title: Absolute rate constants for some intermolecular reactions of alpha-aminoalkylperoxyl radicals. Comparison with alkylperoxyls.
abstract: Seven alpha-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 alpha-aminoalkylperoxyls have similar reactivities toward each specific substrate. More importantly, a comparison with literature data for alkylperoxyls shows that alpha-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.
authors.affiliation: Département de Photochimie Générale, UMR 7525 CNRS, Université de Haute Alsace, ENSCMu, 3 rue Alfred Werner, 68093 Mulhouse Cedex, France. j.lalevee@uha.fr
authors.forename: Jacques
authors.initials: J
authors.lastname: Lalevée
authors.forename: Xavier
authors.initials: X
authors.lastname: Allonas
authors.forename: Jean-Pierre
authors.initials: JP
authors.lastname: Fouassier
authors.forename: K U
authors.initials: KU
authors.lastname: Ingold
mesh_terms: D000042:Absorption; D000478:Alkylation; D000588:Amines / Q000737:chemistry*; D000975:Antioxidants / Q000737:chemistry*; D002264:Carboxylic Acids / Q000737:chemistry*; D005609:Free Radicals / Q000737:chemistry; D006859:Hydrogen / Q000737:chemistry; D007700:Kinetics; D009943:Organophosphorus Compounds / Q000737:chemistry; D010100:Oxygen / Q000737:chemistry; D010545:Peroxides / Q000737:chemistry*; D010782:Photolysis; D013053:Spectrophotometry
chemical_list: D000588:Amines; D000975:Antioxidants; D002264:Carboxylic Acids; D005609:Free Radicals; D009943:Organophosphorus Compounds; D010545:Peroxides; C111570:di-tert-butyl peroxide; C061896:triphenylphosphine; D006859:Hydrogen; D010100:Oxygen