4-Bromophenol → HCID 67393171, compound

HRID 1776934Notes

Reaction equation

HRID 1776934 reaction equation
[F:1][C:2]1[CH:7]=[CH:6][C:5]([C:8](=[O:15])[CH2:9][C:10]([O:12][CH2:13][CH3:14])=[O:11])=[CH:4][CH:3]=1.[Br:16][C:17]1[CH:22]=[CH:21][C:20](O)=[CH:19][CH:18]=1.C(OOC(C)(C)C)(C)(C)C>ClCCCl>[Br:16][C:17]1[CH:18]=[CH:19][C:20]2[O:15][C:8]([C:5]3[CH:4]=[CH:3][C:2]([F:1])=[CH:7][CH:6]=3)=[C:9]([C:10]([O:12][CH2:13][CH3:14])=[O:11])[C:21]=2[CH:22]=1

Participants

5

Reactant 3

HCID 78084-BromophenolHCID 8033Di-tert-butyl peroxideHCID 2758844Ethyl 3-(4-Fluorophenyl)-3-Oxopropanoate

Product 1

HCID 67393171HCID 67393171, compoundYield 17%

Reagents, catalysts & solvents 1

HCID 111,2-DichloroethaneSolvent

Procedure

A solution of ethyl 3-(4-fluorophenyl)-3-oxopropanoate (130 g, 0.6 mol), 4-bromophenol (311 g, 1.8 mol) and FeCl3.6H2O (19.5 g, 0.09 mol) in DCE (700 mL) was heated to reflux, and then 2-(tert-butylperoxy)-2-methylpropane (193 g, 1.32 mol) was added dropwise under nitrogen. After 6 hours of refluxing, the mixture was cooled to RT, quenched with saturated NaHSO3 and extracted with dichloromethane. The organic phases were washed with water, brine and dried over Na2SO4, filtered and concentrated in vacuo. The resulting residue was purified using column chromatography (petroleum ether/dichloromethane=15/1) to provide the crude product, which was crystallized from cold MeOH to provide ethyl 5-bromo-2-(4-fluorophenyl)benzofuran-3-carboxylate (37 g, yield: 14.3%) as solid. 1H-NMR (CDCl3, 400 MHz) δ 8.12 (s, 1H), 7.97˜8.01 (m, 2H), 7.37 (d, J=4.0 Hz, 1H), 7.32 (d, J=8.0 Hz, 1H), 7.11 (t, J=8.0 Hz, 2H), 4.32˜4.38 (m, 2H), 1.36 (t, J=8.0 Hz, 3H). MS (M+H)+: 363/365.

Workup

  1. temperatureto reflux
  2. temperatureAfter 6 hours of refluxing
  3. customquenched with saturated NaHSO3
  4. extractionextracted with dichloromethane
  5. washThe organic phases were washed with water, brine
  6. dry with materialdried over Na2SO4
  7. filtrationfiltered
  8. concentrationconcentrated in vacuo
  9. customThe resulting residue was purified
  10. customto provide the crude product, which
  11. customwas crystallized from cold MeOH

Sources & evidence

ORD record
ord-7858cac0427c45c79565aa57ce49ab00
Source dataset
uspto-grants-2016_02
Patent number
US09265773B2

Reaction notes

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