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

HRID 906830ノート

反応式

HRID 906830 の反応式
[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

参加物

5

反応物 3

HCID 64791,3-Dibromo-5,5-dimethylhydantoin2 回HCID 21226206Ethyl acetate hexaneHCID 426323562-Ethoxy-3-(trifluoromethyl)pyridine

生成物 1

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

試薬・触媒・溶媒 1

HCID 6422Trifluoroacetic acid溶媒2 回

実験手順

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).

後処理

  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)

出典と根拠

ORDレコード
ord-06cd8a8043644830bda434aefcf682c8
出典データセット
uspto-grants-2011_09
特許番号
US08013001B2

反応ノート

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