Reaktion #507280

Reaktionsgleichung

4-iodobenzotrifluoride

anilinium hypophosphite

3-aminopropyl triethoxysilane

1,3-bis(diphenylphosphino)propane

→

ethyl 4-(trifluoromethyl)phenylphosphinate

Ausbeute 28.0%

Lösungsmittel

ethyl acetate

hydrochloric acid

acetonitrile

Reaktionsbedingungen

Aufarbeitung

1. 1
   TemperaturThe mixture was heated
2. 2
   Temperaturunder reflux for 32 hrs
3. 3
   Sonstigepartitioned
4. 4
   ExtraktionThe aqueous layer was further extracted with ethyl acetate
5. 5
   Waschenthe combined extracts were washed with aqueous sodium hydrogen carbonate and brine
6. 6
   Trocknendried over magnesium sulfate
7. 7
   SonstigeThe solvent was removed in vacuo
8. 8
   Sonstigethe residue was purified by column chromatography
9. 9
   SonstigeFurther purification
10. 10
    workup.DISTILLATIONby distillation
11. 11
    Sonstigeafforded compound AZ1 (1.14 g) in 28% yield

Vorschrift

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.

Quelle