Dimethylformamide → Benzoic acid, 3-chloro-5-cyano-, methyl ester

HRID 431883Notes

Reaction equation

HRID 431883 reaction equation
[Cl:1][C:2]1[CH:3]=[C:4]([CH:9]=[C:10](F)[CH:11]=1)[C:5]([O:7][CH3:8])=[O:6].ClCCl.[CH3:16][N:17](C)C=O>C(OCC)(=O)C.[C-]#N.[Zn+2].[C-]#N.Cl[Pd]Cl.C1(P(C2C=CC=CC=2)[C-]2C=CC=C2)C=CC=CC=1.[C-]1(P(C2C=CC=CC=2)C2C=CC=CC=2)C=CC=C1.[Fe+2]>[Cl:1][C:2]1[CH:3]=[C:4]([CH:9]=[C:10]([C:16]#[N:17])[CH:11]=1)[C:5]([O:7][CH3:8])=[O:6]

Participants

7

Reactant 3

HCID 6228DimethylformamideHCID 6344DichloromethaneHCID 21942504Methyl 3-chloro-5-fluorobenzoate

Product 1

HCID 21942517Benzoic acid, 3-chloro-5-cyano-, methyl ester

Reagents, catalysts & solvents 3

HCID 11186Zinc cyanide (Zn(CN)2)CatalystHCID 178418228Bis(cyclopenta-1,4-dien-1-yl(diphenyl)phosphane);dichloropalladium;iron(2+)CatalystHCID 8857Ethyl AcetateSolvent

Procedure

A mixture of the methyl 3-chloro-5-fluorobenzoate, zinc cyanide (8.46g, 72.3 mmol) zinc (dust, 235 mg, 3.6 mmol), [1,1′bis(diphenylphosphino)ferrocene] dichloropalladium(II), complex with dichloromethane (1:1) (1.5 g, 1.8 mmol) in N,N-dimethylformamide (70 ml) was heated at reflux for 1 hour. The reaction was cooled to ambient temperature and diluted with ethyl acetate. The organic solution was extracted with water and brine and concentrated in vacuo, to afford crude methyl 3-chloro-5-cyanobenzoate.

Workup

  1. temperaturewas heated
  2. temperatureat reflux for 1 hour
  3. extractionThe organic solution was extracted with water and brine
  4. concentrationconcentrated in vacuo

Sources & evidence

ORD record
ord-1efa043914e74c2687dd3828bb3fc117
Source dataset
uspto-grants-2003_12
Patent number
US06660753B2

Reaction notes

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