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

HRID 1917247ノート

反応式

HRID 1917247 の反応式
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

参加物

7

反応物 4

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

生成物 1

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

試薬・触媒・溶媒 2

HCID 8028Tetrahydrofuran溶媒2 回HCID 8857Ethyl Acetate溶媒

反応条件

温度
0 °C

実験手順

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).

後処理

  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

出典と根拠

ORDレコード
ord-a42c923a6d4a48acaa5157fe467b6ba9
出典データセット
uspto-grants-2013_12
特許番号
US08618286B2

反応ノート

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