Реакция #432299

Уравнение реакции

3-Carboethoxy-1-(2,6-dichloro-4-trifluoromethylphenyl)-4-hydroxypyrazole

sodium hydride

2-chloro-1,1,2-trifluoroethylene

→

(RS)-3-carboethoxy-4-(2-chloro-1,1,2-trifluoroethoxy)-1-(2,6-dichloro-4-trifluoromethylphenyl)pyrazole

Растворители

dioxan

Условия реакции

Обработка

1. 1
   Температураthe solution was heated to 80°-900 °C.
2. 2
   Другоеthe solvent was evaporated to dryness
3. 3
   workup.DISSOLUTIONThe residue was dissolved in dilute hydrochloric acid (2M; 10 ml)
4. 4
   Другоеdichloromethane (20 ml) and the layers were separated
5. 5
   ЭкстракцияThe aqueous layer was extracted with dichloromethane (30 ml)
6. 6
   Промывкаthe combined organic layers were washed with water (20 ml)
7. 7
   Сушкаdried over magnesium sulfate
8. 8
   Фильтрацияfiltered
9. 9
   Другоеevaporated
10. 10
    ДругоеThe residue was purified by dry-column chromatography (eluant ether:hexane 1:3)

Методика

3-Carboethoxy-1-(2,6-dichloro-4-trifluoromethylphenyl)-4-hydroxypyrazole (2.0 g) was added to a stirred suspension of sodium hydride (80% dispersion in oil; 0.2 g) in dry dioxan (20 ml). When the resultant effervescence had subsided, the solution was heated to 80°-900 °C. and stirred while 2-chloro-1,1,2-trifluoroethylene was passed through. After 6 hours, the reaction was complete and the solvent was evaporated to dryness. The residue was dissolved in dilute hydrochloric acid (2M; 10 ml) and dichloromethane (20 ml) and the layers were separated. The aqueous layer was extracted with dichloromethane (30 ml) and the combined organic layers were washed with water (20 ml), dried over magnesium sulfate, filtered and evaporated. The residue was purified by dry-column chromatography (eluant ether:hexane 1:3) to give (RS)-3-carboethoxy-4-(2-chloro-1,1,2-trifluoroethoxy)-1-(2,6-dichloro-4-trifluoromethylphenyl)pyrazole (1.0 g). This was recrystallised from hexane to yield colorless needles, m.p. 105°-106.5° C.

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