Cesium carbonate → 4',6'-Dimethyl-2,3,5,6-tetrahydro-[1,2']bipyridinyl-4-one

HRID 37861

Reaktionsgleichung

Reaktionsgleichung von HRID 37861
C(=O)([O-])[O-].[Cs+].[Cs+].Cl.[NH:8]1[CH2:13][CH2:12][C:11](=[O:14])[CH2:10][CH2:9]1.Cl[C:16]1[CH:21]=[C:20]([CH3:22])[CH:19]=[C:18]([CH3:23])[N:17]=1.C1(C2C3C(=CC=CC=3)C=CC=2P(C2C=CC=CC=2)C2C=CC=CC=2)C2C(=CC=CC=2)C=CC=1P(C1C=CC=CC=1)C1C=CC=CC=1>C1(C)C=CC=CC=1.O1CCCC1.O.C([O-])(=O)C.[Pd+2].C([O-])(=O)C>[CH3:22][C:20]1[CH:19]=[C:18]([CH3:23])[N:17]=[C:16]([N:8]2[CH2:13][CH2:12][C:11](=[O:14])[CH2:10][CH2:9]2)[CH:21]=1

Komponenten

9

Edukt 4

HCID 10796Cesium carbonateHCID 634876Binap, (A+-)-HCID 30848514-Piperidone hydrochlorideHCID 125083782-Chloro-4,6-dimethylpyridine

Produkt 1

HCID 668513404',6'-Dimethyl-2,3,5,6-tetrahydro-[1,2']bipyridinyl-4-oneAusbeute 8 %

Reagenzien, Katalysatoren, Lösungsmittel 4

HCID 167845palladium(II) acetateKatalysatorHCID 962WaterLösungsmittelHCID 1140TolueneLösungsmittelHCID 8028TetrahydrofuranLösungsmittel

Reaktionsbedingungen

Temperatur
0 °C

Versuchsvorschrift

Caesium carbonate (48.05 g, 141.3 mmol) was added to a solution of piperidin-4-one hydrochloride (7.6 g, 56.5 mmol) in toluene (20 mL) and stirred for 15-20 min under argon. A solution of 2-chloro-4,6-dimethyl-pyridine (4.0 g, 28.3 mmol) in tetrahydrofuran (10 mL) was added dropwise followed successively by palladium acetate (63 mg, 0.28 mmol) and (±)-(1,1′-binaphthalene-2,2′-diyl)bis(diphenylphosphine) (BINAP) (0.174 g, 0.28 mmol). The reaction mixture was heated at reflux overnight then cooled to 0° C., diluted with water and extracted with ethyl acetate. The organic phase was washed with brine, dried over anhydrous sodium sulfate and concentrated in vacuo to give a residue which was purified by column chromatography over silica gel (60-120 mesh) using 10% ethyl acetate in hexane as eluent to afford 4′,6′-dimethyl-2,3,5,6-tetrahydro-[1,2′]bipyridinyl-4-one (450 mg, 8%) as a yellow solid.

Aufarbeitung

  1. temperatureThe reaction mixture was heated
  2. temperatureat reflux overnight
  3. extractionextracted with ethyl acetate
  4. washThe organic phase was washed with brine
  5. dry with materialdried over anhydrous sodium sulfate
  6. concentrationconcentrated in vacuo
  7. customto give a residue which
  8. customwas purified by column chromatography over silica gel (60-120 mesh)

Quellen und Nachweise

ORD-Eintrag
ord-ca5e7c2f849744208686a0462953cb86
Quelldatensatz
uspto-grants-2013_09
Patentnummer
US08524705B2

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