Copper Phosphotungstate-Catalyzed Microwave-Assisted Synthesis of 5-Hydroxymethylfurfural In A Biphasic System

Abstract

In this paper, we have described a novel route to produce 5-hydroxymethylfurfural (HMF), a valuable platform-molecule obtained from biomass, using transition metal-exchanged Keggin heteropolyacid salts as catalysts, in microwave-assisted reactions carried out in a water-ethyl acetate biphasic system. To avoid the use of homogenous Brønsted acid catalysts, which are corrosive and difficult to be reused, we have exchanged the protons of the Keggin heteropolyacids by transition metal cations. These salts were evaluated in the fructose dehydration, being the Cu3/2PW12O40 the most active and selective catalyst, achieving 81 % of HMF yield, after 15 min reaction at 413 K under microwave irradiation (MWI). The effects of metal cation, anion, and heteropolyanion present in the catalyst were evaluated. The greatest efficiency of Cu3/2PW12O40 was attributed to its high Lewis acidity strength, which allows that it coordinate with water molecules, consequently generating H3O+ ions in the reaction medium. Even though the catalyst has been water-soluble, it was easily reused removing the extracting phase, and adding a new load of the substrate to the remaining aqueous phase. This way, it was successfully reused without loss activity.