Highly Efficient Oxidative Bromination of Alkanes with the HBr-H2O2 System
Experimental
2004, 2536.
5
(a) Adimurthy, S.; Ramachandraiah, G.; Bedekar, A. V.;
Ghosh, S.; Ranu, B. C.; Ghosh, P. K. Green Chem. 2006, 8,
916.
The typical procedure for the bromination of alkane
in aqueous HBr-H2O2 system with catalyst
Methord A: a mixture of cyclohexane (10 g), 40%
aqueous solution of HBr (4.8 g, 23.8 mmol) and the
diatomite (0.8 g) was stirred at 80 ℃, followed by the
addition of 30% H2O2 (3.8 g, 35.6 mmol) with a peri-
staltic pump at slow speed of about 1 mL/h for 3— 4 h.
After the disappearance of the bromine color at about 7
h, the mixture was filtered and the filtrate was washed
with aqueous NaHSO3 to remove the unreacted Br2 and
H2O2 and dried over anhydrous Na2SO4. The product
cyclohexylbromide was recovered by distillation under
reduced pressure. The crude product was then analyzed
(b) Adimurthy, S.; Ghosh, S.; Patoliya, P. U.; Ramachand-
raiah, G.; Agrawal, M.; Gandhi, M. R.; Upadhyay, S. C.;
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Ogibin, Y. N.; Nikishin, G. I. Synthesis 2004, 2845.
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58, 1110.
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Chem. 2004, 6, 110.
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Gopinath, R.; Khan, A. T.; Patel, B. K. Org. Lett. 2000, 2,
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6
7
8
1
by H NMR spectroscopy. The bromocyclohexane was
purified by distillation in vacuum. B.p. 166 ℃; 1H NMR
(CDCl3, 500 MHz) δ: 4.19— 4.21 (m, 1H, CHBr),
2.14— 2.17 (m, 2H, CH2), 1.78— 1.83 (m, 4H, CH2),
1.56— 1.58 (m, 1H, CH2), 1.35— 1.37 (m, 3H, CH2).
The dibromocyclohexane was isolated by silica gel
column chromatography with petroleum ether as the
1
eluent. H NMR (CDCl3, 500 MHz) δ: 4.40— 4.53 (m,
2H, CHBr), 2.44— 2.48 (m, 2H, CH2), 1.79— 1.91(m,
4H, CH2), 1.50— 1.59 (m, 2H, CH2); EI-MS (70 eV) m/z
(%): 242.9 (10), 240.9 (20), 238.9 (10) [C6H9Br2+],
163.0,+ 161.0 (40) [C6H10Br + ], 159.0, 81.1 (100)
[C6H9 ].
Methord B: the mixture of 1,2-dichloroethane (5
mL), n-octane (2 g, 17.5 mmol), 40% aqueous solution
of HBr (3.6 g, 17.5 mmol) and the diatomite (0.8 g) was
stirred at 80 ℃, followed by the addition of 30% H2O2
(3.0 mL, 26.3 mmol) with a peristaltic pump at slow
speed of about 1 mL/h for 3 h, stirred until the color
disappeared for 7 h. The mixture was filtered and the
filtrate was washed with aqueous NaHSO3 to remove
the unreacted Br2 and H2O2 and dried over anhydrous
Na2SO4. The product was recovered by distillation un-
der reduced pressure. The crude product was then ana-
lyzed by 1H NMR spectroscopy.
9
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