Electrolysis of Potassium Butyrate in Acetonitrile. A Deuterium NMR Study

Article abstract of DOI:10.1021/jo01309a025

The anodic oxidation of 2,2-dideuteriobutyrate ion in acetonitrile gives rise to radical-derived and cation-derived C3 products.By 2H FT NMR spectroscopy, the radical-derived propane and propene are found to be formed without scrambling of the label.Similarly, the products derived from the intermediate isopropyl cation, i.e., the remainder of the propene and N-isopropylamides, bear deuterium only at the terminal C-1 and C-3 positions of the C3 fragment.However, the 1:1:1 label distribution found in the N-n-propylamides and the formation of cyclopropane strongly suggest that ring closure of the n-propyl cation to rapidly scrambling pr otonated cyclopropane is an important reaction pathway.Atom scrambling at the level of protonated cyclopropane shows a large H/D isotope effect.