Acetonitrile → 4-Chloro-6-phenylpyrimidine

HRID 1482165Notes

Reaction equation

HRID 1482165 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 CarbonateHCID 66827Phenylboronic AcidHCID 709434,6-Dichloropyrimidine

Product 1

HCID 5934294-Chloro-6-phenylpyrimidineYield 23%

Reagents, catalysts & solvents 2

HCID 178418476HCID 178418476, compoundCatalyst2×HCID 962WaterSolvent

Procedure

First, 5.0 g of 4,6-dichloropyrimidine, 4.9 g of phenylboronic acid, 7.1 g of sodium carbonate, 0.34 g of bis(triphenylphosphine)palladium(II) dichloride, namely PdCl2(PPh3)2, 20 mL of acetonitrile, and 20 mL of water were put into a 100-mL round-bottom flask equipped with a reflux pipe, and the air in the flask was replaced with argon. Then, heating was performed by irradiation with microwaves (2.45 GHz, 100 W) for 1 hour. An organic layer was extracted from the obtained mixture with the use of dichloromethane and was washed with water and saturated brine. Magnesium sulfate was added and gravity filtration was performed. The solvent in the obtained filtrate was distilled off, and the given residue was purified by flash column chromatography using dichloromethane as a developing solvent, whereby 1.6 g of the objective substance was obtained (yield: 23%, a pale yellow solid). Note that the irradiation with microwaves was performed using a microwave synthesis system (Discover, manufactured by CEM Corporation). A synthesis scheme of Step 1 is shown in (a-1) below.

Workup

  1. customequipped with a reflux pipe
  2. temperatureThen, heating
  3. customwas performed by irradiation 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. washwas washed with water and saturated brine
  6. additionMagnesium sulfate was added
  7. filtrationgravity filtration
  8. distillationThe solvent in the obtained filtrate was distilled off
  9. customthe given residue was purified by flash column chromatography
  10. customwas obtained (yield: 23%
  11. customNote that the irradiation with microwaves
  12. customa microwave synthesis system (Discover, manufactured by CEM Corporation)
  13. customA synthesis scheme of Step 1

Sources & evidence

ORD record
ord-2016f2c16e0c40b6ae4ca406f74aa072
Source dataset
uspto-grants-2016_08
Patent number
US09412956B2

Reaction notes

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