Nitromethane → 2-(3-Fluoro-phenoxy)-5-(2-nitro-ethyl)-pyridine

HRID 1691096ノート

反応式

HRID 1691096 の反応式
[F:1][C:2]1[CH:3]=[C:4]([CH:14]=[CH:15][CH:16]=1)[O:5][C:6]1[N:11]=[CH:10][C:9]([CH:12]=O)=[CH:8][CH:7]=1.[N+:17]([CH3:20])([O-:19])=[O:18].C([O-])(=O)C.[NH4+].[BH4-].[Na+].C(=O)([O-])O.[Na+]>O.C(O)(=O)C.CS(C)=O>[F:1][C:2]1[CH:3]=[C:4]([CH:14]=[CH:15][CH:16]=1)[O:5][C:6]1[CH:7]=[CH:8][C:9]([CH2:12][CH2:20][N+:17]([O-:19])=[O:18])=[CH:10][N:11]=1

参加物

9

反応物 5

HCID 6375NitromethaneHCID 516892Sodium BicarbonateHCID 517165Ammonium AcetateHCID 4311764Sodium borohydrideHCID 59255292HCID 59255292、化合物

生成物 1

HCID 592554082-(3-Fluoro-phenoxy)-5-(2-nitro-ethyl)-pyridine収率 66%

試薬・触媒・溶媒 3

HCID 176Acetic Acid溶媒2 回HCID 679Dimethyl Sulfoxide溶媒HCID 962Water溶媒2 回

反応条件

温度
100 °C

実験手順

To an acetic acid (20 mL) solution of 6-(3-fluoro-phenoxy)-pyridine-3-carbaldehyde (2.47 g, 11.4 mmol) described in Manufacturing Example 71-1-2 was added nitromethane (3.09 mL, 57.0 mmol) and ammonium acetate (1.76 g, 22.8 mmol), which was stirred for 6 hours at 100° C. Water was added to the reaction solution at room temperature, which was then extracted with ethyl acetate. The organic layer was separated, washed with saturated aqueous sodium chloride, dried over anhydrous magnesium sulfate, and filtered. The filtrate was concentrated under a reduced pressure. To a dimethyl sulfoxide (35 mL) and acetic acid (5 mL) solution of the residue was added sodium borohydride (681 mg, 17.1 mmol), which was stirred for 40 minutes at room temperature. Sodium hydrogencarbonate and water were added to the reaction mixture at room temperature while cooling appropriately, which was then extracted with ethyl acetate. The organic layer was separated, washed with saturated aqueous sodium chloride, dried over anhydrous magnesium sulfate, and filtered. The filtrate was concentrated under a reduced pressure, and the residue was purified by NH silica gel column chromatography (heptane:ethyl acetate=2:1) to obtain the title compound (1.96 g, 66%).

後処理

  1. extractionwhich was then extracted with ethyl acetate
  2. customThe organic layer was separated
  3. washwashed with saturated aqueous sodium chloride
  4. dry with materialdried over anhydrous magnesium sulfate
  5. filtrationfiltered
  6. concentrationThe filtrate was concentrated under a reduced pressure
  7. stirringwas stirred for 40 minutes at room temperature
  8. temperaturewhile cooling appropriately
  9. extractionwhich was then extracted with ethyl acetate
  10. customThe organic layer was separated
  11. washwashed with saturated aqueous sodium chloride
  12. dry with materialdried over anhydrous magnesium sulfate
  13. filtrationfiltered
  14. concentrationThe filtrate was concentrated under a reduced pressure
  15. customthe residue was purified by NH silica gel column chromatography (heptane:ethyl acetate=2:1)

出典と根拠

ORDレコード
ord-a5c4469d11d3455d871762c48c964e2c
出典データセット
uspto-grants-2012_04
特許番号
US08153662B2

反応ノート

読み込み中…