A Kinetic Electron Spin Resonance Study of the Transfer of a Hydrogen Atom from α-Tetralin Hydroperoxide to a Tertiary Alkylperoxy Radical
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 (k 1 ) are given by the equation log (k 1 /M −1 s −1 ) = (6.0 ± 0.5 ) − (4.5 ± 0.5 )/θ...
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| Published in | Canadian journal of chemistry Vol. 53; no. 5; pp. 623 - 627 |
|---|---|
| Main Authors | , |
| Format | Journal Article |
| Language | English |
| Published |
Ottawa, Canada
NRC Research Press
01.03.1975
|
| Online Access | Get full text |
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| Summary: | 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 (k
1
) are given by the equation log (k
1
/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. k
1
H
/k
1
D
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-C
10
H
11
OOH. |
|---|---|
| ISSN: | 0008-4042 1480-3291 |
| DOI: | 10.1139/v75-088 |