Formation of Carbonium Ions from Electrooxidation of Alkyl Bromides

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Primary, secondary, and tertiary bromoalkanes were potentiostatically oxidized at platinum gauze. The anolyte was acetonitrile–lithium perchlorate or tetraethylammonium fluoborate and the reference electrode Ag/0.1 M AgNO3. Carbon–bromine bond cleavage, leading to the formation of N-alkylacetamides, was observed to be the exclusive route of these oxidations. Each of the oxidations of 2-bromopropane, 2-bromobutane, tert-butyl bromide, and neopentyl bromide yielded a sole amide, whereas 1-bromobutane, 1-bromopentane, 1-bromohexane, 1-bromo- 2-methylpropane, 1-bromo-3-methylbutane, 2-bromopentane and 3-bromohexane gave mixtures of amides. A mechanism involving an initial electron transfer from the nonbonding orbital of the bromine is proposed. This intermediate is thought to undergo attack by the nucleophilic solvent and/or undergo carbon–bromine bond breaking to generate highly energetic carbonium ions, which react with the acetonitrile directly or after rearrangement.

Original languageEnglish
Pages (from-to)3997-4000
Number of pages4
JournalJournal of Organic Chemistry
Issue number25
StatePublished - 1 Dec 1977

ASJC Scopus subject areas

  • Organic Chemistry


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