Dimethylformamide → Methyl 2-chloro-5-cyanobenzoate

HRID 2216776Notes

Reaction equation

HRID 2216776 reaction equation
Cl[C:2]1[CH:3]=[C:4]([CH:9]=[C:10](Cl)[CH:11]=1)[C:5]([O:7][CH3:8])=[O:6].[Cl:13]CCl.C[N:17]([CH3:20])C=O>C(OCC)(=O)C.[C-]#N.[Zn+2].[C-]#N.C1C=CC(P(C2C=CC=CC=2)[C-]2C=CC=C2)=CC=1.C1C=CC(P(C2C=CC=CC=2)[C-]2C=CC=C2)=CC=1.Cl[Pd]Cl.[Fe+2]>[Cl:13][C:9]1[CH:10]=[CH:11][C:2]([C:20]#[N:17])=[CH:3][C:4]=1[C:5]([O:7][CH3:8])=[O:6]

Participants

7

Reactant 3

HCID 6228DimethylformamideHCID 6344DichloromethaneHCID 76192Methyl 3,5-dichlorobenzoate

Product 1

HCID 16659388Methyl 2-chloro-5-cyanobenzoateYield 17%

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 methyl 3,5-dichlorobenzoate (14.66 g, 71.5 mmol), zinc cyanide (5.04 g, 42.9 mmol) zinc (dust, 0.21 g, 3.21 mmol), [1,1′Bis(diphenylphosphino)ferrocene]dichloropalladium(II), complex with dichloromethane (1:1) (1.3 g, 1.57 mmol) in N,N-dimethylformamide (70 mL) was heated at reflux for 5 hours. After cooling the reaction was diluted with ethyl acetate and extracted with water and brine. Silica gel chromatography afforded 2.34 g (17%) methyl 2-chloro-5-cyanobenzoate.

Workup

  1. temperaturewas heated
  2. temperatureat reflux for 5 hours
  3. temperatureAfter cooling the reaction
  4. extractionextracted with water and brine

Sources & evidence

ORD record
ord-8f89ffe0b9db45e3947bf7020f254cea
Source dataset
uspto-grants-2006_09
Patent number
US07112595B2

Reaction notes

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