反応 #78379

反応方程式

water

methyl isobutyrylacetate

4-fluorobenzonitrile

tin tetrachloride

→

methyl 2-[1-amino-1-(4-fluorophenyl)methylene]-4-methyl-3-oxopentanoate

収率 81.5%

溶媒

toluene

ethyl acetate

n-hexane

toluene

反応条件

後処理

1. 1
   workup.WAITAfter half an hour at room temperature
2. 2
   温度the suspension was cooled to room temperature
3. 3
   その他the phases were separated
4. 4
   抽出After extraction of the aqueous phase with ethyl acetate (2×100 ml)
5. 5
   洗浄the combined organic phases were washed with 100 ml of saturated aqueous sodium hydrogencarbonate solution, and 100 ml of 1N sodium hydroxide solution
6. 6
   乾燥dried over magnesium sulphate
7. 7
   濃縮After concentration in vacuo
8. 8
   その他46.46 g of crude product were obtained in the form of a yellowish solid
9. 9
   温度under reflux
10. 10
    ろ過filtered hot
11. 11
    その他The product precipitated from the filtrate
12. 12
    温度on cooling
13. 13
    ろ過By filtering through a frit
14. 14
    洗浄washing the filter cake with 2×40 ml of n-hexane

実験手順

22.53 g of methyl isobutyrylacetate (0.15 mol, concentration 96%) and 18.54 g of 4-fluorobenzonitrile (0.15 mol, concentration 98%) were dissolved in 150 ml of toluene and treated with 43.32 g of tin tetrachloride (0.165 mol, concentration 99%) at room temperature over the course of 12 min. After half an hour at room temperature, the mixture was heated to 80° C. After 3 h, the suspension was cooled to room temperature and treated with 150 ml of water. It was diluted with 100 ml of ethyl acetate and the phases were separated. After extraction of the aqueous phase with ethyl acetate (2×100 ml), the combined organic phases were washed with 100 ml of saturated aqueous sodium hydrogencarbonate solution, and 100 ml of 1N sodium hydroxide solution and dried over magnesium sulphate. After concentration in vacuo, 46.46 g of crude product were obtained in the form of a yellowish solid. The solid was dissolved in a mixture of 50 ml of n-hexane and 5 ml of toluene under reflux and filtered hot. The product precipitated from the filtrate on cooling. By filtering through a frit and washing the filter cake with 2×40 ml of n-hexane, 32.42 g of methyl 2-[1-amino-1-(4-fluorophenyl)methylene]-4-methyl-3-oxopentanoate were obtained in the form of a spectroscopically pure solid.

出典