Butyl vinyl ether → 1-(4-Fluoro-2-methylphenyl)ethan-1-one

HRID 10210

Reaction equation

Br[C:2]1[CH:7]=[CH:6][C:5]([F:8])=[CH:4][C:3]=1[CH3:9].[CH:10]([O:12]CCCC)=[CH2:11].C1(P(C2C=CC=CC=2)CCCP(C2C=CC=CC=2)C2C=CC=CC=2)C=CC=CC=1.C(=O)([O-])[O-].[K+].[K+]>CN(C=O)C.O.CCOC(C)=O.Cl.C([O-])(=O)C.[Pd+2].C([O-])(=O)C>[F:8][C:5]1[CH:6]=[CH:7][C:2]([C:10](=[O:12])[CH3:11])=[C:3]([CH3:9])[CH:4]=1

Participants

Conditions

Temperature: 80 °C

Procedure

To a solution of 2-bromo-5-fluorotoluene (5 g, 26.5 mmol) in DMF (65 ml) and water (15 ml) was added butyl vinyl ether (6.6 g, 65.9 mmol), palladium acetate (0.18 g, 0.8 mmol), 1,3-bis(diphenylphosphino)propane (0.72 g, 1.75 mmol) and potassium carbonate (4.4 g, 31.8 mmol). The reaction was heated at 80° C. for 48 h under nitrogen. The cooled reaction mixture was diluted with EtOAc (˜250 ml) and concentrated HCl added and shaken. Further EtOAc and water were added to obtain an easier separation of the 2 layers. The organic layer was washed with brine, dried (MgSO4), and concentrated. The residue was purified on a plug of silica eluting with 3% EtOAc/isohexane to give the title compound as an oil (1.95 g, 49%). 1H NMR (400 MHz, d6-DMSO) δ 2.45 (3H, s), 2.54 (3H, s), 7.13–7.17 (2H, m), 7.89–7.93 (1H, m).

Workup

customThe cooled reaction mixture
additionadded
customto obtain
customan easier separation of the 2 layers
washThe organic layer was washed with brine
dry with materialdried (MgSO4)
concentrationconcentrated
customThe residue was purified on a plug of silica eluting with 3% EtOAc/isohexane

Sources & evidence

ORD record: ord-c1acfb3adf39446d8b5e3103b040d2f4
Source dataset: uspto-grants-2006_08
DOI: 10.6084/m9.figshare.5104873.v1
Patent number: US07094777B2

Linked notes

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