반응 #1244265

반응 방정식

HCl

4-(Azidomethyl)-2,2-dimethyl-1,3-dioxolane

water

TsCl

→

14

수율 49.0%

3-Azido-2-hydroxypropyl 4-methylbenzenesulfonate

수율 49.0%

용매

diethyl ether

methanol

반응 조건

후처리

1. 1
   농축concentrated under reduced pressure
2. 2
   기타to afford a yellow oil which
3. 3
   기타was used for the next step without purification
4. 4
   기타After drying for 0.5 hr
5. 5
   workup.DISSOLUTIONthe residue was dissolved in CH2Cl2 (30 mL)
6. 6
   workup.ADDITIONwas treated with Bu2SnO (0.071 mg, 0.3 mmol)
7. 7
   workup.STIRRINGAfter stirring for 3 hr at room temperature
8. 8
   기타the organic layer was separated
9. 9
   추출The aqueous layer was extracted with CH2Cl2 (2×50 mL)
10. 10
    세척the organic layer was consecutively washed with H2O (50 mL) and brine (50 mL)
11. 11
    건조dried over MgSO4
12. 12
    기타The solvent was removed under vacuum
13. 13
    기타the residue was purified on silica gel using 33% EtOAc/hexanes as the eluent

실험 절차

4-(Azidomethyl)-2,2-dimethyl-1,3-dioxolane 13 (2.2 g, 13.99 mmol) was dissolved in methanol (25 mL). To this solution was added a solution of HCl in diethyl ether (2M, 5 mL) at 0° C. The mixture was stirred at room temperature overnight, and then concentrated under reduced pressure to afford a yellow oil which was used for the next step without purification. After drying for 0.5 hr, the residue was dissolved in CH2Cl2 (30 mL) and was treated with Bu2SnO (0.071 mg, 0.3 mmol), followed by TsCl (2.86 g, 15.0 mmol) and TEA (2.2 mL, 16 mmol). After stirring for 3 hr at room temperature, water (30 mL) was added and the organic layer was separated. The aqueous layer was extracted with CH2Cl2 (2×50 mL) and the organic layer was consecutively washed with H2O (50 mL) and brine (50 mL) and dried over MgSO4. The solvent was removed under vacuum and the residue was purified on silica gel using 33% EtOAc/hexanes as the eluent to afford 1.86 g of 14 (48% yield) as a clear, colorless oil. 1H NMR (CDCl3, 400 MHz) δ: 7.77 (d, J=8.0 Hz, 2H), 7.34 (d, J=8.0 Hz, 2H), 3.96-4.09 (m, 3H), 3.31-3.40 (m, 2H), 2.43 (s, 3H). Mass Spec (lo-res): Calc'd for C10H13N3O4S: 271.06. found: 294.1 (M+Na+).

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