Inorganic Chemistry I, Ruhr-Universität Bochum, Universitätsstraße 150, 44801, Bochum, Germany.
Chemistry. 2023 Feb 1;29(7):e202202860. doi: 10.1002/chem.202202860. Epub 2022 Dec 12.
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.
机械化学反应用于替代基于溶液的合成，为即使是传统上不可能的转化提供了可能。然而，其反应途径通常在剧烈振动的、密集的研磨容器内尚未得到探索。在这里，我们展示了如何通过机械化学方法从无机碱碳酸盐合成绿色有机溶剂碳酸二乙酯，以及研磨参数研究、同步加速器 X 射线衍射实时监测和量子化学计算的互补组合如何揭示潜在的反应途径。通过这种方法，确定了反应中间体，并对机械化学中的溶液化学概念提出了挑战或证实。
