The partial anodic oxidation of aliphatic hydrocarbons in aprotic solvents

✍ Scribed by D.B. Clark; M. Fleischmann; D. Pletcher

• Publisher: Elsevier Science
• Year: 1973
• Weight: 320 KB
• Volume: 42
• Category: Article
• ISSN: 0022-0728
• DOI: 10.1016/s0022-0728(73)80083-x

✦ Synopsis

Previous papers t' 2 have reported the partial anodic oxidation of aliphatic hydrocarbons at room temperature at a smooth platinum electrode in acetonitrile containing tetraethylammonium tetrafluoroborate as the base electrolyte. A detailed investigation of the oxidation of propylene 2 has shown that the anode reaction leads to the cleavage of a carbon-hydrogen bond and yields a proton and an allyl cation; the major product isolated is N-allylacetamide formed by attack of the carbonium ion on the solvent. Further, the reaction of acetonitrile with the carbonium ion is too rapid for the addition of 1~/o water or 5~o acetic acid to be effective in trapping the intermediate as an alcohol or ester, respectively, and the major product isolated from such electrolyses remains the N-allylacetamide.

The work discussed in this paper was carried out in order to determine which other aprotic solvents are sufficiently stable to oxidation to allow the anode reactions of aliphatic hydrocarbons to be studied. In particular, it was considered important to find solvents which were less susceptible to attack by carbonium ions and hence would allow trapping of intermediates by added nucleophiles.