Phosphorus oxychloride → 4-Chloro-3-nitropyridine

HRID 1020200Notes

Reaction equation

HRID 1020200 reaction equation
[N+:1]([C:4]1[CH:5]=[N:6][CH:7]=[CH:8][C:9]=1O)([O-:3])=[O:2].O=P(Cl)(Cl)[Cl:13]>C1(C)C=CC=CC=1>[Cl:13][C:9]1[CH:8]=[CH:7][N:6]=[CH:5][C:4]=1[N+:1]([O-:3])=[O:2]

Participants

4

Reactant 2

HCID 24813Phosphorus oxychlorideHCID 178526806HCID 178526806, compound

Product 1

HCID 27357814-Chloro-3-nitropyridineYield 75%

Reagents, catalysts & solvents 1

HCID 1140TolueneSolvent

Procedure

To a suspension of 3-nitropyridin-4-ol (4.342 g, 31 mmol) in toluene (60 mL) was added POCl3 (11.6 mL, 124.4 mmol) at 0° C. The resulting mixture was warmed to room temperature, then heated to 110° C. for 14 hours. After cooling to room temperature, the solvent was removed in vacuo and the residue was poured into ice, and basified with saturated aqueous NH4Cl solution. The mixture was extracted with EtOAc (40 mL×2). The combined organic layers was washed with water, brine, dried (MgSO4) and concentrated to a brown oil, which solidified on standing. (3.68 g, 75% yield).

Workup

  1. temperatureheated to 110° C. for 14 hours
  2. temperatureAfter cooling to room temperature
  3. customthe solvent was removed in vacuo
  4. additionthe residue was poured into ice
  5. extractionThe mixture was extracted with EtOAc (40 mL×2)
  6. washThe combined organic layers was washed with water, brine
  7. dry with materialdried (MgSO4)
  8. concentrationconcentrated to a brown oil, which

Sources & evidence

ORD record
ord-7265be2cddc64ae8908c6b8cd7ecbabc
Source dataset
uspto-grants-2014_05
Patent number
US08716318B2

Reaction notes

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