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DOI: 10.1055/s-2002-35600
A Novel and One Step Procedure for Preparation of α-Bromo-α,β-unsaturated Carbonyl Compounds
Publication History
Publication Date:
20 November 2002 (online)
Abstract
A new one step method is developed for the preparation of α-bromo-α,β-unsaturated carbonyl compounds in moderate to good yields from corresponding α,β-unsaturated carbonyl compounds using DMP [1,1,1-triacetoxy-1,1-dihydro-1,2-benziodoxol-3(1H)-one] and tetraethylammonium bromide under neutral and mild reaction conditions at room temperature.
Key words
DMP - tetraethylammonium bromide - α-bromo-α,β- unsaturated carbonyl compounds - bromination.
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References
Typical procedure:
3-Bromo-2H-1-benzopyran-2-one (entry
8): To a suspension of DMP (6.97 g, 16.4 mmol) in dry dichloromethane
(30 mL) was added Et4N+Br- (3.45
g, 16.4 mmol) in one portion with stirring and the color of solution
turned to orange-yellow. After 10 min of stirring at room temperature
coumarin (2.00 g, 13.7 mmol) was added. The reaction was monitored
by TLC. At the end of the reaction (24 h) the precipitate formed
was filtered, washed with dichloromethane (2 × 20mL). The
filtrate was then washed with saturated sodium bisulphite solution,
followed by saturated bicarbonate solution and water. The organic layer
was dried over anhydrous sodium sulfate and concentrated in vacuo
to get a crude product, which was purified by column chromatography
to give 3-bromo-2H-1-benzopyran-2-one
(2.14 g, 70%) as off-white solid. Mp 108 °C (ref.
[24]
110 °C).
IR (KBr): 1735, 1606 cm-1. 1H
NMR (500 MHz, CDCl3): δ 8.10 (s, 1 H, Ha), 7.57
(t, 1 H, J = 7.6 Hz, Hb), 7.46
(d, 1 H, J = 7.6 Hz, Hc), 7.36
(d, 1 H, J = 8.4 Hz, Hd), 7.32
(t, 1 H, J = 7.6 Hz, He). 13C
NMR (CDCl3): δ 157.0 (d, J = 8.4
Hz, C-1), 153.1 (s, C-2), 144.4 (d, J = 167.6
Hz, C-3), 132.0 (dd, J = 161.2
Hz, 8.4 Hz, C-4), 127.1 (d,
J = 162.1
Hz, C-5), 125.0 (dd, J = 164.0
Hz, 6.9 Hz, C-6), 119.2 (s, C-7), 116.7 (dd, J = 164.4
Hz, 6.8 Hz, C-8), 111.7 (s, C-9).