1,4-bis(2-bromolbicyclo[2.2.2]octen-1-yl)butadiyne | 196716-38-8

• 分子结构分类: 有机化合物 - 有机卤素化合物 - 乙烯基卤化物
• 英文名称: 1,4-bis(2-bromolbicyclo[2.2.2]octen-1-yl)butadiyne
• 英文别名: 2-Bromo-3-[4-(3-bromo-2-bicyclo[2.2.2]oct-2-enyl)buta-1,3-diynyl]bicyclo[2.2.2]oct-2-ene
• CAS: 196716-38-8
• 化学式: C₂₀H₂₀Br₂
• 分子量: 420.187
• InChiKey: GYIMNAVZSLJMEK-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  5.5
• 重原子数：
  22
• 可旋转键数：
  3
• 环数：
  6.0
• sp3杂化的碳原子比例：
  0.6
• 拓扑面积：
  0
• 氢给体数：
  0
• 氢受体数：
  0

反应信息

• 作为反应物：
  描述：

  1,4-bis(2-bromolbicyclo[2.2.2]octen-1-yl)butadiyne 、 三甲基乙炔基硅 在 bis-triphenylphosphine-palladium(II) chloride 、 copper(l) iodide 作用下， 以 二氯甲烷 、 二乙胺 为溶剂， 反应 24.0h， 以66.7%的产率得到Trimethyl-[2-[3-[4-[3-(2-trimethylsilylethynyl)-2-bicyclo[2.2.2]oct-2-enyl]buta-1,3-diynyl]-2-bicyclo[2.2.2]oct-2-enyl]ethynyl]silane
  参考文献：
  名称：

  Synthesis, Structure, and Redox Behavior of the Dehydroannulenes Fused with Bicyclo[2.2.2]octene Frameworks

  摘要：

  Two series of dehydroannulenes fused with bicyclo[2.2.2]octene (BCO) units were synthesized either by an oxidative coupling with copper(I) under air or by a palladium-copper-catalyzed coupling. The first series of dehydroannulenes consisted of tetradehydro[l2]annulene (12), hexadehydro[l8]annulene (13), octadehydro[24]annulene (14), and decadehydro[30]annulene (15), which all have the BCO units connected by the butadiyne linkage. The second consisted of tridehydro[12]annulene (16) and tetradehydro[16]annulene (17), which have the BCO units connected by the acetylene bond. The molecular structures of the relatively stable annulenes 13 and 17 were determined by X-ray crystallography, which showed that 13 has a planar ct-system, whereas 17 has a tub structure like cyclooctatetraene. The H-1 NMR signal for the bridgehead proton of the BCO units is a good measure for the ring current effect. This signal clearly indicated the presence of diatropicity in [18]annulene 13 and paratropicity in [12]annulenes 12 and 16. The redox properties of these annulenes were examined by cyclic voltammetry. The antiaromatic [12]- and [16]annulenes 18 and la having only one acetylene bond between the BCO units were found to be more readily oxidized than the other annulenes as expected from the energy level of HOMOs calculated by the PM3 semiempirical MO method.

  DOI：

  10.1021/jo9705531
• 作为产物：
  描述：

  2,3-dibromobicyclo(2.2.2)oct-2-ene 在 bis-triphenylphosphine-palladium(II) chloride 、 氢氧化钾 、 copper(l) iodide 作用下， 以 四氢呋喃 、 甲醇 、 水 、 二乙胺 为溶剂， 反应 15.5h， 生成 1,4-bis(2-bromolbicyclo[2.2.2]octen-1-yl)butadiyne
  参考文献：
  名称：

  Synthesis, Structure, and Redox Behavior of the Dehydroannulenes Fused with Bicyclo[2.2.2]octene Frameworks

  摘要：

  Two series of dehydroannulenes fused with bicyclo[2.2.2]octene (BCO) units were synthesized either by an oxidative coupling with copper(I) under air or by a palladium-copper-catalyzed coupling. The first series of dehydroannulenes consisted of tetradehydro[l2]annulene (12), hexadehydro[l8]annulene (13), octadehydro[24]annulene (14), and decadehydro[30]annulene (15), which all have the BCO units connected by the butadiyne linkage. The second consisted of tridehydro[12]annulene (16) and tetradehydro[16]annulene (17), which have the BCO units connected by the acetylene bond. The molecular structures of the relatively stable annulenes 13 and 17 were determined by X-ray crystallography, which showed that 13 has a planar ct-system, whereas 17 has a tub structure like cyclooctatetraene. The H-1 NMR signal for the bridgehead proton of the BCO units is a good measure for the ring current effect. This signal clearly indicated the presence of diatropicity in [18]annulene 13 and paratropicity in [12]annulenes 12 and 16. The redox properties of these annulenes were examined by cyclic voltammetry. The antiaromatic [12]- and [16]annulenes 18 and la having only one acetylene bond between the BCO units were found to be more readily oxidized than the other annulenes as expected from the energy level of HOMOs calculated by the PM3 semiempirical MO method.

  DOI：

  10.1021/jo9705531

文献信息

• Synthesis, Structure, and Redox Behavior of the Dehydroannulenes Fused with Bicyclo[2.2.2]octene Frameworks
  作者：Tohru Nishinaga、Tetsu Kawamura、Koichi Komatsu

  DOI：10.1021/jo9705531

  日期：1997.8.1

  Two series of dehydroannulenes fused with bicyclo[2.2.2]octene (BCO) units were synthesized either by an oxidative coupling with copper(I) under air or by a palladium-copper-catalyzed coupling. The first series of dehydroannulenes consisted of tetradehydro[l2]annulene (12), hexadehydro[l8]annulene (13), octadehydro[24]annulene (14), and decadehydro[30]annulene (15), which all have the BCO units connected by the butadiyne linkage. The second consisted of tridehydro[12]annulene (16) and tetradehydro[16]annulene (17), which have the BCO units connected by the acetylene bond. The molecular structures of the relatively stable annulenes 13 and 17 were determined by X-ray crystallography, which showed that 13 has a planar ct-system, whereas 17 has a tub structure like cyclooctatetraene. The H-1 NMR signal for the bridgehead proton of the BCO units is a good measure for the ring current effect. This signal clearly indicated the presence of diatropicity in [18]annulene 13 and paratropicity in [12]annulenes 12 and 16. The redox properties of these annulenes were examined by cyclic voltammetry. The antiaromatic [12]- and [16]annulenes 18 and la having only one acetylene bond between the BCO units were found to be more readily oxidized than the other annulenes as expected from the energy level of HOMOs calculated by the PM3 semiempirical MO method.