Relative Rates of Reactions of Oxygen Atoms with Olefins

Abstract

Relative rates of addition of oxygen atoms in their ground electronic state to a number of olefins in the gas phase have been determined at room temperature. These reactions exhibit the following regularities: (1) systematic variation of the rates with the structure of the olefins; (2) specificity with respect to the position of addition of oxygen atoms; and (3) partial molecular rearrangement of the addition products according to definite rules. The observed structural effects and some close analogies with certain olefin addition reactions in solution are discussed in the light of electronic theories of organic chemical reactions. A comparison is made of the absolute values of the rate constants of the reactions of oxygen atoms with olefins, derived from various sources.