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Methanol → 1-(2-Bromo-3-hydroxyphenyl)ethanone

HRID 1920804
ノート
印刷プレビュー

反応式

HRID 1920804 の反応式
[Br:1][C:2]1[C:7]([O:8]C)=[CH:6][CH:5]=[CH:4][C:3]=1[C:10](=[O:12])[CH3:11].BrP(Br)Br.CO>C(Cl)Cl>[Br:1][C:2]1[C:7]([OH:8])=[CH:6][CH:5]=[CH:4][C:3]=1[C:10](=[O:12])[CH3:11]
参加物反応条件実験手順後処理出典と根拠反応ノート

参加物

5

反応物 3

HCID 887MethanolHCID 24614Phosphorus tribromideHCID 19702329HCID 19702329、化合物

生成物 1

HCID 232169621-(2-Bromo-3-hydroxyphenyl)ethanone収率 47%

試薬・触媒・溶媒 1

HCID 6344Dichloromethane溶媒2 回

反応条件

温度
-40 °C

実験手順

Under a nitrogen atmosphere, 1-(2-bromo-3-methoxy phenyl)ethanone (30.5 g, 229 mmol) which had been obtained in Reference example 3 (3b) was dissolved in methylene chloride (500 mL), and added dropwise with a 1.0 M solution of tribromo phosphine in dichloromethane (293 mL, 293 mmol) at −80° C. over 5 hours. Upon the completion of the dropwise addition, the mixture was stirred for 17 hours at −40° C. Subsequently, the reaction solution was cooled to −80° C. and added dropwise with methanol (500 mL). Upon the completion of the dropwise addition, the temperature was raised to −40° C. followed by stirring for 3 hours. The temperature of the reaction solution was raised to room temperature. The solvent was distilled off under reduced pressure until the solution turned green. After adding ethanol, the mixture was extracted with ethyl acetate/hexane (1:1, V/V). After neutralization with a saturated aqueous solution of sodium hydrogen carbonate, the solvent was distilled off under reduced pressure. The residue was purified by silica gel chromatography (hexane:ethyl acetate, 100:0-55:45, V/V) to give the title compound as a colorless oily substance (13.5 g, yield 47%).

後処理

  1. additionUpon the completion of the dropwise addition
  2. temperatureSubsequently, the reaction solution was cooled to −80° C.
  3. additionUpon the completion of the dropwise addition
  4. temperaturethe temperature was raised to −40° C.
  5. stirringby stirring for 3 hours
  6. temperatureThe temperature of the reaction solution was raised to room temperature
  7. distillationThe solvent was distilled off under reduced pressure until the solution
  8. additionAfter adding ethanol
  9. extractionthe mixture was extracted with ethyl acetate/hexane (1:1, V/V)
  10. distillationAfter neutralization with a saturated aqueous solution of sodium hydrogen carbonate, the solvent was distilled off under reduced pressure
  11. customThe residue was purified by silica gel chromatography (hexane:ethyl acetate, 100:0-55:45, V/V)

出典と根拠

ORDレコード
ord-7617058e45494fd2a7bb1858fe0424a3
出典データセット
uspto-grants-2012_05
DOI
10.6084/m9.figshare.5104873.v1
特許番号
US08173631B2

反応ノート

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