Paper
Green Chemistry
Representative procedure for decarbonylation
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A suspension of 0.125 g (1.0 mmol) of HMF and 0.1 g of 5 wt%
Pd/C in 5 mL of dioxane was heated at reflux (oil bath tempera-
ture: 120 °C) in air for 15 h with stirring.
Representative procedure for DMF synthesis
A pressure reactor was charged with HMF (0.5 mmol, 63 mg),
5 wt% Pd/C (100 mg, 10 mol%), dioxane (5 mL), and formic
acid (190 μL). The mixture was stirred at 120 °C (oil bath temp-
erature) for 15 h and cooled to room temperature. A known
amount of MeNO2 was added to the reaction mixture as
internal standard and the product yield was assayed by 1H
NMR spectroscopy.
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Representative procedure for hydrogenation/hydrogenolysis of
HMF
In a typical experiment, a Fisher–Porter reactor (150 mL) was 19 Y. Nakagawa, M. Tamura and K. Tomishige, ACS Catal.,
charged with HMF (0.50 mmol, 63 mg), 5 wt% Pd/C (100 mg, 2013, 3, 2655–2668.
10 mol%), and dioxane (5 mL). The reactor was refilled with 20 M. Chidambaram and A. T. Bell, Green Chem., 2010, 12,
H2 (30 psi) and the closed system was stirred at 120 °C (oil 1253–1262.
bath temperature). After 15 h, the mixture was cooled to room 21 Y. Kwon, E. de Jong, S. Raoufmoghaddam and
temperature. A known amount of MeNO2 was added as M. T. M. Koper, ChemSusChem, 2013, 6, 1659–1667.
internal standard and an aliquot was taken for analysis. Con- 22 Y. Nakagawa and K. Tomishige, Catal. Commun., 2010, 12,
version and selectivity of the product mixture were determined
by 1H NMR.
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Acknowledgements
This research was conducted under contract DEFG02-
90ER14146 with the U.S. Department of Energy by its Division 26 Y. Roman-Leshkov, C. J. Barrett, Z. Y. Liu and
of Chemical Sciences, Office of Basic Energy Sciences. Support J. A. Dumesic, Nature, 2007, 447, 982–985.
for JM and XY was provided in part by the Energy Biosciences 27 J. M. R. Gallo, D. M. Alonso, M. A. Mellmer and
Institute, funded by British Petroleum.
J. A. Dumesic, Green Chem., 2013, 15, 85–90.
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