Catalytic Conversion of Fructose, Glucose, and Sucrose to 5-(Hydroxymethyl)furfural and Levulinic and Formic Acids in γ-Valerolactone As a Green Solvent

Abstract

The conversion of fructose, glucose, and sucrose to 5-(hydroxymethyl)furfural (HMF) and levulinic acid (LA)/formic acid (FA) was investigated in detail using sulfuric acid as the catalyst and γ-valerolactone (GVL) as a green solvent. The H2SO4/GVL/H2O system can be tuned to produce either HMF or LA/FA by changing the acid concentration and thus allowing selective switching between the products. Although the best yields of HMF were around 75%, the LA/FA yields ranged from 50% to 70%, depending on the structure of the carbohydrates and the reaction parameters, including temperature, acid, and carbohydrate concentrations. While the conversion of fructose is much faster than glucose, sucrose behaves like a 1:1 mixture of fructose and glucose, indicating facile hydrolysis of the glycosidic bond in sucrose. The mechanism of the conversion of glucose to HMF or LA/FA in GVL involves three intermediates: 1,6-anhydro-β-d-glucofuranose, 1,6-anhydro-β-d-glucopyranose, and levoglucosenone.