Ethyl chloroformate → carbonic acid 9-benzhydryloxy-7-(2,4-dimethoxy-benzyl)-6,8-dioxo-7,8-dihydro-6H-pyrrolo [3,4-g]quinolin-5-yl ester ethyl ester

HRID 853698

反応式

HRID 853698 の反応式
[CH3:1][O:2][C:3]1[CH:26]=[C:25]([O:27][CH3:28])[CH:24]=[CH:23][C:4]=1[CH2:5][N:6]1[C:18](=[O:19])[C:17]2[C:16]([OH:20])=[C:15]3[C:10]([CH:11]=[CH:12][CH:13]=[N:14]3)=[C:9]([OH:21])[C:8]=2[C:7]1=[O:22].[OH-].[Na+].[CH2:31]([O:33][C:34](Cl)=[O:35])[CH3:32].[C:37]1([CH:43]([C:46]2[CH:51]=[CH:50][CH:49]=[CH:48][CH:47]=2)[N+]#N)[CH:42]=[CH:41][CH:40]=[CH:39][CH:38]=1>O1CCOCC1.ClCCl.O>[CH2:31]([O:33][C:34](=[O:35])[O:21][C:9]1[C:8]2[C:7](=[O:22])[N:6]([CH2:5][C:4]3[CH:23]=[CH:24][C:25]([O:27][CH3:28])=[CH:26][C:3]=3[O:2][CH3:1])[C:18](=[O:19])[C:17]=2[C:16]([O:20][CH:43]([C:37]2[CH:42]=[CH:41][CH:40]=[CH:39][CH:38]=2)[C:46]2[CH:51]=[CH:50][CH:49]=[CH:48][CH:47]=2)=[C:15]2[C:10]=1[CH:11]=[CH:12][CH:13]=[N:14]2)[CH3:32]

参加物

8

反応物 4

HCID 10928Ethyl chloroformate2 回HCID 14798Sodium HydroxideHCID 58928810Diphenyl-methanediazoniumHCID 178490840HCID 178490840、化合物

生成物 1

HCID 58928675carbonic acid 9-benzhydryloxy-7-(2,4-dimethoxy-benzyl)-6,8-dioxo-7,8-dihydro-6H-pyrrolo [3,4-g]quinolin-5-yl ester ethyl ester収率 66%

試薬・触媒・溶媒 3

HCID 962Water溶媒HCID 6344Dichloromethane溶媒HCID 312751,4-Dioxane溶媒2 回

反応条件

温度
0 °C

実験手順

7-(2,4-Dimethoxy-benzyl)-5,9-dihydroxy-pyrrolo[3,4-g]quinoline-6,8-dione 300 (1.1 g, 2.9 mmol) was dissolved in dioxane (14.5 ml) and H2O (9.7 ml) and cooled to 0° C. To this reaction mixture was added 1.0 M NaOH (5.8 ml, 5.8 mmol), followed by ethylchloroformate (347.3 mg, 3.2 mmol). After stirring at 0° C. for 30 minutes, dioxane (10 ml) and ethylchloroformate (51 mg, 0.5 mmol) were added and the reaction stirred for another 30 minutes at 0° C. The reaction mixture was quenched with the addition of acetic acid (0.6 ml) and concentrated in vacuo. The crude mixture was diluted with ethyl acetate and washed once with 5% citric Acid (aqueous), twice with water, once with brine, and dried over magnesium sulfate. The resulting residue was dissolved in 1,2-dichloroethane (30 ml) and diphenyl-methanediazonium 38 (diphenyldiazomethane, 1.1 g, 5.6 mmol) was added. The reaction mixture was then stirred overnight at room temperature. Following dilution with dichloromethane, the reaction mixture was washed with once with water, once with brine, dried over magnesium sulfate, and concentrated in vacuo. The residue was purified by silica gel chromatography (1/1-Hexanes/Ethyl Acetate) to afford carbonic acid 9-benzhydryloxy-7-(2,4-dimethoxy-benzyl)-6,8-dioxo-7,8-dihydro-6H-pyrrolo [3,4-g]quinolin-5-yl ester ethyl ester 301 (1.2 g, 1.9 mmol, 66%). 1H NMR (CDCl3) δ 9.10 (dd, 1H), 8.40 (dd, 1H), 7.95 (s, 1H), 7.68 (m, 1H), 7.60 (d, 4H), 7.15 (m, 6H), 7.0 (d, 1H), 6.40 (d, 1H), 6.36 (d, 1H), 4.80 (s, 2H), 4.35 (q, 2H), 3.75 (s, 3H), 3.73 (s, 3H), 1.31 (t, 3H). MS: 641.2 (M+23).

後処理

  1. stirringthe reaction stirred for another 30 minutes at 0° C
  2. customThe reaction mixture was quenched with the addition of acetic acid (0.6 ml)
  3. concentrationconcentrated in vacuo
  4. additionThe crude mixture was diluted with ethyl acetate
  5. washwashed once with 5% citric Acid (aqueous), twice with water, once with brine
  6. dry with materialdried over magnesium sulfate
  7. dissolutionThe resulting residue was dissolved in 1,2-dichloroethane (30 ml)
  8. stirringThe reaction mixture was then stirred overnight at room temperature
  9. washthe reaction mixture was washed with once with water
  10. dry with materialonce with brine, dried over magnesium sulfate
  11. concentrationconcentrated in vacuo
  12. customThe residue was purified by silica gel chromatography (1/1-Hexanes/Ethyl Acetate)

出典と根拠

ORDレコード
ord-9c31d31a39204a35a44349ec9861fc9b
出典データセット
uspto-grants-2007_08
特許番号
US07253180B2

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