Imidazole → Tert-butyl 4-(4-fluoro-2-(2-iodoethylthio)-5-nitrophenylamino)piperidine-1-carboxylate

HRID 1917247Notizen

Reaktionsgleichung

Reaktionsgleichung von HRID 1917247
C1(P(C2C=CC=CC=2)C2C=CC=CC=2)C=CC=CC=1.N1C=CN=C1.[I:25]I.[F:27][C:28]1[C:33]([N+:34]([O-:36])=[O:35])=[CH:32][C:31]([NH:37][CH:38]2[CH2:43][CH2:42][N:41]([C:44]([O:46][C:47]([CH3:50])([CH3:49])[CH3:48])=[O:45])[CH2:40][CH2:39]2)=[C:30]([S:51][CH2:52][CH2:53]O)[CH:29]=1>O1CCCC1.C(OCC)(=O)C>[F:27][C:28]1[C:33]([N+:34]([O-:36])=[O:35])=[CH:32][C:31]([NH:37][CH:38]2[CH2:43][CH2:42][N:41]([C:44]([O:46][C:47]([CH3:50])([CH3:49])[CH3:48])=[O:45])[CH2:40][CH2:39]2)=[C:30]([S:51][CH2:52][CH2:53][I:25])[CH:29]=1

Komponenten

7

Edukt 4

HCID 795ImidazoleHCID 807IodineHCID 11776TriphenylphosphineHCID 59144085tert-Butyl 4-(4-fluoro-2-(2-hydroxyethylthio)-5-nitrophenylamino)piperidine-1-carboxylate

Produkt 1

HCID 59144096Tert-butyl 4-(4-fluoro-2-(2-iodoethylthio)-5-nitrophenylamino)piperidine-1-carboxylateAusbeute 44,6 %

Reagenzien, Katalysatoren, Lösungsmittel 2

HCID 8028TetrahydrofuranLösungsmittel2×HCID 8857Ethyl AcetateLösungsmittel

Reaktionsbedingungen

Temperatur
0 °C

Versuchsvorschrift

To a stirred solution of triphenylphosphine (668 mg, 2.55 mmol) and imidazole (0.693 mL, 5.09 mmol) in tetrahydrofuran (10 mL) cooled to 0° C. was added iodine (732 mg, 2.88 mmol). The resulting mixture was stirred at 0° C. for 5 minutes. To this mixture was then added tert-butyl 4-(4-fluoro-2-(2-hydroxyethylthio)-5-nitrophenylamino)piperidine-1-carboxylate (705 mg, 1.697 mmol) as a solution in tetrahydrofuran (5 mL), and the resulting mixture was stirred at room temperature for 20 minutes. The mixture was then diluted with ethyl acetate and washed with saturated sodium carbonate, water, saturated sodium thiosulfate, and brine. The organic phase was dried, filtered, concentrated, and then chromatographed in 1:9 ethyl acetate:hexanes to afford the desired product (398 mg, 44.6%). 1H NMR (DMSO-d6) δ 7.53 (d, J=11.7 Hz, 1H), 7.27 (d, J=6.6 Hz, 1H), 5.10 (d, J=8.1 Hz, 1H), 3.96-3.85 (m, 2H), 3.64-3.52 (m, 1H), 3.50-3.41 (m, 2H), 3.39-3.32 (m, 2H), 2.99-2.81 (m, 2H), 1.91-1.81 (m, 2H), 1.48-1.32 (m, 11H); ESI-MS (m.z, %): 470 (100), 426 (81).

Aufarbeitung

  1. washwashed with saturated sodium carbonate, water, saturated sodium thiosulfate, and brine
  2. customThe organic phase was dried
  3. filtrationfiltered
  4. concentrationconcentrated
  5. customchromatographed in 1:9 ethyl acetate

Quellen und Nachweise

ORD-Eintrag
ord-a42c923a6d4a48acaa5157fe467b6ba9
Quelldatensatz
uspto-grants-2013_12
Patentnummer
US08618286B2

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