反应详情

3,6,9,12-tetraoxapentadec-14-yn-1-amine 7 (1.0 g, 4.3 mmol, 1 equiv.) was dissolved in EtOH (18 mL), and triethylamine (1.68 mL, 8.6 mmol, 2 equiv.) and 1-chloro-2,4-dinitrobenzene (876 mg, 4.3 mmol, 1 equiv.) were added. The reaction flask was fitted with a reflux condenser and the reaction was heated to reflux for 2 h, cooled, and concentrated to a crude yellow oil. The crude mixture was re-dissolved in H2O (25 mL) and extracted with CH2Cl2 (5×10 mL). Organic layers were dried over Na2SO4 and concentrated to a yellow oil that was purified by flash chromatography (CombiFlash Automated Chromatographer, 25 g column, dryloaded with 25 g pre-packed dry loading column. Run using 10% EtOAc:Hexanes to 50% EtOAc:Hexanes gradient over 30 column volumes, followed by EtOAc flush) to yield 2 as a yellow solid (1.70 g, >98% yield). IR (thin film/NaCl) 3360(m), 3290 (m), 3110 (w), 2873 (m), 2114(w), 1621 (s), 1588 (m), 1336 (s), 1134 (m) cm−1; 1H-NMR (500 MHz, CDCl3) δ 9.13 (d, 1H, J=2.6 Hz), 8.80 (broad peak, 1H), 8.25 (dd, 1H, J=2.6, J=9.5 Hz), 6.94 (d, 1H, J=9.5 Hz), 4.18 (m, 2H), 3.83 (t, 2H, J=5.2 Hz), 3.67 (m, 12H), 3.60 (q, 2H), 2.41 (m, 1H); 13C-NMR (125 MHz, CDCl3) δ 148.6, 136.2, 130.4, 124.4, 114.3, 79.8, 74.7, 70.8, 70.7, 70.5, 69.2, 68.7, 58.5, 43.4; HRMS (EI) calc'd for C17H23N3O8 (MH+) m/z 398.1558. Found 398.1557.

1. customThe reaction flask was fitted with a reflux condenser
2. temperaturethe reaction was heated
3. temperatureto reflux for 2 h
4. temperaturecooled
5. concentrationconcentrated to a crude yellow oil
6. dissolutionThe crude mixture was re-dissolved in H2O (25 mL)
7. extractionextracted with CH2Cl2 (5×10 mL)
8. dry with materialOrganic layers were dried over Na2SO4
9. concentrationconcentrated to a yellow oil that
10. customwas purified by flash chromatography (CombiFlash Automated Chromatographer, 25 g column
11. customflush)