反应详情

A 1000 mL round bottom flask was pre-cooled in an ice-water bath, to which a solution of malononitrile (10.2 g, 0.154 mol) was mixed into a suspension of sodium hydride (6.72 g, 0.28 mol) in THF (100 mL). To this mixture, 4-nitrobenzoyl chloride (26 g, 0.14 mol; Sigma-Aldrich) was added slowly. After 20 minutes, the reaction was removed from the ice-water bath and left stirring for 2 hours. Dimethyl sulfate (16 mL, 0.168 mol) was then added with a syringe. The reaction vessel was placed into an oil bath at 90° C. and almost immediately afterwards a yellow solid began to form. The reaction was left at 90° C. for 2 hours. The reaction mixture was removed from the oil bath and allowed to cool to room temperature. Afterwards, hydrazine (7.5 mL, 0.154 mol) was added, and the reaction was left stirring for 60 minutes. 200 mL of brine and 100 mL of 2N HCl were added and separated from the organic layer. The aqueous phase was extracted two additional times with CH2Cl2. The organic phases were combined and concentrated in vacuo to yield a bright yellow solid. The solid was suspended in 100 mL EtOH, refluxed for 30 minutes, and the insoluble solid was collected by filtration, washed with room temperature EtOH, and dried to yield 5-amino-3-(4-nitrophenyl)-1H-pyrazole-4-carbonitrile (9.1 g, 28% yield).

1. customthe reaction was removed from the ice-water bath
2. waitleft
3. customThe reaction vessel was placed into an oil bath at 90° C.
4. customto form
5. waitThe reaction was left at 90° C. for 2 hours
6. customThe reaction mixture was removed from the oil bath
7. waitthe reaction was left
8. stirringstirring for 60 minutes
9. customseparated from the organic layer
10. extractionThe aqueous phase was extracted two additional times with CH2Cl2
11. concentrationconcentrated in vacuo
12. customto yield a bright yellow solid
13. temperaturerefluxed for 30 minutes
14. filtrationthe insoluble solid was collected by filtration
15. washwashed with room temperature EtOH
16. customdried