Liquid‐phase CO‐oxidation of aldehydes and olefins radical versus non‐radical epoxidation

Abstract

Abstract In co‐oxidations of aldehydes and olefins with molecular oxygen in the liquid phase, epoxides are formed via two different routes: (1) by reaction of intermediate acylperoxy radicals with the olefin, and (2) by a non‐radical reaction of intermediate peracid with the olefin. For the systems benzaldehyde cis ‐1, 2‐D 2 ‐1‐octene and benzaldehyde cis ‐ and trans ‐2‐octene the ratio of radical to non‐radical epoxidation has been calculated with the aid of the kinetic relationships derived for this type of reaction and has been determined experimentally from the stereo selectivity of the expoxidation and from the production of carbon dioxide. The results show that the ratio of radical to non‐radical epoxidation increases with increasing reactivity of the olefin as well with increasing olefin/aldehyde ratio.