Reaktion #51527

Reaktionsgleichung

Thionyl chloride

4-nitrophenylacetic acid

ethyl malonate

magnesium ethoxide

→

4-nitrophenylacetone

Ausbeute 75.0%

Lösungsmittel

water

t-butyl methyl ether

ethanol

t-butyl methyl ether

Reaktionsbedingungen

Aufarbeitung

1. 1
   Temperaturwas heated
2. 2
   Temperaturto reflux for 30 minutes
3. 3
   Sonstigereturned to room temperature
4. 4
   workup.DISTILLATIONThionyl chloride was distilled off under reduced pressure
5. 5
   workup.ADDITIONt-butyl methyl ether (132 ml) was added to the azeotropic residue
6. 6
   workup.DISSOLUTIONto dissolve it, which
7. 7
   workup.ADDITIONwas added dropwise to Solution A
8. 8
   workup.STIRRINGAfter stirred at 65° C. for 30 minutes
9. 9
   Temperaturthe mixture was cooled to room temperature
10. 10
    workup.ADDITION2N hydrochloric acid (264 ml) was added
11. 11
    Temperaturdropwise under cooling
12. 12
    SonstigeThe organic layer was separated
13. 13
    Extraktionthe aqueous layer was reverse-extracted with t-butyl methyl ether (132 ml)
14. 14
    workup.DISTILLATIONthe solvent was distilled off under reduced pressure
15. 15
    workup.ADDITIONAcetic acid (111 ml), water (74 ml) and concentrated sulfuric acid (14 ml) were added to the concentrated residue
16. 16
    Temperaturthe mixture was refluxed at an outer temperature of 125° C. for 5 hours
17. 17
    workup.STIRRINGwhile stirring vigorously
18. 18
    SonstigeAfter completion of the reaction
19. 19
    Temperaturcooled
20. 20
    Sonstigereturned to room temperature
21. 21
    Extraktionfollowed by extraction
22. 22
    workup.ADDITIONAn aqueous saturated sodium hydrogen carbonate solution (264 ml) and ethyl acetate (80 ml) were added to the organic layer
23. 23
    Waschento wash the layer
24. 24
    Waschenby further washing with an aqueous saturated sodium bicarbonate solution (264 ml)
25. 25
    WaschenAfter washed with brine (264 ml) twice
26. 26
    workup.DISTILLATIONthe solvent was distilled off under reduced pressure
27. 27
    Sonstigethe residue was purified by silica gel column chromatography

Vorschrift

t-butyl methyl ether (290 ml), ethanol (40 ml) and ethyl malonate (70.04 g, 0.437 mol) were added to magnesium ethoxide (50.00 g, 0.437 mol), which was heated to reflux for 30 minutes and returned to room temperature (hereinafter, abbreviated as Solution A). Thionyl chloride (104.04 g, 0.875 mol) was added to 4-nitrophenylacetic acid (66.00 g, 0.364 mol), which was stirred at 70-75° C. for 45 minutes. Thionyl chloride was distilled off under reduced pressure, followed by azeotropy with toluene (66 ml) two times. t-butyl methyl ether (132 ml) was added to the azeotropic residue to dissolve it, which was added dropwise to Solution A. After stirred at 65° C. for 30 minutes, the mixture was cooled to room temperature, and 2N hydrochloric acid (264 ml) was added thereto dropwise under cooling. The organic layer was separated, the aqueous layer was reverse-extracted with t-butyl methyl ether (132 ml), the organic layers were combined, and the solvent was distilled off under reduced pressure. Acetic acid (111 ml), water (74 ml) and concentrated sulfuric acid (14 ml) were added to the concentrated residue, and the mixture was refluxed at an outer temperature of 125° C. for 5 hours while stirring vigorously. After completion of the reaction, the mixture was ice-cooled, returned to room temperature, and t-butyl methyl ether (264 ml) and water (264 ml) were added thereto, followed by extraction. An aqueous saturated sodium hydrogen carbonate solution (264 ml) and ethyl acetate (80 ml) were added to the organic layer to wash the layer, followed by further washing with an aqueous saturated sodium bicarbonate solution (264 ml). After washed with brine (264 ml) twice, the solvent was distilled off under reduced pressure, and the residue was purified by silica gel column chromatography to give 4-nitrophenylacetone (48.96 g, 0.273 mol, 75%).

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