5‐(Chloromethyl)Furfural as a Potential Source for Continuous Hydrogenation of 5‐(Hydroxymethyl)Furfural to 2,5‐Bis(Hydroxymethyl)Furan

Abstract

5-(Chloromethyl)furfural (CMF) is cheaper than sugars, because it can be obtained from biomass waste. Herein, the stepwise conversion of CMF to 2,5-bis(hydroxymethyl)furan (BHMF) via 5-(hydroxymethyl)furfural (HMF) was demonstrated for the first time. The purified CMF was hydrolyzed in continuous mode followed by extraction with ethyl acetate (EA), resulting in a HMF yield of 70 mol%. The following factors were assessed during continuous hydrogenation of the produced HMF: the presence of EA in the reaction solvent, HMF concentrations of up to 10 wt% in the feed, the mass production of mesoporous Cu-Al 2 O 3 (meso-CuA-kg), the shaping of meso-CuA-kg into cylindrical pellets, and the setup of the catalytic reactor. Through these efforts, the hydrogenation of HMF over meso-CuA-kg could be sustained for 100 h under the above optimized conditions, affording BHMF in 98 % yield. The approach described in this study can greatly contribute to the valueadded transformation of CMF into HMF and BHMF.

Production and Synthetic Possibilities of 5-Chloromethylfurfural as Alternative Biobased Furan

“…Hydrolysis of CMF to HMF was reported with a reasonable molar yield of 72% at 100 • C under continuous flow conditions with a space-time of 1 min using 4 wt.% CMF in acetone solution and subsequently extracted with ethyl acetate (Scheme 6) [76]. This HMF product was then utilised through further hydrogenation to 2,5-bis(hydroxymethyl)furan, a precursor for polymeric materials and resins.…”

“…Catalysts 2024, 14, x FOR PEER REVIEW 19 of 31 Scheme 6. CMF hydrolysis followed by extraction with ethyl acetate [76].…”