반응 #604192

반응 방정식

4-iodobenzotrifluoride

anilinium hypophosphite

3-aminopropyl triethoxysilane

1,3-bis(diphenylphosphino)propane

→

ethyl 4-(trifluoromethyl)phenylphosphinate

수율 28.0%

용매

ethyl acetate

hydrochloric acid

acetonitrile

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후처리

1. 1
   온도The mixture was refluxed for 32 hrs
2. 2
   기타partitioned
3. 3
   추출The aqueous layer was further extracted with ethyl acetate
4. 4
   세척The combined extracts were washed sequentially with aqueous sodium hydrogen carbonate and brine
5. 5
   건조dried over magnesium sulfate, and concentration in vacuo
6. 6
   기타The resulting residue was purified by column chromatography
7. 7
   기타Further purification
8. 8
   workup.DISTILLATIONby distillation
9. 9
   기타afforded compound AZ1 (1.14 g) in 28% yield

실험 절차

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.

출처