Synthesis, functionalization and applications of 2,5-bis(hydroxymethyl)furan (BHMF): a stable bio-based diol

In the last twenty years biorefinery has gained exceptional attention in the scientific community. This interest has been prompted by the substitution of petroleum-based compounds with renewable substances with the aim of establishing a bio-based economically self-sustained industry. In this view, C6 furan-based compounds, usually referred as furanics, have been extensively investigated as aromatic promising building blocks from renewables. 5-Hydroxymethylfurfural (HMF) and 2,5-furan dicarboxylic acid (FDCA) are well known examples of furanics whose syntheses and applications have been extensively reviewed in the literature.[1] This presentation is focused on our latest results on the synthesis, functionalization and application of yet another interesting furanic bio-based platform chemicals, i.e., 2,5-bis(hydroxymethyl)furan (BHMF).[2] BHMF is a stable bio-based diol with numerous applications as monomer for bio-materials and fuels. In our most recent works we have reported that BHMF can be prepared in large scale via a two-steps reaction. First HMF was prepared from D-fructose via acid catalyzed reaction employing dimethyl carbonate:tetraethyl ammonium bromide as biphasic solvent system. Thus, HMF - recovered from the reaction mixture with minimal work-up was converted to BHMF by reduction.[3] BHMF was consequently alkylated to achieve a library of 2,5-bis(alkoxymethyl) furans (BAMFs) with potential applications as biofuel candidates.[4] Furthermore, reaction of BHMF with several dialkyl carbonates allowed the preparation of BHMF alkyl carbonates in mild conditions.[5] These new compounds resulted stable over time and they are suitable monomers for new bio-based polycarbonates and polyurethanes.