Phosphorus oxychloride → 4-Chloro-5-nitropyrimidine

HRID 587453Notes

Reaction equation

HRID 587453 reaction equation
[N+:1]([C:4]1[C:5](O)=[N:6][CH:7]=[N:8][CH:9]=1)([O-:3])=[O:2].P(Cl)(Cl)([Cl:13])=O>C(#N)C.C(OCC)(=O)C>[Cl:13][C:5]1[C:4]([N+:1]([O-:3])=[O:2])=[CH:9][N:8]=[CH:7][N:6]=1

Participants

5

Reactant 2

HCID 24813Phosphorus oxychlorideHCID 178526815HCID 178526815, compound

Product 1

HCID 249037774-Chloro-5-nitropyrimidineYield 33%

Reagents, catalysts & solvents 2

HCID 6342AcetonitrileSolventHCID 8857Ethyl AcetateSolvent2×

Procedure

The mixture of 5-nitropyrimidin-4-ol (1.04 g) and phosphorus oxychloride (5.66 g) in acetonitrile (10 mL) was stirred at reflux for 2 h. After this time, the reaction mixture was cooled to ambient temperature, diluted with ethyl acetate (50 mL), and filtered and the filtrate was concentrated under reduced pressure. The residue obtained was diluted with ethyl acetate (100 mL), washed with saturated aqueous sodium bicarbonate (50 mL) then brine (50 mL), and filtered and the filtrate was concentrated under reduced pressure. The residue obtained was purified by chromatography (silica, heptane to 1:3 ethyl acetate/heptane) to afford 4-chloro-5-nitropyrimidine (383 mg, 33%) as a colorless oil.

Workup

  1. temperatureat reflux for 2 h
  2. filtrationfiltered
  3. concentrationthe filtrate was concentrated under reduced pressure
  4. customThe residue obtained
  5. washwashed with saturated aqueous sodium bicarbonate (50 mL)
  6. filtrationbrine (50 mL), and filtered
  7. concentrationthe filtrate was concentrated under reduced pressure
  8. customThe residue obtained
  9. customwas purified by chromatography (silica, heptane to 1:3 ethyl acetate/heptane)

Sources & evidence

ORD record
ord-8b807a1174f64bd2a63bcaed6ea2cb1c
Source dataset
uspto-grants-2016_01
Patent number
US09226921B2

Reaction notes

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