Nitrogen → HCID 86715333, Verbindung

HRID 2272646Notizen

Reaktionsgleichung

Reaktionsgleichung von HRID 2272646
[NH2:1][C:2]1[CH:7]=[C:6]([CH:8]2[CH2:10][CH2:9]2)[CH:5]=[CH:4][N:3]=1.[Br:11][C:12]1[CH:17]=[C:16]([CH3:18])[CH:15]=[C:14](Br)[N:13]=1.N#N.CC(C)([O-])C.[Na+]>[Pd](Cl)Cl.C(P(C(C)(C)C)[C-]1C=CC=C1)(C)(C)C.[C-]1(P(C(C)(C)C)C(C)(C)C)C=CC=C1.[Fe+2].O.O1CCOCC1>[Br:11][C:12]1[N:13]=[C:14]([NH:1][C:2]2[CH:7]=[C:6]([CH:8]3[CH2:10][CH2:9]3)[CH:5]=[CH:4][N:3]=2)[CH:15]=[C:16]([CH3:18])[CH:17]=1

Komponenten

8

Edukt 4

HCID 947NitrogenHCID 112881742,6-Dibromo-4-methylpyridineHCID 23676156Sodium t-butoxideHCID 457879154-Cyclopropylpyridin-2-amine

Produkt 1

HCID 86715333HCID 86715333, Verbindung

Reagenzien, Katalysatoren, Lösungsmittel 3

HCID 178454861HCID 178454861, VerbindungKatalysatorHCID 962WaterLösungsmittelHCID 312751,4-DioxaneLösungsmittel

Versuchsvorschrift

A dry round bottomed flask was charged with 2-amino-4-cyclopropylpyridine (5.00 g, 31.7 mmol) and 2,6-dibromo-4-methylpyridine (7.95 g, 31.7 mmol). The reaction vessel was placed under an atmosphere of nitrogen (3× vacuum/N2 cycle), then 1,4-dioxane (100 mL) was added and the mixture was degassed with a steady stream of nitrogen for 30 minutes. Sodium tert-butoxide (3.35 g, 34.8 mmol) and 1,1′-bis(di-tert-butylphosphino)ferrocene palladium dichloride (0.49 g, 0.75 mmol) were added to the reaction flask, then the reaction was stirred at room temperature for 15 minutes then heated to 50° C. for five hours. After cooling to room temperature for 14 hours, the resulting reaction mixture was poured into water (200 mL) and extracted with ethyl acetate (2×100 mL). The combined organic layers were further washed with water and brine (200 mL portions). The organic phase was dried over sodium sulfate, filtered, and concentrated under reduced pressure to yield an oil. The crude product was purified by silica gel chromatography (0-30% ethyl acetate/hexanes) to give the title compound as a brown solid. 1H NMR (600 MHz, DMSO-d6) δ 9.80 (s, 1H), 8.06 (d, J=5.3 Hz, 1H), 7.70 (s, 1H), 7.23 (s, 1H), 6.92 (s, 1H), 6.61 (dd, J=1.4, 5.3 Hz, 1H), 2.25 (s, 3H), 1.91-1.78 (m, 1H), 1.09-0.98 (m, 2H), 0.82-0.66 (m, 2H).

Aufarbeitung

  1. customthe mixture was degassed with a steady stream of nitrogen for 30 minutes
  2. temperaturethen heated to 50° C. for five hours
  3. temperatureAfter cooling to room temperature for 14 hours
  4. customthe resulting reaction mixture
  5. extractionextracted with ethyl acetate (2×100 mL)
  6. washThe combined organic layers were further washed with water and brine (200 mL portions)
  7. dry with materialThe organic phase was dried over sodium sulfate
  8. filtrationfiltered
  9. concentrationconcentrated under reduced pressure
  10. customto yield an oil
  11. customThe crude product was purified by silica gel chromatography (0-30% ethyl acetate/hexanes)

Quellen und Nachweise

ORD-Eintrag
ord-90f62ac3e317431cb90a5392bd290ca9
Quelldatensatz
uspto-grants-2015_09
Patentnummer
US09120785B2

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