Ethyl pyruvate → Ethyl 7-bromo-5-fluoro-1H-indole-2-carboxylate

HRID 853102

반응식

HRID 853102 반응식
[Br:1][C:2]1[CH:7]=[C:6]([F:8])[CH:5]=[CH:4][C:3]=1[NH:9]N.[C:11]([O:16][CH2:17][CH3:18])(=[O:15])[C:12]([CH3:14])=O.C(=O)([O-])O.[Na+]>C(O)C.CS(O)(=O)=O.O=P12OP3(OP(OP(O3)(O1)=O)(=O)O2)=O.ClCCl>[CH2:17]([O:16][C:11]([C:12]1[NH:9][C:3]2[C:4]([CH:14]=1)=[CH:5][C:6]([F:8])=[CH:7][C:2]=2[Br:1])=[O:15])[CH3:18]

참가 물질

7

반응물 3

HCID 12041Ethyl pyruvateHCID 516892Sodium BicarbonateHCID 1381943(2-Bromo-4-fluorophenyl)hydrazine

생성물 1

HCID 21014457Ethyl 7-bromo-5-fluoro-1H-indole-2-carboxylate수율 68%

시약·촉매·용매 3

HCID 702Ethanol용매HCID 6344Dichloromethane용매HCID 86584057Phosphorus Pentoxide-Methanesulfonic Acid용매

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온도
0 °C

실험 절차

2-Bromo-4-fluoro-phenylhydrazine (20 g, 0.097 mol) was dissolved in ethanol and the solution cooled to 0° C. (ice-bath). Ethyl pyruvate (11.3 ml, 0.101 mol) was added dropwise and the solution stirred 15 h at room temperature. The solvent was evaporated under reduced pressure, and the residue stirred with hexane. The mixture of hydrazones that formed upon cooling in an ice-bath was filtered and dried under vacuum. Yield 24.4 g, 82%. The hydrazone mixture (22 g, 0.073 mol) was dissolved in Eaton's reagent (230 ml) and the mixture heated 3 h at 50° C. The mixture was cooled to room temperature, diluted with dichloromethane and added to saturated aqueous sodium hydrogen carbonate. The phases were separated and the aqueous phase extracted twice with dichloromethane. The combined organic phases were washed with water, dried over magnesium sulfate and evaporated. The residue was taken up in diethyl ether, and hexane added whereupon part of the product precipitated. This was filtered and the mother liquor purified by column chromatography on silica gel (5:1 toluene/hexane eluant) to afford the product as a light yellow solid (14.1 g, 68%). Mp: 125° C., EI MS: 285.0 (M+)

후처리

  1. customThe solvent was evaporated under reduced pressure
  2. stirringthe residue stirred with hexane
  3. additionThe mixture of hydrazones that
  4. customformed
  5. temperatureupon cooling in an ice-bath
  6. filtrationwas filtered
  7. customdried under vacuum
  8. temperaturethe mixture heated 3 h at 50° C
  9. temperatureThe mixture was cooled to room temperature
  10. customThe phases were separated
  11. extractionthe aqueous phase extracted twice with dichloromethane
  12. washThe combined organic phases were washed with water
  13. dry with materialdried over magnesium sulfate
  14. customevaporated
  15. additionhexane added whereupon part of the product
  16. customprecipitated
  17. filtrationThis was filtered
  18. customthe mother liquor purified by column chromatography on silica gel (5:1 toluene/hexane eluant)

출처 및 근거

ORD 기록
ord-6d4bc2fc4f22432f9d3c46c1ee9bc783
출처 데이터셋
uspto-grants-2007_08
특허 번호
US07253281B2

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