Dimethylformamide → Methyl 4-cyano-3-methylbenzoate

HRID 2242240Notes

Reaction equation

HRID 2242240 reaction equation
[CH3:1][O:2][C:3](=[O:12])[C:4]1[CH:9]=[CH:8][C:7](Br)=[C:6]([CH3:11])[CH:5]=1.[CH3:13][N:14](C=O)C>CCOC(C)=O.[Zn].[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>[CH3:1][O:2][C:3](=[O:12])[C:4]1[CH:9]=[CH:8][C:7]([C:13]#[N:14])=[C:6]([CH3:11])[CH:5]=1

Participants

6

Reactant 2

HCID 6228DimethylformamideHCID 3294148Methyl 4-bromo-3-methylbenzoate

Product 1

HCID 19969932Methyl 4-cyano-3-methylbenzoateYield 39.8%

Reagents, catalysts & solvents 3

HCID 23994ZincCatalystHCID 11979704Tetrakis(triphenylphosphine)palladiumCatalystHCID 8857Ethyl AcetateSolvent

Conditions

Temperature
120 °C

Procedure

Zinc cyamide (6.2 g, 52 mmol) and tetrakis(triphenylphosphine) palladium (0) (4 g, 3 mmol) was added to a solution of 4-bromo-3-methyl-benzoic acid methyl ester (20 g, 87 mmol) and DMF (100 mL) and stirred for 4 hours at 120° C. The reaction mixture was cooled to room temperature, diluted with EtOAc (700 mL), washed with water and brine, dried (Na2SO4), filtered and concentrated in vacuo. Purification by flash chromatography (silica, 1:3 EtOAc:hexanes) provided the title compound (12.3 g, 39.8% yield) as a solid.

Workup

  1. temperatureThe reaction mixture was cooled to room temperature
  2. washwashed with water and brine
  3. dry with materialdried (Na2SO4)
  4. filtrationfiltered
  5. concentrationconcentrated in vacuo
  6. customPurification by flash chromatography (silica, 1:3 EtOAc:hexanes)

Sources & evidence

ORD record
ord-bb414ad1d4094b26aaf142f9ea734053
Source dataset
uspto-grants-2010_03
Patent number
US07671043B2

Reaction notes

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