Department of Chemical Engineering, Institute of ChemicalTechnology, Matunga (E), Mumbai, Maharashtra, 400019, India.
Global Innovative Center for Advanced Nanomaterials (GICAN), School of Engineering, Faculty of Engineering and Built Environment, The University of Newcastle, Callaghan, NSW 2308, Australia.
Chempluschem. 2021 Feb;86(2):259-269. doi: 10.1002/cplu.202000713.
One-pot synthesis of furan-2,5-dimethylcarboxylate (FDMC) from 5-hydroxymethylfurfural (HMF) is highly demanding for the commercial production of polyethylene furanoate (PEF). Herein, a direct synthesis of FDMC is reported from oxidative esterification of HMF using ultrafine CuO particles dispersed on nitrogen-doped hollow carbon nanospheres (CuO/N-C-HNSs) as a catalyst and tert-butyl hydroperoxide (TBHP) as an oxidizing and methylating reagent. The CuO/N-C-HNSs was prepared through a template protection-sacrifice strategy using SiO as a sacrificial template and histidine as the precursor for N and C. N-doping facilitated a strong interaction between the support and copper species, affording formation of CuO nanoparticles of less than 10 nm in size. By virtue of the highly dispersed CuO nanoparticles and a high BET surface area 373 m /g, the CuO/N-C-HNSsshows excellent catalytic performance in the selective conversion of HMF into FDMC affording 93 % yield of the desired product with a TON value of 49. Furthermore, the oxidative esterification involving SP C-H bond functionalization is also demonstrated using the same catalyst.
一锅法从 5-羟甲基糠醛（HMF）合成呋喃-2,5-二甲酸甲酯（FDMC）是商业化生产聚呋喃酸酯（PEF）的迫切需求。本文报道了一种使用氮掺杂中空碳纳米球（CuO/N-C-HNSs）上分散的超细 CuO 颗粒作为催化剂，叔丁基过氧化氢（TBHP）作为氧化和甲基化试剂，从 HMF 的氧化酯化直接合成 FDMC 的方法。CuO/N-C-HNSs 通过使用 SiO2 作为牺牲模板和组氨酸作为 N 和 C 的前体制备的模板保护-牺牲策略制备。N 掺杂促进了载体与铜物种之间的强相互作用，形成了小于 10nm 的 CuO 纳米颗粒。由于高度分散的 CuO 纳米颗粒和高 BET 表面积 373m2/g，CuO/N-C-HNSs 在 HMF 选择性转化为 FDMC 中表现出优异的催化性能，得到了 93%的目标产物收率和 49 的TON 值。此外，还使用相同的催化剂证明了涉及 SP C-H 键功能化的氧化酯化反应。
