Reactions of alkoxy radicals. IV. The kinetics and absolute rate constants for some t-butyl hypochlorite chlorinations

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DOIResolve DOI: http://doi.org/10.1021/ja00995a012
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TypeArticle
Journal titleJournal of the American Chemical Society
ISSN0002-7863
Volume89
Issue19
Pages48914894; # of pages: 4
AbstractThe kinetics during the early stages of the photochemically initiated radical chain chlorinations of toluene, p-xylene, t-butylbenzene, triphenylmethane, cyclohexane, and chloroform with t-butyl hypochlorite have been studied at 24°. With the exception of chloroform, the kinetics are consistent with chain termination by the combination of t-butoxy radicals and hydrogen atom abstraction by these radicals as the rate-determining propagation step. The absolute rate constants for the rate-determining steps in the chlorination of the above substrates have been measured. The rate constant for the combination of t-butoxy radicals in solution (2k6) is about 2 × 108 M-1 sec-1. The rate constant for hydrogen abstraction from toluene by t-butoxy radicals is given by k2 = 6.7 × 107 exp(-5600/RT) M-1 sec-1.
Publication date
LanguageEnglish
AffiliationNational Research Council Canada (NRC-CNRC)
Peer reviewedYes
NPARC number21276759
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Record identifier390cd69a-c040-44f6-bc4d-a329e444273e
Record created2015-10-13
Record modified2016-05-09
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