Preparation of 5-(Acyloxymethyl)furfurals from Carbohydrates Using Zinc Chloride/Acetic Acid Catalyst System and Their Synthetic Value Addition.

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 ZnCl 2 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 ZnCl 2 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 ZnCl 2 , 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.