Boron trifluoride etherate → 2-Bromo-4-(4-ethoxybenzyl)benzyl acetate

HRID 1716949Notes

Reaction equation

HRID 1716949 reaction equation
[C:1]([O:4][CH2:5][C:6]1[CH:11]=[CH:10][C:9]([C:12](=O)[C:13]2[CH:18]=[CH:17][C:16]([O:19][CH2:20][CH3:21])=[CH:15][CH:14]=2)=[CH:8][C:7]=1[Br:23])(=[O:3])[CH3:2].[SiH](CC)(CC)CC.B(F)(F)F.CCOCC>ClCCCl.CC#N>[C:1]([O:4][CH2:5][C:6]1[CH:11]=[CH:10][C:9]([CH2:12][C:13]2[CH:18]=[CH:17][C:16]([O:19][CH2:20][CH3:21])=[CH:15][CH:14]=2)=[CH:8][C:7]=1[Br:23])(=[O:3])[CH3:2]

Participants

5

Reactant 3

HCID 8000Boron trifluoride etherateHCID 12052TriethylsilaneHCID 590134512-Bromo-4-(4-ethoxybenzoyl)benzyl acetate

Product 1

HCID 590134702-Bromo-4-(4-ethoxybenzyl)benzyl acetateYield 60.6%

Reagents, catalysts & solvents 1

HCID 22402149Acetonitrile 1,2-dichloroethaneSolvent

Conditions

Temperature
25 °C

Procedure

To a stirred solution of 2-bromo-4-(4-ethoxybenzoyl)benzyl acetate (0.41 g, 1.09 mmol) and Et3SiH (0.44 μL, 2.76 mmoL) in 1,2-dichloroethane/MeCN (2.5 mL, 1:2), was added dropwise BF3.Et2O (0.21 mL, 1.66 mmol). The reaction was complete after stirring for about 17 h at 25° C. Upon cooling, the reaction was quenched with 0.5 mL of 28.5% NaOH aqueous solution. The aqueous layer was extracted 2× with CH2Cl2, the combined organic layers were washed once with 2M KOH, 2× with H2O containing 10% brine and 2× with brine prior to drying over Na2SO4. After removal of the volatiles, the residue was purified by silica gel column (10:1 petroleum ether/ethyl acetate) to yield 0.24 g of title compound. 1H NMR (CDCl3, 300 MHz): δ 7.39 (s, 1H), 7.20 (d, J=8.0 Hz, 1H), 7.12 (d, J=8.0 Hz, 1H), 7.07 (d, J=8.4 Hz, 2H), 6.83 (d, J=8.4 Hz, 2H), 5.15 (s, 2H), 4.01 (q, J=7.0 Hz, 2H), 3.88 (s, 2H), 2.12 (s, 3H), 1.40 (t, J=7.0 Hz, 3H); MS ESI (m/z) 380 (M+NH4)+, calc. 362.

Workup

  1. temperatureUpon cooling
  2. customthe reaction was quenched with 0.5 mL of 28.5% NaOH aqueous solution
  3. extractionThe aqueous layer was extracted 2× with CH2Cl2
  4. washthe combined organic layers were washed once with 2M KOH, 2× with H2O containing 10% brine and 2× with brine
  5. dry with materialto drying over Na2SO4
  6. customAfter removal of the volatiles
  7. customthe residue was purified by silica gel column (10:1 petroleum ether/ethyl acetate)

Sources & evidence

ORD record
ord-35620e65f3314fc3bbd5415d78ef87ff
Source dataset
uspto-grants-2010_09
Patent number
US07803778B2

Reaction notes

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