Accession Number : AD0655139

Title :   REARRANGEMENT OF CARBONIUM IONS AND FREE RADICALS IN THE BICYCLO(3.1.0)HEXYL SYSTEM.

Descriptive Note : Rept. from Sep 62-30 Sep 66,

Corporate Author : IDAHO UNIV MOSCOW DEPT OF CHEMISTRY

Personal Author(s) : Freeman,Peter K.

Report Date : 30 SEP 1966

Pagination or Media Count : 13

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)

Descriptors :   (*POLYCYCLIC COMPOUNDS, CHEMICAL REACTIONS), (*FREE RADICALS, POLYCYCLIC COMPOUNDS), CYCLOALKENES, CYCLOALKANES, ADDITION REACTIONS, STEREOCHEMISTRY, MOLECULAR STRUCTURE, SUBSTITUTION REACTIONS, KETONES, HYDRAZONES, ORGANIC SULFUR COMPOUNDS, CHLORINATION

Subject Categories : Organic Chemistry

Distribution Statement : APPROVED FOR PUBLIC RELEASE