Potassium Carbonate → HCID 66600239, Verbindung

HRID 1621870

Reaktionsgleichung

Reaktionsgleichung von HRID 1621870
C(=O)([O-])[O-].[K+].[K+].[C:7]([B-](F)(F)F)([CH3:9])=[CH2:8].[K+].Br[C:16]1[C:17]([O:25][CH3:26])=[N:18][CH:19]=[C:20]([N+:22]([O-])=O)[CH:21]=1.[H][H]>O1CCOCC1.O.[Pd].[Pd](Cl)Cl.C(P(C(C)(C)C)C1C=CC(N(C)C)=CC=1)(C)(C)C.C(P(C(C)(C)C)C1C=CC(N(C)C)=CC=1)(C)(C)C.CO>[CH:7]([C:16]1[CH:21]=[C:20]([NH2:22])[CH:19]=[N:18][C:17]=1[O:25][CH3:26])([CH3:9])[CH3:8]

Komponenten

10

Edukt 4

HCID 11430Potassium CarbonateHCID 215844513-Bromo-2-methoxy-5-nitropyridineHCID 23670158Potassium (prop-1-en-2-yl)trifluoroborateHCID 178418361HCID 178418361, Verbindung

Produkt 1

HCID 66600239HCID 66600239, VerbindungAusbeute 101,5 %

Reagenzien, Katalysatoren, Lösungsmittel 5

HCID 23938PalladiumKatalysatorHCID 11714597Bis(di-tert-butyl(4-dimethylaminophenyl)phosphine)dichloropalladium(II)KatalysatorHCID 887MethanolLösungsmittelHCID 962WaterLösungsmittelHCID 312751,4-DioxaneLösungsmittel

Reaktionsbedingungen

Temperatur
80 °C

Versuchsvorschrift

Argon was bubbled through a slurry of potassium carbonate (4.45 g, 32.2 mmol), potassium isopropenyltrifluoroborate (3.18 g, 21.46 mmol), bis(4-(di-tert-butylphosphino)-N,N-dimethylbenzenamine) palladium dichloride (Aldrich, St. Louis, Mo., 0.152 g, 0.215 mmol), and 3-bromo-2-methoxy-5-nitropyridine (2.50 g, 10.73 mmol) in 50 mL dioxane and 20 mL water for 5 min. The reaction was sealed and heated to 80° C. for 1 h. The dark red reaction was cooled and partitioned between water and DCM. The aqueous layer was extracted with DCM 3 times, and the combined organics were dried over anhydrous sodium sulfate, filtered, and concentrated in vacuo, to give a red solid, which was used without further purification. The solid was treated 10% palladium on carbon (50% water wet) (2.62 g, 2.464 mmol) and 75 mL MeOH and was fitted with hydrogen balloon and stirred rapidly for 3 h. The reaction was flushed with nitrogen, filtered through Celite® (diatomaceous earth), rinsing with 400 mL MeOH, and concentrated in vacuo to give 5-isopropyl-6-methoxypyridin-3-amine (1.81 g, 10.89 mmol, quantitative yield) as a brown oil. m/z (ESI, +ve ion) 167 (M+H)+. 1H NMR (400 MHz, CDCl3) δ 7.51 (d, J=2.9 Hz, 1H), 6.94 (d, J=2.7 Hz, 1H), 3.90 (s, 3H), 3.13 (m, 1H), 1.14-1.22 (m, 6H).

Aufarbeitung

  1. customThe reaction was sealed
  2. customThe dark red reaction
  3. temperaturewas cooled
  4. custompartitioned between water and DCM
  5. extractionThe aqueous layer was extracted with DCM 3 times
  6. dry with materialthe combined organics were dried over anhydrous sodium sulfate
  7. filtrationfiltered
  8. concentrationconcentrated in vacuo
  9. customto give a red solid, which
  10. customwas used without further purification
  11. customThe reaction was flushed with nitrogen
  12. filtrationfiltered through Celite® (diatomaceous earth)
  13. washrinsing with 400 mL MeOH
  14. concentrationconcentrated in vacuo

Quellen und Nachweise

ORD-Eintrag
ord-1d7a50cf58be4b65931c77a3e537028d
Quelldatensatz
uspto-grants-2014_07
Patentnummer
US08772480B2

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