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Ethyl Acetate → 9-Chloro-2,2,4-trimethyl-1,4-dihydro-2H-6-oxa-1,4-diazachrysen-3,5-dione

HRID 1038476
ノート
印刷プレビュー

反応式

HRID 1038476 の反応式
[Cl:1][C:2]1[CH:3]=[CH:4][C:5]([O:26]C)=[C:6]([C:8]2[C:17]([C:18](OC)=[O:19])=[C:16]3[C:11]([NH:12][C:13]([CH3:25])([CH3:24])[C:14](=[O:23])[N:15]3[CH3:22])=[CH:10][CH:9]=2)[CH:7]=1.B(Br)(Br)Br.C(OCC)(=O)C.[H-].[Na+]>ClCCl.O.C(OCC)C>[Cl:1][C:2]1[CH:7]=[C:6]2[C:5]([O:26][C:18](=[O:19])[C:17]3[C:8]2=[CH:9][CH:10]=[C:11]2[C:16]=3[N:15]([CH3:22])[C:14](=[O:23])[C:13]([CH3:25])([CH3:24])[NH:12]2)=[CH:4][CH:3]=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

8

反応物 4

HCID 8857Ethyl Acetate2 回HCID 24758Sodium hydride2 回HCID 25134Boron tribromideHCID 247809987-(5-Chloro-2-methoxyphenyl)-8-methoxycarbonyl-1,3,3-trimethyl-3,4-dihydro-1H-quinoxalin-2-one

生成物 1

HCID 576717409-Chloro-2,2,4-trimethyl-1,4-dihydro-2H-6-oxa-1,4-diazachrysen-3,5-dione収率 61%

試薬・触媒・溶媒 3

HCID 962Water溶媒HCID 3283Diethyl Ether溶媒HCID 6344Dichloromethane溶媒

反応条件

温度
-78 °C

実験手順

7-(5-Chloro-2-methoxyphenyl)-8-methoxycarbonyl-1,3,3-trimethyl-3,4-dihydro-1H-quinoxalin-2-one (Reference Compound No. 10-1, 3.81 g, 9.80 mmol) was dissolved in anhydrous dichloromethane (30 mL), boron tribromide (7.62 g, 30.4 mmol) was added thereto at −78° C., and then stirred at room temperature for 1 hour. The reaction mixture was poured into ice water (500 mL), ethyl acetate (500 mL) was added thereto and partitioned. The organic layer was washed with saturated brine (200 mL), dried over anhydrous magnesium sulfate, and then the solvent was removed under reduced pressure. The obtained residue was dissolved in N,N-dimethylformamide (50 mL), 60% sodium hydride (23.1 mg, 0.578 mmol) was added thereto, and then stirred at 70° C. overnight. 60% sodium hydride (31.2 mg, 0.780 mmol) was added more thereto and stirred at 80° C. overnight. After cooling down, ethyl acetate (200 mL), diethylether (200 mL) and water (300 mL) were added and partitioned. The organic layer was washed with water (200 mL) and saturated brine (200 mL) successively, dried over anhydrous magnesium sulfate, and then the solvent was removed under reduced pressure. The obtained residue was filtered with ethyl acetate/hexane (¼, 30 mL) to give the titled reference compound (2.04 g) as a pale yellow solid. (Yield 61%)

後処理

  1. additionwas added
  2. custompartitioned
  3. washThe organic layer was washed with saturated brine (200 mL)
  4. dry with materialdried over anhydrous magnesium sulfate
  5. customthe solvent was removed under reduced pressure
  6. dissolutionThe obtained residue was dissolved in N,N-dimethylformamide (50 mL)
  7. stirringstirred at 70° C. overnight
  8. stirringstirred at 80° C. overnight
  9. temperatureAfter cooling down
  10. custompartitioned
  11. washThe organic layer was washed with water (200 mL) and saturated brine (200 mL) successively
  12. dry with materialdried over anhydrous magnesium sulfate
  13. customthe solvent was removed under reduced pressure
  14. filtrationThe obtained residue was filtered with ethyl acetate/hexane (¼, 30 mL)

出典と根拠

ORDレコード
ord-532d514be7714f65befcb251a9099299
出典データセット
uspto-grants-2013_10
DOI
10.6084/m9.figshare.5104873.v1
特許番号
US08551991B2

反応ノート

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