Phosphorus oxychloride → 6-Chloro-1,3-diphenylpyrimidine-2,4-dione

HRID 75636Notes

Reaction equation

HRID 75636 reaction equation
[C:1]1([N:7]2[C:12](=O)[CH2:11][C:10](=[O:14])[N:9]([C:15]3[CH:20]=[CH:19][CH:18]=[CH:17][CH:16]=3)[C:8]2=[O:21])[CH:6]=[CH:5][CH:4]=[CH:3][CH:2]=1.P(Cl)(Cl)([Cl:24])=O>O>[Cl:24][C:12]1[N:7]([C:1]2[CH:6]=[CH:5][CH:4]=[CH:3][CH:2]=2)[C:8](=[O:21])[N:9]([C:15]2[CH:20]=[CH:19][CH:18]=[CH:17][CH:16]=2)[C:10](=[O:14])[CH:11]=1

Participants

4

Reactant 2

HCID 24813Phosphorus oxychlorideHCID 27849521,3-diphenyl-2,4,6(1H,3H,5H)-pyrimidinetrione

Product 1

HCID 27755636-Chloro-1,3-diphenylpyrimidine-2,4-dioneYield 74%

Reagents, catalysts & solvents 1

HCID 962WaterSolvent

Procedure

To 1,3-diphenyl-pyrimidine-2,4,6-trione 19 (78.0 g) obtained in Step 1 was added water (16 ml). Phosphorus oxychloride (422 ml) was added dropwise under stirring at room temperature over 50 min. After the completion of the dropwise addition, the mixture was stirred under heating at 110° C. for 3 hrs. After allowing to cool to room temperature, the reaction mixture was added to ice water by small portions and the mixture was stirred at room temperature and extracted with ethyl acetate. The organic layer was washed with brine and saturated aqueous sodium hydrogen carbonate, and dried over anhydrous sodium sulfate. Anhydrous sodium sulfate was filtered off and the filtrate was concentrated under reduced pressure. The residue was purified by column chromatography (hexane:ethyl acetate=2:1→3:2) to give 6-chloro-1,3-diphenyl-1H-pyrimidine-2,4-dione 20 (61.5 g, yield 74%) as pale-yellow crystals.

Workup

  1. additionAfter the completion of the dropwise addition
  2. stirringthe mixture was stirred
  3. temperatureunder heating at 110° C. for 3 hrs
  4. temperatureto cool to room temperature
  5. stirringthe mixture was stirred at room temperature
  6. extractionextracted with ethyl acetate
  7. washThe organic layer was washed with brine and saturated aqueous sodium hydrogen carbonate
  8. dry with materialdried over anhydrous sodium sulfate. Anhydrous sodium sulfate
  9. filtrationwas filtered off
  10. concentrationthe filtrate was concentrated under reduced pressure
  11. customThe residue was purified by column chromatography (hexane:ethyl acetate=2:1→3:2)

Sources & evidence

ORD record
ord-5d49f36766504c24851bc6133e7d6d0c
Source dataset
uspto-grants-2014_09
Patent number
US08835443B2

Reaction notes

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