ISSN:
0538-8066
Keywords:
Chemistry
;
Physical Chemistry
Source:
Wiley InterScience Backfile Collection 1832-2000
Topics:
Chemistry and Pharmacology
Notes:
Decomposition of (R1R2CXON=)2 (R1 = R2 = Ph; R1 = R2 = p—ClC6H4; R1 = Ph, R2 = CH3; X = H or D) in hydrocarbon solvents at 31-75°C afforded R1R2CO in 6-8% lower yield when X = D than when X = H. This result is ascribed to cage escape of secondary alkoxyl radicals in competition with dismutation. Deuterium isotope effects for alkoxyl cage dismutation of 1.35-2.4 are estimated from the data. It is suggested that this same competition may account for the experimentally slower termination rate constants in solution of primary and secondary alkylperoxyl radicals on α-deuteration.
Additional Material:
1 Tab.
Type of Medium:
Electronic Resource
URL:
http://dx.doi.org/10.1002/kin.550171104
