Sodium hydride → Benzyl 3-(2-cyano-3-nitrophenoxy)-2,2-dimethylpropanoate

HRID 2047803ノート

反応式

HRID 2047803 の反応式
[OH:1][CH2:2][C:3]([CH3:15])([CH3:14])[C:4]([O:6][CH2:7][C:8]1[CH:13]=[CH:12][CH:11]=[CH:10][CH:9]=1)=[O:5].[H-].[Na+].[N+:18]([C:21]1[CH:28]=[CH:27][CH:26]=[C:25]([N+]([O-])=O)[C:22]=1[C:23]#[N:24])([O-:20])=[O:19]>C1COCC1>[C:23]([C:22]1[C:21]([N+:18]([O-:20])=[O:19])=[CH:28][CH:27]=[CH:26][C:25]=1[O:1][CH2:2][C:3]([CH3:15])([CH3:14])[C:4]([O:6][CH2:7][C:8]1[CH:13]=[CH:12][CH:11]=[CH:10][CH:9]=1)=[O:5])#[N:24]

参加物

5

反応物 3

HCID 24758Sodium hydrideHCID 520718DinitrobenzonitrileHCID 18922595Benzyl 3-hydroxy-2,2-dimethylpropanoate

生成物 1

HCID 66747122Benzyl 3-(2-cyano-3-nitrophenoxy)-2,2-dimethylpropanoate収率 87.9%

試薬・触媒・溶媒 1

HCID 8028Tetrahydrofuran溶媒

反応条件

温度
0 °C

実験手順

To a solution of benzyl 3-hydroxy-2,2-dimethylpropanoate (Yang, D. et al. J. Am. Chem. Soc. 2002, 124, 9966. 6.68 g, 32.1 mmol) in dry THF (200 mL) was carefully added NaH (60% in mineral oil, 3.5 g, 87.5 mmol) in small portions at 0° C. under nitrogen. The reaction mixture was stirred at 0° C. under nitrogen for 2 hrs. To this solution was added 2,6-dinitrobenzonitrile (6.19 g, 32.1 mmol), and the reaction solution was stirred at 0° C.—RT under nitrogen overnight. The reaction mixture was quenched with brine, and extracted with EtOAc (3×). The combined organic layers were washed with brine, dried over Na2SO4. After evaporation of the solvent, the residue was purified by chromatography on silica gel eluting (Eluent: 20% EtOAc in hexanes) to give the title compound as a brown solid (10.0 g, 87%). MS 355 (MH+).

後処理

  1. customat 0° C.
  2. stirringthe reaction solution was stirred at 0° C.—RT under nitrogen overnight
  3. customThe reaction mixture was quenched with brine
  4. extractionextracted with EtOAc (3×)
  5. washThe combined organic layers were washed with brine
  6. dry with materialdried over Na2SO4
  7. customAfter evaporation of the solvent
  8. customthe residue was purified by chromatography on silica gel eluting (Eluent: 20% EtOAc in hexanes)

出典と根拠

ORDレコード
ord-f593be52d1a24904af41696c5f9655a1
出典データセット
uspto-grants-2013_11
特許番号
US08592592B2

反応ノート

読み込み中…