Dimethylformamide → Methyl 3-bromo-5-cyanobenzoate

HRID 2216752Notes

Reaction equation

HRID 2216752 reaction equation
[Br:1][C:2]1[CH:3]=[C:4]([CH:9]=[C:10](I)[CH:11]=1)[C:5]([O:7][CH3:8])=[O:6].[CH3:13][N:14](C)C=O>C(OCC)(=O)C.[C-]#N.[Zn+2].[C-]#N.C1C=CC(P(C2C=CC=CC=2)C2C=CC=CC=2)=CC=1.C1C=CC(P(C2C=CC=CC=2)C2C=CC=CC=2)=CC=1.C1C=CC(P(C2C=CC=CC=2)C2C=CC=CC=2)=CC=1.C1C=CC(P(C2C=CC=CC=2)C2C=CC=CC=2)=CC=1.[Pd]>[Br:1][C:2]1[CH:3]=[C:4]([CH:9]=[C:10]([C:13]#[N:14])[CH:11]=1)[C:5]([O:7][CH3:8])=[O:6]

Participants

6

Reactant 2

HCID 6228DimethylformamideHCID 21942573Methyl 3-bromo-5-iodobenzoate

Product 1

HCID 21942615Methyl 3-bromo-5-cyanobenzoateYield 61%

Reagents, catalysts & solvents 3

HCID 11186Zinc cyanide (Zn(CN)2)CatalystHCID 11979704Tetrakis(triphenylphosphine)palladiumCatalystHCID 8857Ethyl AcetateSolvent

Conditions

Temperature
80 °C

Procedure

A solution of methyl 3-bromo-5-iodobenzoate (4.5 g, 13.2 mmol) in N,N-dimethylformamide (36 mL) was treated with zinc cyanide (1.7 g, 14.5 mmol) and tetrakis(triphenylphosphine)palladium(O) (Pd(PPh3)4, 1.5 g, 1.3 mmol). The reaction mixture was heated, under an argon atmosphere, for 1 hour at 80° C. After cooling the mixture was diluted with ethyl acetate. The resulting organic solution was washed with water (3×), saturated brine, dried over anhydrous sodium sulfate, filtered and concentrated in vacuo. Silica gel chromatography using a gradient of hexane to 10% ethyl acetate in hexane afforded 1.9 g (61%) of methyl 3-bromo-5-cyanobenzoate.

Workup

  1. temperatureAfter cooling the mixture
  2. washThe resulting organic solution was washed with water (3×), saturated brine
  3. dry with materialdried over anhydrous sodium sulfate
  4. filtrationfiltered
  5. concentrationconcentrated in vacuo

Sources & evidence

ORD record
ord-34a08694b12d4ef09a225cc2569cc8c1
Source dataset
uspto-grants-2006_09
Patent number
US07112595B2

Reaction notes

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