Nitromethane → 2-(4-Fluoro-phenoxy)-5-(2-nitro-ethyl)-thiophene

HRID 1694015ノート

反応式

HRID 1694015 の反応式
[F:1][C:2]1[CH:15]=[CH:14][C:5]([O:6][C:7]2[S:11][C:10]([CH:12]=O)=[CH:9][CH:8]=2)=[CH:4][CH:3]=1.[N+:16]([CH3:19])([O-:18])=[O:17].C([O-])(=O)C.[NH4+].[BH4-].[Na+]>O.C(O)(=O)C.CS(C)=O.C(OCC)(=O)C>[F:1][C:2]1[CH:15]=[CH:14][C:5]([O:6][C:7]2[S:11][C:10]([CH2:12][CH2:19][N+:16]([O-:18])=[O:17])=[CH:9][CH:8]=2)=[CH:4][CH:3]=1

参加物

9

反応物 4

HCID 6375NitromethaneHCID 517165Ammonium AcetateHCID 4311764Sodium borohydrideHCID 194222425-(4-Fluorophenoxy)-2-thiophenecarboxaldehyde

生成物 1

HCID 592553432-(4-Fluoro-phenoxy)-5-(2-nitro-ethyl)-thiophene収率 45.7%

試薬・触媒・溶媒 4

HCID 176Acetic Acid溶媒2 回HCID 679Dimethyl Sulfoxide溶媒HCID 962Water溶媒2 回HCID 8857Ethyl Acetate溶媒

反応条件

温度
110 °C

実験手順

To an acetic acid (20.0 mL) solution of 5-(4-fluoro-phenoxy)-thiophene-2-carbaldehyde (2.60 g, 11.7 mmol) described in Manufacturing Example 91-1-2 were added nitromethane (3.57 g, 58.5 mmol) and ammonium acetate (1.80 g, 23.4 mmol) under nitrogen atmosphere at room temperature, which was stirred for 4 hours at 110° C. Water and ethyl acetate were added to the reaction mixture, and the organic layer was extracted with ethyl acetate. This organic layer was washed with water and saturated aqueous sodium chloride, dried over anhydrous magnesium sulfate, and filtered. The filtrate was concentrated under a reduced pressure to obtain a crude product (3.00 g). To a dimethyl sulfoxide (30.0 mL) solution of this crude product (3.00 g) and acetic acid (3.00 mL) was added sodium borohydride (684 g, 18.1 mol) at room temperature while cooling appropriately, which was stirred for 20 minutes at room temperature. Water was then added dropwise at room temperature while cooling appropriately. The reaction mixture was extracted with ethyl acetate, and the organic layer was washed with water and 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 (ethyl acetate:heptane=1:5) to obtain the title compound (1.38 g, 45.7%).

後処理

  1. extractionthe organic layer was extracted with ethyl acetate
  2. washThis organic layer was washed with water and saturated aqueous sodium chloride
  3. dry with materialdried over anhydrous magnesium sulfate
  4. filtrationfiltered
  5. concentrationThe filtrate was concentrated under a reduced pressure
  6. customto obtain a crude product (3.00 g)
  7. temperaturewhile cooling appropriately
  8. stirringwhich was stirred for 20 minutes at room temperature
  9. temperaturewhile cooling appropriately
  10. extractionThe reaction mixture was extracted with ethyl acetate
  11. washthe organic layer was washed with water and 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 (ethyl acetate:heptane=1:5)

出典と根拠

ORDレコード
ord-6bccc68c40be497293eac310d47092d9
出典データセット
uspto-grants-2012_04
特許番号
US08158657B2

反応ノート

読み込み中…