3
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J. Tao et al.
SHORT PAPER
PEG-NO 8
(2) (a) Collins, T. J. Acc. Chem. Res. 1994, 27, 279. (b) Hill, C.
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2
A gas stream containing NO was obtained by drying and oxidizing
the feed gas NOx, which was produced by the reaction of NaNO
2
2
–
1
with H SO (0.5 mol·L ). The process of drying and oxidation was
2
4
achieved by passing the NOx flow through an oxidizing column,
which was packed with oxide sand (CrO /sand = 1:20) to ensure the
conversion of NO to NO , the absorption was performed by bub-
3
2
bling NO through PEG-400 (20 g) until the weight was increased
(3) (a) Grinstaff, M. W.; Hill, M. G.; Labinger, J. A.; Gray, H.
B. Science 1994, 264, 1311. (b) Sorokin, A.; Seris, J. L.;
Meunier, B. Science 1995, 268, 1163. (c) Horwitz, C. P.;
Fooksman, D. R.; Vuocolo, L. D.; Gordon-Wylie, S. W.;
Cox, N. J.; Collins, T. J. J. Am. Chem. Soc. 1998, 120, 4867.
(d) Gupta, S. S.; Stadler, M.; Noser, C. A.; Ghosh, A.;
Steinhoff, B.; Lenoir, D.; Horwitz, C. P.; Schramm, K. W.;
Collins, T. J. Science 2002, 296, 326. (e) Chang, C. K.;
Ebina, F. J. Chem. Soc., Chem. Commun. 1981, 778.
(4) (a) Dijksman, A.; Marino-Gonzalez, A.; Mairata i payeras,
A.; Arends, I. W. C. E.; Sheldon, R. A. J. Am. Chem. Soc.
2001, 123, 6826. (b) Zhang, M.; Chen, C.; Ma, W.; Zhao, J.
Angew. Chem. Int. Ed. 2008, 47, 9730. (c) He, X.; Shen, Z.;
Mo, W.; Sun, N.; Hu, B.; Hu, X. Adv. Synth. Catal. 2009,
351, 89. (d) Figiel, P. J.; Leskelä, M.; Repo, T. Adv. Synth.
Catal. 2007, 349, 1173. (e) Wang, N.; Liu, R.; Chen, J.;
Liang, X. Chem. Commun. 2005, 5322. (f) Gamez, P.;
Arends, I. W. C. E.; Reedijk, J.; Sheldon, R. A. Chem.
Commun. 2003, 2414.
2
to about 27.3 g containing 26% of NO in the mixture.
2
Preparation of Catalyst Solution
A solution of 4-MeO-TEMPO (18.6 mg) in DCE was put into a 10
mL volumetric flask, and it was set to the marked volume. Thus, 50
mL of this solution contained 0.093 mg of 4-MeO-TEMPO.
Oxidation of Benzyl Alcohols with 4-MeO-TEMPO/PEG-NO2/
HCl Catalytic System; General Procedure
A mixture of PEG-NO (26.7%, w/w, 86 mg, 0.5 mmol, based on
2
NO ), aq 12 M HCl (25.3 mg, 0.25 mmol), 4-MeO-TEMPO (0.093
2
mg, 0.0005 mmol), and the respective benzyl alcohol (5.0 mmol) in
DCE (10 mL) was connected to an O balloon and stirred at 40 °C
2
until the alcohol was totally consumed (Table 1). After completion
of the reaction, a mixture of DCE (20 mL), sat. aq Na SO (5 mL),
2
3
and sat. aq NaHCO (5 mL) was added, the organic layer was sepa-
3
rated and washed with H O (5 mL). The conversion and selectivity
2
of the product were detected by GC without further purification.
(
5) (a) Fey, T.; Fischer, H.; Bachmann, S.; Albert, K.; Bolm, C.
J. Org. Chem. 2001, 66, 8154. (b) Ciriminna, R.; Bolm, C.;
Fey, T.; Pagliaro, M. Adv. Synth. Catal. 2002, 344, 159.
