Muzyka Claire, Renson Sébastien, Grignard Bruno, Detrembleur Christophe, Monbaliu Jean-Christophe M
Center for Integrated Technology and Organic Synthesis (CiTOS), MolSys Research Unit, University of Liège, Allée du Six Août 13, 4000, Liège (Sart Tilman), Belgium.
Center for Education and Research on Macromolecules (CERM), CESAM Research Unit, University of Liège, Allée du Six Août 13, 4000, Liège (Sart Tilman), Belgium.
Angew Chem Int Ed Engl. 2024 Mar 4;63(10):e202319060. doi: 10.1002/anie.202319060. Epub 2024 Jan 24.
A subtle combination of fundamental and applied organic chemistry toward process intensification is demonstrated for the large-scale production of bio-based glycerol carbonate under flow conditions. The direct carbonation of bio-based glycidol with CO is successfully carried out under intensified flow conditions, with Barton's base as a potent homogeneous organocatalyst. Process metrics for the CO coupling step (for the upstream production, output: 3.6 kg day , Space Time Yield (STY): 2.7 kg h L , Environmental factor (E-factor): 4.7) outclass previous reports. High conversion and selectivity are achieved in less than 30 s of residence time at pilot scale with a stoichiometric amount of CO . Supporting DFT computations reveal the unique features of the mechanism in presence of Brønsted bases.
在流动条件下大规模生产生物基碳酸甘油酯时，展示了基础有机化学与应用有机化学为实现过程强化而进行的精妙结合。以巴顿碱作为高效均相有机催化剂，在强化流动条件下成功实现了生物基缩水甘油与一氧化碳的直接碳酸化反应。一氧化碳偶联步骤的工艺指标（用于上游生产，产量：3.6千克/天，时空产率（STY）：2.7千克·小时⁻¹·升⁻¹，环境因子（E-factor）：4.7）优于以往报道。在中试规模下，使用化学计量的一氧化碳，停留时间不到30秒即可实现高转化率和高选择性。支持性的密度泛函理论计算揭示了在布朗斯特碱存在下该反应机理的独特特征。
