Sustainable Catalytic Synthesis of 2,5-Diformylfuran from Various Carbohydrates

Abstract

Versatile homogeneous and heterogeneous catalysts that convert carbohydrates to 2,5-diformylfuran (DFF) are essential for the development of sustainable processes for producing high-value chemicals from biomass-derived carbohydrates. An efficient catalytic system consisting of Br−, disulfide, and dimethylsulfoxide (DMSO) promoted the sustainable and selective synthesis of DFF in modest-to-good yields from various carbohydrates, such as fructose, glucose, mannose, galactose, and sucrose. Heterogeneous catalysts containing Br− also facilitated this reaction with recyclable high yields.

Hollow Microporous Organic Polymer@Hypercrosslinked Polymer Catalysts Bearing N-Heterocyclic Carbene–Iron Species for the Synthesis of Biomass-Derived Polymer Platforms

“…The chemical structures of the materials were investigated by FT-IR and solid-state 13 C NMR spectroscopy (Figure ). The IR spectra of HCP and HMOP@HCP-2 showed characteristic vibration peaks at 2922–2920, 1609–1605, 1453, and 1215–1210 cm –1 , corresponding to aliphatic C–H vibrations of CH 2 groups, aromatic CC vibrations, CH 2 scissoring, and CH 2 rocking, respectively (Figure a,b). , In the IR spectra of HCP-Im and HMOP@HCP-Im, main vibration peaks were observed at 1681–1605, 1461, and 1160 cm –1 , corresponding to aromatic CN/CC vibrations, CH 2 stretching, and the characteristic C–N + vibrations of imidazolium rings, respectively, indicating the successful introduction of imidazolium rings through PSM (Figure a,b). , After the coordination of Fe, the IR spectra of HCP-Fe and HMOP@HCP-Fe showed characteristic peaks at 1680–1600, 1453, 1285–1263, and 1104–1020 cm –1 , corresponding to aromatic CN/CC vibrations, CH 2 stretching, and two kinds of C–N vibrations, respectively, matching with the results in the literature (Figure a,b) . These observations indicate that the imidazolium rings and NHC–Fe species were successfully generated through the corresponding PSM of MOP materials.…”

One‐Pot, One‐Step Synthesis of 2,5‐Diformylfuran from an Abundant Biomass Source and Low‐Cost Bromide Salts

“…This can be attributed to the hydrolysis of glycosidic bonds in sucrose, which slowed down the rates of fructose dehydration and HMF oxidation steps. However, direct DFF preparation from sucrose provided a low‐cost way for DFF production due to the high cost of fructose and the unsuitability of glucose [1,6, 13] . Table sugar, made from sucrose, also gave an acceptable DFF yield of 51.1 % without any trace of HMF after 6 h. Other disaccharides, maltose and lactose, were found unsuitable for the conversion to DFF, with both DFF yields lower than 1 %.…”

“…The supporting information includes the experimental, the calibration curves of the products, 1 H-NMR and 13 C-NMR spectra of isolated product, HPLC chromatograms, and LC-MS/MS chromatograms…”

“…However, direct DFF preparation from sucrose provided a low-cost way for DFF production due to the high cost of fructose and the unsuitability of glucose. [1,6,13] Table sugar, made from sucrose, also gave an acceptable DFF yield 51.1 % without any trace of HMF after 6 h. Other disaccharides, maltose and lactose, were found unsuitable for the conversion to DFF, with both DFF yields lower than 1 %. This is because maltose consists of two glucose molecules, which lack of fructose units, and lactose has a β-1,4-glycosidic bond, which might be hard for the hydrolysis step by KBr.…”