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.

5‐(Chloromethyl)furfural (CMF), a bio‐renewable chemical building block, has been produced in good isolated yields from biomass‐derived carbohydrates within a closed aqueous HCl‐1,2‐dichloroethane biphasic reactor in the presence of benzyltributylammonium chloride (BTBAC) as a phase transfer catalyst (PTC). The solvent‐economic, one‐pot strategy afforded CMF in 73% isolated yield (90 °C, 3 h) from sucrose with a combined yield of 84% for CMF and levulinic acid. The process was optimized on temperature, duration, solvent, type, and loading of PTC. Use of BTBAC led to nearly 10% increase in yield of CMF for all substrates when compared to control reactions.

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Levulinic acid (LA), a bio-renewable chemical building block, has been produced in good isolated yields by treating biomassderived carbohydrates with aqueous hydrochloric acid in the presence of quaternary ammonium salts as cationic surfaceactive agent (SAA). Under optimized conditions (120°C, 3 h, 20.2% HCl), the one-pot process afforded LA in 80% isolated yield from glucose using only 5.77 mol% (10 wt%) of benzyltributylammonium chloride (BTBAC) at the SAA. The control reaction (no BTBAC) provided LA in only 64% yield from glucose under identical conditions. The process was optimized on the reaction temperature, loading of BTBAC, and the concentration of HCl. The use of BTBAC led to a nearly 8-17% increase in yield of LA (compared to the control reaction) for all the carbohydrates studied.