Dehydrogenation of 5-hydroxymethylfurfural to diformylfuran in compressed carbon dioxide: an oxidant free approach?

Green Chemistry Pub Date: 2017-01-16 DOI: 10.1039/C6GC02977A

Abstract

The dehydrogenation of biomass-based 5-hydroxymethylfurfural (HMF) to 2,5-diformylfuran (DFF) was achieved utilizing an activated carbon supported rhodium (Rh/C) catalyst under mild reaction conditions. The developed method successfully afforded complete conversion and the highest selectivity of DFF (>99%) without any additive, conventional hydrogen acceptor and oxidant. The efficiency of the method is achieved by the addition of compressed carbon dioxide (scCO2) and the synergistic effect of scCO2 and Rh/C, where scCO2 plays a pivotal role in accelerating the reaction by removing hydrogen, and consequently shifting the equilibrium to the forward direction. Optimization of different reaction parameters ensures the achievement of high conversion and selectivity. Characterization of the catalyst using different spectroscopic techniques suggests an interaction between the substrate and the catalyst and provides an indication of the possible reaction pathway, thus a mechanism would be outlined. The rate determining step of the reaction was calculated through mechanistic investigations involving theoretical calculations together with experimental analysis. One of the most attractive features of the method developed in this study is the reverse reaction of DFF, which can be achieved in one-pot without the addition of any external hydrogen. This process has successful application to the dehydrogenation of a variety of alcohols with different substituents.

Graphical abstract: Dehydrogenation of 5-hydroxymethylfurfural to diformylfuran in compressed carbon dioxide: an oxidant free approach
Recommended Literature