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

HRID 1171053Notes

Reaction equation

HRID 1171053 reaction equation
Br[C:2]1[CH:9]=[C:8]([F:10])[C:5]([C:6]#[N:7])=[CH:4][CH:3]=1.C(OCC)(=O)C.[CH3:17][N:18](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:8]1[CH:9]=[C:2]([C:17]#[N:18])[CH:3]=[CH:4][C:5]=1[C:6]#[N:7]

Participants

6

Reactant 3

HCID 6228DimethylformamideHCID 8857Ethyl AcetateHCID 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

Conditions

Temperature
90 °C

Procedure

To a solution of 4-bromo-6-fluorobenzonitrile (5 g, 25 mmol) in anhydrous DMF (20 mL) was added Zinc cyanide (1.75 g, 14.9 mmol) and tetrakis(triphenylphosphine)-palladium(0) (0.6 g, 0.519 mmol). The reaction mixture was heated overnight under argon at 90° C. After cooling to room temperature, the reaction mixture was poured into ethyl acetate (150 mL) and extracted with water 50 mL, 2×30 mL, brine (30 mL), then dried over anhydrous sodium sulfate. After rotary evaporation of most solvent, the concentrated solution was loaded onto a silica column and eluted with EtOAc/Hexane (1:6). A white solid was obtained (3.73 g). 1H-NMR (300 MHz, CDCl3) δ 7.80 (m, 1H), 7.58 (m, 2H).

Workup

  1. temperatureAfter cooling to room temperature
  2. extractionextracted with water 50 mL, 2×30 mL, brine (30 mL)
  3. dry with materialdried over anhydrous sodium sulfate
  4. customAfter rotary evaporation of most solvent
  5. washeluted with EtOAc/Hexane (1:6)
  6. customA white solid was obtained (3.73 g)

Sources & evidence

ORD record
ord-cbceaffc3d724ba588ab5a5ce8604d6d
Source dataset
uspto-grants-2010_11
Patent number
US07829584B2

Reaction notes

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