Sodium Carbonate → HCID 12034427, compound

HRID 2275446Notes

Reaction equation

HRID 2275446 reaction equation
Cl[C:2]1[C:7](Cl)=[N:6][CH:5]=[CH:4][N:3]=1.[CH3:9][C:10]1[CH:11]=[C:12](B(O)O)[CH:13]=[C:14]([CH3:16])[CH:15]=1.C(=O)([O-])[O-].[Na+].[Na+]>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.C(#N)C>[CH3:9][C:10]1[CH:11]=[C:12]([C:2]2[C:7]([C:12]3[CH:13]=[C:14]([CH3:16])[CH:15]=[C:10]([CH3:9])[CH:11]=3)=[N:6][CH:5]=[CH:4][N:3]=2)[CH:13]=[C:14]([CH3:16])[CH:15]=1

Participants

7

Reactant 3

HCID 10340Sodium Carbonate2×HCID 785752,3-DichloropyrazineHCID 27343493,5-Dimethylphenylboronic acid2×

Product 1

HCID 12034427HCID 12034427, compoundYield 44%

Reagents, catalysts & solvents 3

HCID 178418476HCID 178418476, compoundCatalyst2×HCID 962WaterSolvent3×HCID 6342AcetonitrileSolvent2×

Procedure

First, 5.00 g of 2,3-dichloropyrazine, 10.23 g of 3,5-dimethylphenylboronic acid, 7.19 g of sodium carbonate, 0.29 g of bis(triphenylphosphine)palladium(II) dichloride (Pd(PPh3)2Cl2), 20 mL of water, and 20 mL of acetonitrile were put into a recovery flask equipped with a reflux pipe, and the air in the flask was replaced with argon. This reaction container was subjected to irradiation with microwaves (2.45 GHz, 100 W) for 60 minutes to be heated. Here, into the flask were further put 2.55 g of 3,5-dimethylphenylboronic acid, 1.80 g of sodium carbonate, 0.070 g of Pd(PPh3)2Cl2, 5 mL of water, and 5 mL of acetonitrile, and irradiation with microwaves (2.45 GHz, 100 W) was performed again for 60 minutes so that heating was performed. Then, water was added to this solution and the organic layer was extracted with dichloromethane. The obtained organic layer was washed with a saturated aqueous solution of sodium hydrogen carbonate, water, and saturated brine, and was dried with magnesium sulfate. After the drying, the solution was filtered. The solvent of this solution was distilled off, and the obtained residue was purified by flash column chromatography using hexane and ethyl acetate as a developing solvent in a ratio of 5:1. The solvent was distilled off, and the obtained solid was purified by flash column chromatography using dichloromethane and ethyl acetate as a developing solvent in a ratio of 10:1, so that Hdmdppr (abbreviation), which was the pyrazine derivative to be produced, was obtained as a white powder in a yield of 44%. 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 (f-1).

Workup

  1. customequipped with a reflux pipe
  2. customThis reaction container was subjected to irradiation with microwaves (2.45 GHz, 100 W) for 60 minutes
  3. temperatureto be heated
  4. temperatureso that heating
  5. extractionthe organic layer was extracted with dichloromethane
  6. washThe obtained organic layer was washed with a saturated aqueous solution of sodium hydrogen carbonate, water, and saturated brine
  7. dry with materialwas dried with magnesium sulfate
  8. filtrationAfter the drying, the solution was filtered
  9. distillationThe solvent of this solution was distilled off
  10. customthe obtained residue was purified by flash column chromatography
  11. distillationThe solvent was distilled off
  12. customthe obtained solid was purified by flash column chromatography
  13. customto be produced
  14. customwas obtained as a white powder in a yield of 44%
  15. customNote that the irradiation with microwaves
  16. customa microwave synthesis system (Discover, manufactured by CEM Corporation)
  17. customA synthesis scheme of Step 1

Sources & evidence

ORD record
ord-43734e7d6f414d7aba3eedbeab166b32
Source dataset
uspto-grants-2015_09
Patent number
US09127032B2

Reaction notes

Loading…