Hydrochloric Acid → 4-Cyclopropyl-8-((S)-2,2-dimethyl-[1,3]dioxolan-4-yl methoxy)-6,6-dimethyl-11-oxo-6,11-dihydro-5H-benzo[b]carbazole-3-carbonitrile

HRID 61851Notizen

Reaktionsgleichung

Reaktionsgleichung von HRID 61851
[CH:1]1(B2OC(C)(C)C(C)(C)O2)[CH2:3][CH2:2]1.P([O-])([O-])([O-])=O.[K+].[K+].[K+].Br[C:22]1[C:23]([C:51]#[N:52])=[CH:24][CH:25]=[C:26]2[C:34]=1[NH:33][C:32]1[C:31]([CH3:36])([CH3:35])[C:30]3[CH:37]=[C:38]([O:41][CH2:42][C@H:43]4[CH2:47][O:46][C:45]([CH3:49])([CH3:48])[O:44]4)[CH:39]=[CH:40][C:29]=3[C:28](=[O:50])[C:27]2=1.C1(P(C2CCCCC2)C2CCCCC2)CCCCC1.Cl>O.C([O-])(=O)C.[Pd+2].C([O-])(=O)C>[CH:1]1([C:22]2[C:23]([C:51]#[N:52])=[CH:24][CH:25]=[C:26]3[C:34]=2[NH:33][C:32]2[C:31]([CH3:35])([CH3:36])[C:30]4[CH:37]=[C:38]([O:41][CH2:42][C@H:43]5[CH2:47][O:46][C:45]([CH3:48])([CH3:49])[O:44]5)[CH:39]=[CH:40][C:29]=4[C:28](=[O:50])[C:27]3=2)[CH2:3][CH2:2]1

Komponenten

8

Edukt 5

HCID 313Hydrochloric AcidHCID 62657Potassium Phosphate, TribasicHCID 75806TricyclohexylphosphineHCID 27580152-Cyclopropyl-4,4,5,5-tetramethyl-1,3,2-dioxaborolaneHCID 668348924-bromo-8-((S)-2,2-dimethyl-[1,3]dioxolan-4-yl methoxy)-6,6-dimethyl-11-oxo-6,11-dihydro-5H-benzo[b]carbazole-3-carbonitrile

Produkt 1

HCID 668351654-Cyclopropyl-8-((S)-2,2-dimethyl-[1,3]dioxolan-4-yl methoxy)-6,6-dimethyl-11-oxo-6,11-dihydro-5H-benzo[b]carbazole-3-carbonitrileAusbeute 49,2 %

Reagenzien, Katalysatoren, Lösungsmittel 2

HCID 167845palladium(II) acetateKatalysatorHCID 962WaterLösungsmittel

Versuchsvorschrift

Under nitrogen atmosphere, 2-cyclopropyl-4,4,5,5-tetramethyl-[1,3,2]dioxaborolane (13.2 mg, 78.73 μmol) and potassium phosphate (212.27 mg, 212.0 μmol) were dissolved in water (0.20 mL), and the mixture was stirred at room temperature for 15 min. To the reaction solution, 4-bromo-8-((S)-2,2-dimethyl-[1,3]dioxolan-4-yl methoxy)-6,6-dimethyl-11-oxo-6,11-dihydro-5H-benzo[b]carbazole-3-carbonitrile (Compound U8-1, 30.0 mg, 60.56 μmol), palladium acetate (1.36 mg, 6.056 μmol), and tricyclohexylphosphine (toluene solution, 20 wt %, 17.0 mg, 12.11 μmol) were added and the mixture was stirred at 80° C. for 24 hr. The reaction solution was poured into hydrochloric acid (1 M), extracted with ethyl acetate, washed with saturated aqueous solution of sodium bicarbonate and 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) to obtain the title compound (13.6 mg, 49%).

Aufarbeitung

  1. stirringthe mixture was stirred at 80° C. for 24 hr
  2. extractionextracted with ethyl acetate
  3. washwashed with saturated aqueous solution of sodium bicarbonate and saturated brine
  4. dry with materialdried over sodium sulfate
  5. filtrationfiltered
  6. customThe residues obtained
  7. concentrationafter concentration under reduced pressure
  8. customwere purified by silica gel column chromatography (ethyl acetate/hexane)

Quellen und Nachweise

ORD-Eintrag
ord-e34aee097cbf4f0dbff5d66cd7535adc
Quelldatensatz
uspto-grants-2016_09
Patentnummer
US09440922B2

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