Dehydration of Different Ketoses and Aldoses to 5-Hydroxymethylfurfural

5‐Hydroxymethylfurfural (HMF) is considered an important building block for future bio‐based chemicals. Here, we present an experimental study using different ketoses (fructose, sorbose, tagatose) and aldoses (glucose, mannose, galactose) under aqueous acidic conditions (65 g L−1 substrate, 100–160 ...

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Veröffentlicht in:ChemSusChem Jg. 6; H. 9; S. 1681 - 1687
Hauptverfasser: van Putten, Robert-Jan, Soetedjo, Jenny N. M., Pidko, Evgeny A., van der Waal, Jan C., Hensen, Emiel J. M., de Jong, Ed, Heeres, Hero J.
Format: Journal Article
Sprache:Englisch
Veröffentlicht: Weinheim WILEY-VCH Verlag 01.09.2013
WILEY‐VCH Verlag
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Schlagworte:
5-hydroxymethylfurfural
aldose
biomass
Carbohydrate Conformation
Furaldehyde - analogs & derivatives
Furaldehyde - chemistry
ketose
Ketoses - chemistry
Kinetics
Models, Molecular
Quantum Theory
sugar dehydration
Water - chemistry
biomass
ketose
sugar dehydration
5-hydroxymethylfurfural
aldose
ISSN:1864-5631, 1864-564X, 1864-564X
Online-Zugang:Volltext
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Zusammenfassung:5‐Hydroxymethylfurfural (HMF) is considered an important building block for future bio‐based chemicals. Here, we present an experimental study using different ketoses (fructose, sorbose, tagatose) and aldoses (glucose, mannose, galactose) under aqueous acidic conditions (65 g L−1 substrate, 100–160 °C, 33–300 mM H2SO4) to gain insights into reaction pathways for hexose dehydration to HMF. Both reaction rates and HMF selectivities were significantly higher for ketoses than for aldoses, which is in line with literature. Screening and kinetic experiments showed that the reactivity of the different ketoses is a function of the hydroxyl group orientation at the C3 and C4 positions. These results, in combination with DFT calculations, point to a dehydration mechanism involving cyclic intermediates. For aldoses, no influence of the hydroxyl group orientation was observed, indicating a different rate‐determining step. The combination of the knowledge from the literature and the findings in this work indicates that aldoses require an isomerization to ketose prior to dehydration to obtain high HMF yields. Ketose dries out: Hexose dehydration to 5‐hydroxymethylfurfural is studied using different ketoses and aldoses. The reactivity of the different ketoses is found to be a function of the hydroxyl group orientation at the C3 and C4 positions. The results point to a dehydration mechanism involving cyclic intermediates. For aldoses, no influence of the hydroxyl group orientation is observed, indicating a different rate‐determining step.
Bibliographie:European Community - No. 311956
ark:/67375/WNG-FWTRGW1Q-P
Avantium Chemicals
istex:50EB87FC15D4B0D4BD1E0AC5969B87880C3AB43E
ArticleID:CSSC201300345
ObjectType-Article-1
SourceType-Scholarly Journals-1
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ISSN:1864-5631
1864-564X
1864-564X
DOI:10.1002/cssc.201300345