Water → 4-Cyano-2-fluoropyridine

HRID 1255907Notes

Reaction equation

HRID 1255907 reaction equation
[F-:1].[Cs+].Cl[C:4]1[CH:5]=[C:6]([CH:9]=[CH:10][N:11]=1)[C:7]#[N:8].O>S1(CCCC1)(=O)=O>[F:1][C:4]1[CH:5]=[C:6]([CH:9]=[CH:10][N:11]=1)[C:7]#[N:8]

Participants

5

Reactant 3

HCID 962WaterHCID 25953Cesium fluorideHCID 5686382-Chloro-4-cyanopyridine

Product 1

HCID 120025874-Cyano-2-fluoropyridineYield 89,345.703%

Reagents, catalysts & solvents 1

HCID 31347SulfolaneSolvent

Conditions

Temperature
100 °C

Procedure

Cesium fluoride (30 g, 0.22 mmol) was slurried in dry sulfolane (150 mL) and concentrated via vacuum distillation at 0.5 mm Hg. After removal of 20% of the solvent, the suspension was cooled and 2-chloroisonicotinonitrile (15 g, 0.11 mmol) was added, then stirred and heated at 100° C. for 20 h. It was cooled to 25° C., poured into H2O (200 mL) and extracted with Et2O. The Et2O phase was washed with H2O, then brine, dried over Na2SO4, filtered and concentrated in vacuo. The residue was purified by column chromatography over SiO2 with CH2Cl2 to give 2-fluoroisonicotinonitrile (12.0 g) as a low-melting colorless solid: EIMS m/z: 122 ([M]+); 1H NMR (CDCl3): δ 8.45 (dd, 1H), 7.47 (dd, 1H), 7.24 (m, 1H).

Workup

  1. concentrationconcentrated via vacuum distillation at 0.5 mm Hg
  2. customAfter removal of 20% of the solvent
  3. temperaturethe suspension was cooled
  4. temperatureIt was cooled to 25° C.
  5. extractionextracted with Et2O
  6. washThe Et2O phase was washed with H2O
  7. dry with materialbrine, dried over Na2SO4
  8. filtrationfiltered
  9. concentrationconcentrated in vacuo
  10. customThe residue was purified by column chromatography over SiO2 with CH2Cl2

Sources & evidence

ORD record
ord-4fe7bb59ad13484380e02311fc49e7d7
Source dataset
uspto-grants-2013_06
Patent number
US08461164B2

Reaction notes

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