State Key Laboratory of Catalysis, Dalian Institute of Chemical Physics, Chinese Academy of Sciences, Dalian, 116023, China.
University of the Chinese Academy of Sciences, Beijing, 100049, China.
Chem Asian J. 2019 Oct 1;14(19):3329-3334. doi: 10.1002/asia.201901001. Epub 2019 Aug 27.
Producing polyester monomer 2,5-furandicarboxylic acid (FDCA) from biomass as an alternative to fossil-derived terephthalic acid has drawn much attention from both academy and industry. In this work, an efficient FDCA synthesis was proposed from 10.6 wt % 2,5-diformylfuran (DFF) in acetic acid using a combined catalytic system of Co/Mn acetate and N-hydroxyimides. The intermediate product of 5-formyl-2-furandicarboxylic acid (FFCA) possesses the least reactive formyl group. N-hydroxysuccinimide was found to be superior to N-hydroxyphthalimide in catalyzing the oxidation of the formyl group in FFCA intermediate, affording a near 95 % yield of FDCA under mild conditions of 100 °C. Trace maleic anhydride was detected as by-product, which mainly came from the oxidative cleavage of DFF via furfural, furoic acid and 5-acetoxyl-2(5H)-furanone as intermediates.
从生物质中生产聚酯单体 2,5-呋喃二甲酸（FDCA）替代化石衍生的对苯二甲酸引起了学术界和工业界的广泛关注。在这项工作中，提出了一种使用乙酸中的钴/锰醋酸盐和 N-羟基亚胺的组合催化体系，从 10.6wt% 2,5-二糠醛（DFF）高效合成 FDCA。中间产物 5-糠醛-2-羧酸（FFCA）具有最少反应性的甲酰基。发现 N-羟基琥珀酰亚胺在催化 FFCA 中间产物中甲酰基的氧化方面优于 N-羟基邻苯二甲酰亚胺，在 100°C 的温和条件下，FDCA 的收率接近 95%。检测到痕量马来酸酐作为副产物，其主要来自 DFF 通过糠醛、糠酸和 5-乙酰氧基-2(5H)-呋喃酮作为中间体的氧化裂解。
