N-[2-(2-bromo-4,5-dimethoxyphenyl)ethyl]-2,3-didehydro-3-ethyl-4-oxo-6-phenylpiperidine | 190511-13-8

• 分子结构分类: 有机化合物 - 苯类化合物 - 苯和取代衍生物
• 英文名称: N-[2-(2-bromo-4,5-dimethoxyphenyl)ethyl]-2,3-didehydro-3-ethyl-4-oxo-6-phenylpiperidine
• 英文别名: 1-[2-(2-Bromo-4,5-dimethoxyphenyl)ethyl]-5-ethyl-2-phenyl-2,3-dihydropyridin-4-one
• CAS: 190511-13-8
• 化学式: C₂₃H₂₆BrNO₃
• 分子量: 444.368
• InChiKey: MGUJFUJKPLMCBX-UHFFFAOYSA-N

物化性质

• 沸点：
  554.6±50.0 °C(Predicted)
• 密度：
  1.271±0.06 g/cm3(Predicted)

计算性质

• 辛醇/水分配系数(LogP)：
  5
• 重原子数：
  28
• 可旋转键数：
  7
• 环数：
  3.0
• sp3杂化的碳原子比例：
  0.35
• 拓扑面积：
  38.8
• 氢给体数：
  0
• 氢受体数：
  4

反应信息

• 作为反应物：
  描述：

  N-[2-(2-bromo-4,5-dimethoxyphenyl)ethyl]-2,3-didehydro-3-ethyl-4-oxo-6-phenylpiperidine 在 tris(dibenzylideneacetone)dipalladium(0) chloroform complex 、 四乙基氯化铵 、 potassium carbonate 、 三苯基膦 作用下， 以 甲苯 为溶剂， 反应 26.0h， 以53%的产率得到
  参考文献：
  名称：

  Construction of the tricyclic benzoquinolizine ring system by combination of a tandem Mannich-Michael reaction with a Heck reaction

  摘要：

  Tetrahydro- and hexahydrobenzo[a]quinolizinones can be built up efficiently by means of a two step reaction sequence consisting of a tandem Mannich-Michael reaction and a Heck reaction. (C) 1997 Elsevier Science Ltd.

  DOI：

  10.1016/s0040-4039(97)00494-2
• 作为产物：
  描述：

  2-(2-溴-4,5-二甲氧基苯基)乙胺盐酸盐 在 magnesium sulfate 、 zinc(II) chloride 作用下， 以 四氢呋喃 、 二氯甲烷 为溶剂， 反应 20.0h， 生成 N-[2-(2-bromo-4,5-dimethoxyphenyl)ethyl]-2,3-didehydro-3-ethyl-4-oxo-6-phenylpiperidine
  参考文献：
  名称：

  Three-Step Access to the Tricyclic Benzo[a]quinolizine Ring System

  摘要：

  Access to the tricyclic benzo[a]quinolizine ring system, which forms the characteristic framework of alkaloids of the berberine and emetine type, is readily obtained by a three-step reaction sequence. This sequence includes the formation of a Schiff base, derived from a 2-bromo-substituted phenylethylamine, and its tandem Mannich/conjugate addition reaction with an electron-rich silyloxy diene forming an intermediate enaminone, which subsequently undergoes a Heck-type cyclization. Highest yields of the tandem Mannich/conjugate addition for aromatic Schiff bases and formaldehyde imines are observed in the presence of ZnCl2 in THF, whereas aromatic imines give the best results in the presence of EtAlCl2 in CH2Cl2. The best results for the Heck-type cyclizations are obtained either under heterogeneous conditions in the presence of K2CO3/NEt4Cl at 120 degrees C in DMF or in refluxing toluene or under homogeneous conditions at 100 degrees C in DMF in the presence of NEt-(i-Pr)(2). Depending on the substitution pattern of the diene and the steric demand of the base employed in the Heck cyclization, benzo[a]quinolizines carrying a double bond in the 11b,1- or 3,4-position or in an exocyclic position are obtained with fair to good results. A mechanistic rationale for this behavior is proposed. If chiral amines, e.g., derived from an amino acid ester, are employed in the three-step reaction sequence, chiral tricyclic benzo[a]quinolizines become accessible in a straightforward manner.

  DOI：

  10.1021/jo972035w

文献信息

• Three-Step Access to the Tricyclic Benzo[<i>a</i>]quinolizine Ring System
  作者：Stephan Kirschbaum、Herbert Waldmann

  DOI：10.1021/jo972035w

  日期：1998.7.1

  Access to the tricyclic benzo[a]quinolizine ring system, which forms the characteristic framework of alkaloids of the berberine and emetine type, is readily obtained by a three-step reaction sequence. This sequence includes the formation of a Schiff base, derived from a 2-bromo-substituted phenylethylamine, and its tandem Mannich/conjugate addition reaction with an electron-rich silyloxy diene forming an intermediate enaminone, which subsequently undergoes a Heck-type cyclization. Highest yields of the tandem Mannich/conjugate addition for aromatic Schiff bases and formaldehyde imines are observed in the presence of ZnCl2 in THF, whereas aromatic imines give the best results in the presence of EtAlCl2 in CH2Cl2. The best results for the Heck-type cyclizations are obtained either under heterogeneous conditions in the presence of K2CO3/NEt4Cl at 120 degrees C in DMF or in refluxing toluene or under homogeneous conditions at 100 degrees C in DMF in the presence of NEt-(i-Pr)(2). Depending on the substitution pattern of the diene and the steric demand of the base employed in the Heck cyclization, benzo[a]quinolizines carrying a double bond in the 11b,1- or 3,4-position or in an exocyclic position are obtained with fair to good results. A mechanistic rationale for this behavior is proposed. If chiral amines, e.g., derived from an amino acid ester, are employed in the three-step reaction sequence, chiral tricyclic benzo[a]quinolizines become accessible in a straightforward manner.
• Construction of the tricyclic benzoquinolizine ring system by combination of a tandem Mannich-Michael reaction with a Heck reaction
  作者：Stephan Kirschbaum、Herbert Waldmann

  DOI：10.1016/s0040-4039(97)00494-2

  日期：1997.4

  Tetrahydro- and hexahydrobenzo[a]quinolizinones can be built up efficiently by means of a two step reaction sequence consisting of a tandem Mannich-Michael reaction and a Heck reaction. (C) 1997 Elsevier Science Ltd.