Реакция #507280

Уравнение реакции

4-iodobenzotrifluoride

anilinium hypophosphite

3-aminopropyl triethoxysilane

1,3-bis(diphenylphosphino)propane

→

ethyl 4-(trifluoromethyl)phenylphosphinate

Выход 28.0%

Растворители

ethyl acetate

hydrochloric acid

acetonitrile

Условия реакции

Обработка

1. 1
   ТемператураThe mixture was heated
2. 2
   Температураunder reflux for 32 hrs
3. 3
   Другоеpartitioned
4. 4
   ЭкстракцияThe aqueous layer was further extracted with ethyl acetate
5. 5
   Промывкаthe combined extracts were washed with aqueous sodium hydrogen carbonate and brine
6. 6
   Сушкаdried over magnesium sulfate
7. 7
   ДругоеThe solvent was removed in vacuo
8. 8
   Другоеthe residue was purified by column chromatography
9. 9
   ДругоеFurther purification
10. 10
    workup.DISTILLATIONby distillation
11. 11
    Другоеafforded compound AZ1 (1.14 g) in 28% yield

Методика

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.

Источник