Tetrahydrofuran → 2-Methyl-6-[(1-methylpiperidin-4-yl)-methyl]-3-nitropyridine

HRID 2388002

Reaktionsgleichung

Reaktionsgleichung von HRID 2388002
B1C2CCCC1CCC2.C1COCC1.[CH3:15][N:16]1[CH2:21][CH2:20][C:19](=[CH2:22])[CH2:18][CH2:17]1.C[C:24]1[CH:29]=[CH:28][C:27]([N+:30]([O-:32])=[O:31])=[C:26]([CH3:33])[N:25]=1.C(=O)([O-])[O-].[K+].[K+]>CN(C=O)C.Cl[Pd]Cl.C1(P(C2C=CC=CC=2)[C-]2C=CC=C2)C=CC=CC=1.[C-]1(P(C2C=CC=CC=2)C2C=CC=CC=2)C=CC=C1.[Fe+2]>[CH3:33][C:26]1[C:27]([N+:30]([O-:32])=[O:31])=[CH:28][CH:29]=[C:24]([CH2:22][CH:19]2[CH2:20][CH2:21][N:16]([CH3:15])[CH2:17][CH2:18]2)[N:25]=1

Komponenten

8

Edukt 5

HCID 8028TetrahydrofuranHCID 11430Potassium CarbonateHCID 789669-Borabicyclo(3.3.1)nonaneHCID 849582,6-Dimethyl-3-nitropyridineHCID 139537Piperidine, 1-methyl,4-methylene-

Produkt 1

HCID 584766172-Methyl-6-[(1-methylpiperidin-4-yl)-methyl]-3-nitropyridineAusbeute 11,5 %

Reagenzien, Katalysatoren, Lösungsmittel 2

HCID 178418228Bis(cyclopenta-1,4-dien-1-yl(diphenyl)phosphane);dichloropalladium;iron(2+)KatalysatorHCID 6228DimethylformamideLösungsmittel

Reaktionsbedingungen

Temperatur
75 °C

Versuchsvorschrift

To a solution of 9-BBN in THF (0.5 M, 4.93 mL, 2.46 mmol) was added 1-methyl-4-methylenepiperidine (274 mg, 2.46 mmol). The reaction mixture was allowed to stir at 75° C. for 1 h and was then allowed to cool to rt. The resulting solution was transferred into a solution of 2-methyl-5-nitro-6-methylpyridine (486 mg, 2.24 mmol) in DMF (11 mL). To the mixture were added [1,1′-bis(diphenylphosphino)ferrocene]-dichloropalladium(II) (1:1 complex with DCM, 54.9 mg, 0.0672 mmol) and potassium carbonate (402 mg, 2.91 mmol). The reaction mixture was allowed to stir for 3 h at rt. The mixture was quenched by the addition of water (10 mL). The aqueous solution was extracted with DCM. The organic solutions were combined, washed with brine, dried over Na2SO4, filtered and concentrated. The residue was purified by column chromatography to give 2-methyl-6-[(1-methylpiperidin-4-yl)-methyl]-3-nitropyridine (64 mg, 10%) as a white solid. LCMS (FAL): Rt=3.38 min, m/z=250.2 (M+H).

Aufarbeitung

  1. temperatureto cool to rt
  2. stirringto stir for 3 h at rt
  3. customThe mixture was quenched by the addition of water (10 mL)
  4. extractionThe aqueous solution was extracted with DCM
  5. washwashed with brine
  6. dry with materialdried over Na2SO4
  7. filtrationfiltered
  8. concentrationconcentrated
  9. customThe residue was purified by column chromatography

Quellen und Nachweise

ORD-Eintrag
ord-2ac7720623b243bd8e0ebd4f06f23dfc
Quelldatensatz
uspto-grants-2012_09
Patentnummer
US08268992B2

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