Hydrochloric Acid → 7a-(3-Quinolinyl)-hexahydro-1h-pyrrolizine

HRID 3286

반응식

HRID 3286 반응식
[Li]CCCC.Br[C:7]1[CH:8]=[N:9][C:10]2[C:15]([CH:16]=1)=[CH:14][CH:13]=[CH:12][CH:11]=2.Cl([O-])(=O)(=O)=O.[CH2:22]1[C:29]2[CH2:28][CH2:27][CH2:26][N+:25]=2[CH2:24][CH2:23]1.Cl>C1COCC1.CCOC(C)=O>[N:9]1[C:10]2[C:15](=[CH:14][CH:13]=[CH:12][CH:11]=2)[CH:16]=[C:7]([C:29]23[CH2:28][CH2:27][CH2:26][N:25]2[CH2:24][CH2:23][CH2:22]3)[CH:8]=1

참가 물질

7

반응물 4

HCID 313Hydrochloric AcidHCID 214133-BromoquinolineHCID 10878400Pyrrolizinium, 1,2,3,5,6,7-hexahydro-, perchlorateHCID 178418339Butyllithium

생성물 1

HCID 189347257a-(3-Quinolinyl)-hexahydro-1h-pyrrolizine수율 48.5%

시약·촉매·용매 2

HCID 8028Tetrahydrofuran용매HCID 8857Ethyl Acetate용매

반응 조건

온도
-100 °C

실험 절차

A solution of 2.5M nBuLi (1.2 mL, 2.8 mmol) in hexanes was added to 3-bromoquinoline (386 μL, 2.8 mmol) in THF (10 mL) at -100° C. followed immediately by 1,2,3,5,6,7-hexahydropyrrolizinium perchlorate (200 mg, 0.9 mmol). The reaction mixture was allowed to stir for 2 hours at -100° C. and then 2N HCl was added at 0° C. After warming to ambient temperature, the mixture was poured over EtOAc and the phases were separated. The aqueous phase was basified with 15% NaOH solution and extracted with CH2Cl2 (3×). The organic fractions were combined, dried (MgSO4) and concentrated, and the residue was chromatographed (silica gel; EtOAc) to afford a pale solid (104 mg, 46%). mp 80°-83° C. MS (CI/NH3) m/e: 239 (M+H)+. 1 H NMR (CDCl3, 300 MHz) δ1.61-1.75 (m, 2H), 1.83-1.94 (m, 2H), 2.03-2.17 (m, 4H), 2.71-2.80 (m, 2H), 3.20-3.27 (m, 2H), 7.52 (ddd, J=7.0, 7.0, 1.1 Hz, 1H), 7.65 (ddd, J=7.0, 7.0, 1.5 Hz, 1H), 7.82 (d, J=8.1 Hz, 1H), 8.05 (d, J=8.5 Hz, 1H), 8.32 (d, J=2.2, Hz, 1H), 8.97 (d, J=2.2 Hz, 1H).

후처리

  1. temperatureAfter warming to ambient temperature
  2. customthe phases were separated
  3. extractionextracted with CH2Cl2 (3×)
  4. dry with materialdried (MgSO4)
  5. concentrationconcentrated
  6. customthe residue was chromatographed (silica gel; EtOAc)

출처 및 근거

ORD 기록
ord-56ddd89618f84964b94d7784a2774ae5
출처 데이터셋
uspto-grants-1998_03
특허 번호
US05733912

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