Diethyl (cyanomethyl)phosphonate → 2-(Spiro[3.3]heptan-2-ylidene)acetonitrile

HRID 1853087노트

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HRID 1853087 반응식
[C:1]([CH2:3]P(=O)(OCC)OCC)#[N:2].CC([O-])(C)C.[K+].[CH2:18]1[C:21]2([CH2:24][CH2:23][CH2:22]2)[CH2:20][C:19]1=O>C1COCC1>[CH2:20]1[C:21]2([CH2:24][CH2:23][CH2:22]2)[CH2:18][C:19]1=[CH:3][C:1]#[N:2]

참가 물질

5

반응물 3

HCID 75676Diethyl (cyanomethyl)phosphonateHCID 23665647Potassium tert-butoxideHCID 59814883Spiro(3.3)heptan-2-one

생성물 1

HCID 674519072-(Spiro[3.3]heptan-2-ylidene)acetonitrile수율 55.1%

시약·촉매·용매 1

HCID 8028Tetrahydrofuran용매2회

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온도
0 °C

실험 절차

Diethyl cyanomethylphosphonate (3.15 mL, 20.0 mmol) was suspended in THF (30 mL) and cooled to 0° C. Potassium 2-methylpropan-2-olate (2.35 g, 21.0 mmol) was added portion-wise and stirred at 0° C. for 15 minutes. Spiro[3.3]heptan-2-one (2.100 g, 19.06 mmol) as a solution in THF (20 mL) was added dropwise and the reaction mixture was allowed to warm to ambient temperature overnight. The reaction mixture was partitioned between water, saturated aqueous NH4Cl and EtOAc. The organic layer was washed with saturated aqueous NH4Cl, brine, dried (MgSO4), filtered and concentrated under reduced pressure to afford the crude material. The crude was purified by flash column chromatography, eluting with 2.5% EtOAc/Hexanes to provide 2-(spiro[3.3]heptan-2-ylidene)acetonitrile (1.40 g, 10.5 mmol, 55% yield). 1H NMR (CDCl3) δ 5.14-5012 (m, 1H), 2.93-2.91 (m, 2H), 2.82-2.80 (m, 2H), 2.10-2.04 (m, 4H), 1.91-1.85 (m, 2H).

후처리

  1. temperatureto warm to ambient temperature overnight
  2. customThe reaction mixture was partitioned between water, saturated aqueous NH4Cl and EtOAc
  3. washThe organic layer was washed with saturated aqueous NH4Cl, brine
  4. dry with materialdried (MgSO4)
  5. filtrationfiltered
  6. concentrationconcentrated under reduced pressure
  7. customto afford the crude material
  8. customThe crude was purified by flash column chromatography
  9. washeluting with 2.5% EtOAc/Hexanes

출처 및 근거

ORD 기록
ord-2b543f94f7434138a5f9f01e1a1b7622
출처 데이터셋
uspto-grants-2015_02
특허 번호
US08962596B2

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