Anodic α-Cleavage of Ketones

James Y. Becker, Larry L. Miller, Theodore M. Siegel

Research output: Contribution to journalArticlepeer-review

40 Scopus citations


Ketones with branching at the α position were potentiostatically oxidized at platinum gauze. The anolyte was acetonitrile-lithium perchlorate and the reference electrode Ag|0.1 M AgNO3. α-Cleavage was observed to be the main route of these oxidations. 2,2-Dimethyl-3-butanone, 2,2-dimethyl-3-hexanone, acetyladamantane, 2-methyl-3-butanone, and 2,5-dimethyl-3-pentanone of the general formula RCOR′ gave α-cleavage products of the type RNHCOCH3 and R′COOH. 2,2-Dimethylpropanal and 2,2,4,4-tetramethyl-3-pentanone gave acetylpivaloylimide in addition to acid and amide products. It was found that small amounts of water are necessary for the obtention of high amide (RNHCOCH3) yields. A mechanism involving generation of carbonium ions from α-cleavage of a ketone cation radical is proposed, and analogies with photochemistry and mass spectrometry are drawn.

Original languageEnglish
Pages (from-to)849-853
Number of pages5
JournalJournal of the American Chemical Society
Issue number4
StatePublished - 1 Feb 1975
Externally publishedYes

ASJC Scopus subject areas

  • Catalysis
  • Chemistry (all)
  • Biochemistry
  • Colloid and Surface Chemistry


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