PNNL

Abstract

The reactions of net olefins or solutions of olefins in acetone at low temperature with oxygen atoms were examined. O(3P) atoms were produced by microwave irradiation of He/O2 mixtures, followed by contact of the plasma with the fluid at low pressure and temperature. Addition of oxygen atoms to olefins results in skeletal rearrangements involving hydrogen and alkyl migration reactions and ring rearrangements of the intermediate oxygen adducts in competition with epoxide formation. While epoxide formation predominates for simple olefins such as 1- and 4-octene with minor yields of rearrangement products, for highly sunstituted or strained olefins, such as norbornadiene is carried out in the presence of a radical inhinitor to suppress secondary oxidation of norbornadiene is carried out in the presence of a radical inhibitor to suppress secondary oxidation leading to benzene, the novel ring-rearrangement product, bicyclo [3,2,31.0] hex-3-ene-endo-6-carboxaldehyde, is produced from norbornadiene in significant yields.