2,3-Dichloro-5,6-dicyano-1,4-benzoquinone → 3-Bromo-9-methoxy-6,6-dimethyl-5,6-dihydro-benzo[b]carbazol-11-one

HRID 2275178ノート

反応式

HRID 2275178 の反応式
[CH3:1][O:2][C:3]1[CH:4]=[C:5]2[C:10](=[CH:11][CH:12]=1)[C:9]([CH3:14])([CH3:13])[C:8](=O)[CH2:7][CH2:6]2.Cl.[Br:17][C:18]1[CH:19]=[C:20]([NH:24]N)[CH:21]=[CH:22][CH:23]=1.C(OCC)(=[O:28])C.C(C1C(=O)C(Cl)=C(Cl)C(=O)C=1C#N)#N>C(O)(=O)C.O.CC(OC)(C)C>[Br:17][C:18]1[CH:19]=[C:20]2[C:21]([C:7]3[C:6](=[O:28])[C:5]4[CH:4]=[C:3]([O:2][CH3:1])[CH:12]=[CH:11][C:10]=4[C:9]([CH3:14])([CH3:13])[C:8]=3[NH:24]2)=[CH:22][CH:23]=1

参加物

8

反応物 4

HCID 67752,3-Dichloro-5,6-dicyano-1,4-benzoquinoneHCID 8857Ethyl AcetateHCID 337573-Bromophenylhydrazine hydrochlorideHCID 125619446-Methoxy-1,1-dimethyl-3,4-dihydronaphthalen-2-one

生成物 1

HCID 668345203-Bromo-9-methoxy-6,6-dimethyl-5,6-dihydro-benzo[b]carbazol-11-one収率 46%

試薬・触媒・溶媒 3

HCID 176Acetic Acid溶媒HCID 962Water溶媒HCID 15413tert-Butyl methyl ether溶媒

反応条件

温度
100 °C

実験手順

6-Methoxy-1,1-dimethyl-3,4-dihydro-1H-naphthalen-2-one (Compound J2, 2.15 g, 10.5 mmol) and 3-bromophenylhydrazine hydrochloric acid salt (3.11 g, 1.3 eq.) were dissolved in acetic acid (12 mL), and stirred at 100° C. for 2.5 hr under nitrogen atmosphere. After cooling, the reaction solution was added with ethyl acetate, washed with water, saturated aqueous solution of sodium hydrogen carbonate, and saturated brine, and dried over magnesium sulfate. After the filtration, it was concentrated under reduced pressure. The resulting residues were dissolved in THF (30 mL) and water (3 mL), added with DDQ (5.96 g, 2.5 eq.) at 0° C., and then stirred at room temperature overnight. The reaction solution was added with MTBE, washed with 0.5 N aqueous solution of sodium hydroxide and saturated brine, and dried over magnesium sulfate. After filtration and the concentration under reduced pressure, the resulting residues were washed with MTBE to obtain the title compound (brown solid, 1.80 g, 46%).

後処理

  1. temperatureAfter cooling
  2. washwashed with water, saturated aqueous solution of sodium hydrogen carbonate, and saturated brine
  3. dry with materialdried over magnesium sulfate
  4. filtrationAfter the filtration, it
  5. concentrationwas concentrated under reduced pressure
  6. dissolutionThe resulting residues were dissolved in THF (30 mL)
  7. stirringstirred at room temperature overnight
  8. washwashed with 0.5 N aqueous solution of sodium hydroxide and saturated brine
  9. dry with materialdried over magnesium sulfate
  10. filtrationAfter filtration
  11. concentrationthe concentration under reduced pressure
  12. washthe resulting residues were washed with MTBE

出典と根拠

ORDレコード
ord-7f95c33e8b6a4c9aa237d5e0cc34be95
出典データセット
uspto-grants-2015_09
特許番号
US09126931B2

反応ノート

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