The reaction of cyclopentyl radicals with carbon tetrachloride

Abstract

The photolysis of azocyclopentane in the presence of cyclopentane-carbon tetrachloride mixtures has been investigated in the gas phase. Product analysis data have been used to determine the Arrhenius parameters for the reactionsThe rate data for chlorine atom abstraction from CC4 by the cyclopentyl radical were compared with available data for other alkyl radicals in both the gas and the solution phases. The results indicate that the rate constant for chlorine atom abstraction in the gas phase is fairly insensitive to the nature of the attacking alkyl radical and that the activation energy for a secondary radical is about 4 kcal/mol higher than the corresponding reaction in the solution phase.c-CsHg. + C c 4 -c-CsHgCl+ CC13. cc13. t c-C~HIO -CC13H + c-CsHg.

Selective Alkane Transformations via Radicals and Radical Cations: Insights into the Activation Step from Experiment and Theory

“…The rate constants for eq 17 measured in solution 550 are very similar to those in the gas phase, 551,552 in contrast to the rates of the propagation step (eq 18) which is 2-3 orders of magnitude faster in solution. The initiation depends somewhat on the nature of the radical starter (AIBN, t-BuOOBu-t, or BrCCl 3 ).…”