Abstract
5-(Acyloxymethyl)furfurals (AMFs) have received considerable attention as hydrophobic, stable, and halogen-free congeners of 5-(hydroxymethyl)furfural (HMF) for synthesizing biofuels and biochemicals. In this work, AMFs have been prepared directly from carbohydrates in satisfactory yields using the combination of ZnCl2 as the Lewis acid catalyst and carboxylic acid as the Brønsted acid catalyst. The process was initially optimized for 5-(acetoxymethyl)furfural (AcMF) and then extended to producing other AMFs. The effects of reaction temperature, duration, loading of the substrate, and dosage of ZnCl2 on AcMF yield were explored. Fructose and glucose provided AcMF in 80% and 60% isolated yield, respectively, under optimized parameters (5 wt % substrate, AcOH, 4 equiv ZnCl2, 100 °C, 6 h). Finally, AcMF was converted into high-value chemicals, such as 5-(hydroxymethyl)furfural, 2,5-bis(hydroxymethyl)furan, 2,5-diformylfuran, levulinic acid, and 2,5-furandicarboxylic acid in satisfactory yields to demonstrate the synthetic versatility of AMFs as carbohydrate-derived renewable chemical platforms.