(c) Brunel, D.; Fajula, F.; Nagy, J. B.; Deroide, B.; Verhoef,
M. J.; Veum, L.; Peters, J. A.; van Bekkum, H. Appl. Catal.,
A 2001, 213, 73. (d) Karimi, B.; Biglari, A.; Clark, J. H.;
Budarin, V. Angew. Chem. Int. Ed. 2007, 46, 7210.
(e) Pozzi, G.; Cavazzini, M.; Quici, S.; Benaglia, M.;
Dell’Anna, G. Org. Lett. 2004, 6, 441.
Oxidation of Aliphatic Alcohols with 4-MeO-TEMPO/HCl/
PEG-NO Catalytic System; General Procedure
2
To a Teflon-lined 316 L stainless steel autoclave were added PEG-
NO (86 mg, 0.5 mmol, based on NO ), aq 12 M HCl (25.3 mg, 0.25
2
2
mmol), 4-MeO-TEMPO (9.3 mg, 0.05 mmol), and the aliphatic al-
cohol (5 mmol) in DCE (10 mL). Then the autoclave was closed and
charged O to 0.4 MPa. The autoclave was heated to 60 °C (oil bath)
2
for the desired time (Table 1). After completion of the reaction, the
autoclave was cooled to r.t. and carefully depressurized. Then, a
mixture of DCE (20 mL), sat. aq Na SO (5 mL) and sat. aq
(6) Liu, R.; Liang, X.; Dong, C.; Hu, X. J. Am. Chem. Soc. 2004,
126, 4112.
2
3
NaHCO (5 mL) was added, the organic layer was separated and
(7) (a) Liu, R.; Dong, C.; Liang, X.; Wang, X.; Hu, X. J. Org.
Chem. 2005, 70, 729. (b) Liang, X.; Fu, D.; Liu, R.; Zhang,
Q.; Zhang, T. Y.; Hu, X. Angew. Chem. Int. Ed. 2005, 44,
3
washed with H O (5 mL). The conversion and selectivity of the
2
product were determined by GC without further purification.
5520. (c) Wang, X.; Liu, R.; Jin, Y.; Liang, X. Chem. Eur. J.
2
008, 14, 2679. (d) Dobbs, A. P.; Penny, M. J.; Jones, P.
Supporting Information for this article is available online at
http://www.thieme-connect.com/ejournals/toc/synthesis.
Tetrahedron Lett. 2008, 49, 6955. (e) Kloth, K.; Brünjes,
M.; Kunst, E.; Joge, T.; Gallier, F.; Adibekian, A.;
Kirschning, A. Adv. Synth. Catal. 2005, 347, 1423. (f) Xie,
Y.; Mo, W.; Xu, D.; Shen, Z.; Sun, N.; Hu, B.; Hu, X. J. Org.
Chem. 2007, 72, 4288. (g) Yang, G.; Zhu, W.; Zhang, P.;
Xue, H.; Wang, W.; Tian, J.; Song, M. Adv. Synth. Catal.
Acknowledgment
We acknowledge the financial support from National High Techno-
logy Research and Development Program of China (863 Program)
2008, 350, 542. (h) Huang, J.; Li, S.; Wang, Y. Tetrahedron
Lett. 2006, 47, 5637. (i) Lei, M.; Hu, R.; Wang, Y.
Tetrahedron 2006, 62, 8928. (j) Yin, W.; Chu, C.; Lu, Q.;
Tao, J.; Liang, X.; Liu, R. Adv. Synth. Catal. 2010, 352, 113.
8) Qiao, R.; Zhang, Y.; Hui, X.; Xu, P.; Zhang, Z.; Wang, X.;
Wang, Y. Green Chem. 2001, 3, 186.
(
No. 2008AA06Z306) and the National Natural Science Foundation
of China (No. 21072055)
(
References
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1) (a) Gallezot, P. Catal. Today 1997, 37, 405. (b) Thomas, J.
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Synthesis 2010, No. 23, 3974–3976 © Thieme Stuttgart · New York