Hydrochloric Acid → 3-Azido-2-hydroxypropyl 4-methylbenzene-1-sulfonate

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+).

1. concentrationconcentrated under reduced pressure
2. customto afford a yellow oil which
3. customwas used for the next step without purification
4. customAfter drying for 0.5 hr
5. dissolutionthe residue was dissolved in CH2Cl2 (30 mL)
6. additionwas treated with Bu2SnO (0.071 mg, 0.3 mmol)
7. stirringAfter stirring for 3 hr at room temperature
8. customthe organic layer was separated
9. extractionThe aqueous layer was extracted with CH2Cl2 (2×50 mL)
10. washthe organic layer was consecutively washed with H2O (50 mL) and brine (50 mL)
11. dry with materialdried over MgSO4
12. customThe solvent was removed under vacuum
13. customthe residue was purified on silica gel using 33% EtOAc/hexanes as the eluent

ORD-Eintrag

ord-6efb7480e095427484b46922b5eaf57a

Quelldatensatz

uspto-grants-2011_07

DOI

10.6084/m9.figshare.5104873.v1

Patentnummer

US07977361B2