Jump to main content
Jump to site search

Issue 31, 2012
Previous Article Next Article

Reactivity of α-amino-peroxyl radicals and consequences for amine oxidation chemistry

Author affiliations

Abstract

A comparative theoretical study is presented on the formation and fate of α-amino-peroxyl radicals, recently proposed as important intermediates in the aerobic oxidation of amines. After radical abstraction of the weakly bonded αH-atom in the amine substrate, the α-amino-alkyl radical reacts irreversibly with O2, forming the corresponding α-amino-peroxyl radical. HO2˙-elimination from various types of α-amino-peroxyl radicals (forming the corresponding imine) and the kinetically competing substrate H-abstraction (forming the α-amino-hydroperoxide) were computationally characterized. Polar solvents were found to reduce the HO2˙-elimination barrier, but increase the barrier for H-abstraction. Depending on the reaction conditions (gas or liquid phase, amine concentration, nature of the solvent, and temperature), either of the two mechanisms is favored. The consequences for aerobic amine oxidation chemistry are discussed.

Graphical abstract: Reactivity of α-amino-peroxyl radicals and consequences for amine oxidation chemistry

Back to tab navigation

Supplementary files

Publication details

The article was received on 08 Mar 2012, accepted on 11 Jun 2012 and first published on 13 Jun 2012


Article type: Paper
DOI: 10.1039/C2CP41306J
Citation: Phys. Chem. Chem. Phys., 2012,14, 11002-11007
  •   Request permissions

    Reactivity of α-amino-peroxyl radicals and consequences for amine oxidation chemistry

    M. T. Schümperli, C. Hammond and I. Hermans, Phys. Chem. Chem. Phys., 2012, 14, 11002
    DOI: 10.1039/C2CP41306J

Search articles by author

Spotlight

Advertisements