Ammonium Hydroxide → 1,3-dimethyl-4-nitro-1H-pyrazole-5-carboxamide

HRID 72184

反応式

HRID 72184 の反応式
[CH3:1][N:2]1[C:6]([C:7](O)=[O:8])=[C:5]([N+:10]([O-:12])=[O:11])[C:4]([CH3:13])=[N:3]1.C(Cl)(=O)C(Cl)=O.[OH-].[NH4+:21]>ClCCl.CN(C=O)C>[CH3:1][N:2]1[C:6]([C:7]([NH2:21])=[O:8])=[C:5]([N+:10]([O-:12])=[O:11])[C:4]([CH3:13])=[N:3]1

参加物

6

反応物 3

HCID 14923Ammonium HydroxideHCID 65578Oxalyl chlorideHCID 12297711,3-dimethyl-4-nitro-1H-pyrazole-5-carboxylic acid

生成物 1

HCID 12297641,3-dimethyl-4-nitro-1H-pyrazole-5-carboxamide収率 51.5%

試薬・触媒・溶媒 2

HCID 6228Dimethylformamide溶媒HCID 6344Dichloromethane溶媒

実験手順

To 1,3-dimethyl-4-nitro-1H-pyrazole-5-carboxylic acid (1.08 g, 5.84 mmol) in anhydrous dichloromethane (DCM) (25 mL) and DMF (0.5 mL) was added dropwise oxalyl chloride (0.74 mL, 8.77 mmol, 1.5 eq.) over 10 minutes. The reaction mixture was stirred at RT under N2 for 17 hours. Volatile solvent was evaporated in vacuo, and the crude material dissolved in anhydrous THF (20 mL) and acetone (10 mL). Concentrated aqueous ammonium hydroxide (5.0 mL, 128.4 mmol, 22 eq.) was added slowly, and the reaction mixture was stirred at RT for 16 hours. The reaction mixture was concentrated in vacuo, and the residue was diluted with ethyl acetate. The organic layer was washed with saturated aqueous solution of sodium bicarbonate, water and brine, dried (Na2SO4), filtered and concentrated in vacuo. Trituration from ether-heptane afforded the desired product as a white solid (550.0 mg, 51.5%). 1H NMR (DMSO-d6, 500 MHz) δ ppm 8.39 (broad s, 1H), 8.21 (broad s, 1H), 3.77 (s, 3H), 2.42 (s, 3H).

後処理

  1. customVolatile solvent was evaporated in vacuo
  2. dissolutionthe crude material dissolved in anhydrous THF (20 mL)
  3. stirringthe reaction mixture was stirred at RT for 16 hours
  4. concentrationThe reaction mixture was concentrated in vacuo
  5. additionthe residue was diluted with ethyl acetate
  6. washThe organic layer was washed with saturated aqueous solution of sodium bicarbonate, water and brine
  7. dry with materialdried (Na2SO4)
  8. filtrationfiltered
  9. concentrationconcentrated in vacuo

出典と根拠

ORDレコード
ord-4b58e871d86145eebf6b50e2046d0fbe
出典データセット
uspto-grants-2014_09
特許番号
US08828990B2

関連ノート

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