Propionitrile → methyl (E)-11-(1-cyanoethylidene)-6,11-dihydrodibenzo[b,e]oxepine-3-carboxylate

HRID 885427ノート

反応式

HRID 885427 の反応式
[CH:1]([N-]C(C)C)(C)C.[Li+].[C:9](#[N:12])[CH2:10][CH3:11].P(Cl)(OCC)([O:15][CH2:16]C)=O.O=[C:23]1[C:29]2[CH:30]=[CH:31][C:32]([C:34]([OH:36])=[O:35])=[CH:33][C:28]=2CC[C:25]2[CH:37]=[CH:38][CH:39]=[CH:40][C:24]1=2>C1COCC1.O.C(OCC)(=O)C>[C:9](/[C:10](=[C:23]1/[C:29]2[CH:30]=[CH:31][C:32]([C:34]([O:36][CH3:1])=[O:35])=[CH:33][C:28]=2[O:15][CH2:16][C:25]2[CH:37]=[CH:38][CH:39]=[CH:40][C:24]/1=2)/[CH3:11])#[N:12].[C:9](/[C:10](=[C:23]1\[C:29]2[CH:30]=[CH:31][C:32]([C:34]([O:36][CH3:1])=[O:35])=[CH:33][C:28]=2[O:15][CH2:16][C:25]2[CH:37]=[CH:38][CH:39]=[CH:40][C:24]\1=2)/[CH3:11])#[N:12]

参加物

9

反応物 4

HCID 7854PropionitrileHCID 13139Diethyl chlorophosphateHCID 2724682Lithium diisopropylamideHCID 125258755-Oxo-10,11-dihydro-5H-dibenzo[a,d]cycloheptene-2-carboxylic acid

生成物 2

HCID 67210386methyl (Z)-11-(1-cyanoethylidene)-6,11-dihydrodibenzo[b,e]oxepine-3-carboxylate収率 36.7%HCID 67210387methyl (E)-11-(1-cyanoethylidene)-6,11-dihydrodibenzo[b,e]oxepine-3-carboxylate収率 52.6%

試薬・触媒・溶媒 3

HCID 962Water溶媒HCID 8028Tetrahydrofuran溶媒3 回HCID 8857Ethyl Acetate溶媒

実験手順

[step 1] Lithium diisopropylamide (2.0 mol/L heptane/THF/ethylbenzene solution, 100 mL, 200 mmol) was diluted with THF (40 mL), and a solution of propiononitrile (7.13 mL, 100 mmol) in THF (40 mL) was added dropwise at 0° C. over 15 min with stirring. After stirring at 0° C. for 30 min, a solution of diethyl chlorophosphate (14.4 mL, 100 mmol) in THF (40 mL) was added dropwise over 45 min. After stirring at room temperature for 2 hr, methyl 11-oxo-6,11-dihydrodibenzo[b,e]oxepine-3-carboxylate (JP-B-2526005, 10.7 g, 40 mmol) was added, and the mixture was stirred at room temperature for 1.5 hr. Ethyl acetate and water were added to the reaction mixture, and the mixture was extracted 3 times with ethyl acetate. The organic layer was washed with brine, dried over anhydrous magnesium sulfate, and concentrated under reduced pressure. The residue was purified by silica gel column chromatography (ethyl acetate:hexane=15:85) to give methyl (E)-11-(1-cyanoethylidene)-6,11-dihydrodibenzo[b,e]oxepine-3-carboxylate (6.40 g, 21.0 mmol, 52.6%) and methyl (Z)-11-(1-cyanoethylidene)-6,11-dihydrodibenzo[b,e]oxepine-3-carboxylate (4.47 g, 14.6 mmol, 36.7%).

後処理

  1. stirringAfter stirring at 0° C. for 30 min
  2. stirringAfter stirring at room temperature for 2 hr
  3. stirringthe mixture was stirred at room temperature for 1.5 hr
  4. extractionthe mixture was extracted 3 times with ethyl acetate
  5. washThe organic layer was washed with brine
  6. dry with materialdried over anhydrous magnesium sulfate
  7. concentrationconcentrated under reduced pressure
  8. customThe residue was purified by silica gel column chromatography (ethyl acetate:hexane=15:85)

出典と根拠

ORDレコード
ord-bd9566a184c541de9b0b68342e449b9f
出典データセット
uspto-grants-2012_08
特許番号
US08242151B2

反応ノート

読み込み中…