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

HRID 1530124

반응식

HRID 1530124 반응식
[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]

참가 물질

6

반응물 4

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

생성물 1

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

시약·촉매·용매 1

HCID 962Water용매

반응 조건

온도
80 °C

실험 절차

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).

후처리

  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

출처 및 근거

ORD 기록
ord-676a2a23aa074d96b60980af44780747
출처 데이터셋
uspto-grants-2015_07
특허 번호
US09090601B2

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