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

HRID 36623

Reaction equation

HRID 36623 reaction equation
[C:1]12[C:18](=[O:19])[O:17][C:15](=[O:16])[C:13]3[C:14]1=[C:5]([C:6]1[C:11]([CH:12]=3)=[CH:10][CH:9]=[CH:8][N:7]=1)[CH:4]=[CH:3][CH:2]=2.[N+:20]([O-])([O-:22])=[O:21].[Na+].O>S(=O)(=O)(O)O>[N+:20]([C:3]1[CH:2]=[C:1]2[C:18](=[O:19])[O:17][C:15](=[O:16])[C:13]3=[CH:12][C:11]4[C:6]([C:5]([CH:4]=1)=[C:14]23)=[N:7][CH:8]=[CH:9][CH:10]=4)([O-:22])=[O:21]

Participants

5

Reactant 3

HCID 962WaterHCID 24268Sodium Nitrate2×HCID 106343315-Azaphenanthrene-1,10-dicarboxylic anhydride

Product 1

HCID 152918203-Nitro-5-azaphenanthrene-1,10-dicarboxylic AnhydrideYield 182.5%

Reagents, catalysts & solvents 1

HCID 1118Sulfuric AcidSolvent

Conditions

Temperature
65 °C

Procedure

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).

Workup

  1. customcaused about a 20° C.
  2. customstabilizing again at about 65° C
  3. temperatureThe solution was heated for an additional 14 h
  4. additionafter the last addition
  5. temperatureThe clear orange solution was cooled to room temperature
  6. washwashing the residue from the reaction flask with water (5×40 mL)
  7. temperatureto cool to room temperature
  8. customThe suspended solid was collected on a frit
  9. washwashed with water (2×50 mL)
  10. customdried
  11. temperatureThis cream colored solid was heated
  12. temperatureat reflux in acetic acid (100 mL)
  13. additioncontaining acetic anhydride (10 mL) for 2 h
  14. temperaturecooled to room temperature
  15. customThe solid was collected on a frit
  16. washwashed with acetic acid (25 mL) and ether (2×25 mL)
  17. customdried

Sources & evidence

ORD record
ord-9ce3c8a41f8e488399ebd1ee2d303c9d
Source dataset
uspto-grants-1995_05
Patent number
US05416089

Linked notes

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