Effective Oxidation of (5-Hydroxymethyl)furfural to 2,5-Diformylfuran by an Acetal Protection Strategy

An acetal protection strategy for (5-hydroxymethyl)furfural (HMF) was used to obtain 2,5-diformyfuran (DFF) using concentrated HMF solutions and a γ-Al 2 O 3 -supported Ru catalyst (Ru/γ-Al 2 O 3 ). The HMF-acetal with 1,3-propanediol can be oxidized to DFF-acetal with a yield of 84.0% at an HMF conversion of 94.2% from a 50 wt% solution. In contrast, aerobic oxidation of nonprotected HMF using a 10 wt% solution afforded DFF only in a moderate yield (52.3%). Kinetic studies indicate that the six-membered ring acetal group not only prevents side reactions but also accelerates aerobic oxidation of the -CH 2 OH moiety to -CHO under retention of the acetal functionality. Organic deposits formed during the reaction explained the significant decrease in the activity of the Ru/γ-Al 2 O 3 catalyst, which could be recovered neither by washing in water or organic solvents, nor by a calcination-reduction treatment. Sonication of the used Ru/γ-Al 2 O 3 catalyst in an aqueous NaOH solution successfully removed the deposits and allowed reuse of the catalyst for at least four times without activity loss.