Nitric Acid → 2,3,8,9-Tetramethoxybenzo[i]phenanthridine

HRID 369758

Reaction equation

HRID 369758 reaction equation
[CH3:1][O:2][C:3]1[CH:4]=[C:5](Br)[C:6]([N+:11]([O-])=O)=[CH:7][C:8]=1[O:9][CH3:10].[CH3:15][O:16][C:17]1[CH:18]=[C:19](Br)[CH:20]=[CH:21][C:22]=1[O:23][CH3:24].[N+]([O-])(O)=O>C(O)(=O)C>[CH3:15][O:16][C:17]1[C:22]([O:23][CH3:24])=[CH:21][C:20]2[C:8]3[CH:7]=[N:11][C:6]4[CH:7]=[C:8]([O:9][CH3:10])[C:3]([O:2][CH3:1])=[CH:4][C:5]=4[C:3]=3[CH:4]=[CH:5][C:19]=2[CH:18]=1

Participants

5

Reactant 3

HCID 944Nitric AcidHCID 76114Benzene, 4-bromo-1,2-dimethoxy-HCID 1709684-Bromo-5-nitroveratrole2×

Product 1

HCID 98847232,3,8,9-Tetramethoxybenzo[i]phenanthridineYield 92%

Reagents, catalysts & solvents 1

HCID 176Acetic AcidSolvent

Conditions

Temperature
10 °C

Procedure

3,4-Dimethoxy-6-nitro-bromobenzene (16). 3,4-Dimethoxybromobenzene (5 g, 23 mmol) was slowly added to a stirred solution of 35 mL concentrated nitric acid and 105 mL glacial acetic acid maintained at 10° C. The reaction mixture was stirred at 15° C. for 1 h and then diluted with 200 mL ice cold water. The resulting mixture was extracted thrice with 200 mL portions of ether. The combined organic phase was dried and evaporated in vacuo. The crude product was recrystallized from ethanol to give bright yellow needle shaped crystals of compound 16 in 92% yield; mp=122-124° C.; IR (Nujol) 1510, 1312; 1H NMR δ 3.94 (3H, s), 3.97 (3H, s), 7.12 (1H, s), 7.57 (1H, s); 13C NMR δ 56.9, 57.2, 108.0, 109.5, 117.0, 148.7, 153.3; Anal. calcd for C8H8NO4Br: C, 36.72, H, 3.14, N, 5.30; Found: C, 36.70, H, 3.13, N, 5.29.

Workup

  1. extractionThe resulting mixture was extracted thrice with 200 mL portions of ether
  2. customThe combined organic phase was dried
  3. customevaporated in vacuo
  4. customThe crude product was recrystallized from ethanol
  5. customto give bright yellow needle

Sources & evidence

ORD record
ord-c1ca8439c99c47b08db926ebbb9216b9
Source dataset
uspto-grants-2000_10
Patent number
US06140328

Linked notes

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