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L. Xu et al.
LETTER
Table 3 NaNO2-Catalyzed Aerobic Oxybromination of Various
References and Notes
Phenols Using Br2 as the Bromine Sourcea (continued)
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Entry Product
Temp Method Time Yield
(°C)
(min) (%)b
7
15
A
B
40
120
92
92
OH
Br
(4) (a) Venkateswarlu, K.; Suneel, K.; Das, B.; Reddy, K. N.;
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8
15
35
A
B
60
180
96
95
Br
OH
9
A
B
60
300
94
OH
90c
Br
Br
Cl
10
35
A
B
60
300
94
91
(8) Barhate, N. B.; Gajare, A. S.; Wakharkar, R. D.; Bedekar,
OH
A. V. Tetrahedron 1999, 55, 11127.
Br
Cl
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Raghavan, K. V. J. Chem. Res., Synop. 2003, 9, 597.
(b) Narender, N.; Srinivasu, P.; Prasad, M. R.; Kulkarni,
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Cl
a Reaction conditions: phenol (5.00 mmol), Br2 (2.63 mmol), NaNO2
(0.15 mmol), MeCN (10.0 mL). Method A: 0.1 MPa oxygen pressure
(oxygen balloon); Method B: 0.1 MPa air pressure (air balloon).
b Isolated yield.
c Phenol (1.00 mmol), Br2 (1.05 mmol), NaNO2 (0.03 mmol), MeCN
(3.0 mL).
In summary, we have developed an efficient method for
the aerobic oxybromination of a variety of phenols using
sodium nitrite as the catalyst and dioxygen or air as termi-
nal oxidant under mild conditions. Both aqueous solution
of hydrobromic acid and molecular bromine can be used
as the brominating reagents.17 The excellent performance
of the newly developed oxybromination protocol was ex-
pected to provide a valuable synthetic method for practi-
cal applications in laboratory or industry.
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Supporting Information for this article is available online at
4, 1213.
(16) Zhang, G. F.; Liu, R. H.; Xu, Q.; Ma, L. X.; Liang, X. M.
Adv. Synth. Catal. 2006, 348, 862.
(17) Representative Procedure
Acknowledgment
In a 250 mL Schlenk flask equipped with magnetic stirrer,
filled with dioxygen beforehand, was placed phenol (0.4706
g, 5.00 mmol) dissolved in MeCN (10.0 mL) under O2. Then
a 42% aq solution of HBr (1.0125 g, 5.25 mmol) was added
to the solution. Next, the NaNO2 (0.0103 g, 0.15 mmol) was
added in one portion, and the system was immediately
sealed. The reaction mixture was stirred at 25 °C. After the
reaction, the solvent was removed under vacuum, and the
The authors gratefully acknowledge the financial support from the
National Natural Science Foundation of China (No. 20572110 and
20702051), and Educational Commission of Zhejiang Province (Y
200907685)
Synlett 2011, No. 15, 2265–2269 © Thieme Stuttgart · New York