Potassium Iodide → HCID 46896511, Verbindung

HRID 241986

Reaktionsgleichung

Reaktionsgleichung von HRID 241986
[N+:1](=[C:3]1[C:7]([C:8]2[CH:13]=[CH:12][CH:11]=[CH:10][C:9]=2[F:14])=[N:6][N:5]([C:15]2[CH:20]=[CH:19][CH:18]=[CH:17][C:16]=2[F:21])[C:4]1=[O:22])=[N-:2].C(P(CCCC)CCCC)CCC.Cl[CH2:37][C:38]1[CH:43]=[CH:42][C:41]([N:44]2[CH:48]=[CH:47][N:46]=[CH:45]2)=[CH:40][CH:39]=1.[I-].[K+].C(=O)([O-])[O-].[K+].[K+]>C(#N)C.O>[F:14][C:9]1[C:8]2[C:7]3[C:3]([C:4](=[O:22])[N:5]([C:15]4[CH:20]=[CH:19][CH:18]=[CH:17][C:16]=4[F:21])[N:6]=3)=[N:1][N:2]([CH2:37][C:38]3[CH:39]=[CH:40][C:41]([N:44]4[CH:48]=[CH:47][N:46]=[CH:45]4)=[CH:42][CH:43]=3)[C:13]=2[CH:12]=[CH:11][CH:10]=1

Komponenten

8

Edukt 5

HCID 4875Potassium IodideHCID 11430Potassium CarbonateHCID 13831TributylphosphineHCID 70638591-(4-(Chloromethyl)phenyl)-1H-imidazoleHCID 178514319HCID 178514319, Verbindung

Produkt 1

HCID 46896511HCID 46896511, Verbindung

Reagenzien, Katalysatoren, Lösungsmittel 2

HCID 962WaterLösungsmittelHCID 6342AcetonitrileLösungsmittel

Versuchsvorschrift

4-Diazo-2,5-bis(2-fluorophenyl)-2,4-dihydro-3H-pyrazol-3-one (0.17 g, 0.56 mmol) was dissolved in acetonitrile (5 mL) and treated with tri-n-butylphosphine (0.11 g, 0.56 mmol, 1.0 equiv). After stirring for 30 minutes at ambient temperature, 1-[4-(chloromethyl)phenyl]-1H-imidazole (0.11 g, 0.56 mmol, 1.0 equiv), potassium iodide (47 mg, 0.28 mmol, 0.5 equiv) and potassium carbonate (97 mg, 0.70 mmol, 1.25 equiv) were added at ambient temperature. After 45 minutes, the reaction mixture was warmed to 85° C., stirred for 2.5 hours and then cooled to ambient temperature. The mixture was poured into water (100 mL), extracted with ethyl acetate (2×75 mL) and the combined organic extracts were dried with sodium sulfate, filtered and concentrated in vacuo. The residue was purified twice by silica gel gradient chromatography (100:0 to 0:100; hexanes:ethyl acetate containing 10% methanol; and then 100:0 to 90:10; dichloromethane:methanol containing 10% ammonium hydroxide), providing the titled compound as a deep red solid: 1H-NMR (400 MHz, CDCl3) δ 8.33 (1H, dd, J=7.6, 1.8 Hz), 7.85 (1H, br s), 7.67-7.53 (4H, m), 7.46 (2H, d, J=8.5 Hz), 7.40 (2H, d, J=8.5 Hz), 7.42-7.37 (1H, m), 7.31-7.20 (4H, m), 5.88 (2H, s) ppm; high resolution mass spectrometry (ES+) m/z 437.1526 [(M+H)+; calculated for C25H18FN6O: 437.1521].

Aufarbeitung

  1. waitAfter 45 minutes
  2. temperaturethe reaction mixture was warmed to 85° C.
  3. stirringstirred for 2.5 hours
  4. temperaturecooled to ambient temperature
  5. extractionextracted with ethyl acetate (2×75 mL)
  6. dry with materialthe combined organic extracts were dried with sodium sulfate
  7. filtrationfiltered
  8. concentrationconcentrated in vacuo
  9. customThe residue was purified twice by silica gel gradient chromatography (100:0 to 0:100

Quellen und Nachweise

ORD-Eintrag
ord-7f12b7f3609f415dab3821db2a863fff
Quelldatensatz
uspto-grants-2014_02
Patentnummer
US08653079B2

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