Hydrochloric Acid → 4-Hydroxy-8-methoxy-6,6-dimethyl-11-oxo-6,11-dihydro-5H-benzo[b]carbazole-3-carbonitrile

HRID 61854Notes

Reaction equation

HRID 61854 reaction equation
Br[C:2]1[C:3]([C:24]#[N:25])=[CH:4][CH:5]=[C:6]2[C:14]=1[NH:13][C:12]1[C:11]([CH3:16])([CH3:15])[C:10]3[CH:17]=[C:18]([O:21][CH3:22])[CH:19]=[CH:20][C:9]=3[C:8](=[O:23])[C:7]2=1.CC(C1C=C(C(C)C)C(C2C=CC=CC=2P(C2CCCCC2)C2CCCCC2)=C(C(C)C)C=1)C.[OH-:60].[Na+].C(Cl)(Cl)Cl.Cl>O1CCOCC1.C1C=CC(/C=C/C(/C=C/C2C=CC=CC=2)=O)=CC=1.C1C=CC(/C=C/C(/C=C/C2C=CC=CC=2)=O)=CC=1.C1C=CC(/C=C/C(/C=C/C2C=CC=CC=2)=O)=CC=1.[Pd].[Pd].O>[OH:60][C:2]1[C:3]([C:24]#[N:25])=[CH:4][CH:5]=[C:6]2[C:14]=1[NH:13][C:12]1[C:11]([CH3:16])([CH3:15])[C:10]3[CH:17]=[C:18]([O:21][CH3:22])[CH:19]=[CH:20][C:9]=3[C:8](=[O:23])[C:7]2=1

Participants

9

Reactant 5

HCID 313Hydrochloric AcidHCID 6212ChloroformHCID 14798Sodium HydroxideHCID 111557942-Dicyclohexylphosphino-2',4',6'-triisoprophylbiphenylHCID 668344664-Bromo-8-methoxy-6,6-dimethyl-11-oxo-6,11-dihydro-5H-benzo[b]carbazole-3-carbonitrile

Product 1

HCID 668339264-Hydroxy-8-methoxy-6,6-dimethyl-11-oxo-6,11-dihydro-5H-benzo[b]carbazole-3-carbonitrileYield 64.2%

Reagents, catalysts & solvents 3

HCID 9811564Bis(dibenzylideneacetone)palladiumCatalystHCID 962WaterSolventHCID 312751,4-DioxaneSolvent

Procedure

Under nitrogen atmosphere, 4-bromo-8-methoxy-6,6-dimethyl-11-oxo-6,11-dihydro-5H-benzo[b]carbazole-3-carbonitrile (Compound U5, 10.0 mg, 25.30 μmol), X-phos (1.07 mg, 2.530 μmol), sodium hydroxide (4.36 mg, 75.90 μmol) and Pd2dba3.CHCl3 (1.31 mg, 1.265 μmol) were dissolved in dioxane (0.50 mL) and water (0.50 mL) and the mixture was stirred at 100° C. for 1 hr. The reaction solution was poured into hydrochloric acid (1 M), extracted with ethyl acetate, washed with saturated brine, dried over sodium sulfate, and then filtered. The residues obtained after concentration under reduced pressure were purified by silica gel column chromatography (ethyl acetate/hexane) and washed with dichloromethane to obtain the title compound (5.4 mg, 64%).

Workup

  1. extractionextracted with ethyl acetate
  2. washwashed with saturated brine
  3. dry with materialdried over sodium sulfate
  4. filtrationfiltered
  5. customThe residues obtained
  6. concentrationafter concentration under reduced pressure
  7. customwere purified by silica gel column chromatography (ethyl acetate/hexane)
  8. washwashed with dichloromethane

Sources & evidence

ORD record
ord-2100d5e4c7194f2fb637070091b83463
Source dataset
uspto-grants-2016_09
Patent number
US09440922B2

Reaction notes

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