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Reaction between aminoalkyl radicals and akyl halides: Dehalogenation by electron transfer?

From National Research Council Canada

DOIResolve DOI: https://doi.org/10.1016/j.cplett.2011.05.055
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Affiliation
  1. National Research Council of Canada
FormatText, Article
SubjectBimolecular rate constants; CBr; Cosolvents; Di-tert butyl peroxide; Electron-transfer; Iminium; Low oxidation potential; Acetonitrile; Electron spin resonance spectroscopy; Ions; Organic solvents; Oxidation; Rate constants; Reducing agents; Free radical reactions
Abstract
Aminoalkyl radicals, such as Et2NCHCH3, have low oxidation potentials and are therefore powerful reducing agents. We have found that Et2NCHCH3 reacts with CCl4 and CBr 4 in di-tert-butyl peroxide with bimolecular rate constants (measured by LFP) close, or equal, to the diffusion-controlled limit. For the less reactive halide, CH2Br2, the reaction rate is increased substantially by the addition of acetonitrile as a co-solvent. It is tentatively concluded that these reactions occur by electron-transfer from the aminoalkyl to the organohalide with formation of the iminium ion, Et2N +CHCH3 (NMR detection), halide ion and a halomethyl radical, e.g., CCl3 and CHCl2 (ESR, spin-trapping detection). © 2011 Elsevier B.V. All rights reserved.
Publication date
In
  • Chemical Physics Letters 511, no. 1-Mar (2011): 156–158.
LanguageEnglish
Peer reviewedYes
NPARC number21271669
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Record identifier817a8579-7520-4a16-9953-790a1b2dad1e
Record created2014-03-24
Record modified2020-04-21
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