Hydrogen atom abstraction kinetics from intramolecularly hydrogen bonded ubiquinol-0 and other (poly)methoxy phenols

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DOIResolve DOI: http://doi.org/10.1021/ja9937674
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TypeArticle
Journal titleJournal of the American Chemical Society
ISSN0002-7863
Volume122
Issue10
Pages23552360; # of pages: 6
Subjectantioxidant; hydrogen; phenol derivative; ubiquinol cytochrome c reductase; article; chemical reaction kinetics; chemical structure; hydrogen bond; molecular interaction; photolysis; reaction analysis
AbstractThe effect of methoxy substitution on the abstraction of the phenolic hydrogen atom involved in intramolecular hydrogen bonding by tert-butoxyl and cumyloxyl radicals has been investigated by laser flash photolysis. Also transition state calculations for methoxyl radical and 2-methoxyphenol have been carried out by a density functional theory (DFT) method. Hydrogen atom abstraction is surprisingly easy from intramolecularly hydrogen bonded methoxyphenols, in contrast to intermolecularly hydrogen bonded molecules. The kinetic solvent effect, investigated in six solvents with different hydrogen bond accepting properties, on the hydrogen atom abstraction reaction from o-methoxy phenols was shown to be smaller than for non-hydrogen bonded phenols, and is independent of further methoxy substitution. The high rate constant for hydrogen atom abstraction from ubiquinol-0 (2.8 x 109 M-1 s- 1 in CCl4) and the small kinetic solvent effect make it a good antioxidant, even in a polar environment.
Publication date
LanguageEnglish
AffiliationNational Research Council Canada (NRC-CNRC)
Peer reviewedYes
NPARC number21276755
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Record identifier47376ce1-b4d9-4e6a-8549-cd9aee4f8ba6
Record created2015-10-13
Record modified2016-05-09
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