Ethanol → (1R,2R)-ethyl 2-(4-hydroxyphenyl)cyclopropanecarboxylate

HRID 625706

反応式

HRID 625706 の反応式
[CH2:1]([O:3][C:4]([C@@H:6]1[CH2:8][C@H:7]1[C:9]1[CH:14]=[CH:13][C:12]([O:15]C)=[CH:11][CH:10]=1)=[O:5])[CH3:2].B(Br)(Br)Br.C(O)C>ClCCl.C(=O)(O)[O-].[Na+]>[CH2:1]([O:3][C:4]([C@@H:6]1[CH2:8][C@H:7]1[C:9]1[CH:10]=[CH:11][C:12]([OH:15])=[CH:13][CH:14]=1)=[O:5])[CH3:2]

参加物

6

反応物 3

HCID 702EthanolHCID 25134Boron tribromideHCID 818082rac-ethyl (1R,2R)-2-(4-methoxyphenyl)cyclopropane-1-carboxylate

生成物 1

HCID 71114948(1R,2R)-ethyl 2-(4-hydroxyphenyl)cyclopropanecarboxylate収率 43.2%

試薬・触媒・溶媒 2

HCID 6344Dichloromethane溶媒HCID 516892Sodium Bicarbonate溶媒

反応条件

温度
-78 °C

実験手順

2-(4-Methoxy-phenyl)-trans-cyclopropanecarboxylic acid ethyl ester (1.43 g, 6.51 mmol) is dissolved in dry dichloromethane (30 mL) and cooled to −78° C. Boron tribromide solution (1 M in dichloromethane, 7.81 mL, 7.81 mmol) is added dropwise then the mixture is allowed to warm to −20° C. and stirred overnight at −20° C. Ethanol (3 mL) is added and the mixture warmed to room temperature then diluted with saturated aqueous sodium bicarbonate solution. The phases are separated and the aqueous phase extracted with dichloromethane. The combined organic phases are dried through a phase separator and the solvent removed under vacuum. The residue is purified by flash chromatography (10% ethyl acetate in cyclohexane) and then crystallized from 10% ethyl acetate in cyclohexane to give the title compound (yield 0.58 g). LC (METHOD 11): tR=6.25 min; Mass spectrum (ESI+): m/z=248 [M+H+MeCN]+.

後処理

  1. temperatureto warm to −20° C.
  2. temperaturethe mixture warmed to room temperature
  3. customThe phases are separated
  4. extractionthe aqueous phase extracted with dichloromethane
  5. customThe combined organic phases are dried through a phase separator
  6. customthe solvent removed under vacuum
  7. customThe residue is purified by flash chromatography (10% ethyl acetate in cyclohexane)
  8. customcrystallized from 10% ethyl acetate in cyclohexane

出典と根拠

ORDレコード
ord-4f6af052fac2458eacd2d86195962001
出典データセット
uspto-grants-2016_04
特許番号
US09308194B2

関連ノート

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