Reaktion #64901

Reaktionsgleichung

water

sodium nitrate

5-Azaphenanthrene-1,10-dicarboxylic anhydride

sodium nitrate

→

nitro

Ausbeute 182.5%

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

Ausbeute 182.5%

Lösungsmittel

sulfuric acid

Reaktionsbedingungen

Aufarbeitung

1. 1
   Sonstigecaused about a 20° C.
2. 2
   Sonstigestabilizing again at about 65° C
3. 3
   TemperaturThe solution was heated for an additional 14 h
4. 4
   workup.ADDITIONafter the last addition
5. 5
   TemperaturThe clear orange solution was cooled to room temperature
6. 6
   Waschenwashing the residue from the reaction flask with water (5×40 mL)
7. 7
   Temperaturto cool to room temperature
8. 8
   SonstigeThe suspended solid was collected on a frit
9. 9
   Waschenwashed with water (2×50 mL)
10. 10
    Sonstigedried
11. 11
    TemperaturThis cream colored solid was heated
12. 12
    Temperaturat reflux in acetic acid (100 mL)
13. 13
    workup.ADDITIONcontaining acetic anhydride (10 mL) for 2 h
14. 14
    Temperaturcooled to room temperature
15. 15
    SonstigeThe solid was collected on a frit
16. 16
    Waschenwashed with acetic acid (25 mL) and ether (2×25 mL)
17. 17
    Sonstigedried

Vorschrift

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).

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