[2-(2-Bromo-4,5-dimethoxy-phenyl)-ethyl]-[2-methyl-prop-(E)-ylidene]-amine | 210181-42-3

• 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: [2-(2-Bromo-4,5-dimethoxy-phenyl)-ethyl]-[2-methyl-prop-(E)-ylidene]-amine
• 英文别名: N-[2-(2-bromo-4,5-dimethoxyphenyl)ethyl]-2-methylpropan-1-imine
• CAS: 210181-42-3
• 化学式: C₁₄H₂₀BrNO₂
• 分子量: 314.222
• InChiKey: YTPSKKRXJJRNHN-UHFFFAOYSA-N

物化性质

• 沸点：
  385.823±42.00 °C(Press: 760.00 Torr)(predicted)
• 密度：
  1.226±0.14 g/cm3(Temp: 25 °C; Press: 760 Torr)(predicted)

计算性质

• 辛醇/水分配系数(LogP)：
  3.5
• 重原子数：
  18
• 可旋转键数：
  6
• 环数：
  1.0
• sp3杂化的碳原子比例：
  0.5
• 拓扑面积：
  30.8
• 氢给体数：
  0
• 氢受体数：
  3

反应信息

• 作为反应物：
  描述：

  [2-(2-Bromo-4,5-dimethoxy-phenyl)-ethyl]-[2-methyl-prop-(E)-ylidene]-amine 在 tris(dibenzylideneacetone)dipalladium(0) chloroform complex 、 四乙基氯化铵 、 二氯乙基铝 、 potassium carbonate 、 三苯基膦 作用下， 以 二氯甲烷 、 甲苯 为溶剂， 反应 19.0h， 生成 4-Isopropyl-9,10-dimethoxy-1,6,7,11b-tetrahydro-pyrido[2,1-a]isoquinolin-2-one
  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
• 作为产物：
  描述：

  2-(2-溴-4,5-二甲氧基苯基)乙胺盐酸盐 、 异丁醛 以 二氯甲烷 为溶剂， 反应 8.0h， 生成 [2-(2-Bromo-4,5-dimethoxy-phenyl)-ethyl]-[2-methyl-prop-(E)-ylidene]-amine
  参考文献：
  名称：

  通过分子内加成二氢吡啶酮来立体选择性地合成苯并喹喔啉和相关同系物

  摘要：

  描述了一种合成苯并喹喔啉和苯并吲哚并核生物碱支架的有效方法。合成策略基于将锂-卤素交换引发的芳基锂分子内共轭加成到2,3-二氢-4-吡啶酮中。在自由基条件下也进行了类似的环化反应，提供了预期的环状化合物，尽管收率明显降低。研究了链长和受体取代方式对环构建可行性的影响。

  DOI：

  10.1016/j.tet.2016.04.022

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.
• Stereoselective synthesis of benzoquinolizidines and related homologues via intramolecular addition to dihydropyridones
  作者：Piotr Szcześniak、Artur Ulikowski、Olga Staszewska-Krajewska、Grzegorz Lipner、Bartłomiej Furman

  DOI：10.1016/j.tet.2016.04.022

  日期：2016.6

  An efficient method for the synthesis of benzoquinolizidine and benzoindolizidine alkaloid scaffolds is described. The synthetic strategy is based on the lithium–halogen exchange-initiated intramolecular conjugate addition of aryllithiums to 2,3-dihydro-4-pyridones. A similar cyclization was also carried out under free radical conditions providing the expected cyclic compounds, although with significantly

  描述了一种合成苯并喹喔啉和苯并吲哚并核生物碱支架的有效方法。合成策略基于将锂-卤素交换引发的芳基锂分子内共轭加成到2,3-二氢-4-吡啶酮中。在自由基条件下也进行了类似的环化反应，提供了预期的环状化合物，尽管收率明显降低。研究了链长和受体取代方式对环构建可行性的影响。