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Copper-catalyzed oxidative methyl-esterification of 5-hydroxymethylfurfural using TBHP as an oxidizing and methylating reagent: A new approach for the synthesis of furan-2,5-dimethylcarboxylate
Journal of Catalysis ( IF 6.5 ) Pub Date : 2020-06-04 , DOI: 10.1016/j.jcat.2020.05.032
Shyam Sunder R. Gupta , Ajayan Vinu , Mannepalli Lakshmi Kantam

Catalytic conversion of 5-hydroxymethylfurfural (HMF) into furan-2,5-dimethylcarboxylate (FDMC) is of great significance in the production of polyethylene furanoate (PEF), a renewable biomass-derived polymer that can replace the fossil dependent polyethylene terephthalate (PET). Herein, for the first time, we report the synthesis of FDMC from oxidative methyl-esterification of HMF using tert-butyl hydroperoxide (TBHP) as an oxidizing and methylating reagent catalyzed by mesoporous alumina nanospheres-embedded with CuO nanoparticles (CuO/m-Al2O3). The CuO/m-Al2O3 catalysts with different copper contents were prepared by evaporation-induced self-assembly of a structure-directing agent (Pluronic P-123). The decomposition of P-123 during calcination in air results into the formation of a mesoporous structure with highly dispersed CuO nanoparticles. The as-prepared 6-CuO/m-Al2O3 exhibits excellent catalytic activity towards oxidative methyl-esterification of HMF into FDMC with 92% yield and turnover frequency (TOF) of 0.56 h−1. Furthermore, oxidative methyl-esterification of a range of substrates through SP3 CH bond functionalization has also been demonstrated using the same catalyst.



中文翻译:

TBHP作为氧化和甲基化试剂的铜催化5-羟甲基糠醛的氧化甲基酯化:合成呋喃-2,5-二甲基羧酸酯的新方法

5-羟甲基糠醛(HMF)催化转化为呋喃-2,5-二甲基羧酸酯(FDMC)在生产聚乙烯呋喃酸酯(PEF)中具有重要意义。 )。在这里,我们首次报道了使用嵌入过氧化氢的介孔氧化铝纳米球(CuO / m-Al)将过氧化丁基过氧化氢(TBHP)作为氧化和甲基化试剂,由HMF的氧化甲基酯化合成FDMC。2 O 3)。CuO / m-Al 2 O 3通过蒸发诱导的结构导向剂(Pluronic P-123)自组装制备了具有不同铜含量的催化剂。在空气中煅烧过程中P-123的分解导致形成具有高度分散的CuO纳米粒子的中孔结构。所制备的6-CuO / m-Al 2 O 3表现出对HMF氧化成FDMC的氧化甲基酯化的优异催化活性,产率为92%,转换频率(TOF)为0.56 h -1。此外,还已经证明了使用相同的催化剂通过SP 3 C H键官能化对多种底物进行氧化甲基酯化。

更新日期:2020-06-23
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