Sodium Sulfite → 6-[1-(3-Pyridyl)pyrazol-4-yl]-2,3-dihydropyrano[3,2-b]pyridin-4-one

HRID 1478549Notizen

Reaktionsgleichung

Reaktionsgleichung von HRID 1478549
CS(N)(=O)=O.C=[C:7]1[C:12]2=[N:13][C:14]([C:17]3[CH:18]=[N:19][N:20]([C:22]4[CH:23]=[N:24][CH:25]=[CH:26][CH:27]=4)[CH:21]=3)=[CH:15][CH:16]=[C:11]2[O:10][CH2:9][CH2:8]1.S([O-])([O-])=[O:29].[Na+].[Na+].I([O-])(=O)(=O)=O.[Na+]>C1COCC1.O1CCOCC1.O.C(Cl)Cl.CC(O)(C)C.O>[N:24]1[CH:25]=[CH:26][CH:27]=[C:22]([N:20]2[CH:21]=[C:17]([C:14]3[N:13]=[C:12]4[C:7](=[O:29])[CH2:8][CH2:9][O:10][C:11]4=[CH:16][CH:15]=3)[CH:18]=[N:19]2)[CH:23]=1

Komponenten

10

Edukt 4

HCID 24437Sodium SulfiteHCID 72879MethanesulfonamideHCID 23667635Sodium periodateHCID 900430134-Methylene-6-[1-(3-pyridyl)pyrazol-4-yl]-2,3-dihydropyrano[3,2-b]pyridine

Produkt 1

HCID 900430706-[1-(3-Pyridyl)pyrazol-4-yl]-2,3-dihydropyrano[3,2-b]pyridin-4-one

Reagenzien, Katalysatoren, Lösungsmittel 5

HCID 962WaterLösungsmittel2×HCID 6344DichloromethaneLösungsmittelHCID 8028TetrahydrofuranLösungsmittelHCID 312751,4-DioxaneLösungsmittelHCID 714019492-Methylpropan-2-ol--water (1/1)Lösungsmittel

Versuchsvorschrift

AD-mix-a (13.9 g, 1.44 g/mmol) was added to t-BuOH/H2O (45 ml/45 ml), stirred at rt for 5 min. MeSO2NH2 (936 mg, 9.85 mmol) and K2OsO4.2H2O (21 mg, 0.058 mmol) was added to the reaction mixture. The mixture was then cooled with ice, 4-methylene-6-[1-(3-pyridyl) pyrazol-4-yl]-2,3-dihydropyrano[3,2-b]pyridine (2.8 g, 9.66 mmol) in THF (25 ml) was added slowly to the above solution. Sodium sulfite (22 g, 2.25 g/mmol) was then added. After stirring for 15 min at 0° C., the ice bath was removed and the reaction mixture was stirred at rt for 45 min. The mixture was diluted with DCM (100 ml) and H2O (100 ml) and the two layers were separated. The organic layer was washed with brine, dried over Na2SO4, filtered and concentrated, which was used directly for the next step. The crude product was dissolved in a 1:1 mixture of dioxane (30 ml) and H2O (30 ml), and sodium periodate (1.9 g, 9.26 mmol) was added. The reaction mixture was stirred at rt for 1 h. The reaction mixture was diluted with DCM (50 ml) and H2O (50 ml) and the two layers were separated. The organic layer was dried over Na2SO4, filtered and concentrated. The resulting residue was purified by silica gel chromatography (EtOAc/MeOH, 50/1) to afford the title compound as red solid.

Aufarbeitung

  1. additionwas added slowly to the above solution
  2. stirringAfter stirring for 15 min at 0° C.
  3. customthe ice bath was removed
  4. stirringthe reaction mixture was stirred at rt for 45 min
  5. additionThe mixture was diluted with DCM (100 ml) and H2O (100 ml)
  6. customthe two layers were separated
  7. washThe organic layer was washed with brine
  8. dry with materialdried over Na2SO4
  9. filtrationfiltered
  10. concentrationconcentrated
  11. additionwas added
  12. stirringThe reaction mixture was stirred at rt for 1 h
  13. customthe two layers were separated
  14. dry with materialThe organic layer was dried over Na2SO4
  15. filtrationfiltered
  16. concentrationconcentrated
  17. customThe resulting residue was purified by silica gel chromatography (EtOAc/MeOH, 50/1)

Quellen und Nachweise

ORD-Eintrag
ord-07557e96fd1d49a6898254bb3a80caa9
Quelldatensatz
uspto-grants-2016_08
Patentnummer
US09403845B2

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