Ethyl cyanoacetate → Cyano-(4-methoxy-2-nitro-phenyl)-acetic acid ethyl ester

HRID 1913426

反応式

HRID 1913426 の反応式
[C:1]([CH2:3][C:4]([O:6][CH2:7][CH3:8])=[O:5])#[N:2].[H-].[Na+].Cl[C:12]1[CH:17]=[CH:16][C:15]([O:18][CH3:19])=[CH:14][C:13]=1[N+:20]([O-:22])=[O:21]>CN(C=O)C.[F-].[Cs+]>[CH2:7]([O:6][C:4](=[O:5])[CH:3]([C:1]#[N:2])[C:12]1[CH:17]=[CH:16][C:15]([O:18][CH3:19])=[CH:14][C:13]=1[N+:20]([O-:22])=[O:21])[CH3:8]

参加物

6

反応物 3

HCID 7764Ethyl cyanoacetateHCID 24758Sodium hydrideHCID 251404-Chloro-3-nitroanisole

生成物 1

HCID 11086625Cyano-(4-methoxy-2-nitro-phenyl)-acetic acid ethyl ester収率 87%

試薬・触媒・溶媒 2

HCID 25953Cesium fluoride触媒HCID 6228Dimethylformamide溶媒2 回

実験手順

Ethyl cyanoacetate (2.56 mL, 24.0 mmol) was added dropwise to a suspension of 959 mg of NaH (60%, 24.0 mmol) in 10 mL of DMF. The mixture was stirred for 1 h at room temperature. CsF (61 mg, 0.4 mmol) and a solution of 4-chloro-3-nitro-anisole (1.5 g, 8.0 mmol) in 2 mL of DMF were added and the mixture was stirred overnight at 70° C. The reaction mixture was cooled to room temperature and was quenched by the addition of 5 mL of water. Aqueous 1N HCl (5 mL) was added to adjust the pH to 3-4 and the mixture was diluted with dichloromethane. The organic layer was washed with saturated brine, dried over Na2SO4, and dried in vacuo. The crude product was purified on a Biotage (Biotage Inc.) 50 g silica column, eluting with 0-40% EtOAc in heptane over 40 minutes to provide 1.83 g (87%) of cyano-(4-methoxy-2-nitro-phenyl)-acetic acid ethyl ester.

後処理

  1. stirringthe mixture was stirred overnight at 70° C
  2. temperatureThe reaction mixture was cooled to room temperature
  3. customwas quenched by the addition of 5 mL of water
  4. additionAqueous 1N HCl (5 mL) was added
  5. additionthe mixture was diluted with dichloromethane
  6. washThe organic layer was washed with saturated brine
  7. dry with materialdried over Na2SO4
  8. customdried in vacuo
  9. customThe crude product was purified on a Biotage (Biotage Inc.) 50 g silica column
  10. washeluting with 0-40% EtOAc in heptane over 40 minutes

出典と根拠

ORDレコード
ord-787dbb9468c6412a852339dfba28a500
出典データセット
uspto-grants-2013_12
特許番号
US08609680B2

関連ノート

読み込み中…