反応 #503065

反応方程式

2,3-dimethyl-5-oxo-1-phenyl-2,5-dihydro-1H-pyrazole-4-carboxylic acid

oxalyl chloride

→

methyl 1,5-dimethyl-3-oxo-2-phenyl-2,3-dihydro-1H-pyrazole-4-carboxylate

収率 77.0%

溶媒

dichlormethane

反応条件

後処理

1. 1
   その他resulting in vigorous bubbling
2. 2
   その他the reaction was cautiously quenched with MeOH (100 ml)
3. 3
   workup.ADDITIONThe methanol was added slowly at first as vigorous gas evolution
4. 4
   workup.STIRRINGThe reaction was stirred at room temperature for 1 hour
5. 5
   濃縮concentrated
6. 6
   その他partitioned between dichlormethane (125 ml) and saturated sodium bicarbonate (125 ml)
7. 7
   workup.ADDITIONMore dichlormethane and saturated sodium bicarbonate were added
8. 8
   その他the layers of the biphasic, homogeneous solution were separated
9. 9
   抽出The aqueous phase was extracted with dichlormethane (3×100 ml)
10. 10
    その他the organic phases were collected
11. 11
    乾燥dried over sodium sulfate
12. 12
    ろ過filtered
13. 13
    濃縮concentrated

実験手順

2,3-dimethyl-5-oxo-1-phenyl-2,5-dihydro-1H-pyrazole-4-carboxylic acid (7.55 g, 33 mmol) was dissolved in dichlormethane (145 ml) and oxalyl chloride (4.1 ml, 46 mmol) was added via syringe over about 10 minutes, resulting in vigorous bubbling. After stirring at room temperature for about 30 minutes, the reaction was cautiously quenched with MeOH (100 ml). The methanol was added slowly at first as vigorous gas evolution was observed. The reaction was stirred at room temperature for 1 hour, concentrated, and then partitioned between dichlormethane (125 ml) and saturated sodium bicarbonate (125 ml). More dichlormethane and saturated sodium bicarbonate were added, and the layers of the biphasic, homogeneous solution were separated. The aqueous phase was extracted with dichlormethane (3×100 ml), and the organic phases were collected, dried over sodium sulfate, filtered, and concentrated to give desired methyl 1,5-dimethyl-3-oxo-2-phenyl-2,3-dihydro-1H-pyrazole-4-carboxylate (7.82 g, 79% purity by HPLC, 25 mmol, 77% yield). MS (ESI pos. ion) m/z: 247 (MH+). Calc'd exact mass for C13H14N2O3: 246.

出典