Methanol → (4-Bromo-6-methylpyridin-2-yl)methanol

HRID 1908808ノート

反応式

HRID 1908808 の反応式
[Br:1][C:2]1[CH:7]=[CH:6]N=[C:4]([CH3:8])[CH:3]=1.S(OOS([O-])(=O)=O)([O-])(=O)=O.[NH4+:19].[NH4+].[CH3:21][OH:22]>OS(O)(=O)=O.O>[Br:1][C:2]1[CH:3]=[C:4]([CH3:8])[N:19]=[C:6]([CH2:21][OH:22])[CH:7]=1

参加物

6

反応物 3

HCID 887MethanolHCID 62648Ammonium Persulfate2 回HCID 27628354-Bromo-2-methylpyridine

生成物 1

HCID 67027007(4-Bromo-6-methylpyridin-2-yl)methanol

試薬・触媒・溶媒 2

HCID 962Water溶媒HCID 1118Sulfuric Acid溶媒

実験手順

To a solution of 4-bromo-2-methyl-pyridine (5.70 g, 32.14 mmol) in methanol (100 mL), H2SO4 (0.3 mL) is added. The mixture is heated to reflux before a solution of ammonium peroxydisulfate (7.33 g, 32.14 mmol) in water (53 mL) is carefully added. The mixture is stirred at reflux für 2 h before two more portions of ammonium peroxydisulfate (2×7.33 g) is added as a sat. aq. solution. Stirring is continued at reflux for 3 h. Methanol is removed under reduced pressure and the remaining solution is diluted with sat. aq. NaHCO3 solution and extracted with EA. The org. extract is dried over MgSO4, filtered and concentrated. The crude product is purified by CC on silica gel eluting with heptane:EA 3:7 to give (4-bromo-6-methyl-pyridin-2-yl)-methanol (1.31 g) as pale yellow solid; LC-MS: tR=0.31 min; [M+1]+=201.96; 1H NMR (CDCl3): δ 2.55 (s, 3H), 3.59 (s br, 1H), 4.72 (s br, 2H), 7.28 (s, 2H).

後処理

  1. temperatureThe mixture is heated
  2. additionis carefully added
  3. additionis added as a sat. aq. solution
  4. stirringStirring
  5. temperatureat reflux for 3 h
  6. customMethanol is removed under reduced pressure
  7. additionthe remaining solution is diluted with sat. aq. NaHCO3 solution
  8. extractionextracted with EA
  9. extractionextract
  10. dry with materialis dried over MgSO4
  11. filtrationfiltered
  12. concentrationconcentrated
  13. customThe crude product is purified by CC on silica gel eluting with heptane:EA 3:7

出典と根拠

ORDレコード
ord-7e025bac529c49719d72726152d01bac
出典データセット
uspto-grants-2013_12
特許番号
US08598208B2

反応ノート

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