反应 #604192

反应方程式

4-iodobenzotrifluoride

anilinium hypophosphite

3-aminopropyl triethoxysilane

1,3-bis(diphenylphosphino)propane

→

ethyl 4-(trifluoromethyl)phenylphosphinate

收率 28.0%

溶剂

ethyl acetate

hydrochloric acid

acetonitrile

反应条件

后处理

1. 1
   温度The mixture was refluxed for 32 hrs
2. 2
   其他partitioned
3. 3
   萃取The aqueous layer was further extracted with ethyl acetate
4. 4
   洗涤The combined extracts were washed sequentially with aqueous sodium hydrogen carbonate and brine
5. 5
   干燥dried over magnesium sulfate, and concentration in vacuo
6. 6
   其他The resulting residue was purified by column chromatography
7. 7
   其他Further purification
8. 8
   workup.DISTILLATIONby distillation
9. 9
   其他afforded compound AZ1 (1.14 g) in 28% yield

实验过程

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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