Реакция #536015

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

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