反应 #1244265

反应方程式

HCl

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

water

TsCl

→

14

收率 49.0%

3-Azido-2-hydroxypropyl 4-methylbenzenesulfonate

收率 49.0%

溶剂

diethyl ether

methanol

反应条件

后处理

1. 1
   浓缩concentrated under reduced pressure
2. 2
   其他to afford a yellow oil which
3. 3
   其他was used for the next step without purification
4. 4
   其他After 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
   其他the organic layer was separated
9. 9
   萃取The aqueous layer was extracted with CH2Cl2 (2×50 mL)
10. 10
    洗涤the organic layer was consecutively washed with H2O (50 mL) and brine (50 mL)
11. 11
    干燥dried over MgSO4
12. 12
    其他The solvent was removed under vacuum
13. 13
    其他the residue was purified on silica gel using 33% EtOAc/hexanes as the eluent

实验过程

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+).

来源