Reacción #604192

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 refluxed for 32 hrs
2. 2
   Otropartitioned
3. 3
   ExtracciónThe aqueous layer was further extracted with ethyl acetate
4. 4
   LavadoThe combined extracts were washed sequentially with aqueous sodium hydrogen carbonate and brine
5. 5
   Secadodried over magnesium sulfate, and concentration in vacuo
6. 6
   OtroThe resulting residue was purified by column chromatography
7. 7
   OtroFurther purification
8. 8
   workup.DISTILLATIONby distillation
9. 9
   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 refluxed for 32 hrs. After cooling down to room temperature, the reaction mixture was diluted with ethyl acetate and hydrochloric acid (1M), and partitioned. The aqueous layer was further extracted with ethyl acetate. The combined extracts were washed sequentially with aqueous sodium hydrogen carbonate and brine, dried over magnesium sulfate, and concentration in vacuo. The resulting 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. 1H NMR (CDCl3, 400 MHz): δ (ppm) 1.35-1.43 (m, 3H), 4.12-4.27 (m, 2H), 7.63 (d, J=570.8 Hz, 1H), 7.75-7.80 (m, 2H), 7.90-7.94 (m, 2H); 31P NMR (CDCl3, 161.8 MHz): δ (ppm) 22.6.

Fuente