Thanheuser Nico, Groteguth Jonas T, Leitner Walter, Esteban Jesús, Vorholt Andreas J
Max Planck Institute for Chemical Energy Conversion, 45470, Mülheim an der Ruhr, Germany.
Institute for Technical and Macromolecular Chemistry, RWTH Aachen, 52074, Aachen, Germany.
ChemSusChem. 2025 Feb 1;18(3):e202401485. doi: 10.1002/cssc.202401485. Epub 2024 Oct 25.
The reaction with in situ extraction to yield 5-hydroxymethylfurfural (HMF) from d-fructose (Fru) was investigated using a biphasic system based on a self-consuming deep eutectic solvent (DES) as reaction phase. The significance of choline chloride (ChCl), a cost-effective and safe quaternary ammonium salt, was evident in enhancing HMF yield through fructose dehydration and concurrently suppressing side reactions. The DES system demonstrated fast reactions with high selecivities and recyclability across five cycles. The observed decline in HSiWO activity, primarily due to proton leaching, was successfully restored with the addition of HCl. Furthermore, ChCl exhibited ease of recrystallization in the presence of acetonitrile. This research proposes an environmentally friendlier approach for HMF production through a reusable-biphasic process. The presented reaction system suppresses completely the formation of levulinic and formic acid leading to HMF yields of up to 84 % of selectivities of up to 88 % after 30 minutes at 80 °C. The system was recycled over 16 runs and after an initial slight loss of activity the system in the run 0-5, run 6-15 has shown a constant HMF output as in the first recycling run.
研究了基于自消耗型低共熔溶剂（DES）作为反应相的双相体系中，原位萃取d-果糖（Fru）生成5-羟甲基糠醛（HMF）的反应。氯化胆碱（ChCl）是一种经济高效且安全的季铵盐，它在通过果糖脱水提高HMF产率并同时抑制副反应方面的作用显著。DES体系在五个循环中表现出快速反应、高选择性和可回收性。观察到的HSiWO活性下降主要是由于质子浸出，通过添加HCl成功恢复。此外，在乙腈存在下，ChCl表现出易于重结晶的特性。本研究提出了一种通过可重复使用的双相工艺生产HMF的更环保方法。所提出的反应体系完全抑制了乙酰丙酸和甲酸的形成，在80℃下反应30分钟后，HMF产率高达84%，选择性高达88%。该体系经过16次循环，在最初活性略有损失后，0-5次循环和6-15次循环中的体系HMF产量与第一次循环时保持恒定。
