The Transformation of Inorganic to Organic Carbonates: Chasing for Reaction Pathways in Mechanochemistry.

Mechanochemical reactions are solvent-free alternatives to solution-based syntheses enabling even conventionally impossible transformations. Their reaction pathways, however, usually remain unexplored within the heavily vibrating, dense milling vessels. Here, we showcase how the green organic solvent diethyl carbonate is synthesized mechanochemically from inorganic alkali carbonates and how the complementary combination of milling parameter studies, synchrotron X-ray diffraction real time monitoring, and quantum chemical calculations reveal the underlying reaction pathways. With this, reaction intermediates are identified, and chemical concepts of solution-chemistry are challenged or corroborated for mechanochemistry.