2-Bromo-1-fluoro-4-nitrobenzene → 2-(2-Fluoro-5-nitrophenyl)pyridine

HRID 1061815Notes

Reaction equation

HRID 1061815 reaction equation
Br[C:2]1[CH:7]=[C:6]([N+:8]([O-:10])=[O:9])[CH:5]=[CH:4][C:3]=1[F:11].CCCC[Sn]([C:25]1[N:30]=[CH:29][CH:28]=[CH:27][CH:26]=1)(CCCC)CCCC>C1COCC1.CN(C=O)C>[F:11][C:3]1[CH:4]=[CH:5][C:6]([N+:8]([O-:10])=[O:9])=[CH:7][C:2]=1[C:29]1[CH:28]=[CH:27][CH:26]=[CH:25][N:30]=1

Participants

5

Reactant 2

HCID 696992-Bromo-1-fluoro-4-nitrobenzene2×HCID 6077842-(Tributylstannyl)pyridine

Product 1

HCID 222853002-(2-Fluoro-5-nitrophenyl)pyridine

Reagents, catalysts & solvents 2

HCID 6228DimethylformamideSolventHCID 8028TetrahydrofuranSolvent

Procedure

A mixture of 2-bromo-1-fluoro-4-nitrobenzene (2.0 g, 9.1 mmol) and 2-(1,1,1-tributylstannyl)pyridine (3.36 g, 9.11 mmol) in THF (80 mL) and DMF (10 mL) was degassed with nitrogen. [1,1′-Bis(diphenylphosphino)ferrocene]-dichloropalladium(II) complex with dichloromethane (200 mg, 3 mol %) was added, and the mixture was heated at reflux for 24 h. More 2-bromo-1-fluoro-4-nitrobenzene (0.60 g, 2.7 mmol) and catalyst (100 mg, 1.5 mol %) were added, and the mixture was heated as before for another 24 h. The solvent was removed in vacuo, and the residue was purified by flash chromatography on silica gel, eluting with 50% dichloromethane in isohexane, then 100% dichloromethane, then 100% ethyl acetate (UV detection). 2-(2-Fluoro-5-nitrophenyl)pyridine was isolated as a colourless solid (2.11 g, 100%). δH (400 MHz, CDCl3) 7.30-7.37 (2H, m), 7.80-7.87 (2H, m), 8.27 (1H, m), 8.78 (1H, m), 9.01 (1H, dd, J 3.1, 6.7); MS (ES+) m/z 219 [M+H]+.

Workup

  1. customwas degassed with nitrogen
  2. addition[1,1′-Bis(diphenylphosphino)ferrocene]-dichloropalladium(II) complex with dichloromethane (200 mg, 3 mol %) was added
  3. temperaturethe mixture was heated
  4. temperatureat reflux for 24 h
  5. temperaturethe mixture was heated as before for another 24 h
  6. customThe solvent was removed in vacuo
  7. customthe residue was purified by flash chromatography on silica gel
  8. washeluting with 50% dichloromethane in isohexane

Sources & evidence

ORD record
ord-ff2b92eaac584799b5ca50977734b7e7
Source dataset
uspto-grants-2005_11
Patent number
US06960598B2

Reaction notes

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