Methanol → 1-(3-Bromophenyl)-4-fluorobutan-1-one

HRID 30568Notes

Reaction equation

[Br:1][C:2]1[CH:7]=[CH:6][CH:5]=[C:4]([C:8]#[C:9][CH2:10][CH2:11][F:12])[CH:3]=1.CO.[OH:15]S(O)(=O)=O>[CH3-].C1C=CC(P(C2C=CC=CC=2)C2C=CC=CC=2)=CC=1.[Au+].O>[Br:1][C:2]1[CH:3]=[C:4]([C:8](=[O:15])[CH2:9][CH2:10][CH2:11][F:12])[CH:5]=[CH:6][CH:7]=1

Participants

Conditions

Temperature: 72 °C

Procedure

A mixture of 0.2 gm (0.89 mmol) of 1-bromo-3-(4-fluorobut-1-ynyl)benzene, 2 mL of MeOH, 1 mg of methyl(triphenylphosphine)gold (I), 25 μL of conc. H2SO4 and 0.44 mL of H2O was placed in a sealed tube, flushed with argon, heated to 72° C. for 2 h and was cooled. The reaction mixture was diluted with EtOAc, washed sequentially with water and brine, dried over Na2SO4 and concentrated under reduced pressure. Chromatography of the concentrate on silica gel with a gradient of 0% to 20% EtOAc-hexanes gave 1-(3-bromophenyl)-4-fluorobutan-1-one as an oil, 0.086 gm (40% yield); 1H NMR (400 MHz, CDCl3) δ: 2.13 (m, 2H), 3.09 (t, 2H, J=7.1 Hz), 4.53 (dt, 2H, J=5.8, 47.1 Hz), 7.33 (t, 1H, J=7.8 Hz), 7.66 (dq, 1H, J=1.0, 7.8 Hz), 7.55 (dq, 1H, J=1.0, 7.8 Hz), 8.07 (t, 1H, J=1.7 Hz).

Workup

customwas placed in a sealed tube
customflushed with argon
temperaturewas cooled
additionThe reaction mixture was diluted with EtOAc
washwashed sequentially with water and brine
dry with materialdried over Na2SO4
concentrationconcentrated under reduced pressure
concentrationChromatography of the concentrate on silica gel with a gradient of 0% to 20% EtOAc-hexanes

Sources & evidence

ORD record: ord-ba0799ae1a6447ff9dcddb78cfe9dd4b
Source dataset: uspto-grants-2008_09
DOI: 10.6084/m9.figshare.5104873.v1
Patent number: US07423158B2

Reaction notes

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