Dimethylformamide → 5-Chloro-2-cyanopyridine

HRID 431850Notes

Reaction equation

HRID 431850 reaction equation
Cl[C:2]1[CH:7]=[CH:6][C:5]([Cl:8])=[CH:4][N:3]=1.ClCCl.[CH3:12][N:13](C)C=O>C(OCC)(=O)C.[C-]#N.[Zn+2].[C-]#N.[Zn].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]>[C:12]([C:2]1[CH:7]=[CH:6][C:5]([Cl:8])=[CH:4][N:3]=1)#[N:13]

Participants

8

Reactant 3

HCID 6228DimethylformamideHCID 6344DichloromethaneHCID 276852,5-Dichloropyridine

Product 1

HCID 38339425-Chloro-2-cyanopyridineYield 53%

Reagents, catalysts & solvents 4

HCID 11186Zinc cyanide (Zn(CN)2)CatalystHCID 23994ZincCatalystHCID 178418228Bis(cyclopenta-1,4-dien-1-yl(diphenyl)phosphane);dichloropalladium;iron(2+)CatalystHCID 8857Ethyl AcetateSolvent

Procedure

A mixture of 2,5-dichloropyridine (1.48 g, 10 mmol), zinc cyanide (705 mg, 6 mmol), zinc (dust, 29 mg, 0.45 mmol), [1,1′-bis(diphenylphosphino)ferrocene] dichloropalladium(II), complex with dichloromethane (1:1) (0.18 g, 0.22 mmol) in N,N-dimethylformamide (10 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 735 mg (53%) of 2-cyano-5-chloropyridine.

Workup

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

Sources & evidence

ORD record
ord-4a9d6a200c5d421782e93efb811202cd
Source dataset
uspto-grants-2003_12
Patent number
US06660753B2

Reaction notes

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