Addition-Abstraction Competition of Acylperoxy Radicals Reacting With Alkenes. Cooxidation of Cyclohexene and Valeraldehyde
Document Type
Article
Publication Date
1-1-1973
Description
Cyclohexene and valeraldehyde were cooxidized at various feed ratios and, from the product analysis, rate constant ratios were calculated for (1) the relative reactivities of cyclohexene and valeraldehyde toward valerylperoxy and cyclohexenylperoxy radicals and (2) the addition-abstraction reactions of valerylperoxy radicals with cyclohexene. The rate constant ratios (1) indicate that valeraldehyde is more reactive than cyclohexene toward both valerylperoxy radical (by a factor of 1.2) and cyclohexenylperoxy radical (by a factor of 7). The rate constant ratio (2) indicates that addition is 1.5 times faster than abstraction. Since the abstraction-addition rate constant ratio for the attack of cyclohexenylperoxy radical on cyclohexene is 22:1, this work shows quantitatively the greatly altered selectivity of the acylperoxy radical compared to the selectivity of the alkylperoxy radical.
Citation Information
Simmons, Kenneth E.; and Van Sickle, Dale E.. 1973. Addition-Abstraction Competition of Acylperoxy Radicals Reacting With Alkenes. Cooxidation of Cyclohexene and Valeraldehyde. Journal of the American Chemical Society. Vol.95(23). 7759-7763. https://doi.org/10.1021/ja00804a036 ISSN: 0002-7863