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

HRID 36623

反応式

HRID 36623 の反応式
[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]

参加物

5

反応物 3

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

生成物 1

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

試薬・触媒・溶媒 1

HCID 1118Sulfuric Acid溶媒

反応条件

温度
65 °C

実験手順

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).

後処理

  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

出典と根拠

ORDレコード
ord-9ce3c8a41f8e488399ebd1ee2d303c9d
出典データセット
uspto-grants-1995_05
特許番号
US05416089

関連ノート

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