Diethyl (cyanomethyl)phosphonate → HCID 69205138, 화합물

HRID 2378282노트

반응식

HRID 2378282 반응식
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

참가 물질

5

반응물 3

HCID 75676Diethyl (cyanomethyl)phosphonateHCID 2733832Lithium HexamethyldisilazideHCID 69205734HCID 69205734, 화합물

생성물 1

HCID 69205138HCID 69205138, 화합물수율 89%

시약·촉매·용매 1

HCID 8028Tetrahydrofuran용매2회

실험 절차

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.

후처리

  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

출처 및 근거

ORD 기록
ord-0575a70ea7bc4c5db4231dd4ac2cf418
출처 데이터셋
uspto-grants-2008_12
특허 번호
US07470723B2

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