Hydrochloric Acid → 3-Methoxy-8,9-methylenedioxydibenzo[c,h]cinnoline

HRID 1582892Notizen

Reaktionsgleichung

Reaktionsgleichung von HRID 1582892
[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:20]=[C:19]2[C:14]([CH:15]=[CH:16][C:17]([O:21][CH3:22])=[CH:18]2)=[CH:13][CH:12]=1.Cl.[N:24]([O-])=O.[Na+].O>C(O)(=O)C>[CH3:22][O:21][C:17]1[CH:16]=[CH:15][C:14]2=[CH:13][CH:12]=[C:11]3[C:20]([N:24]=[N:1][C:2]4[CH:7]=[C:6]5[O:8][CH2:9][O:10][C:5]5=[CH:4][C:3]3=4)=[C:19]2[CH:18]=1

Komponenten

6

Edukt 4

HCID 313Hydrochloric AcidHCID 962WaterHCID 227164427-(2-Amino-4,5-methylenedioxyphenyl)-2-methoxynaphthaleneHCID 23668193Sodium Nitrite

Produkt 1

HCID 98829143-Methoxy-8,9-methylenedioxydibenzo[c,h]cinnolineAusbeute 83 %

Reagenzien, Katalysatoren, Lösungsmittel 1

HCID 176Acetic AcidLösungsmittel

Versuchsvorschrift

7-(2-Amino-4,5-methylenedioxyphenyl)-2-methoxynaphthalene 49 (70 mg, 0.24 mmol) was dissolved in acetic acid (2.0 mL) and concentrated hydrochloric acid (0.4 mL). The solution was cooled in an ice bath and diazotized by the dropwise addition of a solution of sodium nitrite (0.16 g in 1.6 mL water). The resulting diazonium solution was allowed to warm slowly to room temperature and left overnight. To the resulting red solution containing some precipitate was added 50 mL water and the reaction mixture was extracted with ethyl acetate (30 mL×3). The organic layers were combined and washed with diluted sodium hydroxide solution first, then with water and brine. The organic layer was dried over anhydrous sodium sulfate and evaporated in vacuo. The crude product was purified by column chromatography on silica gel using 55:45 hexanes:ethyl acetate to give compound 44 (60 mg 83%); mp 259-261° C.; IR (KBr) 2923, 1612, 1498, 1468, 1234, 1199 cm−1; UV (MeOH) 270, 250, 228 nm (log ε=4.68, 4.37, 4.44); 1H NMR (CDCl3) δ4.12 (3H, s), 6.24 (2H, s), 7.37 (1H, dd, J1=8.8, J2=2.7), 7.80 (1H, s), 7.88 (1H, d, J=8.8), 7.96 (1H, s), 8.03 (1H, d, J=9.1), 8.09 (1H, d, J=9.0), 9.15 (1H, d, J=2.7); 13C NMR δ56.32, 98.31, 102.93, 104.03, 107.49, 116.36, 120.40, 120.50, 121.09, 127.96, 130.00, 132.54, 133.34, 141.99, 146.10, 150.53, 152.09, 160.28; HRMS (EI) calcd for C18H12N2O3 m/z: 304.0848; found: 304.0852.

Aufarbeitung

  1. temperatureThe solution was cooled in an ice bath
  2. additionTo the resulting red solution containing some precipitate
  3. extractionthe reaction mixture was extracted with ethyl acetate (30 mL×3)
  4. washwashed with diluted sodium hydroxide solution first
  5. dry with materialThe organic layer was dried over anhydrous sodium sulfate
  6. customevaporated in vacuo
  7. customThe crude product was purified by column chromatography on silica gel using 55:45 hexanes

Quellen und Nachweise

ORD-Eintrag
ord-c0e5bef820424966a7d21d755aba904c
Quelldatensatz
uspto-grants-2004_05
Patentnummer
US06740650B2

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