反应详情

To a stirred solution of (S)-2-(N-tert-butoxycarbonylamino)-1-propanol (0.90 g, 5.13 mmol), methyl 4-hydroxy-3-nitrobenzoate (1.01 g, 5.12 mmol), and Ph3P (1.75 g, 6.67 mmol) in THF (15 mL) was added diisopropyl azodicarboxylate (DIAD) (1.31 mL, 6.65 mmol) at room temp, and the resulting mixture was heated under reflux overnight. The solution was evaporated and the residue was dissolved in CH2Cl2 (20 mL) and TFA (10 mL). The mixture was stirred at room temp for 3 hr. The mixture was concentrated in vacuo. The residue was dissolved in CHCl3, washed with sat. NaHCO3, brine, dried over Na2SO4 and evaporated. The residue was purified by column chromatography on silica-gel with 5% MeOH in CHCl3 as eluent to give 313 mg (24%) methyl(S)-3-nitro-4-(2-amino-1-propoxy)benzoate as a pale yellow oil. 1H-NMR (CDCl3) δ 1.22 (d, 3 H, J=6.8 Hz), 3.43–3.48 (m, 1 H), 3.69–3.87 (m, 2 H), 3.89 (s, 3 H), 6.93–6.95 (m, 1 H), 7.99–8.02 (m, 1 H), 8.18–8.21 (m, 1 H).

1. temperaturethe resulting mixture was heated
2. temperatureunder reflux overnight
3. customThe solution was evaporated
4. dissolutionthe residue was dissolved in CH2Cl2 (20 mL)
5. concentrationThe mixture was concentrated in vacuo
6. dissolutionThe residue was dissolved in CHCl3
7. washwashed with sat. NaHCO3, brine
8. dry with materialdried over Na2SO4
9. customevaporated
10. customThe residue was purified by column chromatography on silica-gel with 5% MeOH in CHCl3 as eluent