Dehydration of different ketoses and aldoses to 5-hydroxymethylfurfural

R.-J. Putten, van, J.N.M. Soetedjo, E.A. Pidko, J.C. Waal, van der, E.J.M. Hensen, E. Jong, de, H.J. Heeres

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Abstract

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.
Original languageEnglish
Pages (from-to)1681-1687
Number of pages7
JournalChemSusChem
Volume6
Issue number9
DOIs
Publication statusPublished - 2013

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Ketoses
Dehydration
dehydration
Hydroxyl Radical
Fructose
Catalyst selectivity
Sorbose
Isomerization
Discrete Fourier transforms
reaction rate
Reaction rates
Hexoses
Glucose
Screening
glucose
experimental study
Mannose
Galactose
substrate
kinetics

Cite this

Putten, van, R-J., Soetedjo, J. N. M., Pidko, E. A., Waal, van der, J. C., Hensen, E. J. M., Jong, de, E., & Heeres, H. J. (2013). Dehydration of different ketoses and aldoses to 5-hydroxymethylfurfural. ChemSusChem, 6(9), 1681-1687. https://doi.org/10.1002/cssc.201300345
Putten, van, R.-J. ; Soetedjo, J.N.M. ; Pidko, E.A. ; Waal, van der, J.C. ; Hensen, E.J.M. ; Jong, de, E. ; Heeres, H.J. / Dehydration of different ketoses and aldoses to 5-hydroxymethylfurfural. In: ChemSusChem. 2013 ; Vol. 6, No. 9. pp. 1681-1687.
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abstract = "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.",
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Putten, van, R-J, Soetedjo, JNM, Pidko, EA, Waal, van der, JC, Hensen, EJM, Jong, de, E & Heeres, HJ 2013, 'Dehydration of different ketoses and aldoses to 5-hydroxymethylfurfural', ChemSusChem, vol. 6, no. 9, pp. 1681-1687. https://doi.org/10.1002/cssc.201300345

Dehydration of different ketoses and aldoses to 5-hydroxymethylfurfural. / Putten, van, R.-J.; Soetedjo, J.N.M.; Pidko, E.A.; Waal, van der, J.C.; Hensen, E.J.M.; Jong, de, E.; Heeres, H.J.

In: ChemSusChem, Vol. 6, No. 9, 2013, p. 1681-1687.

Research output: Contribution to journalArticleAcademicpeer-review

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T1 - Dehydration of different ketoses and aldoses to 5-hydroxymethylfurfural

AU - Putten, van, R.-J.

AU - Soetedjo, J.N.M.

AU - Pidko, E.A.

AU - Waal, van der, J.C.

AU - Hensen, E.J.M.

AU - Jong, de, E.

AU - Heeres, H.J.

PY - 2013

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N2 - 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.

AB - 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.

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Putten, van R-J, Soetedjo JNM, Pidko EA, Waal, van der JC, Hensen EJM, Jong, de E et al. Dehydration of different ketoses and aldoses to 5-hydroxymethylfurfural. ChemSusChem. 2013;6(9):1681-1687. https://doi.org/10.1002/cssc.201300345