반응 #64901

반응 방정식

water

sodium nitrate

5-Azaphenanthrene-1,10-dicarboxylic anhydride

sodium nitrate

→

nitro

수율 182.5%

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

수율 182.5%

용매

sulfuric acid

반응 조건

후처리

1. 1
   기타caused about a 20° C.
2. 2
   기타stabilizing again at about 65° C
3. 3
   온도The solution was heated for an additional 14 h
4. 4
   workup.ADDITIONafter the last addition
5. 5
   온도The clear orange solution was cooled to room temperature
6. 6
   세척washing the residue from the reaction flask with water (5×40 mL)
7. 7
   온도to cool to room temperature
8. 8
   기타The suspended solid was collected on a frit
9. 9
   세척washed with water (2×50 mL)
10. 10
    기타dried
11. 11
    온도This cream colored solid was heated
12. 12
    온도at reflux in acetic acid (100 mL)
13. 13
    workup.ADDITIONcontaining acetic anhydride (10 mL) for 2 h
14. 14
    온도cooled to room temperature
15. 15
    기타The solid was collected on a frit
16. 16
    세척washed with acetic acid (25 mL) and ether (2×25 mL)
17. 17
    기타dried

실험 절차

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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