Water → 2,3-Dimethoxy-8,9-methylenedioxy-dibenzo[c,h]cinnoline

HRID 1582871Notes

Reaction equation

HRID 1582871 reaction equation
[NH2:1][C:2]1[CH:7]=[C:6]2[O:8][CH2:9][O:10][C:5]2=[CH:4][C:3]=1[C:11]1[CH:12]=[C:13]2[C:18](=[CH:19][CH:20]=1)[CH:17]=[C:16]([O:21][CH3:22])[C:15]([O:23][CH3:24])=[CH:14]2.[N:25]([O-])=O.[Na+].O.C(OCC)(=O)C>C(O)(=O)C.Cl>[CH3:22][O:21][C:16]1[C:15]([O:23][CH3:24])=[CH:14][C:13]2[C:18]([CH:17]=1)=[CH:19][CH:20]=[C:11]1[C:12]=2[N:25]=[N:1][C:2]2[CH:7]=[C:6]3[O:8][CH2:9][O:10][C:5]3=[CH:4][C:3]1=2

Participants

7

Reactant 4

HCID 962WaterHCID 8857Ethyl AcetateHCID 227164376-(2-Amino-4,5-methylenedioxyphenyl)-2,3-dimethoxy-naphthaleneHCID 23668193Sodium Nitrite

Product 1

HCID 99057072,3-Dimethoxy-8,9-methylenedioxy-dibenzo[c,h]cinnolineYield 50%

Reagents, catalysts & solvents 2

HCID 176Acetic AcidSolventHCID 313Hydrochloric AcidSolvent

Procedure

6-(2-Amino-4,5-methylenedioxyphenyl)-2,3-dimethoxy-naphthalene (13, 40 mg, 0.13 mmol) in acetic acid (2 mL) and concentrated hydrochloric acid (0.3 mL) was cooled to 0° C. and diazotised with a solution of sodium nitrite (0.09 g in 1.5 mL water). The diazonium solution was allowed to rise slowly to room temperature and left overnight. Water (50 mL) was added to the red solution with some precipitate. The resulting mixture was extracted with ethyl acetate, washed with diluted sodium hydroxide solution, then with water, dried (anhydrous Na2SO4) and rotaevaporated to give the crude product. Chromatography on silica gel using 40:60 hexanes:ethyl acetate afforded the title compound (20 mg) in 50% yield; 1H NMR (CDCl3) d 4.09(3H, s), 4.22(3H, s), 6.24(2H, s), 7.31(1H, s), 7.80(1H s), 7.95(1H, s), 8.00(1H, d, J=9.2), 8.13(1H, d, J=8.9), 9.14(1H, s); 13C NMR d 56.5 56.9, 98.1, 102.9, 104.6, 107.5, 107.9, 117.1, 119.6, 120.6, 126.8, 128.5, 131.7, 141.9, 145.6, 150.2, 151.2, 152.1.

Workup

  1. customto rise slowly to room temperature
  2. extractionThe resulting mixture was extracted with ethyl acetate
  3. washwashed with diluted sodium hydroxide solution
  4. dry with materialwith water, dried (anhydrous Na2SO4)
  5. customto give the crude product

Sources & evidence

ORD record
ord-fec3dca9695c4b5bb0a64db93ce728f7
Source dataset
uspto-grants-2004_05
Patent number
US06740650B2

Reaction notes

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