反应 #64901

反应方程式

water

sodium nitrate

5-Azaphenanthrene-1,10-dicarboxylic anhydride

sodium nitrate

→

nitro

收率 182.5%

3-Nitro-5-azaphenanthrene-1,10-dicarboxylic Anhydride

收率 182.5%

溶剂

sulfuric acid

反应条件

后处理

1. 1
   其他caused about a 20° C.
2. 2
   其他stabilizing again at about 65° C
3. 3
   温度The solution was heated for an additional 14 h
4. 4
   workup.ADDITIONafter the last addition
5. 5
   温度The clear orange solution was cooled to room temperature
6. 6
   洗涤washing the residue from the reaction flask with water (5×40 mL)
7. 7
   温度to cool to room temperature
8. 8
   其他The suspended solid was collected on a frit
9. 9
   洗涤washed with water (2×50 mL)
10. 10
    其他dried
11. 11
    温度This cream colored solid was heated
12. 12
    温度at reflux in acetic acid (100 mL)
13. 13
    workup.ADDITIONcontaining acetic anhydride (10 mL) for 2 h
14. 14
    温度cooled to room temperature
15. 15
    其他The solid was collected on a frit
16. 16
    洗涤washed with acetic acid (25 mL) and ether (2×25 mL)
17. 17
    其他dried

实验过程

5-Azaphenanthrene-1,10-dicarboxylic anhydride (17.0 g, 68.2 mmol) was dissolved in concentrated sulfuric acid (70 mL) and sodium nitrate (2.90 g, 34.1 mmol) was added to the warm solution. This mixture was heated to 65° C. and three additional aliquots of sodium nitrate (2.90 g, 34.1 mmol) were added after 5, 22, and 30 h. Each aliquot caused about a 20° C. temperature rise, with the temperature stabilizing again at about 65° C. The solution was heated for an additional 14 h after the last addition. The clear orange solution was cooled to room temperature and poured into water (500 mL), washing the residue from the reaction flask with water (5×40 mL). The aqueous suspension was allowed to cool to room temperature. The suspended solid was collected on a frit, washed with water (2×50 mL), and dried. This cream colored solid was heated at reflux in acetic acid (100 mL) containing acetic anhydride (10 mL) for 2 h and cooled to room temperature. The solid was collected on a frit, washed with acetic acid (25 mL) and ether (2×25 mL), and dried to give 18.31 g (91%) of the nitro compound as a cream colored solid: mp 268°-269° C.; 1H NMR (DMSO-d6, 300 MHz) δ 8.05 (dd, 1H, J=8.0, 4.4 Hz), 8.97 (dd, 1H, J=8.0, 1.5 Hz), 9.11 (d, 1H, J=2.2 Hz), 9.33-9.40 (m, 2H), 10.16 (d, 1H, J=2.2 Hz); MS (CI, CH4) m/e (%) 295 (M+H+, 100), 265 (6), 250 (5).

来源