Cesium carbonate → 3-Amino-6-chloro-4-picoline

HRID 34088

Reaktionsgleichung

Reaktionsgleichung von HRID 34088
Br[C:2]1[C:3]([CH3:9])=[CH:4][C:5]([Cl:8])=[N:6][CH:7]=1.C(=O)([O-])[O-].[Cs+].[Cs+].C(=[NH:29])(C1C=CC=CC=1)C1C=CC=CC=1.C1(P(C2C=CC=CC=2)C2C=CC3C(=CC=CC=3)C=2C2C3C(=CC=CC=3)C=CC=2P(C2C=CC=CC=2)C2C=CC=CC=2)C=CC=CC=1>C1(C)C=CC=CC=1.[Cl-].[Na+].O>[Cl:8][C:5]1[CH:4]=[C:3]([CH3:9])[C:2]([NH2:29])=[CH:7][N:6]=1

Komponenten

7

Edukt 4

HCID 10796Cesium carbonateHCID 136809Benzophenone imineHCID 634876Binap, (A+-)-HCID 27344275-Bromo-2-chloro-4-methylpyridine

Produkt 1

HCID 27344253-Amino-6-chloro-4-picoline

Reagenzien, Katalysatoren, Lösungsmittel 2

HCID 1140TolueneLösungsmittelHCID 57417360Sodium chloride; waterLösungsmittel

Reaktionsbedingungen

Temperatur
110 °C

Versuchsvorschrift

308 mg of 5-bromo-2-chloro-4-methylpyridine was dissolved in 6 mL of toluene, added with 680 mg cesium carbonate, 0.3 mL of benzophenoneimine, 42 mg of 2,2′-bis(diphenylphosphino)-1,1′-binaphtyl and 46 mg of tris(dibenzylideneacetone)bis palladium, and stirred under nitrogen atmosphere at 110° C. for 15 hours. The reaction solution was allowed to cool to room temperature, then added with saturated brine, extracted with ethylacetate, dried over magnesium sulfate, and then the solvent was evaporated. The residue was added with 10 mL of tetrahydrofuran and 10 mL of 5N hydrochloric acid, and stirred at room temperature for 1 hour. The reaction solution was added with aqueous sodium hydrogen carbonate, extracted with ethyl acetate, and the organic layer was washed with saturated brine, and dried over magnesium sulfate. The solvent was evaporated, and the residue was purified by silica gel column chromatography (ethyl acetate:hexane=1:1), to afford 56 mg of the title compound.

Aufarbeitung

  1. temperatureto cool to room temperature
  2. extractionextracted with ethylacetate
  3. dry with materialdried over magnesium sulfate
  4. customthe solvent was evaporated
  5. additionThe residue was added with 10 mL of tetrahydrofuran and 10 mL of 5N hydrochloric acid
  6. stirringstirred at room temperature for 1 hour
  7. additionThe reaction solution was added with aqueous sodium hydrogen carbonate
  8. extractionextracted with ethyl acetate
  9. washthe organic layer was washed with saturated brine
  10. dry with materialdried over magnesium sulfate
  11. customThe solvent was evaporated
  12. customthe residue was purified by silica gel column chromatography (ethyl acetate:hexane=1:1)

Quellen und Nachweise

ORD-Eintrag
ord-ef94ad0750e14a13b98b7e11465dff73
Quelldatensatz
uspto-grants-2008_09
Patentnummer
US07429609B2

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