Hydroxymethylfurfural (HMF) derivatives such as
2,5-bis(hydroxymethyl)furan (
BHMF) and furandicarboxylic
acid (FDCA) are promising alternative of fossil-based diols and
dicarboxylic acids for synthesis of
polyesters such as
polyethylene terephthalate (PET). However, high cost for preparing HMF from biomass discourages the commercialization of HMF-derived
polyesters. Since producing
furfural (FUR) from five-
carbon sugars (e.g.,
xylose) via
dehydration is an inexpensive and commercialized process, we herein reported a method to synthesize
BHMF derivatives (5-(ethoxymethyl)
furan-2-
methanol (EMFM), 2,5-bis(hydroxymethyl)
furan monoacetate (BHMFM) and 2,5-bis(hydroxymethyl)
furan diacetate (BHMFD) from
furfural derivatives, i.e., (2-(ethoxymethyl)
furan (EMF) and furfuryl
acetate (FA)). To avoid strong
acid-induced side reactions (e.g.,
furan ring opening, condensation and carbonization), two reaction systems, i.e., a low-concentration HCl aqueous
solution combined with
formaldehyde and anhydrous
acetic acid combined with
paraformaldehyde, were found to be suitable for such a hydroxymethylation reaction and could lead to decent product yields. In order to improve the
carbon utilization, condensed furanic byproducts were further converted into
hydrocarbon fuels via a reported two-step hydrodeoxygenation (HDO) process. This study not only validates the possibility of synthesizing functional HMF derivatives (EMFM, BHMFM, and BHMFD) from commercially-available FUR derivatives (EMF and FA), but also provide a new way to transform condensed furanics to value-added
hydrocarbon fuels.