반응 #80263

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Methyl 8-(N-Cbz-amino)-3-oxo-octanoate

methyl 8-(N-Cbz-amino)-3-oxo-octanoate

methanol

→

8-(N-Cbz-amino)-1,3-octanediol

수율 48.7%

용매

tetrahydrofuran

반응 조건

후처리

1. 1
   기타equipped with a magnetic stirbar
2. 2
   온도reflux condenser
3. 3
   workup.ADDITIONaddition funnel and nitrogen gas inlet
4. 4
   workup.ADDITIONwas cautiously added
5. 5
   온도The mixture was then heated
6. 6
   온도to reflux
7. 7
   workup.STIRRINGStirring
8. 8
   온도at reflux temperature for 60 minutes
9. 9
   workup.ADDITIONafter the addition
10. 10
    workup.DISTILLATIONdistilled water (78 mL)
11. 11
    workup.ADDITIONwas added
12. 12
    workup.ADDITION3N HCl was added to pH 3
13. 13
    기타The mixture was evaporated in vacuo
14. 14
    기타to remove the organic solvents, and solid potassium carbonate
15. 15
    workup.ADDITIONwas added
16. 16
    추출The mixture was then extracted with ethyl acetate (5×100 mL)
17. 17
    세척The extract was washed with saturated sodium chloride (2×50 mL)
18. 18
    건조dried over sodium sulfate
19. 19
    여과filtered
20. 20
    기타evaporated in vacuo
21. 21
    workup.DISSOLUTIONThe residue was dissolved in methanol (200 mL)
22. 22
    기타evaporated again
23. 23
    기타The residue was crystallized from ether (700 mL)

실험 절차

Methyl 8-(N-Cbz-amino)-3-oxo-octanoate (3, 51.5 g, 0.16 moles) was dissolved in anhydrous tetrahydrofuran (350 mL) in a reaction flask equipped with a magnetic stirbar, reflux condenser, pressure equalizing addition funnel and nitrogen gas inlet. While stirring the mixture under nitrogen sodium borohydride (15.1 g, 0.4 moles) was cautiously added. The mixture was then heated to reflux and methanol was added dropwise over 90 minutes. Stirring was continued at reflux temperature for 60 minutes after the addition was complete. After allowing the solution to cool to ambient temperature, distilled water (78 mL) was added and 3N HCl was added to pH 3. The mixture was evaporated in vacuo to remove the organic solvents, and solid potassium carbonate was added to adjust the pH back to 12. The mixture was then extracted with ethyl acetate (5×100 mL). The extract was washed with saturated sodium chloride (2×50 mL), dried over sodium sulfate, filtered and evaporated in vacuo. The residue was dissolved in methanol (200 mL) and evaporated again. This was repeated a total of five times. The residue was crystallized from ether (700 mL) giving 8-(N-Cbz-amino)-1,3-octanediol (4, 23 g). A second crop was collected on addition of cyclohexane (300 mL) to the mother liquor (6.8 g). Mass Spectrum: (M+H)+ (M+H)+ @m/z 296, (M+NH4)+ @m/z 313.

출처