Sodium Carbonate → 2-Chloro-3-methyl-6-(pyrimidin-4-YL)pyrimidin-4-one

HRID 1671488Notes

Reaction equation

HRID 1671488 reaction equation
S[C:2]1[N:3]([CH3:15])[C:4](=[O:14])[CH:5]=[C:6]([C:8]2[CH:13]=[CH:12][N:11]=[CH:10][N:9]=2)[N:7]=1.P(Cl)(Cl)([Cl:18])=O.C(=O)([O-])[O-].[Na+].[Na+].C(=O)([O-])O.[Na+].Cl[O-].[Na+]>O.ClCCl.ClCCCl.CN(C)C=O>[Cl:18][C:2]1[N:3]([CH3:15])[C:4](=[O:14])[CH:5]=[C:6]([C:8]2[CH:13]=[CH:12][N:11]=[CH:10][N:9]=2)[N:7]=1

Participants

10

Reactant 5

HCID 10340Sodium CarbonateHCID 24813Phosphorus oxychlorideHCID 516892Sodium BicarbonateHCID 23665760Sodium HypochloriteHCID 1784816782-Mercapto-3-methyl-6-(pyrimidin-4-YL)-3H-pyrimidin-4-one

Product 1

HCID 179544602-Chloro-3-methyl-6-(pyrimidin-4-YL)pyrimidin-4-one

Reagents, catalysts & solvents 4

HCID 111,2-DichloroethaneSolventHCID 962WaterSolventHCID 6228DimethylformamideSolventHCID 6344DichloromethaneSolvent

Conditions

Temperature
65 °C

Procedure

A suspension of 2-mercapto-1-methyl-1H-[4,4′]bipyrimidinyl-6-one (8.8 g, 40 mmol) in a mixed solvent of dimethylformamide (30 ml) and 1,2-dichloroethane (30 ml) was added to phosphorus oxychloride (11.2 ml, 120 mmol), and the mixture was stirred at 65° C. for 50 min. The solution was poured into ice-cooled dichloromethane (300 ml), water was added and the mixture was vigorously stirred for 5 min. Aqueous sodium carbonate solution (25.4 g, 240 mmol, in water (100 ml)) was added and the pH was adjusted to 8 with saturated aqueous sodium hydrogencarbonate solution. Aqueous sodium hypochlorite solution (5% in water, 120 ml) was added. After filtration through celite, the organic layer was extracted twice with dichloromethane, and washed with saturated aqueous sodium bicarbonate solution and dried over sodium sulfate. The solvent was evaporated under reduced pressure, and the obtained residue was purified by silica gel column chromatography (eluent; ethyl acetate/hexane=1/1) and washed with diethyl ether to give 2-chloro-1-methyl-1H-[4,4′]bipyrimidinyl-6-one as a pale-yellow solid (2.2 g, 62%, purity 98.7%).

Workup

  1. additionThe solution was poured into ice-
  2. additionwas added
  3. stirringthe mixture was vigorously stirred for 5 min
  4. filtrationAfter filtration through celite
  5. extractionthe organic layer was extracted twice with dichloromethane
  6. washwashed with saturated aqueous sodium bicarbonate solution
  7. dry with materialdried over sodium sulfate
  8. customThe solvent was evaporated under reduced pressure
  9. customthe obtained residue was purified by silica gel column chromatography (eluent; ethyl acetate/hexane=1/1)
  10. washwashed with diethyl ether

Sources & evidence

ORD record
ord-50c51c4a7a0642e282178f15e431885d
Source dataset
uspto-grants-2011_08
Patent number
US07994315B2

Reaction notes

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