| DOI | Resolve DOI: https://doi.org/10.1021/jo800925g |
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| Author | Search for: Lalevée, J.; Search for: Allonas, X.; Search for: Fouassier, J.-P.; Search for: Ingold, K. U.1 |
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| Affiliation | - National Research Council of Canada
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| Format | Text, Article |
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| Subject | Atomic 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; 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 |
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| 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. |
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| Publication date | 2008 |
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| In | |
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| Language | English |
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| Peer reviewed | Yes |
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| NPARC number | 21276548 |
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| Export citation | Export as RIS |
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| Report a correction | Report a correction (opens in a new tab) |
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| Record identifier | c9a3e476-ff65-4ecd-93c0-4545c4f52e1a |
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| Record created | 2015-10-13 |
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| Record modified | 2020-04-15 |
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