2,3-Dichloro-5,6-dicyano-1,4-benzoquinone → 3-Chloro-8-methoxy-2,6,6-trimethyl-5,6-dihydro-benzo[b]carbazol-11-one

HRID 61823

反応式

HRID 61823 の反応式
[CH3:1][O:2][C:3]1[CH:12]=[C:11]2[C:6]([CH2:7][CH2:8][C:9](=O)[C:10]2([CH3:14])[CH3:13])=[CH:5][CH:4]=1.Cl.[Cl:17][C:18]1[CH:19]=[C:20]([NH:25]N)[CH:21]=[CH:22][C:23]=1[CH3:24].C(C1C(=O)C(Cl)=C(Cl)C(=[O:32])C=1C#N)#N>C(O)(C(F)(F)F)=O.C1COCC1.O.C(OCC)(=O)C.CCCCCC>[Cl:17][C:18]1[CH:19]=[C:20]2[C:21]([C:8]3[C:7](=[O:32])[C:6]4[CH:5]=[CH:4][C:3]([O:2][CH3:1])=[CH:12][C:11]=4[C:10]([CH3:14])([CH3:13])[C:9]=3[NH:25]2)=[CH:22][C:23]=1[CH3:24]

参加物

9

反応物 3

HCID 67752,3-Dichloro-5,6-dicyano-1,4-benzoquinoneHCID 3085075(3-Chloro-4-methylphenyl)hydrazine monohydrochlorideHCID 130110077-Methoxy-1,1-dimethyl-3,4-dihydronaphthalen-2(1H)-one2 回

生成物 1

HCID 668350153-Chloro-8-methoxy-2,6,6-trimethyl-5,6-dihydro-benzo[b]carbazol-11-one収率 12%

試薬・触媒・溶媒 5

HCID 962Water溶媒HCID 6422Trifluoroacetic acid溶媒HCID 8028Tetrahydrofuran溶媒HCID 8058Hexane溶媒HCID 8857Ethyl Acetate溶媒2 回

実験手順

7-Methoxy-1,1-dimethyl-3,4-dihydro-1H-naphthalen-2-one (Compound A2, 99.1 mg, 0.485 mmol) and (3-chloro-4-methyl-phenyl)hydrazine hydrochloric acid salt (100.4 mg, 1.1 eq.) were dissolved in TFA (1 mL) and the mixture was irradiated with microwave at 80° C. for 10 min 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 filtration and concentration under reduced pressure, the residues obtained therefrom were dissolved in THF (2 mL) and water (0.2 mL), added with DDQ (125.7 mg, 1.1 eq.), and stirred at room temperature overnight. The reaction solution was added with the mixture solvent of hexane and ethyl acetate, and the starting-point components were removed by dry type silica gel column. The eluent was concentrated under reduced pressure, and the resulting residues were purified by preparative TLC (methanol/dichloromethane) to obtain the title compound (19.4 mg, 12%).

後処理

  1. customthe mixture was irradiated with microwave at 80° C. for 10 min under nitrogen atmosphere
  2. temperatureAfter cooling
  3. washwashed with water, saturated aqueous solution of sodium hydrogen carbonate and saturated brine
  4. dry with materialdried over magnesium sulfate
  5. filtrationAfter filtration and concentration under reduced pressure
  6. customthe residues obtained
  7. customthe starting-point components were removed
  8. customby dry type silica gel column
  9. concentrationThe eluent was concentrated under reduced pressure
  10. customthe resulting residues were purified by preparative TLC (methanol/dichloromethane)

出典と根拠

ORDレコード
ord-be589b6ffd744c3b97b2e17158d7a3e7
出典データセット
uspto-grants-2016_09
特許番号
US09440922B2

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