ELECTROCHEMICAL OXIDATION OF ALIPHATIC-HYDROCARBONS PROMOTED BY INORGANIC RADICALS .2. NO3 RADICALS

The anodic electrolysis of linear alkanes in tert-butanol/H//2O solutions containing HNO//3 and saturated with oxygen at P//O//2 equals 1 atm results in the partial oxidation of the hydrocarbons to the corresponding isomeric ketones. The experimental data are in support of a mechanism in which the first steps are: (1) one-electron transfer from the nitrate ion to the anode to give a nitrate radical; (2) hydrogen abstraction by the nitrate radical on the alphatic substrate to give an alkyl radical; (3) molecular oxygen addition by the alkyl radical and formation of peroxy radicals. These species decay by bimolecular reactions and a carbonyl function is formed.