Phosphazene-Based Covalent Organic Framework as an Efficient Catalyst (COF-1) for the Dehydration of Fructose to 5-HMF.

5-Hydroxymethylfurfural (HMF) is a promising organic platform for producing value-added chemicals. In this work, we focused on using a covalent organic framework (COF-1) as a heterogeneous catalyst for the dehydration of fructose to 5-HMF. The unique phosphazene unit-functionalized pores of COF-1 are essential active sites for catalytic performance. The results show that under the optimized reaction conditions, a maximum yield of 90% was obtained within 1.5 h at 120 °C. Furthermore, the effects of the catalyst load, reaction temperature, and usage of solvents for the improvement of reaction yield were investigated. The catalyst recyclability results showed that the yield of HMF did not change appreciably (90-82%) over five consecutive recycling runs. This work provides a viable strategy by applying phosphazene-based COF-1 for the efficient synthesis of HMF from renewable biomass. The synthesized HMF was further used for the synthesis of the biopolymer monomer furan-2,5-dimethylcarboxylate (FDMC) through N-heterocyclic carbene (NHC)-catalyzed oxidative esterification.