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1,8-Diazabicyclo(5.4.0)undec-7-ene → 6-bromo-2-(4-methoxybenzyl)-4-phenyl-3-propionyl-2H-isoquinolin-1-one

HRID 750356
ノート
印刷プレビュー

反応式

HRID 750356 の反応式
[C:1]([C:9]1[CH:31]=[C:30]([Br:32])[CH:29]=[CH:28][C:10]=1[C:11]([N:13]([CH2:19][C:20]1[CH:25]=[CH:24][C:23]([O:26][CH3:27])=[CH:22][CH:21]=1)[CH2:14][C:15](=[O:18])[CH2:16][CH3:17])=[O:12])(=O)[C:2]1[CH:7]=[CH:6][CH:5]=[CH:4][CH:3]=1.C1CCN2C(=NCCC2)CC1>C(O)C>[Br:32][C:30]1[CH:31]=[C:9]2[C:10](=[CH:28][CH:29]=1)[C:11](=[O:12])[N:13]([CH2:19][C:20]1[CH:21]=[CH:22][C:23]([O:26][CH3:27])=[CH:24][CH:25]=1)[C:14]([C:15](=[O:18])[CH2:16][CH3:17])=[C:1]2[C:2]1[CH:3]=[CH:4][CH:5]=[CH:6][CH:7]=1
参加物反応条件実験手順後処理出典と根拠反応ノート

参加物

4

反応物 2

HCID 811841,8-Diazabicyclo(5.4.0)undec-7-eneHCID 230608222-benzoyl-4-bromo-N-(4-methoxybenzyl)-N-(2-oxobutyl)benzamide

生成物 1

HCID 230607556-bromo-2-(4-methoxybenzyl)-4-phenyl-3-propionyl-2H-isoquinolin-1-one収率 63.9%

試薬・触媒・溶媒 1

HCID 702Ethanol溶媒

反応条件

温度
90 °C

実験手順

[Step 1] To a solution of 1-amino-2-butanol (3.9 g) in methanol (50 ml) was added anisaldehyde (5.0 g) under ice-cooling. The mixture was stirred at the same temperature for 1 hr., and a solution of sodium borohydride (1.1 g) in 1N sodium hydroxide (17 ml) was added dropwise. The mixture was stirred at 0° C. for 30 min, 2N hydrochloric acid (68 ml) was added dropwise and diisopropyl ether was added to allow partitioning. The aqueous layer was alkalified with potassium carbonate (12.1 g) and ethyl acetate was added to allow partitioning. The ethyl acetate layer was washed with saturated brine, dried over magnesium sulfate, and concentrated under reduced pressure to give 1-(4-methoxybenzylamino)butan-2-ol (5.4 g) as a brown oil. [Step 2] To a mixture of 2-benzoyl-4-bromobenzoic acid (7.5 g), 1-(4-methoxybenzylamino)butan-2-ol (5.4 g) and acetonitrile (100 ml) were added 1-hydroxy-1H-benzotriazole monohydrate (4.3 g) and 1-ethyl-3-(3-dimethylaminopropyl)carbodiimide hydrochloride (5.9 g) at room temperature and the mixture was stirred at the same temperature for 18 hrs. The solvent was evaporated under reduced pressure, and the residue was diluted with ethyl acetate. This solution was washed with 1N hydrochloric acid and saturated aqueous sodium hydrogen carbonate solution, dried over magnesium sulfate and concentrated under reduced pressure. The residue was purified by silica gel chromatography (hexane/ethyl acetate=5/1-2/3) to give 2-benzoyl-4-bromo-N-(2-hydroxybutyl)-N-(4-methoxybenzyl)benzamide (3.2 g) as a colorless powder. [Step 3] To a mixture of 2-benzoyl-4-bromo-N-(2-hydroxybutyl)-N-(4-methoxybenzyl)benzamide (3.2 g), 4-methylmorpholine N-oxide (2.3 g), molecular sieves 4A powder (1.6 g) and dichloromethane (50 ml) was added tetra-n-propylammonium perruthenate (0.23 g) under ice-cooling, and the mixture was stirred at room temperature for 3 hrs. After the completion of the reaction, molecular sieves 4 A was removed by filtration and the filtrate was concentrated under reduced pressure. The residue was purified by silica gel column chromatography (hexane/ethyl acetate=3/2) to give 2-benzoyl-4-bromo-N-(4-methoxybenzyl)-N-(2-oxobutyl)benzamide (2.6 g). [Step 4] To a solution of 2-benzoyl-4-bromo-N-(4-methoxybenzyl)-N-(2-oxobutyl)benzamide (2.6 g) in ethanol (52 ml) was added 1,8-diazabicyclo[5.4.0]-7-undecene (2.7 ml) and the mixture was stirred at 90° C. for 18 hrs. After cooling the reaction mixture, the solvent was evaporated under reduced pressure, ethyl acetate was added to the residue, and the mixture was washed with 1N hydrochloric acid. The organic layer was dried over magnesium sulfate and concentrated under reduced pressure. The residue was purified by medium pressure preparative LC (hexane/ethyl acetate=5/1-1/1), and crystallized from hexane/ethyl acetate=3/1 to give the title compound (1.6 g) as colorless crystals. 1H NMR (CDCl3) δ: 0.43 (3H, t, J=6.9 Hz), 1.46 (2H, q, J=6.9 Hz), 3.75 (3H, s), 5.34 (2H, s), 6.80 (2H, d, J=8.7 Hz), 7.11 (2H, d, J=8.7 Hz), 7.22-7.28 (2H, m), 7.40-7.48 (4H, m), 7.66 (1H, dd, J=1.8, 8.4 Hz), 8.43 (1H, d, J=8.4 Hz). HPLC analysis: purity 99.2% (retention time: 5.16 min). MS (ESI+): 476 (M+H), 478.

後処理

  1. temperatureAfter cooling the reaction mixture
  2. customthe solvent was evaporated under reduced pressure, ethyl acetate
  3. additionwas added to the residue
  4. washthe mixture was washed with 1N hydrochloric acid
  5. dry with materialThe organic layer was dried over magnesium sulfate
  6. concentrationconcentrated under reduced pressure
  7. customThe residue was purified by medium pressure preparative LC (hexane/ethyl acetate=5/1-1/1)
  8. customcrystallized from hexane/ethyl acetate=3/1

出典と根拠

ORDレコード
ord-18e00eda39fe430fa17b8696ef5349b0
出典データセット
uspto-grants-2008_07
DOI
10.6084/m9.figshare.5104873.v1
特許番号
US07402595B2

反応ノート

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