Accession Number : AD0600223

Title :   ADDITION AND DISPLACEMENT REACTIONS WITH UNSATURATED HYDROCARBONS.

Descriptive Note : Rept. for 1 Sep 62-31 Aug 63,

Corporate Author : WISCONSIN UNIV MADISON

Personal Author(s) : Goering,Harlan L.

Report Date : 14 APR 1964

Pagination or Media Count : 20

Abstract : The cuprous-bromide-catalyzed reaction of t-butyl perbenzoate and bicyclo-(3.2.1)-octene-2 (I) results in the formation of exo(axial) -bicyclo-(3.2.1)-oct-3-en-2-yl benzoate (IIIa) which contains < 1% of the endo isomer. Optically active I gives racemic IIIa which means that the allylic carbon atoms (C2 and C4) are completely randomized. These results are consistent with the Kochi mechanism; i.e., abstraction of an allylic hydrogen atom to give the symmetrical bicyclo(3.2.1)oct-3en2-yl radical (II) which is stereoselectively converted to racemic exo benzoate (IIIa). (Progress is also reported of studies concerning the solvolysis of alpha-p-anisylethyl p-nitrobenzoate (ROCOC6H4NO2) under various conditions.) (Author)

Descriptors :   (*BENZOATES, STEREOCHEMISTRY), (*BENZOATES, CHEMICAL REACTIONS), (*STEREOCHEMISTRY, BENZOATES), HYDROCARBONS, MOLECULAR ISOMERISM, MOLECULAR ROTATION, COPPER COMPOUNDS, BROMIDES, NITROBENZENES, IONIZATION, ACETONES

Distribution Statement : APPROVED FOR PUBLIC RELEASE