Sodium hydride → HCID 67485570, compound

HRID 1511099Notes

Reaction equation

HRID 1511099 reaction equation
[CH2:1]([C:3]1[C:8]([OH:9])=[CH:7][CH:6]=[CH:5][N:4]=1)[CH3:2].[H-].[Na+].Br[C:13]1[CH:14]=[C:15]([N+]([O-])=O)[C:16]([C:19]#[N:20])=[N:17][CH:18]=1.[NH:24]1[CH:29]=[CH:28][CH:27]=[CH:26][C:25]1=[S:30]>CN(C=O)C>[CH2:1]([C:3]1[C:8]([O:9][C:15]2[C:16]([C:19]#[N:20])=[N:17][CH:18]=[C:13]([S:30][C:25]3[CH:26]=[CH:27][CH:28]=[CH:29][N:24]=3)[CH:14]=2)=[CH:7][CH:6]=[CH:5][N:4]=1)[CH3:2]

Participants

6

Reactant 4

HCID 24758Sodium hydride2×HCID 27236982-MercaptopyridineHCID 27696985-Bromo-3-nitropyridine-2-carbonitrileHCID 38372322-ethylpyridin-3-ol

Product 1

HCID 67485570HCID 67485570, compoundYield 108.5%

Reagents, catalysts & solvents 1

HCID 6228DimethylformamideSolvent

Procedure

2-Ethylpyridin-3-ol (27.5 g, 223 mmol) was dissolved in DMF (900 mL) and cooled in an ice bath. 60% Sodium hydride (8.93 g, 223 mmol) was added portionwise and stirred in an ice bath for 30 minutes. 5-Bromo-3-nitropicolinonitrile (50.9 g, 223 mmol) was added in one portion and the reaction was stirred in an ice bath for 1 hour. Pyridine-2(1H)-thione (24.8 g, 223 mmol) was added, followed by 60% sodium hydride (8.93 g, 223 mmol) and reaction was stirred in an ice bath slowly warming to ambient temperature overnight. The reaction was concentrated in vacuo to about 300 mL and poured into 3 L water with vigorous stirring. The mixture was extracted with EtOAc, washed with water and brine, dried over sodium sulfate, filtered and concentrated to afford 3-(2-ethylpyridin-3-yloxy)-5-(pyridin-2-ylthio)picolinonitrile (81 g, 242 mmol, 108% yield) as a dark oil.

Workup

  1. temperaturecooled in an ice bath
  2. stirringthe reaction was stirred in an ice bath for 1 hour
  3. stirringwas stirred in an ice bath
  4. concentrationThe reaction was concentrated in vacuo to about 300 mL
  5. additionpoured into 3 L water with vigorous stirring
  6. extractionThe mixture was extracted with EtOAc
  7. washwashed with water and brine
  8. dry with materialdried over sodium sulfate
  9. filtrationfiltered
  10. concentrationconcentrated

Sources & evidence

ORD record
ord-bc4b7ea230254047836ba3f457258d02
Source dataset
uspto-grants-2012_07
Patent number
US08212045B2

Reaction notes

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