反応 #51528

反応方程式

ethyl malonate

aluminium chloride

Thionyl chloride

4-nitrophenylacetic acid

→

4-nitrophenylacetone

収率 52.0%

溶媒

water

t-butyl methyl ether

Dichloromethane

反応条件

後処理

1. 1
   workup.DISTILLATIONThionyl chloride was distilled off under reduced pressure
2. 2
   workup.ADDITIONDichloromethane (3 ml) was added to the azeotropic residue
3. 3
   workup.DISSOLUTIONto dissolve the residue, which
4. 4
   workup.ADDITIONwas added to Solution B dropwise
5. 5
   workup.STIRRINGAfter stirred for 7 hours
6. 6
   温度under reflux
7. 7
   温度the reaction solution was cooled to room temperature
8. 8
   workup.ADDITIONpoured into water (10 ml)
9. 9
   その他The layers were separated
10. 10
    抽出the aqueous layer was extracted with dichloromethane (3 ml)
11. 11
    workup.DISTILLATIONthe solvent was distilled off under reduced pressure
12. 12
    workup.DISTILLATIONAfter the solvent was distilled off
13. 13
    workup.ADDITIONacetic acid (1.7 ml), water (1.1 ml) and concentrated sulfuric acid (0.21 ml) were added
14. 14
    温度which was refluxed at an external temperature of 125° C. for 4 hours
15. 15
    workup.STIRRINGwhile stirring vigorously
16. 16
    その他After completion of the reaction
17. 17
    温度cooled
18. 18
    その他returned to room temperature
19. 19
    抽出followed by extraction
20. 20
    洗浄After the organic layer was washed with an aqueous saturated sodium hydrogen carbonate solution (6 ml) twice
21. 21
    workup.DISTILLATIONbrine (6 ml) twice, the solvent was distilled off under reduced pressure
22. 22
    その他the residue was purified by silica gel column chromatography

実験手順

Dichloromethane (3 ml) and ethyl malonate (1.31 g, 8.15 mmol) were added to aluminium chloride (1.10 g, 8.28 mmol) (hereinafter, abbreviated as Solution B). Thionyl chloride (1.58 g, 13.25 mmol) was added to 4-nitrophenylacetic acid (1.00 g, 5.52 mol), followed by stirring at 70-75° C. for 45 minutes. Thionyl chloride was distilled off under reduced pressure, followed by azeotropy with toluene (3 ml) twice. Dichloromethane (3 ml) was added to the azeotropic residue to dissolve the residue, which was added to Solution B dropwise. After stirred for 7 hours under reflux, the reaction solution was cooled to room temperature and poured into water (10 ml). The layers were separated, and the aqueous layer was extracted with dichloromethane (3 ml). The organic layers were combined, and the solvent was distilled off under reduced pressure. After the solvent was distilled off, acetic acid (1.7 ml), water (1.1 ml) and concentrated sulfuric acid (0.21 ml) were added thereto, which was refluxed at an external temperature of 125° C. for 4 hours while stirring vigorously. After completion of the reaction, the mixture was ice-cooled, returned to room temperature, and t-butyl methyl ether (6 ml) and water (6 ml) were added thereto, followed by extraction. After the organic layer was washed with an aqueous saturated sodium hydrogen carbonate solution (6 ml) twice and brine (6 ml) twice, the solvent was distilled off under reduced pressure, and the residue was purified by silica gel column chromatography to give 4-nitrophenylacetone (0.51 g, 2.87 mmol, 52%).

出典