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

HRID 1917247노트

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HRID 1917247 반응식
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

참가 물질

7

반응물 4

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

생성물 1

HCID 59144096Tert-butyl 4-(4-fluoro-2-(2-iodoethylthio)-5-nitrophenylamino)piperidine-1-carboxylate수율 44.6%

시약·촉매·용매 2

HCID 8028Tetrahydrofuran용매2회HCID 8857Ethyl Acetate용매

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온도
0 °C

실험 절차

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).

후처리

  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

출처 및 근거

ORD 기록
ord-a42c923a6d4a48acaa5157fe467b6ba9
출처 데이터셋
uspto-grants-2013_12
특허 번호
US08618286B2

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