Cesium carbonate → 3-(1-ethyl-1H-pyrazol-5-yloxy)-5-(pyridin-2-ylthio)picolinonitrile

HRID 534037Notes

Reaction equation

HRID 534037 reaction equation
Br[C:2]1[CH:3]=[C:4]([O:10][C:11]2[N:15]([CH2:16][CH3:17])[N:14]=[CH:13][CH:12]=2)[C:5]([C:8]#[N:9])=[N:6][CH:7]=1.C(=O)([O-])[O-].[Cs+].[Cs+].[N:24]1[CH:29]=[CH:28][CH:27]=[CH:26][C:25]=1[SH:30]>CN(C=O)C>[CH2:16]([N:15]1[C:11]([O:10][C:4]2[C:5]([C:8]#[N:9])=[N:6][CH:7]=[C:2]([S:30][C:25]3[CH:26]=[CH:27][CH:28]=[CH:29][N:24]=3)[CH:3]=2)=[CH:12][CH:13]=[N:14]1)[CH3:17]

Participants

5

Reactant 3

HCID 10796Cesium carbonateHCID 674858325-bromo-3-(1-ethyl-1H-pyrazol-5-yloxy)picolinonitrileHCID 178418616HCID 178418616, compound

Product 1

HCID 674862333-(1-ethyl-1H-pyrazol-5-yloxy)-5-(pyridin-2-ylthio)picolinonitrileYield 93.3%

Reagents, catalysts & solvents 1

HCID 6228DimethylformamideSolvent2×

Procedure

5-Bromo-3-(1-ethyl-1H-pyrazol-5-yloxy)picolinonitrile (16.1 g, 55 mmol) and cesium carbonate (17.9 g, 55 mmol) were combined with DMF (160 ml), and pyridine-2-thiol (6.1 g, 55 mmol) dissolved in DMF (40 ml) was added dropwise over 30 minutes. The mixture was agitated for 1 hour, quenched with saturated ammonium chloride solution and extracted with ethyl acetate. The combined organic extracts were washed with water and brine, dried (MgSO4), filtered and evaporated. The residue was purified over silica gel (20-35% ethyl acetate/hexanes) to afford 3-(1-ethyl-1H-pyrazol-5-yloxy)-5-(pyridin-2-ylthio)picolinonitrile (16.6 g, 93% yield) as a white solid.

Workup

  1. additionwas added dropwise over 30 minutes
  2. customquenched with saturated ammonium chloride solution
  3. extractionextracted with ethyl acetate
  4. washThe combined organic extracts were washed with water and brine
  5. dry with materialdried (MgSO4)
  6. filtrationfiltered
  7. customevaporated
  8. customThe residue was purified over silica gel (20-35% ethyl acetate/hexanes)

Sources & evidence

ORD record
ord-f87ff8f1a76241c184f0d0e075aff536
Source dataset
uspto-grants-2014_10
Patent number
US08853409B2

Reaction notes

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