Abstract
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 language | English |
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Pages (from-to) | 849-853 |
Number of pages | 5 |
Journal | Journal of the American Chemical Society |
Volume | 97 |
Issue number | 4 |
DOIs | |
State | Published - 1 Feb 1975 |
Externally published | Yes |
ASJC Scopus subject areas
- Catalysis
- General Chemistry
- Biochemistry
- Colloid and Surface Chemistry