Sodium hydride → Ethyl 3-oxo-3-(4-phenyloxyphenyl)-2-((3-((1,1,2,2-tetrafluoroethyl)oxy)phenyl)methyl)propionate

HRID 1610481노트

반응식

HRID 1610481 반응식
[F:1][C:2]([F:14])([O:6][C:7]1[CH:8]=[C:9]([CH3:13])[CH:10]=[CH:11][CH:12]=1)[CH:3]([F:5])[F:4].BrN1C(=O)CCC1=O.[O:23]([C:30]1[CH:35]=[CH:34][C:33]([C:36](=[O:43])[CH2:37][C:38]([O:40][CH2:41][CH3:42])=[O:39])=[CH:32][CH:31]=1)[C:24]1[CH:29]=[CH:28][CH:27]=[CH:26][CH:25]=1.[H-].[Na+].FC(F)(OC1C=C(CBr)C=CC=1)C(F)F>C(Cl)(Cl)(Cl)Cl.COCCOC.N(C(C)(C)C#N)=NC(C)(C)C#N.O>[O:43]=[C:36]([C:33]1[CH:34]=[CH:35][C:30]([O:23][C:24]2[CH:29]=[CH:28][CH:27]=[CH:26][CH:25]=2)=[CH:31][CH:32]=1)[CH:37]([CH2:13][C:9]1[CH:10]=[CH:11][CH:12]=[C:7]([O:6][C:2]([F:14])([F:1])[CH:3]([F:4])[F:5])[CH:8]=1)[C:38]([O:40][CH2:41][CH3:42])=[O:39]

참가 물질

10

반응물 5

HCID 24758Sodium hydrideHCID 67184N-bromobutanimideHCID 74438Benzene, 1-methyl-3-(1,1,2,2-tetrafluoroethoxy)-HCID 2760258Ethyl 3-oxo-3-(4-phenoxyphenyl)propanoateHCID 114603781-(Bromomethyl)-3-(1,1,2,2-tetrafluoroethoxy)benzene

생성물 1

HCID 22261740Ethyl 3-oxo-3-(4-phenyloxyphenyl)-2-((3-((1,1,2,2-tetrafluoroethyl)oxy)phenyl)methyl)propionate수율 54%

시약·촉매·용매 4

HCID 6547Azobisisobutyronitrile촉매HCID 962Water용매HCID 5943Carbon Tetrachloride용매HCID 80711,2-Dimethoxyethane용매2회

실험 절차

To a solution of 3-(1,1,2,2-tetrafluoroethoxy)toluene (7.8 g, 37.5 mmol) in carbon tetrachloride (80 ml) were added N-bromosuccinimide (7.33 g, 41.2 mmol) and 2,2′-azobis(isobutyronitrile) (300 mg, 1.87 mmol), and the mixture was heated under reflux for 6 hrs. After cooling, the reaction solution was filtered, and the filtrate was concentrated to prepare ethyl 3-(1,1,2,2-tetrafluoroethoxy)-α-bromotoluene. To a solution of ethyl 3-(4-phenoxyphenyl)-3-oxopropionate (10.7 g, 37.5 mmol) in 1,2-dimethoxyethane (120 ml) was added sodium hydride (60% in oil, 1.50 g, 37.5 mmol) under ice-cooling, and the mixture was stirred at room temperature for 30 min. To the reaction solution was dropwise added a solution of 3-(1,1,2,2-tetrafluoroethoxy)-α-bromotoluene prepared earlier in 1,2-dimethoxyethane (10 ml), and the reaction solution was stirred at room temperature for 1 hr. The reaction solution was poured into water (100 ml), and the mixture was extracted with ethyl acetate (100 ml×2). The extract was washed with water and saturated brine, dried over anhydrous magnesium sulfate and evaporated under reduced pressure. The residue was purified by silica gel column chromatography (toluene) to give ethyl 3-oxo-3-(4-phenyloxyphenyl)-2-((3-((1,1,2,2-tetrafluoroethyl)oxy)phenyl)methyl)propionate (9.92 g, 54%) as a colorless oil.

후처리

  1. temperaturethe mixture was heated
  2. temperatureunder reflux for 6 hrs
  3. temperatureAfter cooling
  4. filtrationthe reaction solution was filtered
  5. concentrationthe filtrate was concentrated
  6. customto prepare ethyl 3-(1,1,2,2-tetrafluoroethoxy)-α-bromotoluene
  7. temperaturecooling
  8. stirringthe reaction solution was stirred at room temperature for 1 hr
  9. extractionthe mixture was extracted with ethyl acetate (100 ml×2)
  10. washThe extract was washed with water and saturated brine
  11. dry with materialdried over anhydrous magnesium sulfate
  12. customevaporated under reduced pressure
  13. customThe residue was purified by silica gel column chromatography (toluene)

출처 및 근거

ORD 기록
ord-28fcd81527fe4201803ce9cb4f3a6273
출처 데이터셋
uspto-grants-2006_01
특허 번호
US06982348B2

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