Reaktion #536015

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 refluxed for 32 hrs
2. 2
   Sonstigepartitioned
3. 3
   ExtraktionThe aqueous layer was further extracted with ethyl acetate
4. 4
   WaschenThe combined extracts were washed sequentially with aqueous sodium hydrogen carbonate and brine
5. 5
   Trocknendried over magnesium sulfate, and concentration in vacuo
6. 6
   SonstigeThe resulting residue was purified by column chromatography
7. 7
   SonstigeFurther purification
8. 8
   workup.DISTILLATIONby distillation
9. 9
   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 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.

Quelle