Reverse Micelles of Sodium Bis(2‐Ethylhexyl) Sulfosuccinate Promote Dimethyl Carbonate Hydrolysis in Absence of Added Water

Understanding how chemical reactivity is modulated in confined environments remains a central challenge in chemistry. In this work, a reverse micellar system composed of sodium 1,4-bis(2-ethylhexyl) sulfosuccinate (AOT) and dimethyl carbonate (DMC) is investigated, where no water is deliberately added. Using two solvatochromic molecular probes: 1-methyl-8-oxyquinolinium betaine (QB) and 6-propionyl-2-(N,N-dimethyl)aminonaphthalene (PRODAN), the interfacial region of these reverse micelles behaves as a highly polar and hydrogen-bond-donor environment, unexpectedly similar to that of protic solvents like methanol (MeOH) is demonstrated. Proton nuclear magnetic resonance (1H NMR) spectroscopy reveals the formation of MeOH over time, providing strong evidence for the hydrolysis of DMC within the micellar core, yielding MeOH. Remarkably, even in the complete absence of deliberately added water, trace interfacial water inherently present in AOT reverse micelles is sufficient to hydrolyze DMC to methanol. These strongly confine residual water molecules exhibit exceptional nucleophilicity, enabling a reaction typically associated with bulk aqueous or acidic conditions. This findings highlight the unique reactivity of nanoconfined polar environments and open new avenues for the design of green catalytic platforms based on confinement effects.