicyclo3.1.0hexyl intermediate. Two bivalent intermediates were generated by sodium methoxide induced decomposition of the p-toluenesulfonylhydrozon es of bicyclo3.1.0hexanone and 2-bicyclo3.1.0hexanone. Free radical addition of methanethiol to bicyclo3.1.0hexene-2 yields thiomethoxybicyclohexanes and thiomethoxymethylcyclopentenes. Free radical chlorination, using t-butyl hypochlorite, and chloroformyllation, using oxalyl chloride, generate exclusively 2- and 3-bicyclo3.1.0hexyl radical intermediates, which behave in a completely analogous fashion to the thiomethoxy radicals generated in methanethiol addition. Author
- Organic Chemistry