Reacción #507280

Ecuación de reacción

4-iodobenzotrifluoride

anilinium hypophosphite

3-aminopropyl triethoxysilane

1,3-bis(diphenylphosphino)propane

→

ethyl 4-(trifluoromethyl)phenylphosphinate

Rendimiento 28.0%

Disolventes

ethyl acetate

hydrochloric acid

acetonitrile

Condiciones de reacción

Tratamiento posterior

1. 1
   TemperaturaThe mixture was heated
2. 2
   Temperaturaunder reflux for 32 hrs
3. 3
   Otropartitioned
4. 4
   ExtracciónThe aqueous layer was further extracted with ethyl acetate
5. 5
   Lavadothe combined extracts were washed with aqueous sodium hydrogen carbonate and brine
6. 6
   Secadodried over magnesium sulfate
7. 7
   OtroThe solvent was removed in vacuo
8. 8
   Otrothe residue was purified by column chromatography
9. 9
   OtroFurther purification
10. 10
    workup.DISTILLATIONby distillation
11. 11
    Otroafforded compound AZ1 (1.14 g) in 28% yield

Procedimiento

To a degassed solution of 4-iodobenzotrifluoride (4.70 g, 17.2 mmol), anilinium hypophosphite (3.51 g, 22.1 mmol), and 3-aminopropyl triethoxysilane (4.88 g, 22.1 mmol) in anhydrous acetonitrile (110 mL) were added palladium acetate (82.5 mg, 0.367 mmol, 2 mol %) and 1,3-bis(diphenylphosphino)propane (167 mg, 0.404 mol, 2.2 mol %). The mixture was heated under reflux for 32 hrs, then cooled down to room temperature, diluted with ethyl acetate and hydrochloric acid (IM) and partitioned. The aqueous layer was further extracted with ethyl acetate, and the combined extracts were washed with aqueous sodium hydrogen carbonate and brine and dried over magnesium sulfate. The solvent was removed in vacuo and the residue was purified by column chromatography using 25 to 100% ethyl acetate in petroleum ether. Further purification by distillation afforded compound AZ1 (1.14 g) in 28% yield.

Fuente