Acetonitrile → 4-Chloro-6-phenylpyrimidine

HRID 1482170Notes

Reaction equation

HRID 1482170 reaction equation
[Cl:1][C:2]1[CH:7]=[C:6](Cl)[N:5]=[CH:4][N:3]=1.[C:9]1(B(O)O)[CH:14]=[CH:13][CH:12]=[CH:11][CH:10]=1.C(=O)([O-])[O-].[Na+].[Na+].C(#N)C>Cl[Pd](Cl)([P](C1C=CC=CC=1)(C1C=CC=CC=1)C1C=CC=CC=1)[P](C1C=CC=CC=1)(C1C=CC=CC=1)C1C=CC=CC=1.O>[Cl:1][C:2]1[CH:7]=[C:6]([C:9]2[CH:14]=[CH:13][CH:12]=[CH:11][CH:10]=2)[N:5]=[CH:4][N:3]=1

Participants

7

Reactant 4

HCID 6342AcetonitrileHCID 10340Sodium Carbonate2×HCID 66827Phenylboronic Acid2×HCID 709434,6-Dichloropyrimidine

Product 1

HCID 5934294-Chloro-6-phenylpyrimidineYield 37%

Reagents, catalysts & solvents 2

HCID 178418476HCID 178418476, compoundCatalystHCID 962WaterSolvent

Procedure

Into a 100-mL round-bottom flask equipped with a reflux pipe were put 5.1 g of 4,6-dichloropyrimidine, 8.2 g of phenylboronic acid, 7.16 g of sodium carbonate, 20 mL of acetonitrile, and 20 mL of water, and the air in the flask was replaced with nitrogen. To this mixture, 0.347 g of bis(triphenylphosphine)palladium(II) dichloride was added and the mixture was irradiated with microwaves (2.45 GHz, 100 W) for 1 hour. Further, 2.07 g of phenylboronic acid and 1.79 g of sodium carbonate were added and the mixture was irradiated with microwaves (2.45 GHz, 100 W) for 1 hour. An organic layer was extracted from the obtained mixture with the use of dichloromethane. The obtained organic layer was washed with water and a saturated aqueous solution of sodium chloride and dried over magnesium sulfate. The mixture was subjected to gravity filtration. A residue obtained by distilling off the solvent in the filtrate was purified by silica column chromatography with the use of dichloromethane as a developing solvent to give an objective substance as a white powder in a yield of 37%. Note that the irradiation with microwaves was performed using a microwave synthesis system (Discover, manufactured by CEM Corporation). Synthesis Scheme (D-1) of Step 1 is shown below.

Workup

  1. customInto a 100-mL round-bottom flask equipped with a reflux pipe
  2. customthe mixture was irradiated with microwaves (2.45 GHz, 100 W) for 1 hour
  3. customthe mixture was irradiated with microwaves (2.45 GHz, 100 W) for 1 hour
  4. extractionAn organic layer was extracted from the obtained mixture with the use of dichloromethane
  5. washThe obtained organic layer was washed with water
  6. dry with materiala saturated aqueous solution of sodium chloride and dried over magnesium sulfate
  7. filtrationThe mixture was subjected to gravity filtration
  8. customA residue obtained
  9. distillationby distilling off the solvent in the filtrate
  10. customwas purified by silica column chromatography with the use of dichloromethane as a developing solvent
  11. customto give an objective substance as a white powder in a yield of 37%
  12. customNote that the irradiation with microwaves
  13. customa microwave synthesis system (Discover, manufactured by CEM Corporation)
  14. customSynthesis Scheme (D-1) of Step 1

Sources & evidence

ORD record
ord-388fbe3afdd34ca4835c6449b0879bbe
Source dataset
uspto-grants-2016_08
Patent number
US09412953B2

Reaction notes

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