Absolute rate constants for hydrocarbon autoxidation. 26. Rate constants for reaction of the tert-butylperoxy radical with 1-bromo-2-methylbutane and 1-bromo-3-methylbutane and some related substituted butanes

Rate constants and Arrhenius parameters for reaction of the tert-butylperoxy radical with 1-bromo-2-methylbutane and 1-bromo-3-methylbutane in solution from 30-80 °C have been estimated. The magnitude of these kinetic parameters are consistent with activation of the tertiary hydrogen vicinal to the...

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Bibliographic Details
Published inCanadian journal of chemistry Vol. 57; no. 18; pp. 2484 - 2490
Main Authors Howard, J. A, Chenier, J. H. B
Format Journal Article
LanguageEnglish
Published Ottawa, Canada NRC Research Press 15.09.1979
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Summary:Rate constants and Arrhenius parameters for reaction of the tert-butylperoxy radical with 1-bromo-2-methylbutane and 1-bromo-3-methylbutane in solution from 30-80 °C have been estimated. The magnitude of these kinetic parameters are consistent with activation of the tertiary hydrogen vicinal to the bromine substituent and the involvement of a "bridged" transition state in the hydrogen atom transfer reaction.Chloro, trimethylsilyl, and trimethylstannyl substituents also activate a vicinal tertiary hydrogen and activation increases in the order trimethylsilyl ∼ trimethylstannyl < chloro < bromo.
ISSN:0008-4042
1480-3291
DOI:10.1139/v79-396