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

Zhang, Jing; Das, Anirban; Assary, Rajeev S.; Curtiss, Larry A.; Weitz, Eric

doi:10.1016/j.apcatb.2014.10.056

Title: A combined experimental and computational study of the mechanism of fructose dehydration to 5-hydroxymethylfurfural in dimethylsulfoxide using Amberlyst 70, PO₄^3-/niobic acid, or sulfuric acid catalysts

Journal Article · Mon Feb 01 00:00:00 EST 2016 · Applied Catalysis B: Environmental

DOI:https://doi.org/10.1016/j.apcatb.2014.10.056· OSTI ID:1248733

Zhang, Jing ^[1]; Das, Anirban ^[1]; Assary, Rajeev S. ^[2]; Curtiss, Larry A. ^[2]; Weitz, Eric ^[1]

Northwestern Univ., Evanston, IL (United States)
Argonne National Lab. (ANL), Argonne, IL (United States)

We report on a combined experimental and theoretical study of the acid catalyzed dehydration of d-fructose in dimethylsulfoxide (DMSO) using; Amberlyst 70, PO₄^3-/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.

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Research Organization:: Energy Frontier Research Centers (EFRC) (United States). Institute for Atom-efficient Chemical Transformations (IACT); Argonne National Lab. (ANL), Argonne, IL (United States)

Sponsoring Organization:: USDOE Office of Science (SC), Basic Energy Sciences (BES)

DOE Contract Number:: AC02-06CH11357

OSTI ID:: 1248733

Journal Information:: Applied Catalysis B: Environmental, Vol. 181, Issue C; ISSN 0926-3373

Publisher:: Elsevier

Country of Publication:: United States

Language:: English

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