Pyrrolizinium, 1,2,3,5,6,7-hexahydro-, perchlorate → 7a-(3-benzyloxy-5-pyridinyl)-hexahydro-1H-pyrrolizine

HRID 3310

反応式

HRID 3310 の反応式
[CH2:1]([O:8][C:9]1[CH:10]=[N:11][CH:12]=[C:13](Br)[CH:14]=1)[C:2]1[CH:7]=[CH:6][CH:5]=[CH:4][CH:3]=1.[Li]C(C)(C)C.Cl([O-])(=O)(=O)=O.[CH2:26]1[C:33]2[CH2:32][CH2:31][CH2:30][N+:29]=2[CH2:28][CH2:27]1>CCOCC.CCCCC>[CH2:1]([O:8][C:9]1[CH:10]=[N:11][CH:12]=[C:13]([C:33]23[CH2:32][CH2:31][CH2:30][N:29]2[CH2:28][CH2:27][CH2:26]3)[CH:14]=1)[C:2]1[CH:7]=[CH:6][CH:5]=[CH:4][CH:3]=1

参加物

6

反応物 3

HCID 10878400Pyrrolizinium, 1,2,3,5,6,7-hexahydro-, perchlorateHCID 153891983-(Benzyloxy)-5-bromopyridineHCID 178418306HCID 178418306、化合物

生成物 1

HCID 189347547a-(3-benzyloxy-5-pyridinyl)-hexahydro-1H-pyrrolizine収率 22%

試薬・触媒・溶媒 2

HCID 3283Diethyl Ether溶媒HCID 8003Pentane溶媒

反応条件

温度
-78 °C

実験手順

3-Benzyloxy-5-bromopyridine (1.18 g, 4.47 mmol) was dissolved in Et2O and cooled to -78° C. A solution of 2.5M t-BuLi (5.8 mL, 9.83 mmol) in pentane was added, and the reaction was stirred for 10 minutes. 1,2,3,5,6,7-hexahydropyrrolizinium perchlorate (1.4 g, 6.70 mmol) was added, and the reaction mixture was allowed to stir for 3 hours at -78° C. then allowed to warm to -20° C. and stir for 2 hours. The cold bath was removed, 2N HCl was added, and the mixture was extracted with Et2O. The phases were separated, and the aqueous phase was basified with 15% NaOH and extracted with CH2Cl2 (2×). The CH2Cl2 fractions were combined, dried (MgSO4) and concentrated, and the residue was chromatographed (silica gel; CHCl3 /MeOH, 98:2) to afford a clear oil (286 mg, 22%): mp 45°-49° C. 1H NMR (CDCl3, 300 MHz) δ1.58-1.69 (m, 2H), 1.78-1.83 (m, 2H), 1.89-2.03 (m, 4H), 2.63-2.72 (m, 2H), 3.05-3.18 (m, 2H), 5.12 (s, 2H), 7.31-7.54 (m, 6H), 8.17 (d, J=3.0 Hz, 1H), 8.29 (d, J=1.7 Hz, 1H); MS (CI/NH3) m/z: 295 (M+H)+.

後処理

  1. stirringto stir for 3 hours at -78° C.
  2. temperatureto warm to -20° C.
  3. stirringstir for 2 hours
  4. customThe cold bath was removed
  5. addition2N HCl was added
  6. extractionthe mixture was extracted with Et2O
  7. customThe phases were separated
  8. extractionextracted with CH2Cl2 (2×)
  9. dry with materialdried (MgSO4)
  10. concentrationconcentrated
  11. customthe residue was chromatographed (silica gel; CHCl3 /MeOH, 98:2)

出典と根拠

ORDレコード
ord-227b359fc5e7487cb58b11323a1b2724
出典データセット
uspto-grants-1998_03
特許番号
US05733912

関連ノート

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