Acetonitrile → 5-bromo-3-(1-ethyl-1H-pyrazol-5-yloxy)picolinonitrile

HRID 1523591Notes

Reaction equation

HRID 1523591 reaction equation
[Br:1][C:2]1[CH:3]=[C:4]([N+]([O-])=O)[C:5]([C:8]#[N:9])=[N:6][CH:7]=1.[CH2:13]([N:15]1[C:19]([OH:20])=[CH:18][CH:17]=[N:16]1)[CH3:14].C(=O)([O-])[O-].[Na+].[Na+].C(#N)C>C(OCC)(=O)C.C(Cl)(Cl)Cl.CCCCCC>[Br:1][C:2]1[CH:3]=[C:4]([O:20][C:19]2[N:15]([CH2:13][CH3:14])[N:16]=[CH:17][CH:18]=2)[C:5]([C:8]#[N:9])=[N:6][CH:7]=1

Participants

6

Reactant 4

HCID 6342AcetonitrileHCID 10340Sodium CarbonateHCID 27696985-Bromo-3-nitropyridine-2-carbonitrileHCID 178418331HCID 178418331, compound

Product 1

HCID 674858325-bromo-3-(1-ethyl-1H-pyrazol-5-yloxy)picolinonitrileYield 53.3%

Reagents, catalysts & solvents 1

HCID 22239056Ethyl acetate chloroform hexaneSolvent

Procedure

5-Bromo-3-nitropicolinonitrile (24.0 g, 105 mmol), 1-ethyl-1H-pyrazol-5-ol (13.0 g, 116 mmol), and sodium carbonate (11.2 g, 105 mmol) were combined with acetonitrile (400 ml). The mixture was heated to reflux for 20 hours, then cooled to ambient temperature, filtered and evaporated. The residue was dissolved in ethyl acetate (800 ml) and washed with water (3×200 ml) and brine, dried (MgSO4), filtered and evaporated. The crude material was purified over silica gel (15:35:50, then 20:30:50 ethyl acetate/chloroform/hexane) to afford 5-bromo-3-(1-ethyl-1H-pyrazol-5-yloxy)picolinonitrile (16.4 g, 53% yield) as a white solid.

Workup

  1. temperatureThe mixture was heated
  2. temperatureto reflux for 20 hours
  3. filtrationfiltered
  4. customevaporated
  5. dissolutionThe residue was dissolved in ethyl acetate (800 ml)
  6. washwashed with water (3×200 ml) and brine
  7. dry with materialdried (MgSO4)
  8. filtrationfiltered
  9. customevaporated
  10. customThe crude material was purified over silica gel (15:35:50

Sources & evidence

ORD record
ord-bdfdccf127d64cc491c5918a95ed0237
Source dataset
uspto-grants-2015_07
Patent number
US09079890B2

Reaction notes

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