2,3-Dichloro-5,6-dicyano-1,4-benzoquinone → 9-Bromo-3-chloro-8-methoxy-6,6-dimethyl-5,6-dihydro-benzo[b]carbazol-11-one

HRID 61824

Reaction equation

HRID 61824 reaction equation
[Br:1][C:2]1[CH:3]=[C:4]2[C:9](=[CH:10][C:11]=1[O:12][CH3:13])[C:8]([CH3:15])([CH3:14])[C:7](=O)[CH2:6][CH2:5]2.Cl.[Cl:18][C:19]1[CH:20]=[C:21]([NH:25]N)[CH:22]=[CH:23][CH:24]=1.C(OCC)(=[O:29])C.C(C1C(=O)C(Cl)=C(Cl)C(=O)C=1C#N)#N>C(O)(=O)C.C1COCC1.C1COCC1.C(OCC)C.O>[Br:1][C:2]1[C:11]([O:12][CH3:13])=[CH:10][C:9]2[C:8]([CH3:15])([CH3:14])[C:7]3[NH:25][C:21]4[C:22]([C:6]=3[C:5](=[O:29])[C:4]=2[CH:3]=1)=[CH:23][CH:24]=[C:19]([Cl:18])[CH:20]=4

Participants

9

Reactant 4

HCID 67752,3-Dichloro-5,6-dicyano-1,4-benzoquinoneHCID 8857Ethyl AcetateHCID 75331m-Chlorophenylhydrazine hydrochlorideHCID 545785436-Bromo-7-methoxy-1,1-dimethyl-3,4-dihydronaphthalen-2(1H)-one2×

Product 1

HCID 668349559-Bromo-3-chloro-8-methoxy-6,6-dimethyl-5,6-dihydro-benzo[b]carbazol-11-one

Reagents, catalysts & solvents 4

HCID 176Acetic AcidSolventHCID 962WaterSolventHCID 8028TetrahydrofuranSolventHCID 21868444Ether tetrahydrofuranSolvent

Conditions

Temperature
90 °C

Procedure

6-Bromo-7-methoxy-1,1-dimethyl-3,4-dihydro-1H-naphthalen-2-one (Compound E1, 0.2 g, 0.71 mmol) and 3-chlorophenylhydrazine hydrochloric acid salt (0.17 g, 1.3 eq.) were dissolved in acetic acid (0.5 mL). Under nitrogen atmosphere, the reaction solution was stirred at 90° C. for 8 hr. After cooling to room temperature, 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 (3 mL) comprising 10% water, added with DDQ (227 mg, 3 eq.) at room temperature, and the mixture was stirred at room temperature for 2 hr. The reaction solution was added with the mixture liquid of THF/diethyl ether (1:1) and washed with 0.5 N aqueous solution of sodium hydroxide and saturated brine. After drying with sodium sulfate, the mixture was filtered and the resulting residues obtained after concentration under reduced pressure were washed with the mixture liquid of hexane/diethyl ether (1:1) to obtain the title compound (brown powder, 86 mg).

Workup

  1. temperatureAfter cooling to room temperature
  2. washwashed with water, saturated aqueous solution of sodium hydrogen carbonate and saturated brine
  3. dry with materialdried over magnesium sulfate
  4. filtrationAfter filtration and concentration under reduced pressure
  5. customthe residues obtained
  6. stirringthe mixture was stirred at room temperature for 2 hr
  7. washwashed with 0.5 N aqueous solution of sodium hydroxide and saturated brine
  8. dry with materialAfter drying with sodium sulfate
  9. filtrationthe mixture was filtered
  10. customthe resulting residues obtained
  11. concentrationafter concentration under reduced pressure
  12. washwere washed with the mixture liquid of hexane/diethyl ether (1:1)

Sources & evidence

ORD record
ord-a56d46741b48439aa5aef8419e6a0b34
Source dataset
uspto-grants-2016_09
Patent number
US09440922B2

Linked notes

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