Methyl 4-chloro-3-(trifluoromethyl)benzoate → Methyl 4-cyclopentyl-3-(trifluoromethyl)benzoate

HRID 534256

反応式

HRID 534256 の反応式
[CH:1]1([Mg]Cl)[CH2:5][CH2:4][CH2:3][CH2:2]1.Cl[C:9]1[CH:18]=[CH:17][C:12]([C:13]([O:15][CH3:16])=[O:14])=[CH:11][C:10]=1[C:19]([F:22])([F:21])[F:20]>[Cl-].[Zn+2].[Cl-].CC(C)([P](C(C)(C)C)([Pd][P](C(C)(C)C)(C(C)(C)C)C(C)(C)C)C(C)(C)C)C>[CH:1]1([C:9]2[CH:18]=[CH:17][C:12]([C:13]([O:15][CH3:16])=[O:14])=[CH:11][C:10]=2[C:19]([F:20])([F:22])[F:21])[CH2:5][CH2:4][CH2:3][CH2:2]1

参加物

5

反応物 2

HCID 14148738Methyl 4-chloro-3-(trifluoromethyl)benzoateHCID 178478989HCID 178478989、化合物

生成物 1

HCID 11097668Methyl 4-cyclopentyl-3-(trifluoromethyl)benzoate収率 95.8%

試薬・触媒・溶媒 2

HCID 3007855Zincchloride触媒HCID 178418851HCID 178418851、化合物触媒

実験手順

To zinc(II) chloride (0.5 M solution in tetrahydrofuran, 88.0 mL, 44.0 mmol) was added cyclopentylmagnesium chloride (2 M solution in ether, 20.5 mL, 41.1 mmol). The resulting suspension was stirred at room temperature for 1 h. To the above suspension was added methyl 4-chloro-3-(trifluoromethyl)benzoate (7.00 g, 29.3 mmol) and bis(tri-tert-butylphosphine)palladium (1.35 g, 2.64 mmol) at room temperature. The mixture was heated under reflux for 2 h. The mixture was allowed to cool to room temperature, quenched with saturated aqueous sodium bicarbonate solution and filtered. The filtrate was extracted with ethyl acetate. The organic layer was dried over anhydrous sodium sulfate, concentrated under reduced pressure and purified by silica gel column chromatography to give the title compound as an oil (7.64 g). LCMS m/z=273.2 [M+H]+; 1H NMR (400 MHz, CDCl3) δ ppm 1.57-1.66 (m, 2H), 1.68-1.82 (m, 2H), 1.82-1.94 (m, 2H), 2.04-2.21 (m, 2H), 3.33-3.49 (m, 1H), 3.93 (s, 3H), 7.54 (d, J=8.21 Hz, 1H), 8.13 (dd, J=8.34, 1.77 Hz, 1H), 8.27 (s, 1H).

後処理

  1. temperatureThe mixture was heated
  2. temperatureunder reflux for 2 h
  3. temperatureto cool to room temperature
  4. customquenched with saturated aqueous sodium bicarbonate solution
  5. filtrationfiltered
  6. extractionThe filtrate was extracted with ethyl acetate
  7. dry with materialThe organic layer was dried over anhydrous sodium sulfate
  8. concentrationconcentrated under reduced pressure
  9. custompurified by silica gel column chromatography

出典と根拠

ORDレコード
ord-bb1791824e764e9691aba4869aa6214f
出典データセット
uspto-grants-2014_10
特許番号
US08853419B2

関連ノート

読み込み中…