Triphenylphosphine → 3-chloro-8-((S)-2,2-dimethyl-[1,3]dioxolan-4-yl methoxy)-4-fluoro-6,6-dimethyl-5,6-dihydro-benzo[b]carbazol-11-one

HRID 61828

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HRID 61828 반응식
[Cl:1][C:2]1[C:14]([F:15])=[C:13]2[C:5]([C:6]3[C:7](=[O:23])[C:8]4[CH:21]=[CH:20][C:19]([OH:22])=[CH:18][C:9]=4[C:10]([CH3:17])([CH3:16])[C:11]=3[NH:12]2)=[CH:4][CH:3]=1.[CH3:24][C:25]1([CH3:32])[O:29][C@@H:28]([CH2:30]O)[CH2:27][O:26]1.C1(P(C2C=CC=CC=2)C2C=CC=CC=2)C=CC=CC=1.C(OC(N=NC(OCC)=O)=O)C>C1COCC1>[Cl:1][C:2]1[C:14]([F:15])=[C:13]2[C:5]([C:6]3[C:7](=[O:23])[C:8]4[CH:21]=[CH:20][C:19]([O:22][CH2:30][C@H:28]5[CH2:27][O:26][C:25]([CH3:32])([CH3:24])[O:29]5)=[CH:18][C:9]=4[C:10]([CH3:17])([CH3:16])[C:11]=3[NH:12]2)=[CH:4][CH:3]=1

참가 물질

6

반응물 4

HCID 11776TriphenylphosphineHCID 220568ethyl N-ethoxycarbonyliminocarbamateHCID 736057(+)-SolketalHCID 668346463-Chloro-4-fluoro-8-hydroxy-6,6-dimethyl-5,6-dihydro-benzo[b]carbazol-11-one

생성물 1

HCID 668344233-chloro-8-((S)-2,2-dimethyl-[1,3]dioxolan-4-yl methoxy)-4-fluoro-6,6-dimethyl-5,6-dihydro-benzo[b]carbazol-11-one

시약·촉매·용매 1

HCID 8028Tetrahydrofuran용매

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온도
40 °C

실험 절차

3-Chloro-4-fluoro-8-hydroxy-6,6-dimethyl-5,6-dihydro-benzo[b]carbazol-11-one (Compound S2-3, 20.0 mg, 0.061 mmol) was dissolved in THF (0.25 mL), added with ((S)-2,2-dimethyl-[1,3]dioxolan-4-yl)-methanol (9.8 μL, 0.079 mmol), triphenylphosphine (20.7 mg, 0.079 mmol) and diethyl azodicarboxylic acid (35.9 μl, 0.079 mmol), and then stirred at 40° C. for 5 hr. The reaction solution was concentrated under reduced pressure, and the resulting residues were purified by silica gel column chromatography (ethyl acetate/hexane) to obtain the intermediate, 3-chloro-8-((S)-2,2-dimethyl-[1,3]dioxolan-4-yl methoxy)-4-fluoro-6,6-dimethyl-5,6-dihydro-benzo[b]carbazol-11-one. This compound was dissolved in THF (0.10 mL) and MeOH (0.08 ml), added with sulfuric acid (0.5 M, 0.045 ml), and then stirred at 60° C. for 1 hr. The reaction solution was added with saturated aqueous solution of sodium hydrogen carbonate, extracted with ethyl acetate and dried over anhydrous magnesium sulfate. The yellow solid obtained after concentration under reduced pressure was washed with methylene chloride/hexane solvent and filtered to obtain the title compound (4.3 mg, 18%).

후처리

  1. concentrationThe reaction solution was concentrated under reduced pressure
  2. customthe resulting residues were purified by silica gel column chromatography (ethyl acetate/hexane)

출처 및 근거

ORD 기록
ord-2967183ca22b41af8009032890679a04
출처 데이터셋
uspto-grants-2016_09
특허 번호
US09440922B2

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