Mechanism of the dehydration of D-fructose to 5-hydroxymethylfurfural in dimethyl sulfoxide at 150 degrees C: an NMR study.

The anomeric composition of d-fructose in dimethyl sulfoxide changes when the solution is heated from room temperature to 150 degrees C, with a small increase in the alpha-furanose form at the expense of the beta-pyranose tautomer. Additionally, a small amount of alpha-pyranose form was also observed at 150 degrees C. A mechanism is proposed for the dehydration of D-fructose to 5-hydroxymethylfurfural in DMSO at 150 degrees C, where the solvent acts as the catalyst. A key intermediate in the reaction was identified as (4R,5R)-4-hydroxy-5-hydroxymethyl-4,5-dihydrofuran-2-carbaldehyde by using (1)H and (13)C NMR spectra of the sample during the reaction.

[1]  G. N. Richards,et al.  Mechanism of formation of 5-(hydroxymethyl)-2-furaldehyde from D-fructose an sucrose. , 1990, Carbohydrate research.

[2]  Richard M. Musau,et al.  The preparation of 5-hydroxymethyl-2-furaldehyde (HMF) from d-fructose in the presence of DMSO , 1987 .

[3]  Yuriy Román-Leshkov,et al.  Phase Modifiers Promote Efficient Production of Hydroxymethylfurfural from Fructose , 2006, Science.

[4]  B. Kuster,et al.  The influence of pH and weak-acid anions on the dehydration of d-fructose , 1977 .

[5]  A. Auroux,et al.  Niobic acid and niobium phosphate as highly acidic viable catalysts in aqueous medium: Fructose dehydration reaction , 2006 .

[6]  H. Lichtenthaler,et al.  Distribution of Furanoid and Pyranoid Tautomers of D-Fructose in Water, Dimethyl Sulfoxide, and Pyridine via 1H NMR Intensities of Anomeric Hydroxy Groups in [D6]DMSO , 1985 .

[7]  C. Moreau,et al.  Dehydration of fructose and sucrose into 5-hydroxymethylfurfural in the presence of 1-H-3-methyl imidazolium chloride acting both as solvent and catalyst , 2006 .

[8]  J. Horvat,et al.  Mechanism of levulinic acid formation , 1985 .

[9]  B. Kuster,et al.  5‐Hydroxymethylfurfural (HMF). A Review Focussing on its Manufacture , 1990 .

[10]  C. Moreau,et al.  Dehydration of fructose into 5-hydroxymethylfurfural in the presence of ionic liquids , 2003 .

[11]  A. Corma,et al.  Chemical routes for the transformation of biomass into chemicals. , 2007, Chemical reviews.

[12]  H. Vogel,et al.  Dehydration of fructose to 5-hydroxymethylfurfural in sub- and supercritical acetone , 2003 .

[13]  B. Kuster,et al.  Analytical Procedures for Studying the Dehydration of D-Fructose☆ , 1977 .

[14]  A. R. Galletti,et al.  Heterogeneous catalysts based on vanadyl phosphate for fructose dehydration to 5-hydroxymethyl-2-furaldehyde , 2004 .

[15]  J. Delpuech,et al.  La mutarotation du β-D-fructose en milieu acide dans le dimethylsulfoxyde , 1982 .

[16]  D. Klass.  Biomass for Renewable Energy, Fuels, and Chemicals , 1998 .

[17]  B. Kuster,et al.  The influence of the initial and catalyst concentrations on the dehydration of d-fructose , 1977 .

[18]  H. Vogel,et al.  Dehydration of d-fructose to hydroxymethylfurfural in sub- and supercritical fluids , 2005 .

[19]  A. Perlin,et al.  Two‐dimensional NMR spectral study of the tautomeric equilibria of D‐fructose and related compounds , 1990 .

[20]  B. Kuster,et al.  The influence of water concentration on the dehydration of d-fructose , 1977 .

[21]  H. Yoshida,et al.  Dehydration of fructose to 5-hydroxymethylfurfural in sub-critical water over heterogeneous zirconium phosphate catalysts. , 2006, Carbohydrate research.