Syntheses of 5-hydroxymethylfurfural and levoglucosan by selective dehydration of glucose using solid acid and base catalysts

Selective dehydration of glucose, the most abundant monosaccharide, was examined using a solid acid catalyst individually or a combination of solid acid and base catalysts to form anhydroglucose (levoglucosan) or 5-hydroxymethylfurfural (HMF), respectively. Glucose was dehydrated to anhydroglucose by acid catalysis in polar aprotic solvents including N,N-dimethylformamide. Amberlyst-15, a strongly acidic ion-exchange resin, functioned as an efficient solid acid catalyst for anhydroglucose production with high selectivity. In the presence of solid base, aldose–ketose isomerization of glucose to fructose preferentially occurred by base catalysis, even in coexistence with the solid acid, resulting in successive dehydration of fructose to 5-hydroxymethylfurfural by acid catalysis with high yield in a one-pot reaction. A combination of Amberlyst-15 and hydrotalcite, an anionic layered clay, afforded high HMF selectivity under a moderate reaction temperature, owing to prevention of anhydroglucose formation.

Graphical abstractSelective dehydration of glucose was examined using a solid acid catalyst individually or a combination of solid acid and base catalysts to form anhydroglucose or 5-hydroxymethylfurfural (HMF), respectively. A low reaction temperature is advantageous in formation of fructose by base catalysis and limits the amount of anhydroglucose formation by acid catalysis. The preferential formation of fructose results in high selectivity for HMF.Figure optionsDownload full-size imageDownload high-quality image (76 K)Download as PowerPoint slide