Sodium methanethiolate → 6-benzyloxy-N-[5-(methylthio)pentyl]-3-nitroquinolin-4-amine

HRID 598317ノート

反応式

HRID 598317 の反応式
[CH3:1][S-:2].[Na+].[CH2:4]([O:11][C:12]1[CH:13]=[C:14]2[C:19](=[CH:20][CH:21]=1)[N:18]=[CH:17][C:16]([N+:22]([O-:24])=[O:23])=[C:15]2[NH:25][CH2:26][CH2:27][CH2:28][CH2:29][CH2:30]Cl)[C:5]1[CH:10]=[CH:9][CH:8]=[CH:7][CH:6]=1>CN(C=O)C>[CH2:4]([O:11][C:12]1[CH:13]=[C:14]2[C:19](=[CH:20][CH:21]=1)[N:18]=[CH:17][C:16]([N+:22]([O-:24])=[O:23])=[C:15]2[NH:25][CH2:26][CH2:27][CH2:28][CH2:29][CH2:30][S:2][CH3:1])[C:5]1[CH:10]=[CH:9][CH:8]=[CH:7][CH:6]=1

参加物

4

反応物 2

HCID 4378561Sodium methanethiolate2 回HCID 670510456-benzyloxy-N-(5-chloropentyl)-3-nitroquinolin-4-amine

生成物 1

HCID 670510536-benzyloxy-N-[5-(methylthio)pentyl]-3-nitroquinolin-4-amine収率 79.4%

試薬・触媒・溶媒 1

HCID 6228Dimethylformamide溶媒2 回

実験手順

Under a nitrogen atmosphere, solid sodium thiomethoxide (1.38 g, 18.7 mmol, 95% pure) was added to a solution of 6-benzyloxy-N-(5-chloropentyl)-3-nitroquinolin-4-amine (6.24 g, 15.6 mmol) in DMF. The reaction was stirred at ambient temperature for 30 minutes and then heated at 80° C. for one hour, at which time a yellow precipitate formed. The reaction mixture was partitioned between water (390 mL) and dichloromethane (150 mL). The aqueous layer was washed with dichloromethane (100 mL), and the combined organic fractions were washed with saturated aqueous sodium bicarbonate (100 mL) and brine (100 mL), dried over sodium sulfate, filtered, and concentrated under reduced pressure to provide a red oil. An analysis by nuclear magnetic resonance spectroscopy indicated the presence of a large amount of starting material. The reaction product was dissolved in DMF (78 mL), treated with sodium thiomethoxide, and heated at reflux for two hours. The work-up described above was repeated, and the crude product was purified by column chromatography on silica gel (eluting with 70:30 ethyl acetate:hexane) to provide 5.1 g of 6-benzyloxy-N-[5-(methylthio)pentyl]-3-nitroquinolin-4-amine as a yellow oil.

後処理

  1. temperatureheated at 80° C. for one hour, at which time a yellow precipitate
  2. customformed
  3. customThe reaction mixture was partitioned between water (390 mL) and dichloromethane (150 mL)
  4. washThe aqueous layer was washed with dichloromethane (100 mL)
  5. washthe combined organic fractions were washed with saturated aqueous sodium bicarbonate (100 mL) and brine (100 mL)
  6. dry with materialdried over sodium sulfate
  7. filtrationfiltered
  8. concentrationconcentrated under reduced pressure
  9. customto provide a red oil
  10. temperatureheated
  11. temperatureat reflux for two hours
  12. customthe crude product was purified by column chromatography on silica gel (eluting with 70:30 ethyl acetate:hexane)

出典と根拠

ORDレコード
ord-798f10a0b9ff4063aed1586fa1e761ce
出典データセット
uspto-grants-2011_03
特許番号
US07897597B2

反応ノート

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