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

HRID 37861노트

반응식

HRID 37861 반응식
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

참가 물질

9

반응물 4

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

생성물 1

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

시약·촉매·용매 4

HCID 167845palladium(II) acetate촉매HCID 962Water용매HCID 1140Toluene용매HCID 8028Tetrahydrofuran용매

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온도
0 °C

실험 절차

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.

후처리

  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)

출처 및 근거

ORD 기록
ord-ca5e7c2f849744208686a0462953cb86
출처 데이터셋
uspto-grants-2013_09
특허 번호
US08524705B2

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