A Kinetic Electron Spin Resonance Study of the Transfer of a Hydrogen Atom from α-Tetralin Hydroperoxide to a Tertiary Alkylperoxy Radical
Open Access
- 1 March 1975
- journal article
- Published by Canadian Science Publishing in Canadian Journal of Chemistry
- Vol. 53 (5) , 623-627
- https://doi.org/10.1139/v75-088
Abstract
A kinetic electron spin resonance spectroscopic study of the reaction of tertiary alkylperoxy radicals with α-tetralin hydroperoxide is reported. The absolute rate constants for this hydrogen atom transfer process (k1) are given by the equation log (k1/M−1 s−1) = (6.0 ± 0.5 ) − (4.5 ± 0.5 )/θ, where θ = 2.303 RT kcal mol−1.A significant isotope effect is obtained when the hydroperoxidic hydrogen is replaced by deuterium, e.g. k1H/k1D at 21° = 9.Other alkyl hydroperoxides, e.g. triphenylmethyl, s-butyl, and 9,10-dihydro-9-anthracyl have approximately the same reactivity to t-ROO• as α-C10H11OOH.Keywords
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