Absolute rate constants for some intermolecular reactions of α-aminoalkylperoxyl radicals. Comparison with alkylperoxyls

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DOIResolve DOI: http://doi.org/10.1021/jo800925g
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TypeArticle
Journal titleJournal of Organic Chemistry
ISSN0022-3263
Volume73
Issue17
Pages64896496; # of pages: 8
SubjectAtomic physics; Atoms; Hydrogen; Oxygen; Phenols; Photolysis; Reaction kinetics; Substrates; 355 nm laser; Di-tert-butyl peroxide; Hydrogen atom abstraction; Oxygen atom transfer; Trialkylamine; Rate constants; aliphatic amine; aromatic amine; hydrogen; oxygen; peroxy radical; phenol derivative; triphenylphosphine; absorption; absorption spectroscopy; article; chemical reaction kinetics; mathematical computing; molecular interaction; oxygen saturation; photolysis; ultraviolet spectroscopy; Absorption; Alkylation; Amines; Antioxidants; Carboxylic Acids; Free Radicals; Hydrogen; Kinetics; Organophosphorus Compounds; Oxygen; Peroxides; Photolysis; Spectrophotometry
Abstract(Graph Presented) Seven α-aminoalkylperoxyl radicals have been generated by 355 nm laser flash photolysis (LFP) of oxygen-saturated di-tert-butyl peroxide containing mono-, di-, and trialkylamines and a dialkylarylamine. All these peroxyls possess absorptions in the near-UV (strongest for the trialkylamine-derived peroxyls) which permits direct monitoring of the kinetics of their reactions with many substrates. The measured rate constants for hydrogen atom abstraction from some phenols and oxygen atom transfer to triphenylphosphine demonstrated that all seven α- aminoalkylperoxyls have similar reactivities toward each specific substrate. More importantly, a comparison with literature data for alkylperoxyls shows that α-aminoalkylperoxyls and these alkylperoxyls have essentially the same reactivities. The combination of LFP and alkylamines provides a quick, reliable method for determining absolute rate constants for alkylperoxyl radical reactions, an otherwise laborious task. © 2008 American Chemical Society.
Publication date
LanguageEnglish
AffiliationNational Research Council Canada (NRC-CNRC)
Peer reviewedYes
NPARC number21276548
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Record identifierc9a3e476-ff65-4ecd-93c0-4545c4f52e1a
Record created2015-10-13
Record modified2016-05-09
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