Cesium carbonate → Ethyl 4-[(5,6,6a,7,8,9-hexahydro-4H-2-phenalenyl)amino]benzoate

HRID 1097376ノート

反応式

HRID 1097376 の反応式
[CH:1]1[C:12]2=[C:13]3[CH:8]([CH2:9][CH2:10][CH2:11]2)[CH2:7][CH2:6][CH2:5][C:4]3=[CH:3][C:2]=1[NH2:14].I[C:16]1[CH:26]=[CH:25][C:19]([C:20]([O:22][CH2:23][CH3:24])=[O:21])=[CH:18][CH:17]=1.C1(P(C2C=CC=CC=2)C2C=CC3C(=CC=CC=3)C=2C2C3C(=CC=CC=3)C=CC=2P(C2C=CC=CC=2)C2C=CC=CC=2)C=CC=CC=1.C(=O)([O-])[O-].[Cs+].[Cs+]>C1(C)C=CC=CC=1.C1C=CC(/C=C/C(/C=C/C2C=CC=CC=2)=O)=CC=1.C1C=CC(/C=C/C(/C=C/C2C=CC=CC=2)=O)=CC=1.C1C=CC(/C=C/C(/C=C/C2C=CC=CC=2)=O)=CC=1.[Pd].[Pd]>[CH:1]1[C:12]2=[C:13]3[CH:8]([CH2:9][CH2:10][CH2:11]2)[CH2:7][CH2:6][CH2:5][C:4]3=[CH:3][C:2]=1[NH:14][C:16]1[CH:26]=[CH:25][C:19]([C:20]([O:22][CH2:23][CH3:24])=[O:21])=[CH:18][CH:17]=1

参加物

7

反応物 4

HCID 10796Cesium carbonateHCID 142891Ethyl 4-iodobenzoateHCID 634876Binap, (A+-)-HCID 58420580HCID 58420580、化合物

生成物 1

HCID 66811225Ethyl 4-[(5,6,6a,7,8,9-hexahydro-4H-2-phenalenyl)amino]benzoate収率 36.6%

試薬・触媒・溶媒 2

HCID 9811564Bis(dibenzylideneacetone)palladium触媒HCID 1140Toluene溶媒

反応条件

温度
80 °C

実験手順

5,6,6a,7,8,9-Hexahydro-4H-2-phenalenylamine (0.250 g) and ethyl 4-iodobenzoate (0.360 g) were dissolved in anhydrous toluene (5 ml), the solution was added with tris(dibenzylideneacetone)dipalladium (0.024 g), (±)-2,2′-bis(diphenylphosphino)-1,1′-binaphthyl (0.036 g), and cesium carbonate (0.455 g), and the mixture was stirred overnight at 80° C. under an argon flow. The reaction mixture was left to cool, and then poured into ice water, and the mixture was extracted with diethyl ether. The organic layer was washed successively with 2 N aqueous hydrochloric acid, water and saturated brine, and dried over anhydrous sodium sulfate. The organic layer was concentrated under reduced pressure, and the resulting residue was purified by silica gel column chromatography (developing solvent: ethyl acetate:n-hexane=1:50) to obtain the title compound (0.160 g, yield: 36%). The compound was recrystallized from chloroform-n-hexane to obtain colorless needles (melting point: 154-155° C.).

後処理

  1. waitThe reaction mixture was left
  2. temperatureto cool
  3. extractionthe mixture was extracted with diethyl ether
  4. washThe organic layer was washed successively with 2 N aqueous hydrochloric acid, water and saturated brine
  5. dry with materialdried over anhydrous sodium sulfate
  6. concentrationThe organic layer was concentrated under reduced pressure
  7. customthe resulting residue was purified by silica gel column chromatography (developing solvent: ethyl acetate:n-hexane=1:50)

出典と根拠

ORDレコード
ord-ef64d016c6dd4fb5b881a6f293a6d4ce
出典データセット
uspto-grants-2012_03
特許番号
US08143260B2

反応ノート

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