cis/trans-1,3,4,6,7,11b-Hexahydro-7-hydroxy-7-phenyl-2H-benzoquinolizin-6-one | 137965-18-5

• 分子结构分类: 有机化合物 - 苯类化合物 - 茚满类
• 英文名称: cis/trans-1,3,4,6,7,11b-Hexahydro-7-hydroxy-7-phenyl-2H-benzoquinolizin-6-one
• 英文别名: 7-hydroxy-7-phenyl-2,3,4,11b-tetrahydro-1H-benzo[a]quinolizin-6-one
• CAS: 137965-18-5；137965-19-6
• 化学式: C₁₉H₁₉NO₂
• 分子量: 293.365
• InChiKey: WLQBUQTXMULOFN-UHFFFAOYSA-N

物化性质

• 沸点：
  513.0±50.0 °C(Predicted)
• 密度：
  1.28±0.1 g/cm3(Predicted)

计算性质

• 辛醇/水分配系数(LogP)：
  2.99
• 重原子数：
  22.0
• 可旋转键数：
  1.0
• 环数：
  4.0
• sp3杂化的碳原子比例：
  0.32
• 拓扑面积：
  40.54
• 氢给体数：
  1.0
• 氢受体数：
  2.0

上下游信息

反应信息

• 作为反应物：
  描述：

  cis/trans-1,3,4,6,7,11b-Hexahydro-7-hydroxy-7-phenyl-2H-benzoquinolizin-6-one 在 硼烷四氢呋喃络合物 作用下， 以 四氢呋喃 为溶剂， 生成 trans-1,3,4,6,7,11b-Hexahydro-7-hydroxy-7-phenyl-2H-benzoquinolizine 、 cis-1,3,4,6,7,11b-Hexahydro-7-hydroxy-7-phenyl-2H-benzoquinolizine
  参考文献：
  名称：

  Stereospecific enammonium-iminium rearrangements in a benzo[a]quinolizidine system

  摘要：

  Reductive deoxygenation of amino alcohols 5a.HBr or 5b.HBr with borane-THF in trifluoroacetic acid produced a 68:32 mixture of amines 8a and 8b. This is a significant departure from the 8:92 ratio of amines 2a:2b obtained in the reduction of amino alcohols 1a.HBr or 1b.HBr. The diminished trans selectivity with 5 arises from a reduced bias for a cis ring fusion in the N-protonated 6,6 system relative to the 5,6 system. By proton NMR, we observed dehydration of 5a.HBr in CF3CO2D to a 75:25 mixture of enammonium salts trans-6:cis-6, each of which rearranged stereospecifically to give a 75:25 mixture of iminium salts cis-7:trans-7. Rate data for this rearrangement were acquired and computationally analyzed. The dehydration of free base 5b in CF3CO2D was also studied. In this case, we were able to characterize the rate of disappearance of 5b, as well as the rate of the stereospecific enammonium-iminium rearrangement. We also address slow, "post-rearrangement" epimerization at ring position 7, H/D exchange at ring position 6, and mechanistic aspects of the overall process.

  DOI：

  10.1021/jo00030a027
• 作为产物：
  描述：

  2-苯基哌啶 在 sodium hydroxide 、 PPA 作用下， 以 二甲基亚砜 为溶剂， 生成 cis/trans-1,3,4,6,7,11b-Hexahydro-7-hydroxy-7-phenyl-2H-benzoquinolizin-6-one
  参考文献：
  名称：

  Stereospecific enammonium-iminium rearrangements in a benzo[a]quinolizidine system

  摘要：

  Reductive deoxygenation of amino alcohols 5a.HBr or 5b.HBr with borane-THF in trifluoroacetic acid produced a 68:32 mixture of amines 8a and 8b. This is a significant departure from the 8:92 ratio of amines 2a:2b obtained in the reduction of amino alcohols 1a.HBr or 1b.HBr. The diminished trans selectivity with 5 arises from a reduced bias for a cis ring fusion in the N-protonated 6,6 system relative to the 5,6 system. By proton NMR, we observed dehydration of 5a.HBr in CF3CO2D to a 75:25 mixture of enammonium salts trans-6:cis-6, each of which rearranged stereospecifically to give a 75:25 mixture of iminium salts cis-7:trans-7. Rate data for this rearrangement were acquired and computationally analyzed. The dehydration of free base 5b in CF3CO2D was also studied. In this case, we were able to characterize the rate of disappearance of 5b, as well as the rate of the stereospecific enammonium-iminium rearrangement. We also address slow, "post-rearrangement" epimerization at ring position 7, H/D exchange at ring position 6, and mechanistic aspects of the overall process.

  DOI：

  10.1021/jo00030a027