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

HRID 37861ノート

反応式

HRID 37861 の反応式
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

参加物

9

反応物 4

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

生成物 1

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

試薬・触媒・溶媒 4

HCID 167845palladium(II) acetate触媒HCID 962Water溶媒HCID 1140Toluene溶媒HCID 8028Tetrahydrofuran溶媒

反応条件

温度
0 °C

実験手順

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.

後処理

  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)

出典と根拠

ORDレコード
ord-ca5e7c2f849744208686a0462953cb86
出典データセット
uspto-grants-2013_09
特許番号
US08524705B2

反応ノート

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