Cesium carbonate → HCID 68688049, compound

HRID 2238647Notes

Reaction equation

HRID 2238647 reaction equation
[CH3:1][O:2][C:3](=[O:12])[C:4]1[CH:9]=[CH:8][N:7]=[C:6](Cl)[C:5]=1[CH3:11].C1(P(C2C=CC=CC=2)C2C3OC4C(=CC=CC=4P(C4C=CC=CC=4)C4C=CC=CC=4)C(C)(C)C=3C=CC=2)C=CC=CC=1.C(=O)([O-])[O-].[Cs+].[Cs+].C(=[NH:74])(C1C=CC=CC=1)C1C=CC=CC=1.C(=O)(O)[O-].[Na+]>C1C=CC(/C=C/C(/C=C/C2C=CC=CC=2)=O)=CC=1.C1C=CC(/C=C/C(/C=C/C2C=CC=CC=2)=O)=CC=1.[Pd].O.C1(C)C=CC=CC=1.O1CCOCC1>[CH3:1][O:2][C:3](=[O:12])[C:4]1[CH:9]=[CH:8][N:7]=[C:6]([NH2:74])[C:5]=1[CH3:11]

Participants

10

Reactant 5

HCID 10796Cesium carbonateHCID 136809Benzophenone imineHCID 516892Sodium BicarbonateHCID 6360441,1'-(9,9-Dimethyl-9H-xanthene-4,5-diyl)bis(1,1-diphenylphosphine)HCID 53436889Methyl 2-chloro-3-methylpyridine-4-carboxylate

Product 1

HCID 68688049HCID 68688049, compound

Reagents, catalysts & solvents 4

HCID 6505921(1E,4E)-1,5-diphenylpenta-1,4-dien-3-one; palladiumCatalystHCID 962WaterSolventHCID 1140TolueneSolventHCID 312751,4-DioxaneSolvent

Conditions

Temperature
80 °C

Procedure

The mixture of 520 mg of 2-chloro-3-methylisonicotinic acid methyl ester [48-1], 161 mg of bis(dibenzylideneacetone)palladium, 324 mg of 4,5-bis(diphenylphosphino)-9,9-dimethylxanthene, 1.28 g of cesium carbonate, 564 μL of benzophenoneimine, 5 mL of 1,4-dioxane, and 5 mL of toluene, was stirred overnight at 80° C. After cooling the reaction mixture back to room temperature, water and a saturated aqueous solution of sodium bicarbonate were added, and extracted with ethyl acetate. The organic layer was washed with saturated brine, and then dried over anhydrous sodium sulfate. The insolubles were filtered, the filtrate was concentrated under reduced pressure, and the obtained residue was dissolved in 28 mL of methanol. Thereto, 1.1 g of sodium acetate and 700 mg of hydroxyamine hydrochloride were added, and stirred for 1 hour. Then, a 0.1 N aqueous solution of sodium hydroxide was added, and extracted with chloroform. The organic layer was washed with saturated brine, and then dried over anhydrous sodium sulfate. The insolubles were filtered, the filtrate was concentrated under reduced pressure, and the residue was purified by silica gel column chromatography, to obtain 92.1 mg of 2-amino-3-methylisonicotinic acid methyl ester [48-2] as a yellow solid.

Workup

  1. temperatureAfter cooling the reaction mixture back to room temperature
  2. extractionextracted with ethyl acetate
  3. washThe organic layer was washed with saturated brine
  4. dry with materialdried over anhydrous sodium sulfate
  5. filtrationThe insolubles were filtered
  6. concentrationthe filtrate was concentrated under reduced pressure
  7. dissolutionthe obtained residue was dissolved in 28 mL of methanol
  8. additionThereto, 1.1 g of sodium acetate and 700 mg of hydroxyamine hydrochloride were added
  9. stirringstirred for 1 hour
  10. additionThen, a 0.1 N aqueous solution of sodium hydroxide was added
  11. extractionextracted with chloroform
  12. washThe organic layer was washed with saturated brine
  13. dry with materialdried over anhydrous sodium sulfate
  14. filtrationThe insolubles were filtered
  15. concentrationthe filtrate was concentrated under reduced pressure
  16. customthe residue was purified by silica gel column chromatography

Sources & evidence

ORD record
ord-4066f5f23b93499482dc6f01ef9be577
Source dataset
uspto-grants-2010_05
Patent number
US07718801B2

Reaction notes

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