Phosphorus oxychloride → 4-Chloro-3-nitropyridine

HRID 1678136Notes

Reaction equation

HRID 1678136 reaction equation
O[C:2]1[CH:7]=[CH:6][N:5]=[CH:4][C:3]=1[N+:8]([O-:10])=[O:9].P(Cl)(Cl)(Cl)(Cl)[Cl:12].P(Cl)(Cl)(Cl)=O>>[Cl:12][C:2]1[CH:7]=[CH:6][N:5]=[CH:4][C:3]=1[N+:8]([O-:10])=[O:9]

Participants

4

Reactant 3

HCID 24813Phosphorus oxychlorideHCID 24819Phosphorus pentachlorideHCID 178526806HCID 178526806, compound

Product 1

HCID 27357814-Chloro-3-nitropyridineYield 45.1%

Conditions

Temperature
135 °C

Procedure

4-Hydroxy-3-nitropyridine (10.0 g, 71.4 mmol) is added portionwise to a mechanically stirred mixture of phosphorous pentachloride (16.32 g, 78.6 mmol) and phosphorous oxychloride (16.2 mL) at 55-60° C. After the addition is complete, the temperature is raised to 130-140° C. for 4 hr. After cooling to room temperature, the phosphorous oxychloride is removed and the residue is cautiously treated with ice/water, made basic with sodium carbonate and extracted with ether. The combined extract is dried, filtered and concentrated to yield 4-chloro-3-nitropyridine (5.1 g, 45% yield) as a pale yellow solid.

Workup

  1. additionAfter the addition
  2. temperatureAfter cooling to room temperature
  3. customthe phosphorous oxychloride is removed
  4. additionthe residue is cautiously treated with ice/water
  5. extractionextracted with ether
  6. extractionThe combined extract
  7. customis dried
  8. filtrationfiltered
  9. concentrationconcentrated

Sources & evidence

ORD record
ord-a553d997ab504ca6a6b73fe051c923a8
Source dataset
uspto-grants-2011_08
Patent number
US08008491B2

Reaction notes

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