Li Xing-Long, Qing Shao-Jun, Sun Xun, Yu Zhen, Xu Hua-Jian, Fu Yao
School of Carbon Neutrality Science and Engineering, Aust Hefei Institute for Advanced Research, Anhui University of Science and Technology, Hefei, 231131, P. R. China.
School of Food and Biological Engineering, School of Chemistry and Chemical Engineering, Anhui Province Key Laboratory of Advance Catalytic Materials and Reaction Engineering, Hefei University of Technology, Hefei, 230009, P. R. China.
ChemSusChem. 2025 Jan 14;18(2):e202401527. doi: 10.1002/cssc.202401527. Epub 2024 Oct 25.
2,5-diformylfuran (DFF) is a significant biomass-derived compound with diverse applications in novel furan-based materials, fragrances, fuel additives, and drug synthesis. A pivotal challenge in DFF synthesis was developing a method to produce DFF under mild conditions using sustainable feedstocks. In this study, an affordable 4-hydroxy-2,2,6,6-tetramethylpiperidine (TEMPOL)- assisted Cu(OAc) catalytic system for aerobic oxidation reaction of HMF to DFF in liquid sunlight methanol solvent was developed. The effects of parameters such as metal species, catalyst amount, solvent species, base structure, and reaction temperature were systematically investigated. The evolution of product distribution in the reaction solution at various times was monitored and analyzed using 1H-NMR spectroscopy. FT-IR and ESI-MS characterizations were employed to integrate experimental findings and elucidate the reaction mechanism. The highest DFF yield of 96 % and complete conversion of HMF were obtained. Furthermore, a total DFF yield of 68.6 % was achieved from fructose using a two-steps method, demonstrating the potential for scalable production. The establishment of this catalytic system presents a novel approach for the selective preparation of DFF from sustainable feedstock.
2,5-二甲基呋喃（DFF）是一种重要的生物质衍生化合物，在新型呋喃基材料、香料、燃料添加剂和药物合成等方面有多种应用。DFF合成中的一个关键挑战是开发一种在温和条件下使用可持续原料生产DFF的方法。在本研究中，开发了一种经济实惠的4-羟基-2,2,6,6-四甲基哌啶（TEMPOL）辅助的Cu（OAc）催化体系，用于在液体阳光甲醇溶剂中将HMF有氧氧化为DFF。系统研究了金属种类、催化剂量、溶剂种类、碱结构和反应温度等参数的影响。使用1H-NMR光谱监测和分析了反应溶液中不同时间产物分布的演变。采用FT-IR和ESI-MS表征来整合实验结果并阐明反应机理。获得了96%的最高DFF产率和HMF的完全转化。此外，使用两步法从果糖中获得了68.6%的总DFF产率，证明了可扩展生产的潜力。该催化体系的建立为从可持续原料中选择性制备DFF提供了一种新方法。
