반응 #50705

반응 방정식

KOH

nitrile

1-(benzoyloxymethyl)cyclopropaneacetonitrile

diazomethane

Et2O

→

title compound

수율 50.0%

Methyl 1-(hydroxymethyl)cyclopropaneacetate

수율 50.0%

용매

ethanol

hexane

반응 조건

후처리

1. 1
   온도the reaction mixture was heated
2. 2
   온도to reflux overnight
3. 3
   기타Most of the ethanol was evaporated
4. 4
   workup.ADDITIONice was added to the mixture
5. 5
   workup.ADDITIONConcentrated HCl was added (600 mL) dropwise at 0° C. (
6. 6
   추출The acid was then extracted with EtOAc two times
7. 7
   세척the organic phases were washed 2 times with brine
8. 8
   건조dried over Na2SO4
9. 9
   기타The solvent was evaporated
10. 10
    workup.DISSOLUTIONthe solid was dissolved in THF (500 mL)
11. 11
    기타The solvent was evaporated
12. 12
    기타the residual oil was purified by flash chromatography

실험 절차

The nitrile of Step 3 (0.388 mol) was dissolved in ethanol (400 mL), 8N KOH (800 mL) was added and the reaction mixture was heated to reflux overnight. Most of the ethanol was evaporated and ice was added to the mixture. Concentrated HCl was added (600 mL) dropwise at 0° C. (without warming over 10° C. inside the solution) until obtention of pH approx. 1. The acid was then extracted with EtOAc two times and the organic phases were washed 2 times with brine and dried over Na2SO4. The solvent was evaporated and the solid was dissolved in THF (500 mL). A solution of diazomethane in Et2O (about 1.7 L, 0.85 mol) was added at 0° C. until the yellow color remained and no more acid could be seen by TLC. The solvent was evaporated and the residual oil was purified by flash chromatography using 1:1 to 2:1 EtOAc:hexane to yield 28.2 g, (50% yield) of the title compound. 1H NMR (CDCl3) δ0.55 (4H, m), 2.45 (2H, s), 2.55 (1H, t), 3.5 (2H, d), 3.70 (3H, s).

출처