Potassium Carbonate → Pyriofenone

HRID 242440Notes

Reaction equation

HRID 242440 reaction equation
Br[C:2]1[C:3]([O:10][CH3:11])=[N:4][CH:5]=[C:6]([Cl:9])[C:7]=1[CH3:8].[CH3:12][O:13][C:14]1[C:19]([O:20][CH3:21])=[C:18]([O:22][CH3:23])[CH:17]=[C:16]([CH3:24])[C:15]=1B(O)O.[C:28](=O)([O-])[O-:29].[K+].[K+].C1(P(C2CCCCC2)C2CCCCC2)CCCCC1.[C]=O>[Pd](Cl)Cl.O1CCCC1>[CH3:12][O:13][C:14]1[C:19]([O:20][CH3:21])=[C:18]([O:22][CH3:23])[CH:17]=[C:16]([CH3:24])[C:15]=1[C:28]([C:2]1[C:3]([O:10][CH3:11])=[N:4][CH:5]=[C:6]([Cl:9])[C:7]=1[CH3:8])=[O:29]

Participants

8

Reactant 5

HCID 11430Potassium CarbonateHCID 75806TricyclohexylphosphineHCID 231336432,3,4-Trimethoxy-6-methylphenylboronic acidHCID 231336453-Bromo-5-chloro-2-methoxy-4-methylpyridineHCID 178418416HCID 178418416, compound

Product 1

HCID 23082663PyriofenoneYield 20%

Reagents, catalysts & solvents 2

HCID 24290Palladium ChlorideCatalystHCID 8028TetrahydrofuranSolvent

Conditions

Temperature
120 °C

Procedure

1.0 g (4.3 mmol) of 3-bromo-5-chloro-2-methoxy-4-methylpyridine, 1.2 g (5.4 mmol) of 2,3,4-trimethoxy-6-methylphenylboronic acid, 1.8 g (13 mmol) of potassium carbonate, 46 mg (0.26 mmol) of palladium chloride, 147 mg (0.52 mmol) of tricyclohexylphosphine and 40 ml of tetrahydrofuran were put in a 200 ml autoclave, and carbon monoxide gas was injected to a pressure of 10 atm, followed by stirring at 120° C. for 20 hours. The reaction solution was subjected to filtration on the pad of celite, water was added, and tetrahydrofuran was distilled off under reduced pressure. The aqueous solution was extracted with ethyl acetate, the organic layer was dried over anhydrous magnesium sulfate and subjected to filtration, and the solvent was distilled off under reduced pressure. The crude product was purified by silica gel column chromatography to obtain 0.31 g (yield: 20%) of 3-(2,3,4-trimethoxy-6-methylbenzoyl)-5-chloro-2-methoxy-4-methylpyridine (melting point 92 to 94° C.), and the compound was identified by 1HNMR.

Workup

  1. filtrationThe reaction solution was subjected to filtration on the pad of celite, water
  2. additionwas added
  3. distillationtetrahydrofuran was distilled off under reduced pressure
  4. extractionThe aqueous solution was extracted with ethyl acetate
  5. dry with materialthe organic layer was dried over anhydrous magnesium sulfate
  6. filtrationsubjected to filtration
  7. distillationthe solvent was distilled off under reduced pressure
  8. customThe crude product was purified by silica gel column chromatography

Sources & evidence

ORD record
ord-dc9c20f93af249eb8b094580c178c2a0
Source dataset
uspto-grants-2014_02
Patent number
US08653113B2

Reaction notes

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