Reaktion #536019

Reaktionsgleichung

1-iodo-3,5-bistrifluoromethylbenzene

anilinium hypophosphite

3-aminopropyl triethoxysilane

1,3-bis(diphenylphosphino)propane

→

ethyl 3,5-bis(trifluoromethyl)phenylphosphinate

Ausbeute 52.0%

Lösungsmittel

ethyl acetate

hydrochloric acid

acetonitrile

Reaktionsbedingungen

Aufarbeitung

1. 1
   TemperaturThe mixture was refluxed overnight
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 sodium sulfate
6. 6
   SonstigeThe volatiles were removed in vacuo
7. 7
   Sonstigethe residue was purified by column chromatography
8. 8
   Sonstigeto afford compound AZ3 (4.65 g) as a cloudy oil in 52% yield

Vorschrift

To a degassed solution of 1-iodo-3,5-bistrifluoromethylbenzene (10.0 g, 29.4 mmol), anilinium hypophosphite (5.62 g, 35.3 mmol) and 3-aminopropyl triethoxysilane (7.81 g, 35.3 mmol) in anhydrous acetonitrile (200 mL) were added palladium acetate (132 mg, 0.588 mmol, 2 mol %) and 1,3-bis(diphenylphosphino)propane (267 mg, 0.647 mol, 2.2 mol %). The mixture was refluxed overnight. After cooling down to room temperature, the reaction mixture was diluted with ethyl acetate and hydrochloric acid (1M), and then partitioned. The aqueous layer was further extracted with ethyl acetate. The combined extracts were washed sequentially with aqueous sodium hydrogen carbonate and brine, and dried over sodium sulfate. The volatiles were removed in vacuo, and the residue was purified by column chromatography using 30 to 70% ethyl acetate in petroleum ether to afford compound AZ3 (4.65 g) as a cloudy oil in 52% yield. 1H NMR (CDCl3, 400 MHz): δ (ppm) 1.45 (t, J=7.1 Hz, 3H), 4.18-4.35 (m, 2H), 7.69 (d, J=579.6 Hz, 1H), 8.10 (s, 1H), 8.23 (s, 1H), 8.27 (s, 1H); 31P NMR (CDCl3, 161.8 MHz): δ (ppm) 19.59 (J=580.6 Hz).

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