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

Abstract

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.