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

HRID 1582892ノート

反応式

HRID 1582892 の反応式
[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

参加物

6

反応物 4

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

生成物 1

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

試薬・触媒・溶媒 1

HCID 176Acetic Acid溶媒

実験手順

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.

後処理

  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

出典と根拠

ORDレコード
ord-c0e5bef820424966a7d21d755aba904c
出典データセット
uspto-grants-2004_05
特許番号
US06740650B2

反応ノート

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