1-(2-Bromo-5-fluorophenyl)ethan-1-one → 1654735-54-2

HRID 632660Notes

Reaction equation

HRID 632660 reaction equation
[Li][CH2:2]CCC.[Br:6][C:7]1[CH:12]=[CH:11][C:10]([F:13])=[CH:9][C:8]=1[C:14](=O)[CH3:15]>[Br-].C[P+](C1C=CC=CC=1)(C1C=CC=CC=1)C1C=CC=CC=1.C(OCC)C>[Br:6][C:7]1[CH:12]=[CH:11][C:10]([F:13])=[CH:9][C:8]=1[C:14]([CH3:15])=[CH2:2]

Participants

5

Reactant 2

HCID 227360801-(2-Bromo-5-fluorophenyl)ethan-1-oneHCID 178418339Butyllithium

Product 1

HCID 903591701654735-54-2

Reagents, catalysts & solvents 2

HCID 74505Methyltriphenyliphosphonium bromideCatalystHCID 3283Diethyl EtherSolvent2×

Procedure

To a suspension of methyltriphenylphosphonium bromide (5.69 g, 15.91 mmol) in diethyl ether (80 mL) at room temperature was added n-BuLi (2.5 M in hexanes, 6.37 mL, 15.91 mmol) dropwise. The reaction immediately turned bright orange and the resulting solution was stirred for 35 min at room temperature after which time a solution of l-(2-bromo-5-fluorophenyl)ethanone (3.14 g, 14.47 mmol) in diethyl ether (20 mL) was added dropwise. The reaction lost the bright yellow color and became almost completely white with a significant amount of white precipitate, the reaction was stirred for 89 h after it was quenched by addition of water and extracted with diethyl ether (3×), the combined organic layers were dried over anhydrous MgSO4, filtered and concentrated in vacuo. The resulting crude material was purified by column chromatography (SiO2, 0-5% Diethyl Ether/Hexanes) to afford 1-bromo-4-fluoro-2-(prop-1-en-2-yl)benzene. 1H NMR (400 MHz, CDCl3) δ ppm 7.49 (dd, J=8.8, 5.3 Hz, 1H), 6.92 (dd, J=9.0, 3.1 Hz, 1H), 6.85 (td, J=8.3, 3.1 Hz, 1H), 5.24 (t, J=1.7 Hz, 1H), 4.96 (s, 1H), 2.08 (d, J=1.4 Hz, 3H).

Workup

  1. customThe reaction immediately turned bright orange
  2. additionwas added dropwise
  3. customwas quenched by addition of water
  4. extractionextracted with diethyl ether (3×)
  5. dry with materialthe combined organic layers were dried over anhydrous MgSO4
  6. filtrationfiltered
  7. concentrationconcentrated in vacuo
  8. customThe resulting crude material was purified by column chromatography (SiO2, 0-5% Diethyl Ether/Hexanes)

Sources & evidence

ORD record
ord-c20ee6fbe7de43d3bcf6d8e3d5918697
Source dataset
uspto-grants-2016_04
Patent number
US09321746B2

Reaction notes

Loading…