Dimethylformamide → 5-Methylpicolinonitrile

HRID 1791368Notes

Reaction equation

HRID 1791368 reaction equation
Br[C:2]1[CH:7]=[CH:6][C:5]([CH3:8])=[CH:4][N:3]=1.[CH3:9][N:10](C=O)C>[C-]#N.[C-]#N.[Zn+2].[Zn]>[CH3:8][C:5]1[CH:6]=[CH:7][C:2]([C:9]#[N:10])=[N:3][CH:4]=1

Participants

5

Reactant 2

HCID 6228DimethylformamideHCID 5642162-Bromo-5-methylpyridine

Product 1

HCID 741835-MethylpicolinonitrileYield 57.6%

Reagents, catalysts & solvents 2

HCID 11186Zinc cyanide (Zn(CN)2)CatalystHCID 23994ZincCatalyst

Procedure

2-Bromo-5-methylpyridine ((8.6 g, 50 mmol) was mixed with Zn(CN)2 (4.1 g, 35 mmol), Pd(dppf)2C12 (0.89 g, mmol) and zinc dust (0.14 g, mmol) in DMF (86 ml) at 155° C. for 15 minutes. The reaction mixture was cooled down to room temperature and quenched with water and ethyl acetate. The mixture was filtered through celite and the organic layer was separated and dried with sodium sulfate. The product was purified by column chromatography with 10˜25% ethyl acetate in hexanes to give 3.4 g of 5-methyl-pyridine-2-carbonitrile (yield: 57.6%). 1H NMR (CDCl3), δ(ppm): 8.52 (s, 1H), 7.59 (m, 2H), 2.42 (s, 1H).

Workup

  1. customquenched with water and ethyl acetate
  2. filtrationThe mixture was filtered through celite
  3. customthe organic layer was separated
  4. dry with materialdried with sodium sulfate
  5. customThe product was purified by column chromatography with 10˜25% ethyl acetate in hexanes

Sources & evidence

ORD record
ord-8953b4f38d7b445f9e098e54c522ab57
Source dataset
uspto-grants-2006_07
Patent number
US07074809B2

Reaction notes

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