Toluene → 1,4-Benzenedicarbonitrile, 2-fluoro-

HRID 1275429Notes

Reaction equation

HRID 1275429 reaction equation
Br[C:2]1[CH:9]=[CH:8][C:5]([C:6]#[N:7])=[C:4]([F:10])[CH:3]=1.C1(C)C=CC=CC=1.[Cl-].[NH4+].[CH3:20][N:21](C=O)C>[C-]#N.[Zn+2].[C-]#N.[Pd].C1(P(C2C=CC=CC=2)C2C=CC=CC=2)C=CC=CC=1.C1(P(C2C=CC=CC=2)C2C=CC=CC=2)C=CC=CC=1.C1(P(C2C=CC=CC=2)C2C=CC=CC=2)C=CC=CC=1.C1(P(C2C=CC=CC=2)C2C=CC=CC=2)C=CC=CC=1>[F:10][C:4]1[CH:3]=[C:2]([C:20]#[N:21])[CH:9]=[CH:8][C:5]=1[C:6]#[N:7]

Participants

7

Reactant 4

HCID 1140TolueneHCID 6228DimethylformamideHCID 25517Ammonium ChlorideHCID 7360294-Bromo-2-fluorobenzonitrile

Product 1

HCID 1211941,4-Benzenedicarbonitrile, 2-fluoro-

Reagents, catalysts & solvents 2

HCID 11186Zinc cyanide (Zn(CN)2)CatalystHCID 11979704Tetrakis(triphenylphosphine)palladiumCatalyst

Procedure

A solution of 4-bromo-2-fluorobenzonitrile (20 g, 100 mmol) , zinc cyanide (7 g, 60 mmol) and tetrakis (triphenylphosphine) palladium (4.6 g, 4 mmol) in DMF (100 mL) was heated at 80° C. for 4 hr. Toluene (300 mL) and saturated aqueous ammonium chloride (300 mL) were added and the layers were separated. The organic layer was washed once with saturated aqueous ammonium chloride and twice with brine. The organic phase was dried (MgSO4), filtered and concentrated. The product was purified by silica gel chromatography, eluting with a gradient of hexanes to 30% EtOAc/hexanes (11 g, 75%).

Workup

  1. customthe layers were separated
  2. washThe organic layer was washed once with saturated aqueous ammonium chloride and twice with brine
  3. dry with materialThe organic phase was dried (MgSO4)
  4. filtrationfiltered
  5. concentrationconcentrated
  6. customThe product was purified by silica gel chromatography
  7. washeluting with a gradient of hexanes to 30% EtOAc/hexanes (11 g, 75%)

Sources & evidence

ORD record
ord-b93c1354779345868ae2b11051c93b53
Source dataset
uspto-grants-2000_12
Patent number
US06160176

Reaction notes

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