반응 #93547

반응 방정식

4-fluoroacetophenone

water

diethyl carbonate

sodium hydride

→

product

수율 77.4%

Ethyl 3-(4'-fluorophenyl)-3-oxopropanoate

수율 77.4%

용매

diethyl ether

diethyl ether

pentane

diethyl ether

반응 조건

후처리

1. 1
   기타the pentane is decanted
2. 2
   건조the sodium hydride is dried in a stream of nitrogen, 171 g
3. 3
   workup.ADDITIONthe dropwise addition of a solution of 100 g
4. 4
   workup.ADDITIONis added dropwise over a period 1 hour at a rate such that the reaction mixture
5. 5
   workup.STIRRINGthe reaction mixture being stirred under nitrogen throughout
6. 6
   workup.STIRRINGto facilitate stirring
7. 7
   온도the reaction mixture is refluxed under nitrogen for 3 hours
8. 8
   기타to destroy the excess sodium hydride) until all solids
9. 9
   workup.DISSOLUTIONdissolve (
10. 10
    workup.ADDITIONthe addition
11. 11
    기타is separated
12. 12
    추출extracted twice with diethyl ether
13. 13
    세척washed with saturated sodium chloride solution
14. 14
    건조dried over anhydrous magnesium sulfate
15. 15
    여과filtered
16. 16
    기타evaporated at reduced pressure
17. 17
    기타to obtain an orange oil
18. 18
    workup.DISTILLATIONThe orange oil is fractionally distilled at about 1 mm. Hg

실험 절차

57.92 g. (1.448 moles) of 60% sodium hydride/mineral oil is washed twice with pentane, the pentane is decanted, the sodium hydride is dried in a stream of nitrogen, 171 g. (1.448 moles) of diethyl carbonate is added neat at 20°-25° C., and the dropwise addition of a solution of 100 g. (0.724 mole) of 4-fluoroacetophenone in 100 ml of dry diethyl ether is commenced, the reaction mixture being stirred at 20°-25° C. under nitrogen throughout. After about 10% of the diethyl ether solution is added, 10 drops of ethanol is added (gas evolution commences immediately), and the balance of the solution is added dropwise over a period 1 hour at a rate such that the reaction mixture refluxes, the reaction mixture being stirred under nitrogen throughout. 1 kg. of dry diethyl ether is added to facilitate stirring, and the reaction mixture is refluxed under nitrogen for 3 hours and cooled to 0° C., water is carefully added (to destroy the excess sodium hydride) until all solids dissolve (the addition being exothermic), the diethyl ether phase is separated, the aqueous phase is acidified to pH 1 with concentrated hydrochloric acid and extracted twice with diethyl ether, and the three diethyl ether phases are combined, washed with saturated sodium chloride solution, dried over anhydrous magnesium sulfate, filtered and evaporated at reduced pressure to obtain an orange oil. The orange oil is fractionally distilled at about 1 mm. Hg. to obtain the product as a colorless liquid (117.8 g. (77%)). B.p. 117°-125° C.λ1 mm. Hg.

출처