Methyl iodide → 2-(5-Bromo-2-isopropyl-4-methoxy-phenoxy)-3-methoxy-acrylonitrile

HRID 925156ノート

反応式

HRID 925156 の反応式
[H-].[Na+].[Br:3][C:4]1[C:5]([O:17][CH3:18])=[CH:6][C:7]([CH:14]([CH3:16])[CH3:15])=[C:8]([CH:13]=1)[O:9][CH2:10][C:11]#[N:12].[CH:19]([O:21][CH2:22]C)=O.IC>>[Br:3][C:4]1[C:5]([O:17][CH3:18])=[CH:6][C:7]([CH:14]([CH3:16])[CH3:15])=[C:8]([CH:13]=1)[O:9][C:10](=[CH:19][O:21][CH3:22])[C:11]#[N:12]

参加物

5

反応物 4

HCID 6328Methyl iodideHCID 8025Ethyl formateHCID 24758Sodium hydrideHCID 59598690(5-Bromo-2-isopropyl-4-methoxy-phenoxy)-acetonitrile

生成物 1

HCID 670533812-(5-Bromo-2-isopropyl-4-methoxy-phenoxy)-3-methoxy-acrylonitrile収率 48.2%

反応条件

温度
80 °C

実験手順

Sodium hydride (0.122 g, 5.0 mmol, 60% w/w) was washed with dry hexanes and evaporated under a stream of nitrogen. 10 mL THF was added and the mixture was cooled to 0° C. (5-Bromo-2-isopropyl-4-methoxy-phenoxy)-acetonitrile (0.577 g, 2.03 mmol) was added in portions. After 30 min ethyl formate (4.9 mL, 60.9 mmol) was added and the solution was warmed to 80° C. After 4.5 hours the mixture was cooled and 5.0 mL iodomethane was added in one portion. After 16 hours the solution was quenched with H2O, concentrated in vacuo, extracted with ethyl acetate, washed with H2O and then washed with brine. The combined organic layers were dried over Na2SO4, filtered and concentrated in vacuo. Purification via flash chromatography (9:1 hexane/ethyl acetate) afforded 2-(5-bromo-2-isopropyl-4-methoxy-phenoxy)-3-methoxy-acrylonitrile (0.319 g, 48%) as a white solid.

後処理

  1. customevaporated under a stream of nitrogen
  2. addition10 mL THF was added
  3. additionwas added in portions
  4. temperatureAfter 4.5 hours the mixture was cooled
  5. customAfter 16 hours the solution was quenched with H2O
  6. concentrationconcentrated in vacuo
  7. extractionextracted with ethyl acetate
  8. washwashed with H2O
  9. washwashed with brine
  10. dry with materialThe combined organic layers were dried over Na2SO4
  11. filtrationfiltered
  12. concentrationconcentrated in vacuo
  13. customPurification via flash chromatography (9:1 hexane/ethyl acetate)

出典と根拠

ORDレコード
ord-8298fe9ee9a44029ad9a269e299c26ce
出典データセット
uspto-grants-2016_03
特許番号
US09284279B2

反応ノート

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