抄録
Pyridine N-oxides bearing electron-donating substituents (III) are efficient catalysts for rearrangement of O-alkyl S-methyl dithiocarbonates (xanthates) (I) to the corresponding S-alkyl S-methyl dithiocarbonates (dithiolcarbonates) (II). Of the catalysts tested, 4-piperidinopyridine N-oxide (IIIh) is the best from the viewpoints of catalytic activity and solubility in I. Heating of I in the presence of catalytic amounts (0.02-0.05 molar eq) of IIIh gave II together with the symmetric S, S-dialkyl and S, S-dimethyl dithiocarbonates in good yields. The catalytic behavior of donor-substituted pyridine N-oxides is discussed on the basis of kinetic and molecular orbital calculation data. The complete calculation of the perturbation equation on the initial stage of the reaction was consistent with the experimentally observed activity of the catalysts.
