Dimethylformamide → Methyl 4-cyano-2-fluorobenzoate

HRID 736698Notes

Reaction equation

HRID 736698 reaction equation
Br[C:2]1[CH:11]=[CH:10][C:5]([C:6]([O:8][CH3:9])=[O:7])=[C:4]([F:12])[CH:3]=1.[CH3:13][N:14](C)C=O>[Zn].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.[Pd]>[C:13]([C:2]1[CH:11]=[CH:10][C:5]([C:6]([O:8][CH3:9])=[O:7])=[C:4]([F:12])[CH:3]=1)#[N:14]

Participants

5

Reactant 2

HCID 6228DimethylformamideHCID 113453114-Bromo-2-fluoro-benzoic acid methyl ester

Product 1

HCID 15278726Methyl 4-cyano-2-fluorobenzoateYield 80%

Reagents, catalysts & solvents 2

HCID 23994ZincCatalystHCID 11979704Tetrakis(triphenylphosphine)palladiumCatalyst

Conditions

Temperature
80 °C

Procedure

A solution of methyl 4-bromo-2-fluorobenzoate (10.0 g, 43 mmol), zinc cyamide (10.0 g, 86 mmol) and palladium tetrakis(triphenylphosphine) (2.5 g, 0.64 mmol) in anhydrous N,N-dimethylformamide (100 mL) was purged with nitrogen and the mixture stirred at 80° C. overnight. After cooling, the mixture was partitioned between ethyl acetate and brine and the organic phase washed with water and concentrated. The solid was purified on silica gel using 1:5 ethyl acetate/hexane to afford the title compound (6.1 g, 80%). MS (DCI): m/z 180 (M+H)+.

Workup

  1. temperatureAfter cooling
  2. customthe mixture was partitioned between ethyl acetate and brine
  3. washthe organic phase washed with water
  4. concentrationconcentrated
  5. customThe solid was purified on silica gel using 1:5 ethyl acetate/hexane

Sources & evidence

ORD record
ord-1534588649ae4f6babf2bb03e2a00ee4
Source dataset
uspto-grants-2009_09
Patent number
US07595406B2

Reaction notes

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