X. Tong et al. / Carbohydrate Research 345 (2010) 1698–1701
1701
CH2OH
CH2OH
O
CH2OH
O
OH
O
CH2OH
OH
O
CHOH
OH
H
H
CHO
OH
O
H
N
CH3
OH
OH
OH
-
CH3SO3
Scheme 3. Possible mechanism for the dehydration of
D-fructose.
3.2.3. Synthesis and characterization of [NMM]+[HSO4]À
[NMM]+[HSO4]À is prepared by mixing N-methylmorpholine
with concd H2SO4 (98%) at 0 °C and stirring for 2 h at room temper-
ature. After that the liquid is washed with EtOAc three times and
dried at 80 °C in vacuum. [NMM]+[HSO4]À was obtained in quanti-
tative yield. 1H NMR (DMSO-d6): d 2.79 (s, 3H), 3.186 (s, 4H), 3.735
(s, 4H); 13C NMR (D2O): d 43.26, 53.23, 63.85. ESIMS: m/z (+)
102.23, m/z (À) 96.99.
Acknowledgements
X. Tong thanks the China Postdoctoral Science Foundation
(20080440676 and 200902273) for financial support. Li thanks
the Natural Science Foundation of China for support under contract
number 20425619. The work has been also supported by the Pro-
gram of Introducing Talents to the University Disciplines under file
number B06006, and the Program for Changjiang Scholars and
Innovative Research Teams in Universities under file number IRT
0641.
3.2.4. Synthesis and characterization of [MIM]+[HSO4]À
[MIM]+[HSO4]À was prepared under conditions similar to those
used for [NMM]+[HSO4]À. The corresponding NMR and ESIMS spec-
tral data are as follows: 1H NMR (DMSO-d6): d 3.850 (s, 3H), 7.645–
7.674 (d, 2H, J 25.1 Hz), 9.037 (s, 1H); 13C NMR (D2O): d 35.46,
57.40, 119.48, 122.97. ESIMS: m/z (+) 83.26, m/z (À) 97.02.
Supplementary data
Supplementary data (HPLC measurements for products, original
NMR spetra and ESIMS spectra) associated with this article can be
3.3. Reaction conditions for the dehydration of
sucrose
D-fructose and
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In summary, efficient catalytic syntheses of HMF from D-fructose
and sucrose havebeen successfullyperformed in the presenceof cat-
alytic amounts of protic ILs under mild conditions. The IL
[NMM]+[CH3SO3]À shows very high catalytic activity. A 74.8% or
47.5% yield of HMF is obtained from D-fructose or sucrose, respec-
tively, when [NMM]+[CH3SO3]À is used as the catalyst in the DMF–
LiBr system at 90 °C for 2 h. Furthermore, the acidities of ILs were
measured by the Hammett method, which have a close correlation
to the observed catalytic activities. The effects of reaction tempera-
ture and reaction time on the dehydration reaction were examined,
and a possible reaction mechanism for the
proposed.
D-fructose dehydration is