Boron tribromide → Diethyl 2-(2,6-difluoro-4-hydroxyphenyl)malonate

HRID 1786299ノート

反応式

HRID 1786299 の反応式
[F:1][C:2]1[CH:7]=[C:6]([O:8]C)[CH:5]=[C:4]([F:10])[C:3]=1[CH:11]([C:17]([O:19][CH2:20][CH3:21])=[O:18])[C:12]([O:14][CH2:15][CH3:16])=[O:13].B(Br)(Br)Br.C(=O)(O)[O-].[Na+]>C(Cl)Cl>[F:1][C:2]1[CH:7]=[C:6]([OH:8])[CH:5]=[C:4]([F:10])[C:3]=1[CH:11]([C:17]([O:19][CH2:20][CH3:21])=[O:18])[C:12]([O:14][CH2:15][CH3:16])=[O:13]

参加物

5

反応物 3

HCID 25134Boron tribromideHCID 516892Sodium BicarbonateHCID 11174138Diethyl 2-(2,6-difluoro-4-methoxyphenyl)malonate

生成物 1

HCID 16103023Diethyl 2-(2,6-difluoro-4-hydroxyphenyl)malonate収率 94.7%

試薬・触媒・溶媒 1

HCID 6344Dichloromethane溶媒

反応条件

温度
-78 °C

実験手順

To a solution of diethyl 2-(2,6-difluoro-4-methoxyphenyl)malonate (2.11 g, 7.0 mmol) in 60 mL of methylene chloride at −78° C. is added boron tribromide (2.65 mL, 28 mmol) dropwise. The mixture is then stirred at −78° C. for 10 minutes, warmed to 0° C., and stirred at 0° C. for 1 h. A 5% aqueous solution of sodium bicarbonate is added slowly to quench the reaction. The product is extracted with ethyl acetate. The combined organic extracts are washed with saturated sodium chloride, dried over magnesium sulfate, and concentrated to a residue. The residue is chromatographed over silica gel, eluting with a gradient of 10% ethyl acetate in hexanes to 30% ethyl acetate in hexanes. Concentration provides diethyl 2-(2,6-difluoro-4-hydroxyphenyl)malonate as a colorless oil (1.91 g). MS: m/z 287.2 (M−H).

後処理

  1. temperaturewarmed to 0° C.
  2. stirringstirred at 0° C. for 1 h
  3. customto quench
  4. customthe reaction
  5. extractionThe product is extracted with ethyl acetate
  6. washThe combined organic extracts are washed with saturated sodium chloride
  7. dry with materialdried over magnesium sulfate
  8. concentrationconcentrated to a residue
  9. customThe residue is chromatographed over silica gel
  10. washeluting with a gradient of 10% ethyl acetate in hexanes to 30% ethyl acetate in hexanes
  11. concentrationConcentration

出典と根拠

ORDレコード
ord-46c8f9dfedd640ea8424108be2403a20
出典データセット
uspto-grants-2009_03
特許番号
US07507739B2

反応ノート

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