반응 #46983

반응 방정식

hydrochloric acid

4-acetyltetrahydropyran

dimethyl carbonate

sodium methoxide

→

methyl 3-(4-tetrahydropyranyl)-3-oxopropanoate

수율 80.5%

용매

water

toluene

반응 조건

후처리

1. 1
   기타In a flask made of glass
2. 2
   기타equipped with a stirring device
3. 3
   기타the mixture was reacted at 80 to 85° C. for 2 hours
4. 4
   workup.DISTILLATIONwith distilling
5. 5
   기타by-producing methanol off
6. 6
   기타After completion of the reaction
7. 7
   기타After the organic layer was separated
8. 8
   추출the aqueous layer was extracted twice with 70 ml of toluene
9. 9
   농축The organic layer was concentrated under reduced pressure
10. 10
    기타the concentrate was purified by silica gel column chromatography (Fluent; hexane/ethyl acetate=1/1 (volume ratio))

실험 절차

In a flask made of glass having an inner volume of 500 ml and equipped with a stirring device, a thermometer, a dropping funnel and a distillation device were charged 35.0 g (273 mmol) of 4-acetyltetrahydropyran synthesized in the same manner as in Reference example 2, 280.0 g (3.1 mol) of dimethyl carbonate and 16.3 g (302 mmol) of sodium methoxide, and the mixture was reacted at 80 to 85° C. for 2 hours with distilling by-producing methanol off. After completion of the reaction, the reaction mixture was cooled to 5 to 10° C., and to the reaction mixture were added 175 ml of toluene, 55 ml (330 mmol) of 6 mol/l hydrochloric acid and 35 ml of water in this order. After the organic layer was separated, the aqueous layer was extracted twice with 70 ml of toluene. The organic layer was concentrated under reduced pressure, and the concentrate was purified by silica gel column chromatography (Fluent; hexane/ethyl acetate=1/1 (volume ratio)) to give 40.9 g (Isolation yield: 76%) of methyl 3-(4-tetrahydropyranyl)-3-oxopropanoate with a purity of 93.9% (analytical value by differential diffractometry) as a colorless liquid.

출처