1,3-Dibromo-5,5-dimethylhydantoin → 5-Bromo-2-ethoxy-3-(trifluoromethyl)pyridine

HRID 1455197노트

반응식

HRID 1455197 반응식
[CH2:1]([O:3][C:4]1[C:9]([C:10]([F:13])([F:12])[F:11])=[CH:8][CH:7]=[CH:6][N:5]=1)[CH3:2].[Br:14]N1C(C)(C)C(=O)N(Br)C1=O.CCOC(C)=O.CCCCCC>C(O)(C(F)(F)F)=O>[Br:14][C:7]1[CH:8]=[C:9]([C:10]([F:13])([F:11])[F:12])[C:4]([O:3][CH2:1][CH3:2])=[N:5][CH:6]=1

참가 물질

5

반응물 3

HCID 64791,3-Dibromo-5,5-dimethylhydantoin2회HCID 21226206Ethyl acetate hexaneHCID 426323562-Ethoxy-3-(trifluoromethyl)pyridine

생성물 1

HCID 673899755-Bromo-2-ethoxy-3-(trifluoromethyl)pyridine수율 79%

시약·촉매·용매 1

HCID 6422Trifluoroacetic acid용매2회

실험 절차

2-Ethoxy-3-trifluoromethyl-pyridine (900 mg, 4.71 mmol) and 1,3-dibromo-5,5-dimethylhydantoin (1.35 g, 4.71 mmol) were placed in a round-bottom flask. To this mixture was slowly added 10 mL trifluoroacetic acid. The mixture was stirred at ambient temperature for overnight. More 1,3-dibromo-5,5-dimethylhydantoin (540 mg, 1.9 mmol) was added and the reaction mixture was stirred at ambient temperature for another day. After the completion of the reaction, TFA solvent was evaporated in vacuo and the resulting residue was neutralized to pH 7 by the addition of saturated NaHCO3. The aqueous layer was extracted with dichloromethane three times and the combined extract was washed with brine, dried over sodium sulfate, and concentrated in vacuo to give a mixture of oil and white solid. The residue was redissolved into 20% EtOAc/Hexane, and the unsoluable white solid was filtered out. The filtrate was concentrated and then purified by column chromatography on silica gel (10% EtOAC/Hexane) to give 5-bromo-2-ethoxy-3-trifluoromethyl-pyridine as a colorless liquid (1.0 g, 79% yield). 1H-NMR (400 MHz, CDCl3): δ 1.41 (t, 3H, J=7.07), 4.46 (q, 2H, J=7.07), 7.94 (dd, 1H, J=0.51, J=2.53), 8.34 (dd, 1H, J=0.51, J=2.53).

후처리

  1. stirringthe reaction mixture was stirred at ambient temperature for another day
  2. customwas evaporated in vacuo
  3. additionthe resulting residue was neutralized to pH 7 by the addition of saturated NaHCO3
  4. extractionThe aqueous layer was extracted with dichloromethane three times
  5. extractionthe combined extract
  6. washwas washed with brine
  7. dry with materialdried over sodium sulfate
  8. concentrationconcentrated in vacuo
  9. customto give
  10. additiona mixture of oil and white solid
  11. filtrationthe unsoluable white solid was filtered out
  12. concentrationThe filtrate was concentrated
  13. custompurified by column chromatography on silica gel (10% EtOAC/Hexane)

출처 및 근거

ORD 기록
ord-4e7334038b994f7a84d80a4c49f1f878
출처 데이터셋
uspto-grants-2009_01
특허 번호
US07482366B2

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