Sodium Carbonate → 4-[2-Methyl-5-(methyloxy)-4-nitrophenyl]pyridine

HRID 419520Notizen

Reaktionsgleichung

Reaktionsgleichung von HRID 419520
[CH3:1][O:2][C:3]1[CH:8]=[C:7](Br)[C:6]([CH3:10])=[CH:5][C:4]=1[N+:11]([O-:13])=[O:12].[N:14]1[CH:19]=[CH:18][C:17](B(O)O)=[CH:16][CH:15]=1.C([O-])([O-])=O.[Na+].[Na+]>O1CCOCC1.C1C=CC(P(C2C=CC=CC=2)[C-]2C=CC=C2)=CC=1.C1C=CC(P(C2C=CC=CC=2)[C-]2C=CC=C2)=CC=1.Cl[Pd]Cl.[Fe+2]>[CH3:10][C:6]1[CH:5]=[C:4]([N+:11]([O-:13])=[O:12])[C:3]([O:2][CH3:1])=[CH:8][C:7]=1[C:17]1[CH:18]=[CH:19][N:14]=[CH:15][CH:16]=1

Komponenten

6

Edukt 3

HCID 10340Sodium CarbonateHCID 2734379(Pyridin-4-yl)boronic acidHCID 59441753HCID 59441753, Verbindung

Produkt 1

HCID 594526494-[2-Methyl-5-(methyloxy)-4-nitrophenyl]pyridineAusbeute 57 %

Reagenzien, Katalysatoren, Lösungsmittel 2

HCID 178418228Bis(cyclopenta-1,4-dien-1-yl(diphenyl)phosphane);dichloropalladium;iron(2+)KatalysatorHCID 312751,4-DioxaneLösungsmittel

Reaktionsbedingungen

Temperatur
80 °C

Versuchsvorschrift

A solution of 5-bromo-4-methyl-2-nitrophenyl methyl ether (6.0 g, 24.38 mmol), PdCl2(dppf)*DCM (1.43 g, 1.95 mmol) and 4-pyridylboronic acid (20.4 g, 165.8 mmol) in dioxane was deoxygenated by bubbling with N2 (g) for ca 15 min. To this solution was added degassed 2.0 N Na2CO3 (aq) (170 mL, 14.0 equiv.) and the resulting slurry was warmed to 80° C. for 24 h. The dioxane was removed under reduced pressure and the solids were dissolved in EtOAc and washed with H2O, dried (Na2SO4), and purified by flash chromatography to give the title compound of step A (2.81 g, 11.5 mmol, 57%). 1H NMR (400 MHz, CDCl3) δ ppm 8.72 (d, J=4.77 Hz, 2H), 7.79 (s, 1H), 7.22-7.31 (m, 2H), 6.90 (s, 1H), 3.95 (s, 3H), 2.22 (s, 3H).

Aufarbeitung

  1. customby bubbling with N2 (g) for ca 15 min
  2. additionTo this solution was added
  3. customThe dioxane was removed under reduced pressure
  4. dissolutionthe solids were dissolved in EtOAc
  5. washwashed with H2O
  6. dry with materialdried (Na2SO4)
  7. custompurified by flash chromatography

Quellen und Nachweise

ORD-Eintrag
ord-463722b9566b486ea014b0a3e8f74ce3
Quelldatensatz
uspto-grants-2012_01
Patentnummer
US08093239B2

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