p-Chlorothiophenol → 1-Bromo-2-(4-chlorophenylsulfanyl)-5-(trifluoromethyl)benzene

HRID 15192

Reaction equation

[Br:1][C:2]1[CH:3]=[C:4]([C:9]([F:12])([F:11])[F:10])[CH:5]=[CH:6][C:7]=1I.BrC1C=C(C(F)(F)F)C=CC=1N.[Cl:25][C:26]1[CH:31]=[CH:30][C:29]([SH:32])=[CH:28][CH:27]=1.CC(C)([O-])C.[K+]>C1(C)C=CC=CC=1.C1(P(C2C=CC=CC=2)C2C=CC=CC=2OC2C=CC=CC=2P(C2C=CC=CC=2)C2C=CC=CC=2)C=CC=CC=1>[Br:1][C:2]1[CH:3]=[C:4]([C:9]([F:12])([F:11])[F:10])[CH:5]=[CH:6][C:7]=1[S:32][C:29]1[CH:30]=[CH:31][C:26]([Cl:25])=[CH:27][CH:28]=1

Participants

Conditions

Temperature: 100 °C

Procedure

To a stirred solution of tris(dibenzylidene)dipalladium(0) (Pd2dba3, 0.183 g, 0.2 mmol) and bis(2-diphenylphosphinophenyl)ether (DPEphos, 0.215 g, 0.2 mmol) in toluene (80 mL) was added 3-bromo-4-iodobenzotrifluoride (7.02 g, 20 mmol; prepared from 2-bromo-4-trifluoromethyl-phenylamine by diazotization according to the general procedure by Tunney and Stille J. Org. Chem. 1987, 52, 748-753), 4-chlorothiophenol (2.89 g, 20 mmol) and potassium tert-butoxide (2.46 g, 22 mmol) at room temperature (rt). The reaction mixture was stirred for 2.5 h at 100° C. and then cooled to room temperature (rt) and filtered through celite. The solvent was evaporated off and the crude product was purified by flash chromatography on silica gel (eluent: ethyl acetate/heptane 2:8) to produce 4.53 g (81%) of 1-bromo-2-(4-chloro-phenylsulfanyl)-5-(trifluoromethyl)-benzene as an oil.

Workup

customat room temperature
custom(rt)
temperaturecooled to room temperature (rt)
filtrationfiltered through celite
customThe solvent was evaporated off
customthe crude product was purified by flash chromatography on silica gel (eluent: ethyl acetate/heptane 2:8)

Sources & evidence

ORD record: ord-d9347c96bc4843159a6b8f6dab67a98c
Source dataset: uspto-grants-2010_06
DOI: 10.6084/m9.figshare.5104873.v1
Patent number: US07732463B2

Linked notes

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