Triphenylphosphine → 4-(Bromomethyl)-1-fluoro-2-(methylsulfonyl)benzene

HRID 447834Notes

Reaction equation

C1(P(C2C=CC=CC=2)C2C=CC=CC=2)C=CC=CC=1.[Br:20]Br.[F:22][C:23]1[CH:28]=[CH:27][C:26]([CH2:29]O)=[CH:25][C:24]=1[S:31]([CH3:34])(=[O:33])=[O:32].C(=O)([O-])O.[Na+]>C(#N)C>[Br:20][CH2:29][C:26]1[CH:27]=[CH:28][C:23]([F:22])=[C:24]([S:31]([CH3:34])(=[O:33])=[O:32])[CH:25]=1

Participants

Conditions

Temperature: 85 °C

Procedure

(Step 1) Triphenylphosphine (3.21 g) was suspended in acetonitrile (50 ml), bromine (0.64 ml) was added, and the mixture was stirred for 30 min. [4-Fluoro-3-(methylsulfonyl)phenyl]methanol (2.5 g) was added to the reaction mixture, and the mixture was stirred at 85° C. for 20 hr, treated with aqueous sodium hydrogen carbonate solution, and extracted with ethyl acetate. The extract was washed with saturated brine, and dried over anhydrous magnesium sulfate. The solvent was evaporated under reduced pressure. The obtained residue was purified by basic silica gel chromatography (ethyl acetate:hexane=1:1) to give 4-(bromomethyl)-1-fluoro-2-(methylsulfonyl)benzene (1.64 g). 1H NMR (300 MHz, CDCl3) 8 ppm 3.24 (3H, s), 4.49 (2H, s), 7.19-7.31 (1H, m), 7.62-7.74 (1H, m), 7.99 (1H, dd, J=6.50, 2.35 Hz).

Workup

additionwas added to the reaction mixture
extractionextracted with ethyl acetate
washThe extract was washed with saturated brine
dry with materialdried over anhydrous magnesium sulfate
customThe solvent was evaporated under reduced pressure
customThe obtained residue was purified by basic silica gel chromatography (ethyl acetate:hexane=1:1)

Sources & evidence

ORD record: ord-9d8465140fa548818ea2faaeb4f0fb2d
Source dataset: uspto-grants-2013_07
DOI: 10.6084/m9.figshare.5104873.v1
Patent number: US08481569B2

Reaction notes

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