Sodium hydride → 1-Bromo-4-chloro-3-(2,2-difluoroethoxy)-2-fluorobenzene

HRID 495019

反応式

HRID 495019 の反応式
[Br:1][C:2]1[C:3]([F:10])=[C:4]([OH:9])[C:5]([Cl:8])=[CH:6][CH:7]=1.[H-].[Na+].[F:13][CH:14]([F:21])[CH2:15]OS(C)(=O)=O>CN(C)C=O.O>[Br:1][C:2]1[CH:7]=[CH:6][C:5]([Cl:8])=[C:4]([O:9][CH2:15][CH:14]([F:21])[F:13])[C:3]=1[F:10]

参加物

6

反応物 3

HCID 24758Sodium hydrideHCID 567764922,2-Difluoroethyl methanesulfonateHCID 666010023-Bromo-6-chloro-2-fluorophenol

生成物 1

HCID 866138401-Bromo-4-chloro-3-(2,2-difluoroethoxy)-2-fluorobenzene収率 45.6%

試薬・触媒・溶媒 2

HCID 962Water溶媒HCID 6228Dimethylformamide溶媒3 回

反応条件

温度
70 °C

実験手順

A solution of 3-bromo-6-chloro-2-fluorophenol (15.4 g, 0.068 mol) in dimethylformamide (DMF; 25 mL) was slowly added to a suspension of sodium hydride (60% dispersion in mineral oil) (4.0 g, 0.10 mol) in DMF (100 mL) and the reaction mixture was stirred one hour. A solution of methanesulfonic acid 2,2-difluoroethyl ester (17.5 g, 0.109 mol) in DMF (10 mL) was slowly added. The resulting solution was heated at 70° C. for eighteen hours. The cooled solution was diluted with water (200 mL) and extracted with ethyl ether. The combined organic phases were dried and concentrated. The residual oil was purified by column chromatography (in hexanes) to give 1-bromo-4-chloro-3-(2,2-difluoroethoxy)-2-fluorobenzene (9.0 g, 0.031 mol): 1H NMR (CDCl3): δ 7.26 (m, 1H), 7.09 (m, 1H), 6.12 (tt, 1H), 4.30 (td, 2H).

後処理

  1. extractionextracted with ethyl ether
  2. customThe combined organic phases were dried
  3. concentrationconcentrated
  4. customThe residual oil was purified by column chromatography (in hexanes)

出典と根拠

ORDレコード
ord-934d211430f648cbaa088f2b537ca9f1
出典データセット
uspto-grants-2009_05
特許番号
US07538214B2

関連ノート

読み込み中…