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

HRID 452179
ノート
印刷プレビュー

反応式

HRID 452179 の反応式
[CH:1]([N-]C(C)C)(C)C.[Li+].[C:9](#N)CC.P(Cl)([O:18][CH2:19][CH3:20])(OCC)=O.C(C1N(CC2[CH:53]=[CH:52][C:39]3/[C:40](=[CH:49]/[C:50]#[N:51])/[C:41]4[CH:48]=[CH:47][CH:46]=[CH:45]C=4C[CH2:44][C:38]=3C=2)C2=NC(C)=CC(C)=C2N=1)C.[C:54]([O:57][CH2:58]C)(=[O:56])[CH3:55]>C1COCC1.O>[CH3:58][O:57][C:54]([C:55]1[CH:53]=[CH:52][C:39]2=[C:38]([CH:44]=1)[O:18][CH2:19][C:20]1[CH:45]=[CH:46][CH:47]=[CH:48][C:41]=1/[C:40]/2=[C:49](/[C:50]#[N:51])\[CH3:1])=[O:56].[CH3:58][O:57][C:54]([C:55]1[CH:53]=[CH:52][C:39]2=[C:38]([CH:44]=1)[O:18][CH2:19][C:20]1[CH:45]=[CH:46][CH:47]=[CH:48][C:41]=1/[C:40]/2=[C:49](\[C:50]#[N:51])/[CH3:9])=[O:56]
参加物反応条件実験手順後処理出典と根拠反応ノート

参加物

9

反応物 5

HCID 7854PropionitrileHCID 8857Ethyl AcetateHCID 13139Diethyl chlorophosphateHCID 2724682Lithium diisopropylamideHCID 22858094(E)-[2-(2-ethyl-5,7-dimethyl-3H-imidazo[4,5-b]pyridin-3-yl)methyl-10,11-dihydro-5H-dibenzo[a,d]cyclohepten-5-ylidene]acetonitrile

生成物 2

HCID 67210386
methyl (Z)-11-(1-cyanoethylidene)-6,11-dihydrodibenzo[b,e]oxepine-3-carboxylate
収率 37%
HCID 67210387methyl (E)-11-(1-cyanoethylidene)-6,11-dihydrodibenzo[b,e]oxepine-3-carboxylate収率 53%

試薬・触媒・溶媒 2

HCID 962Water溶媒HCID 8028Tetrahydrofuran溶媒3 回

反応条件

温度
0 °C

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), a solution of propiononitrile (7.13 mL, 100 mmol) in THF (40 mL) was added dropwise while stirring at 0° C. over 15 min. 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. To the mixture were added ethyl acetate and water, and the mixture was extracted with 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 (Z)-11-(1-cyanoethylidene)-6,11-dihydrodibenzo[b,e]oxepine-3-carboxylic acid methyl ester (4.47 g, 14.6 mmol, 37%) and (E)-11-(1-cyanoethylidene)-6,11-dihydrodibenzo[b,e]oxepine-3-carboxylic acid methyl ester (6.40 g, 21.0 mmol, 53%).

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 with 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-7a20a1e54c884dc39bfdbf6905780326
出典データセット
uspto-grants-2013_07
DOI
10.6084/m9.figshare.5104873.v1
特許番号
US08486980B2

反応ノート

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