Dimethylformamide → N-Methoxy-N-methyl-5-ethyl-1-methylpyrazole-3-carboxamide

HRID 1452105ノート

反応式

HRID 1452105 の反応式
[CH2:1]([C:3]1[N:7]([CH3:8])[N:6]=[C:5]([C:9]([OH:11])=O)[CH:4]=1)[CH3:2].[CH3:12][N:13](C=O)C.[C:17](Cl)(=[O:21])C(Cl)=O>ClCCl>[CH3:17][O:21][N:13]([CH3:12])[C:9]([C:5]1[CH:4]=[C:3]([CH2:1][CH3:2])[N:7]([CH3:8])[N:6]=1)=[O:11]

参加物

5

反応物 3

HCID 6228DimethylformamideHCID 65578Oxalyl chlorideHCID 199675945-ethyl-1-methyl-1H-pyrazole-3-carboxylic acid

生成物 1

HCID 19967595N-Methoxy-N-methyl-5-ethyl-1-methylpyrazole-3-carboxamide収率 94%

試薬・触媒・溶媒 1

HCID 6344Dichloromethane溶媒2 回

反応条件

温度
0 °C

実験手順

5-Ethyl-1-methylpyrazole-3-carboxylic acid (2.5g) in dichloromethane (50 ml) was treated with DMF (0.12 ml) and cooled under argon in an ice-bath. The solution was treated with oxalyl chloride (2.2 g) in dichloromethane (25 ml) in a dropwise fashion. After complete addition the reaction mixture was maintained at 0° C. for 2.5 m. and then allowed to warm to room temperature. The solution was evaporated and the residue re-dissolved in toluene (100 ml) and concentrated again. The crude acid chloride was taken up in dichloromethane (50 ml), and treated with N,O-dimethylhydroxylamine hydrochloride (1.72 g), cooled in an ice-bath and pyridine (2.86 ml) added. The reaction mixture was allowed to stir at room temperature for 2 h. The reaction mixture was washed with brine, dried over anhydrous magnesium sulphate and concentrated to an oil. The product was purified by `flash` silica gel chromatography to give the title compound as a yellow oil, (2.995 g, 94%); (Found: M+, 197.1167. C9H15N3O2 requires M, 197.1164); nmax (CH2Cl2) 1640, 1484 and 1374 cm-1 ; dH (CDCl3) 1.28 (3H, t, f7.SHz), 2.62 (2H, q, J7.5 Hz), 3.43 (3H, s), 3.76 (3H, s), 3.83 (3H, s) and 6.72 (1H, s).

後処理

  1. temperaturecooled under argon in an ice-bath
  2. additionAfter complete addition the reaction mixture
  3. temperatureto warm to room temperature
  4. customThe solution was evaporated
  5. dissolutionthe residue re-dissolved in toluene (100 ml)
  6. concentrationconcentrated again
  7. additiontreated with N,O-dimethylhydroxylamine hydrochloride (1.72 g)
  8. temperaturecooled in an ice-bath
  9. additionpyridine (2.86 ml) added
  10. washThe reaction mixture was washed with brine
  11. dry with materialdried over anhydrous magnesium sulphate
  12. concentrationconcentrated to an oil
  13. customThe product was purified by `flash` silica gel chromatography

出典と根拠

ORDレコード
ord-7cfb91a81ce74d0ab2397a94df9e33bc
出典データセット
uspto-grants-1997_02
特許番号
US05606051

反応ノート

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