反応 #60746

反応方程式

4Nitro acetophenone

malonodinitrile

acetic acid

ammonium acetate

→

1,1-dicyano-2-(4-nitrophenyl)-propene

溶媒

brine

ethyl acetate

toluene

反応条件

後処理

1. 1
   温度The system was heated
2. 2
   温度to reflux
3. 3
   洗浄The aqueous layer was washed with 3×10 mL ethyl acetate
4. 4
   洗浄The combined organic layers were washed with 50 mL brine
5. 5
   乾燥dried over anhydrous sodium sulfate
6. 6
   濃縮concentrated to dryness
7. 7
   その他The dark residue was partially purified

実験手順

4Nitro acetophenone (2.0 g, 12.1 mmoles, 1 eq) and malonodinitrile (2.4 g, 36.3 mmoles, 3 eq) were dissolved in 20 mL of anhydrous toluene. To the solution were added glacial acetic acid (0.40 mL, 7.0 mmoles, 0.19 eq) and ammonium acetate (0.26 g, 3.3 mmoles, 0.09 eq). The system was heated to reflux using a Dean-Stark trap and a condenser. After 1 hour, the reaction mixture was cooled to room temperature and poured into brine (50 mL) and ethyl acetate (100 mL). The aqueous layer was washed with 3×10 mL ethyl acetate. The combined organic layers were washed with 50 mL brine, dried over anhydrous sodium sulfate and concentrated to dryness. The dark residue was partially purified using a silica plug (40% ethyl acetate-hexane) affording crude 1,1-dicyano-2-(4-nitrophenyl)-propene. The product was used as such in the next step. TLC (40% ethyl acetate-hexane)=0.61. LC-MS (m/e)=214.2 (MH+).

出典