TY - JOUR
T1 - A combined experimental and computational study of the mechanism of fructose dehydration to 5-hydroxymethylfurfural in dimethylsulfoxide using Amberlyst 70, PO43-/niobic acid, or sulfuric acid catalysts
AU - Zhang, Jing
AU - Das, Anirban
AU - Assary, Rajeev S.
AU - Curtiss, Larry A.
AU - Weitz, Eric
N1 - Funding Information:
The authors thank Dr. Yuyang Wu and Jaekuk Kim of Northwestern University for NMR and LC–MS technical assistance. We also acknowledge Prof. Karl Scheidt for his valuable discussions with regard to the possibility of complexation of DMSO with the dehydrated fructose species that form Int. 1 . We thank Dr. Weiqiang Wu for his help in characterizing acid sites on PO 4 3− /niobic acid. This work has been supported as part of the Institute for Atom-efficient Chemical Transformations (IACT), an Energy Frontier Research Center funded by the U.S. Department of Energy , Office of Science , Office of Basic Energy Sciences . We gratefully acknowledge grants of computer time from EMSL, a national scientific user facility located at Pacific Northwest National Laboratory, the ANL Laboratory Computing Resource Center (LCRC), and the ANL Center for Nanoscale Materials . This research used resources of the National Energy Research Scientific Computing Center, which is supported by the Office of Sciences of the U.S. Department of Energy under Contract no. DE-AC02-05CH11231
Publisher Copyright:
© 2014 Elsevier B.V.
Copyright:
Copyright 2015 Elsevier B.V., All rights reserved.
PY - 2016/2/1
Y1 - 2016/2/1
N2 - We report on a combined experimental and theoretical study of the acid catalyzed dehydration of d-fructose in dimethylsulfoxide (DMSO) using; Amberlyst 70, PO43-/niobic acid, and sulfuric acid as catalysts. The reaction has been studied and intermediates characterized using; 13C, 1H, and 17O NMR, and high resolution electrospray ionization mass spectrometry (HR ESI-MS). High level G4MP2 theory calculations are used to understand the thermodynamic landscape for the reaction mechanism in DMSO. We have experimentally identified two key intermediates in the dehydration of fructose to form HMF that were also identified, using theory, as local minima on the potential surface for reaction. A third intermediate, a species capable of undergoing keto-enol tautomerism, was also experimentally detected. However, it was not possible to experimentally distinguish between the keto and the enol forms. These data with different catalysts are consistent with common intermediates along the reaction pathway from fructose to HMF in DMSO. The role of oxygen in producing acidic species in reactions carried out in DMSO in presence of air is also discussed.
AB - We report on a combined experimental and theoretical study of the acid catalyzed dehydration of d-fructose in dimethylsulfoxide (DMSO) using; Amberlyst 70, PO43-/niobic acid, and sulfuric acid as catalysts. The reaction has been studied and intermediates characterized using; 13C, 1H, and 17O NMR, and high resolution electrospray ionization mass spectrometry (HR ESI-MS). High level G4MP2 theory calculations are used to understand the thermodynamic landscape for the reaction mechanism in DMSO. We have experimentally identified two key intermediates in the dehydration of fructose to form HMF that were also identified, using theory, as local minima on the potential surface for reaction. A third intermediate, a species capable of undergoing keto-enol tautomerism, was also experimentally detected. However, it was not possible to experimentally distinguish between the keto and the enol forms. These data with different catalysts are consistent with common intermediates along the reaction pathway from fructose to HMF in DMSO. The role of oxygen in producing acidic species in reactions carried out in DMSO in presence of air is also discussed.
KW - Fructose dehydration
KW - G4MP2 calculations
KW - Isotope labeling studies
KW - Mechanism
KW - NMR spectroscopy
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U2 - 10.1016/j.apcatb.2014.10.056
DO - 10.1016/j.apcatb.2014.10.056
M3 - Article
AN - SCOPUS:84944346112
VL - 181
SP - 874
EP - 887
JO - Applied Catalysis B: Environmental
JF - Applied Catalysis B: Environmental
SN - 0926-3373
ER -