Examining the Alkaline Stability of Tris(dialkylamino)sulfoniums and Sulfoxoniums

Herein, a synthetic method was developed to prepare a series of tris(dialkylamino)sulfonium and sulfoxonium cations from sulfur monochloride. Alkaline stability studies of these two cation families in 2 M KOH/CD₃OH solution at 80 °C revealed how degradation pathways change as a function of the oxidation state of the S center, as determined by ¹H NMR spectroscopy. The sulfonium cations (⁺S(NR₂)₃) typically degrade by nucleophilic attack at the sulfur atom with loss of an amino group and a proton transfer reaction to produce sulfoxides, while the sulfoxoniums (⁺O═S(NR₂)₃) tend to degrade by loss of an R group to form sulfoximines. From the group of sulfoniums and sulfoxoniums explored in this work, the tris(piperidino)sulfoxonium cation was noted to have excellent alkaline stability. This sulfoxonium should be suitable for future examination as a tethered cation in anion-exchange membranes (AEMs), or as a phase-transfer catalyst in biphasic reactions.