Benzoyl Peroxide → 3-Bromo-2-(bromomethyl)pyridine

HRID 1423010ノート

反応式

HRID 1423010 の反応式
[Br:1][C:2]1[C:3]([CH3:8])=[N:4][CH:5]=[CH:6][CH:7]=1.[Br:9]N1C(=O)CCC1=O.C(OOC(=O)C1C=CC=CC=1)(=O)C1C=CC=CC=1>C(Cl)(Cl)(Cl)Cl.C(=O)(O)[O-].[Na+]>[Br:1][C:2]1[C:3]([CH2:8][Br:9])=[N:4][CH:5]=[CH:6][CH:7]=1

参加物

6

反応物 3

HCID 7187Benzoyl Peroxide2 回HCID 67184N-bromobutanimide2 回HCID 12010033-Bromo-2-methylpyridine

生成物 1

HCID 214410813-Bromo-2-(bromomethyl)pyridine

試薬・触媒・溶媒 2

HCID 5943Carbon Tetrachloride溶媒HCID 516892Sodium Bicarbonate溶媒2 回

実験手順

To a room temperature solution of 3-bromo-2-methylpyridine (2.60 g, 15.1 mmol) and N-bromosuccinimide (NBS) (2.90 g, 16.3 mmol) in CCl4 is added benzoyl peroxide (150 mg, 1.08 mmol). The mixture is heated at reflux for 7 hours, cooled to room temperature, diluted with saturated aqueous sodium bicarbonate (30 mL) and extracted with ethyl acetate (EtOAc) (3×30 mL). The combined organic layers are washed with brine (3×30 mL), dried over magnesium sulfate, filtered and concentrated. LCMS analysis indicated starting material and the desired product. The residue is dissolved in CCl4 (40 mL) and NBS (1.7 g, 9.6 mmol) and benzoyl peroxide (100 mg, 0.72 mmol) is added, and the mixture is warmed at reflux. After 24 hours, the mixture is cooled to room temperature, diluted with saturated aqueous sodium bicarbonate (30 mL) and extracted with EtOAc (3×30 mL). The combined organic layers are washed with brine (3×30 mL), dried over magnesium sulfate, filtered and concentrated. The residue is purified by silica gel chromatography eluting with a mixture of dichloromethane in hexanes (25:75, then 3:7) to afford 3-bromo-2-bromomethyl-pyridine.

後処理

  1. temperatureThe mixture is heated
  2. temperatureat reflux for 7 hours
  3. extractionextracted with ethyl acetate (EtOAc) (3×30 mL)
  4. washThe combined organic layers are washed with brine (3×30 mL)
  5. dry with materialdried over magnesium sulfate
  6. filtrationfiltered
  7. concentrationconcentrated
  8. dissolutionThe residue is dissolved in CCl4 (40 mL)
  9. temperaturethe mixture is warmed
  10. temperatureat reflux
  11. temperaturethe mixture is cooled to room temperature
  12. extractionextracted with EtOAc (3×30 mL)
  13. washThe combined organic layers are washed with brine (3×30 mL)
  14. dry with materialdried over magnesium sulfate
  15. filtrationfiltered
  16. concentrationconcentrated
  17. customThe residue is purified by silica gel chromatography
  18. washeluting with a mixture of dichloromethane in hexanes (25:75

出典と根拠

ORDレコード
ord-98226504901941b9bb65509edb205e97
出典データセット
uspto-grants-2015_01
特許番号
US08927550B2

反応ノート

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