Solvent effects on the competitive β-scission and hydrogen atom abstraction reactions of the cumyloxyl radical. resolution of a long-standing problem

Download
  1. Get@NRC: Solvent effects on the competitive β-scission and hydrogen atom abstraction reactions of the cumyloxyl radical. resolution of a long-standing problem (Opens in a new window)
DOIResolve DOI: http://doi.org/10.1021/ja00055a015
AuthorSearch for: ; Search for: ; Search for: ; Search for:
TypeArticle
Journal titleJournal of the American Chemical Society
ISSN0002-7863
Volume115
Issue2
Pages466470; # of pages: 5
AbstractLaser flash photolysis (LPF) techniques with detection in the infrared and in UV-visible regions of the spectrum have been used in combination with detailed product studies to assess solvent effects on the hydrogen abstraction and β-scission reactions of cumyloxyl radicals. The variation in the ratio of the products of these two competing processes in solvents with different polarities is due to the solvent's influence on β-scission. The rate constants for β-scission at 30°C, k β CumO, were (2.6 3 ± 0.2 4) × 10 5, and (19 .6 ± 3 .4 × 10 5s -1 in CCl4, C 6H 6, C 6H 5Cl, (CH 3) 3COH, CH 3CN, and CH 3COOH, respectively. The rate constant for hydrogen abstraction from cyclohexane were essentially identical in these six solvents, viz., k a CumO = (1.2 4 ± 0.1 2) × 10 6 M -1 s -1. There is a reasonably good linear correlation between log (k β CumO/s -1) and certain cybotactic solvent parameters indicating that solvent effect on k β CumO are due to a localized interaction between the transition state for β-scission and adjacent solvent.
Publication date
LanguageEnglish
AffiliationNational Research Council Canada (NRC-CNRC)
Peer reviewedYes
NPARC number21276446
Export citationExport as RIS
Report a correctionReport a correction
Record identifiere2b9f277-22f9-4c64-8ffa-2587ec7f09c7
Record created2015-10-13
Record modified2016-05-09
Bookmark and share
  • Share this page with Facebook (Opens in a new window)
  • Share this page with Twitter (Opens in a new window)
  • Share this page with Google+ (Opens in a new window)
  • Share this page with Delicious (Opens in a new window)