802
Z. Yang et al. / Catalysis Communications 12 (2011) 798–802
Table 3
Esterification of carboxylic acid with ethanol catalyzed by SS-0.010.
a
b
Entry
Substrate
Reaction
time (h)
Conversion (%)
Selectivity
(%)
Product
TOF
a
(mmol/g·h)
1
2
4
4
99
99
99
99
61.1
61.1
47.0
3
4
5
5
12
5.5
96
71
99
98
99
98
14.6
44.1
6
7
7
94
99
99
94
33.2
35.8
6.5
Reaction condition: ethanol (2.3 g, 50 mmol), carboxylic acid (2.50 mmol), catalyst SS-0.010 (10.0 mg), 100 °C.
a
Conversion and selectivity were determined by GC analysis.
TOF = (carboxylic acid amount (mmol) * substrate conversion * product selectivity) / (catalyst amount (g) * reaction time (h)).
b
Product 3b: 1H NMR (CDCl3, 400 MHz): δ 4.235 (2H), 2.643 (2H),
1.867 (2H), 1.795 (4H). 13C NMR (CDCl3, 100 MHz): δ 171.339, 69.331,
29.636, 22.091, 18.875.
also thank Key Laboratory of Eco-Environment-Related Polymer
Materials (Northwest Normal University), Ministry of Education, for
financial support.
Product 4b: 1H NMR (CDCl3, 400 MHz): δ 4.449 (1H), 2.653 (2H),
1.930 (4H), 1.627 (2H), 1.352 (3H). 13C NMR (CDCl3, 100 MHz): δ
175.60, 76.80, 36.21, 35.00, 28.28, 22.88, 22.57.
Appendix A. Supplementary Data
Product 5b: 1H NMR (CDCl3, 400 MHz): δ 4.188 (2H), 2.630 (2H),
1.912 (2H), 1.862 (1H), 1.498 (1H), 1.343 (1H), 1.002 (3H). 13C NMR
(CDCl3, 100 MHz): δ 175.995, 67.984, 37.097, 35.116, 33.081, 30.634,
22.008.
Supplementary data to this article can be found online at
doi:10.1016/j.catcom.2011.01.028.
Product 6b: 1H NMR (CDCl3, 400 MHz): δ 4.054 (1H), 2.518 (2H),
1.857 (4H), 1.611 (1H), 1.310 (1H), 1.051 (3H), 0.975 (6H). 13C NMR
(CDCl3, 100 MHz): δ 174.951, 84.659, 420493, 37.379, 33.248, 30.848,
30.330, 23.905, 18.319, 17.039.
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The prepared silica sulfate, especially SS-0.010, was acted as an
efficient and recyclable solid acid catalyst for Baeyer–Villiger
oxidation of ketones and esterification of carboxylic acid under mild
conditions. The catalyst exhibits the advantages of high conversion,
high selectivity, recyclability, and multifunction. The results also
showed that SO3H groups were successfully introduced to silica
surface while keeping its structure intact, which suggested that the
immobilizing method described here can be extended for attachment
of other functional groups on the surface of silica to generate diverse
functionalized silica for different applications.
Acknowledgements
The research was financial supported by NSFC (20774074), Gansu
Provincial Natural Science Foundation of China (3ZS061-A25-018)
and Scientific Research Fund of NWNU (NWNU-KJCXGC-03-56). We
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