Dimethylformamide → 4-Bromo-2-(trifluoromethoxy)benzonitrile

HRID 1935404Notes

Reaction equation

[Br:1][C:2]1[CH:7]=[CH:6][C:5](I)=[C:4]([O:9][C:10]([F:13])([F:12])[F:11])[CH:3]=1.[CH3:14][N:15](C)C=O>CCOC(C)=O.[C-]#N.[Zn+2].[C-]#N.C1C=CC([P]([Pd]([P](C2C=CC=CC=2)(C2C=CC=CC=2)C2C=CC=CC=2)([P](C2C=CC=CC=2)(C2C=CC=CC=2)C2C=CC=CC=2)[P](C2C=CC=CC=2)(C2C=CC=CC=2)C2C=CC=CC=2)(C2C=CC=CC=2)C2C=CC=CC=2)=CC=1>[Br:1][C:2]1[CH:7]=[CH:6][C:5]([C:14]#[N:15])=[C:4]([O:9][C:10]([F:13])([F:12])[F:11])[CH:3]=1

Participants

Conditions

Temperature: 80 °C

Procedure

To a solution of 4-bromo-2-(trifluoromethoxy)iodobenzene (25 g, 68 mmol) and zinc(II) cyanide (4.0 g, 34 mmol) in 150 mL of degassed dimethylformamide was added tetrakis(triphenylphosphine)palladium (3.1 g, 4 mole %). The solution was stirred at 80 ° C. for one hour, then cooled to room temperature. Additional portions of zinc(II) cyanide (800 mg) and tetrakis(triphenylphosphine)palladium (700 mg) were added, and the solution was heated at 80° C. for 3 hours. The mixture was diluted with EtOAc and extracted with saturated NaHCO3 solution and brine, dried over sodium sulfate, filtered, and concentrated in vacuo. Purification by silica gel column chromatography (0-5% ether/hexane) gave the titled product.

Workup

temperaturecooled to room temperature
temperaturethe solution was heated at 80° C. for 3 hours
extractionextracted with saturated NaHCO3 solution and brine
dry with materialdried over sodium sulfate
filtrationfiltered
concentrationconcentrated in vacuo
customPurification by silica gel column chromatography (0-5% ether/hexane)

Sources & evidence

ORD record: ord-a876608290204b8eb9547ac55cac622a
Source dataset: uspto-grants-2002_05
DOI: 10.6084/m9.figshare.5104873.v1
Patent number: US06387903B1

Reaction notes

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