Diethyl (cyanomethyl)phosphonate → HCID 69205138、化合物

HRID 2378282ノート

反応式

HRID 2378282 の反応式
C(OP([CH2:9][C:10]#[N:11])(=O)OCC)C.C[Si]([N-][Si](C)(C)C)(C)C.[Li+].[O:22]1[CH2:28][CH2:27][CH2:26][O:25][C:24]2[CH:29]=[C:30]([C:33]([C:35]3[CH:40]=[C:39]([O:41][CH3:42])[CH:38]=[C:37]([O:43][CH3:44])[CH:36]=3)=O)[CH:31]=[CH:32][C:23]1=2>C1COCC1>[O:22]1[CH2:28][CH2:27][CH2:26][O:25][C:24]2[CH:29]=[C:30]([C:33]([C:35]3[CH:36]=[C:37]([O:43][CH3:44])[CH:38]=[C:39]([O:41][CH3:42])[CH:40]=3)=[CH:9][C:10]#[N:11])[CH:31]=[CH:32][C:23]1=2

参加物

5

反応物 3

HCID 75676Diethyl (cyanomethyl)phosphonateHCID 2733832Lithium HexamethyldisilazideHCID 69205734HCID 69205734、化合物

生成物 1

HCID 69205138HCID 69205138、化合物収率 89%

試薬・触媒・溶媒 1

HCID 8028Tetrahydrofuran溶媒2 回

実験手順

To a stirred solution of cyanomethylphosphonic acid diethyl ester (1.3 mL, 8.3 mmol) in THF (10 mL) in an ice bath was added lithium bis(trimethylsilyl)amide (1.0 M solution in THF, 8.2 mL, 8.2 mmol) dropwise. The mixture was stirred at room temperature for 40 min. A solution of (3,4-dihydro-2H-benzo[b][1,4]dioxepin-7-yl)-(3,5-dimethoxy-phenyl)-methanone (1.3 g, 4.1 mmol) in anhydrous THF (10 mL) was added to the mixture. The mixture was refluxed overnight. The solution was poured into ice water (20 mL). The aqueous layer was extracted with ethyl acetate (2×50 mL). The combined organic layers was washed with water (50 mL), sodium hydrogen carbonate (50 mL, sat), brine (50 mL) and dried over magnesium sulfate. Removal of solvent and chromatography (Silica Gel) gave a mixture of (E/Z) 3-(3,4-dihydro-2H-benzo[b][1,4]dioxepin-7-yl)-3-(3,5-dimethoxy-phenyl)-acrylonitrile as an oil (1.23 g, 89% yield): 1H NMR (DMSO-d6) δ 2.09-2.16 (m, 4H, 2CH2), 3.73 (s, 6H, 2CH3), 4.12-4.25 (m, 8H, 4CH2), 6.24 (s, 1H, CH), 6.30 (s, 1H, CH), 6.44-6.45 (m, 4H, Ar), 6.62-6.65 (m, 2H, Ar), 6.93-7.09 (m, 6H, Ar); 13C NMR (DMSO-d6) δ 30.97, 31.13, 55.40, 70.37, 70.52, 95.05, 95.87, 100.90, 101.82, 106.72, 107.06, 118.06, 118.12, 121.09, 121.61, 121.64, 122.39, 123.41, 124.47, 131.71, 132.26, 138.98, 140.12, 150.42, 150.55, 152.09, 152.89, 160.31, 160.39, 160.43.

後処理

  1. temperatureThe mixture was refluxed overnight
  2. extractionThe aqueous layer was extracted with ethyl acetate (2×50 mL)
  3. washThe combined organic layers was washed with water (50 mL), sodium hydrogen carbonate (50 mL, sat), brine (50 mL)
  4. dry with materialdried over magnesium sulfate
  5. customRemoval of solvent and chromatography (Silica Gel)
  6. customgave

出典と根拠

ORDレコード
ord-0575a70ea7bc4c5db4231dd4ac2cf418
出典データセット
uspto-grants-2008_12
特許番号
US07470723B2

反応ノート

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