Acetic Acid → Ethyl 3-(2,4-dichlorophenyl)-3-oxopropanoate

HRID 1530124

反応式

HRID 1530124 の反応式
[Cl:1][C:2]1[CH:7]=[C:6]([Cl:8])[CH:5]=[CH:4][C:3]=1[C:9](=[O:11])[CH3:10].[C:12](=O)([O:16]CC)[O:13][CH2:14][CH3:15].[H-].[Na+].C(O)(=O)C>O>[Cl:1][C:2]1[CH:7]=[C:6]([Cl:8])[CH:5]=[CH:4][C:3]=1[C:9](=[O:11])[CH2:10][C:12]([O:13][CH2:14][CH3:15])=[O:16]

参加物

6

反応物 4

HCID 176Acetic AcidHCID 7766Diethyl CarbonateHCID 166932',4'-DichloroacetophenoneHCID 24758Sodium hydride

生成物 1

HCID 542007Ethyl 3-(2,4-dichlorophenyl)-3-oxopropanoate収率 56%

試薬・触媒・溶媒 1

HCID 962Water溶媒

反応条件

温度
80 °C

実験手順

To a solution of 2′,4′-Dichloroacetophenone (1.50 g, 7.93 mmol) in diethyl carbonate (24.0 mL, 198 mmol) at 0° C. was added slowly NaH (60% suspension in mineral oil, 0.657 g, 16.4 mmol). The mixture was then stirred at 80° C. for 90 minutes. The mixture was cooled to room temperature then poured into an ice cold solution of 2.0 mL acetic acid in 56 mL water. The layers were separated and the aqueous phase was extracted with ether 3 times. The organic extracts were washed with brine, dried over anhydrous sodium sulfate, filtered and concentrated in vacuo. Column chromatography was performed to yield the title compound (1.16 g, 56%). LCMS: (FA) ES+, 262. 1H NMR (400 MHz, d1-chloroform) δ (2 sets of signals, keto and enol): 12.49 (s, 1H), 7.61-7.29 (m, 2 sets of 3H), 5.57 (s, 1H), 4.28 (q, J=7.28 Hz, 2H), 4.19 (q, J=7.28 Hz, 2H), 4.02 (s, 2H), 1.34 (t, J=7.03 Hz, 3H), 1.25 (t, J=7.03 Hz, 3H).

後処理

  1. temperatureThe mixture was cooled to room temperature
  2. customThe layers were separated
  3. extractionthe aqueous phase was extracted with ether 3 times
  4. washThe organic extracts were washed with brine
  5. dry with materialdried over anhydrous sodium sulfate
  6. filtrationfiltered
  7. concentrationconcentrated in vacuo

出典と根拠

ORDレコード
ord-676a2a23aa074d96b60980af44780747
出典データセット
uspto-grants-2015_07
特許番号
US09090601B2

関連ノート

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