Iodine → (6S,9aR)-6-(4-chlorophenyl)-3-iodooctahydroquinolizin-4-one

HRID 16367

반응식

HRID 16367 반응식
C[Si](I)(C)C.[Cl:6][C:7]1[CH:12]=[CH:11][C:10]([C@@H:13]2[CH2:22][CH2:21][CH2:20][C@H:19]3[N:14]2[C:15](=[O:23])[CH2:16][CH2:17][CH2:18]3)=[CH:9][CH:8]=1.CN(C)CCN(C)C.[I:32]I.S([O-])([O-])(=O)=S.[Na+].[Na+]>C(OCC)(=O)C.C(Cl)Cl>[Cl:6][C:7]1[CH:12]=[CH:11][C:10]([C@@H:13]2[CH2:22][CH2:21][CH2:20][C@H:19]3[N:14]2[C:15](=[O:23])[CH:16]([I:32])[CH2:17][CH2:18]3)=[CH:9][CH:8]=1

참가 물질

8

반응물 5

HCID 807IodineHCID 8037N,N,N',N'-TetramethylethylenediamineHCID 24477Sodium ThiosulfateHCID 85247Trimethylsilyl iodideHCID 67462899(6S,9aR)-6-(4-chlorophenyl)octahydroquinolizin-4-one

생성물 1

HCID 67464546(6S,9aR)-6-(4-chlorophenyl)-3-iodooctahydroquinolizin-4-one

시약·촉매·용매 2

HCID 6344Dichloromethane용매HCID 8857Ethyl Acetate용매

반응 조건

온도
0 °C

실험 절차

In nitrogen atmosphere, trimethylsilyl iodide (0.74 mL) was added to a methylene chloride solution (25 mL) of (6S,9aR)-6-(4-chlorophenyl)-octahydroquinolizin-4-one (877 mg) and N,N,N′,N′-tetramethylethylenediamine (1.76 mL) at 0° C. The resulting reaction solution was stirred at 0° C. for 30 min, and then iodine (1.26 g) was added thereto at 0° C. The resulting reaction solution was stirred at 0° C. for 1 hr, and a sodium thiosulfate aqueous solution and ethyl acetate were added thereto. The organic layer was separated, washed with saturated saline, dried over magnesium sulfate, and concentrated under reduced pressure to give (6S,9aR)-6-(4-chlorophenyl)-3-iodooctahydroquinolizin-4-one. A mixture of the (6S,9aR)-6-(4-chlorophenyl)-3-iodooctahydroquinolizin-4-one and triethyl phosphite (10 mL) was stirred at 120° C. for 2 hr. This reaction solution was allowed to cool to room temperature and then concentrated under reduced pressure to give [(6S,9aR)-6-(4-chlorophenyl)-4-oxooctahydroquinolizin-3-yl]phosphonic acid diethyl ester. To a solution mixture of tetrahydrofuran (21 mL) and ethanol (7 mL) of the [(6S,9aR)-6-(4-chlorophenyl)-4-oxooctahydroquinolizin-3-yl]phosphonic acid diethyl ester and 3-methoxy-4-(4-methyl-1H-imidazol-1-yl)benzaldehyde (869 mg), lithium hydroxide monohydrate (422 mg) was added. The resulting reaction solution was stirred at room temperature for 2 hr, and then ethyl acetate and a saturated sodium hydrogencarbonate aqueous solution were added thereto. The organic layer was separated, washed with saturated saline, dried over magnesium sulfate, and concentrated under reduced pressure. The residue was purified by silica gel column chromatography (carrier: Chromatorex NH, eluting solvent: heptane-ethyl acetate system) and then by silica gel column chromatography (eluting solvent: heptane-ethyl acetate system and then ethyl acetate-methanol system) to give 1.07 g of the title compound. The physical property values of this compound were as follows:

후처리

  1. customThe resulting reaction solution
  2. customat 0° C
  3. customThe resulting reaction solution
  4. stirringwas stirred at 0° C. for 1 hr
  5. customThe organic layer was separated
  6. washwashed with saturated saline
  7. dry with materialdried over magnesium sulfate
  8. concentrationconcentrated under reduced pressure

출처 및 근거

ORD 기록
ord-e1dcbf5988a64c3287c323529844435c
출처 데이터셋
uspto-grants-2010_06
특허 번호
US07737141B2

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