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

HRID 1853087ノート

反応式

HRID 1853087 の反応式
[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]

参加物

5

反応物 3

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

生成物 1

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

試薬・触媒・溶媒 1

HCID 8028Tetrahydrofuran溶媒2 回

反応条件

温度
0 °C

実験手順

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).

後処理

  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

出典と根拠

ORDレコード
ord-2b543f94f7434138a5f9f01e1a1b7622
出典データセット
uspto-grants-2015_02
特許番号
US08962596B2

反応ノート

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