ACS Catalysis
Research Article
also possibly the case, which also explains why glucofuranoses
are not favored glucose isomers but AGF is still relatively
abundant in solution in comparison to AGP. The dehydration
of AGP in liquid phase has not been well studied; however, it
has been suggested that the hydration of AGP to glucose is the
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ez, E.; Horvat
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h, I. T.; Sheldon, R. A.; Poliakoff,
(
3
4,35
first step in the reactions leading to HMF.
However, the
(
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Green Chem. 2008, 10, 238−242. (b) Horvat
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presence of AGF and AGP suggests that the conversion of
́
36
glucose to HMF may also proceed through AGF and AGP.
1
́
́
We have also confirmed that LGN can be converted to HMF
with added 5 mol/L H SO at 130 °C in up to 65% yield in
́
2
4
GVL for GVL. Green Solvents Conference; Berchtesgaden, Germany;
only 4 min and reaching almost 80% LA and FA by further
heating. The numerous pathways available for acid-catalyzed
conversion of glucose to HMF makes determining which
pathways are the most dominant challenging, and this will be
October 10−13, 2010.
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37
Valerolactone as a Diesel Blend: Engine Performance and Emission
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the subject of a future publication.
CONCLUSIONS
■
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The conversion of fructose, glucose, and sucrose to HMF or
LA/FA using sulfuric acid as the catalyst and GVL as a green
solvent was investigated in detail. The H SO /GVL/H O
́
Horvath, I. T. “Catalytic Conversion of Carbohydrates to Oxygenates.
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Mika, L. T.; Horvath, I. T. Top. Catal. 2008, 48, 49−54.
2
4
2
system can be tuned to produce either HMF or LA/FA by
changing the acid concentration. The overall performance of
GVL was similar to DMSO, THF, acetonitrile, and acetone.
Although the best yields for HMF were around 75%, the LA/
FA yields ranged from 50% to 70%, depending on the
structures of the carbohydrates and reaction parameters,
including temperature, acid, and carbohydrate concentration.
While the conversion of fructose was much faster and gave
higher yields than glucose, sucrose behaved like the 1:1 mixture
of fructose and glucose, as expected. The mechanism of the
conversion of glucose to HMF or LA/FA in GVL involves three
intermediates: 1,6-anhydro-β-D-glucofuranose, 1,6-anhydro-β-
D-glucopyranose, and levoglucosenone.
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(
AUTHOR INFORMATION
Corresponding Author
■
(
1
2
(
́
Present Addresses
†
1
Department of Chemistry and Biochemistry, University of
Res. 1993, 32, 11−19. (c) Lichtenthaler, F. W. Acc. Chem. Res. 2002,
35, 728−737. (d) Roman-Leshkov, Y.; Chheda, J. N.; Dumesic, J. A.
Science 2006, 312, 1933−1937. (e) Zhao, H. B.; Holladay, J. E.; Brown,
H.; Zhang, Z. C. Science 2007, 316, 1597−1600. (f) Gen, Y.; Zhang, Y.;
Ying, J. Y. Angew. Chem., Int. Ed. 2008, 47, 9345−9348. (g) Takagaki,
A.; Ohara, M.; Nishimura, S.; Ebitani, K. Chem. Commun. 2009, 6276−
California, Santa Barbara, CA 93106, USA.
‡
Center for Environmentally Beneficial Catalysis, 1501
Wakarusa Drive, Lawrence, KS 66047, USA.
Notes
The authors declare no competing financial interest.
6
278. (h) Qi, X. H.; Watanabe, M.; Aida, T. M.; Smith, R. L. Green
Chem. 2009, 11, 1327−1331. (i) Huang, R.; Qi, W.; Su, R. X.; He, Z.
M. Chem. Commun. 2010, 46, 1115−1117. (j) Nikolla, E.; Roman
Leshkov, Y.; Moliner, M.; Davis, M. E. ACS Catal. 2011, 1, 408−410.
k) Akien, G. R.; Qi, L.; Horvath, I. T. Chem. Commun. 2012, 48,
850−5852. (l) Beckerle, K.; Okuda, J. J. Mol. Catal. A: Chem. 2012,
ACKNOWLEDGMENTS
This work was funded by the City University of Hong Kong,
Project No. 9380047.
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dx.doi.org/10.1021/cs401160y | ACS Catal. 2014, 4, 1470−1477