Alkoxycarbenium Ions. Relative Thermodynamic Stabilities via Pairwise Equilibrations.

Article abstract of DOI:10.1021/jo00329a006

Alkoxycarbenium ions were synthesized by direct O-alkylation of the corresponding carbonyl compounds with trimethyloxonium ion salts and methyl fluorosulfate.The thermodynamic stabilities of the alkoxycarbenium ions were determined by stepwise equilibrations of pairs of these ions via transalkylation with the corresponding carbonyl compounds in liquid sulfur dioxide as monitored by 1H NMR.The structures, spectra, and stabilities of alkoxycarbenium ions have been compared with those of the corresponding hydroxycarbenium ions.In general, the relative stability order for alkoxycarbenium ions parallels the order of stabilities for the corresponding hydroxycarbenium ions.