High-Yielding Synthesis of 5-(alkoxymethyl)furfurals from Biomass-Derived 5-(halomethyl)furfural (X=Cl, Br)

Abstract

A series of 5-(alkoxymethyl)furfurals (AMFs) have been synthesized in excellent isolated yields (>90%) by reacting biomass-derived 5-(chloromethyl)furfural (CMF) or 5-(bromomethyl)furfural (BMF) with monohydric alkyl alcohols (methanol to 1-butanol) at slightly elevated temperatures (RT-50 °C) and short reaction time (3 h). The modified work-up procedure minimizes side reactions while simplifying the isolation and purification of AMFs. Although higher primary alcohols like 1-pentanol and 1-hexanol and secondary alcohol like 2-propanol were found to be less reactive, use of N,N-diisopropylethylamine (DIPEA) as a base additive afforded AMFs in excellent yields within 6 h at 65 °C using only slight excess of the alcohol (1.2 eq.) reagent. © 2019 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim