N-methyl-2-pyrrolidone → 3-Nitro-5-(trifluoromethyl)picolinonitrile

HRID 627718Notes

Reaction equation

HRID 627718 reaction equation
Cl[C:2]1[C:7]([N+:8]([O-:10])=[O:9])=[CH:6][C:5]([C:11]([F:14])([F:13])[F:12])=[CH:4][N:3]=1.[CH3:15][N:16]1C(=O)CCC1.C([Cu])#N>CCOC(C)=O>[N+:8]([C:7]1[C:2]([C:15]#[N:16])=[N:3][CH:4]=[C:5]([C:11]([F:14])([F:13])[F:12])[CH:6]=1)([O-:10])=[O:9]

Participants

5

Reactant 3

HCID 13387N-methyl-2-pyrrolidoneHCID 47369502-Chloro-3-nitro-5-(trifluoromethyl)pyridineHCID 178418546HCID 178418546, compound

Product 1

HCID 453821473-Nitro-5-(trifluoromethyl)picolinonitrileYield 33.7%

Reagents, catalysts & solvents 1

HCID 8857Ethyl AcetateSolvent

Procedure

A microwave reaction vial was charged with 2-chloro-3-nitro-5-(trifluoromethyl)pyridine (2 g, 8.83 mmol), NMP (4.41 ml) and CuCN (0.830 g, 9.27 mmol). The vial was sealed and the mixture was irradiated in the MW at 175° C. for 15 min. Upon cooling to RT, the reaction mixture was poured onto ice and EtOAc was added. The mixture was filtered through Celite, washing with EtOAc and a small amount of MeOH. The layers of the filtrate were separated, and the aqueous portion was extracted again with EtOAc. The combined organic portions were dried with sodium sulfate, filtered and concentrated. The crude material was purified by silica gel chromatography, using a gradient of 0-30% EtOAc in heptane to provide 3-nitro-5-(trifluoromethyl)picolinonitrile (645 mg, 2.97 mmol, 33.7% yield) as a yellow oil that solidified upon standing. LC/MS (ESI) m/z=218.1 (M+H).

Workup

  1. customA microwave reaction
  2. customThe vial was sealed
  3. customthe mixture was irradiated in the MW at 175° C. for 15 min
  4. additionwas added
  5. filtrationThe mixture was filtered through Celite
  6. washwashing with EtOAc
  7. customThe layers of the filtrate were separated
  8. extractionthe aqueous portion was extracted again with EtOAc
  9. dry with materialThe combined organic portions were dried with sodium sulfate
  10. filtrationfiltered
  11. concentrationconcentrated
  12. customThe crude material was purified by silica gel chromatography

Sources & evidence

ORD record
ord-95a9440ef85446b7b560fb770869d558
Source dataset
uspto-grants-2016_04
Patent number
US09309263B2

Reaction notes

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