Reaktion #742297

Reaktionsgleichung

2-(Ethoxymethylene)malononitrile

(2,6-Dichlorophenyl)hydrazine hydrochloride

NaOH

→

product

Ausbeute 94.5%

5-amino-1-(2,6-dichlorophenyl)-1H-pyrazole-4-carbonitrile

Ausbeute 94.5%

Lösungsmittel

EtOAc

Reaktionsbedingungen

Aufarbeitung

1. 1
   SonstigeThe organic layer separated
2. 2
   Waschenwashed with water (50 mL), brine (50 mL)
3. 3
   Trocknendried (MgSO4)
4. 4
   Filtrationfiltered
5. 5
   Einengenconcentrated
6. 6
   Sonstigewas suspended in methanol (50 mL) under nitrogen at −5° C
7. 7
   Temperaturheated
8. 8
   Temperaturat reflux under nitrogen for 2 hours
9. 9
   Temperaturto cool
10. 10
    Sonstigeevaporated to dryness

Vorschrift

(2,6-Dichlorophenyl)hydrazine hydrochloride (5 g, 23.42 mmol) was partitioned between EtOAc (100 mL) and NaOH (2M, aq) (40 mL). The organic layer separated and washed with water (50 mL), brine (50 mL), dried (MgSO4), filtered and concentrated. The resultant oil was suspended in methanol (50 mL) under nitrogen at −5° C. 2-(Ethoxymethylene)malononitrile (2.86 g, 23.42 mmol) added portion-wise over 5 mins and the mixture stiffed at 0° C. for 30 mins. The reaction mixture was allowed to warm to room temperature and then heated at reflux under nitrogen for 2 hours. The reaction mixture was allowed to cool and evaporated to dryness to afford the product (5.60 g, 94%) which was used without further purification. 1H NMR (400 MHz, CDCl3) δ 4.47 (2H, s), 7.43-7.47 (1H, m), 7.51-7.53 (2H, m), 7.73 (1H, s); m/z (ES+) (M+H)+=253; HPLC tR=1.62 min. Alternatively the product was obtained by concentrating the reaction mixture to half volume and allowing the product to crystallise.

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