bis(3-bromobicyclo[2.2.2]oct-2-en)-2-yl | 112439-98-2

• 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: bis(3-bromobicyclo[2.2.2]oct-2-en)-2-yl
• 英文别名: 2,2'-Bibicyclo[2.2.2]oct-2-ene, 3,3'-dibromo-；2-bromo-3-(3-bromo-2-bicyclo[2.2.2]oct-2-enyl)bicyclo[2.2.2]oct-2-ene
• CAS: 112439-98-2
• 化学式: C₁₆H₂₀Br₂
• 分子量: 372.143
• InChiKey: AGPBIPTZUQKKKZ-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  4.7
• 重原子数：
  18
• 可旋转键数：
  1
• 环数：
  6.0
• sp3杂化的碳原子比例：
  0.75
• 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：

  bis(3-bromobicyclo[2.2.2]oct-2-en)-2-yl 在 正丁基锂 、 sodium naphthalenide 作用下， 以 四氢呋喃 为溶剂， 生成 9-[3-(2-bicyclo[2.2.2]oct-2-enyl)-2-bicyclo[2.2.2]oct-2-enyl]pentacyclo[10.2.2.24,7.02,11.03,8]octadeca-2,8,10-triene
  参考文献：
  名称：

  双环[2.2.2]辛烯骨架完全退火的萘的合成，结构与性能

  摘要：

  合成了带有四个双环[2.2.2]辛烯骨架的新型萘衍生物4。X射线分析表明4的并苯核芯偏离平面度。循环伏安法显示，去离子化在其可氧化性方面具有显着效果，并且4易于转化为高度稳定的自由基阳离子4 +•和离子4 2+。

  DOI：

  10.1016/s0040-4039(98)80036-1
• 作为产物：
  描述：

  2,3-dibromobicyclo(2.2.2)oct-2-ene 在 dibromobis(triphenylphosphine)nickel(II) 正丁基锂 作用下， 以 四氢呋喃 为溶剂， 以34%的产率得到bis(3-bromobicyclo[2.2.2]oct-2-en)-2-yl
  参考文献：
  名称：

  1,2:3,4:5,6-Tris(bicyclo[2.2.2]octeno)tropylium ion: an all-hydrocarbon carbocation with extraordinary stability

  摘要：

  DOI：

  10.1021/ja00210a072

文献信息

• The stable radical cation of thiophene annelated with bicyclo[2.2.2]octene and its reaction with triplet oxygen to give a protonated cation of 2-butene-1,4-dione derivative
  作者：Atsushi Wakamiya、Tohru Nishinaga、Koichi Komatsu

  DOI：10.1039/b201958b

  日期：2002.5.17

  The first isolable salt of the thiophene radical cation was prepared from the derivative annelated with two bicyclo[2.2.2]octene units, and its reaction with triplet oxygen was found to give a novel cation of a proton-chelating 2-butene-1,4-dione derivative with remarkable stability.

  噻吩自由基阳离子的第一个可分离盐是由与两个双环[2.2.2]辛烯单元退火后的衍生物制备的，发现它与三重态氧的反应产生了质子螯合的2-丁烯-1的新型阳离子，具有显着稳定性的4-二酮衍生物。
• 1,2-Dithiin Annelated with Bicyclo[2.2.2]octene Frameworks. One-Electron and Two-Electron Oxidations and Formation of a Novel 2,3,5,6-Tetrathiabicyclo[2.2.2]oct-7-ene Radical Cation with Remarkable Stability Owing to a Strong Transannular Interaction
  作者：Atsushi Wakamiya、Tohru Nishinaga、Koichi Komatsu

  DOI：10.1021/ja028297j

  日期：2002.12.1

  SbCl(5) in CH(2)Cl(2), a radical cation 4.+ was formed, whose spin distribution was determined by ESR spectroscopy and by the results of theoretical calculations (UB3LYP/6-31G). The electronic absorption spectrum of 4.+ in CH(2)Cl(2) exhibited a maximum absorption at 428 nm (epsilon = 2.3 x 10(3)), which was hypsochromically shifted from that of neutral 4 (469 nm). When the radical cation 4.+ was produced

  通过双环 [2.2.2] 辛烯的二锂化二聚体与元素硫以 59% 的产率反应，合成了与双环 [2.2.2] 辛烯骨架 4 退火的 1,2-二硫辛的稳定衍生物，为红色晶体。在-78 摄氏度的 CH(2)Cl(2) 中 4 的循环伏安法在 E(1/2) +0.18 V 和 +0.72 V 与 Fc/Fc(+) 显示两个可逆氧化波，表明自由基在这些条件下，4 的阳离子和双阳离子是稳定的。在以相当低的浓度 (4.0 x 10(-4) M) 对 4 进行化学单电子氧化后，在 CH(2)Cl(2) 中使用 1.5 当量的 SbCl(5)，形成自由基阳离子 4.+ ，其自旋分布由 ESR 光谱和理论计算结果 (UB3LYP/6-31G) 确定。CH(2)Cl(2) 中 4.+ 的电子吸收光谱在 428 nm (epsilon = 2.3 x 10(3)) 处表现出最大吸收，这是从中性 4 (469 nm)
• Generation and oligomerization of bicyclo[2.2.2]octyne and properties of tris(bicyclo[2.2.2]octeno)benzene obtained from the linear trimer
  作者：Koichi Komatsu、Shuji Aonuma、Yasuhisa Jinbu、Ryotaro Tsuji、Chitaru Hirosawa、Kenichi Takeuchi

  DOI：10.1021/jo00001a039

  日期：1991.1

  Reaction of 2,3-dibromobicyclo[2.2.2]oct-2-ene (10) with n-butyllithium in THF at -78-degrees-C affords a series of oligomeric dibromides 11 (n = 2-5), which are composed of linearly bonded bicyclo[2.2.2]oct-2-ene units. A trapping experiment indicated that the reaction proceeds via formation of a highly strained acetylene, bicyclo[2.2.2]octyne (18), as a reactive intermediate. Upon treatment with sodium naphthalenide, the trimer 11 (n = 3) reductively cyclizes to tris(bicyclo[2.2.2]octeno)benzene (12) in high yield. The benzene 12 exhibits a reversible oxidation wave at +1.25 V vs Ag/AgNO3 on cyclic voltammetry and gives a stable cation radical 12.+ electrolytically or by oxidation with H2SO4 in air. In FSO3H, 12 is 100% protonated to give the arenium ion 22. The results of variable-temperature C-13 NMR study indicate that the activation energy for the intermolecular proton transfer of 22 is lower than that for the hexamethylbenzenium ion (23). The rate of intramolecular hydrogen migration is also much faster in 22. These results are in agreement with the relative instability of 22 (pK(AH+) -10.2) as compared with 23 (pK(AH+) -9.01).
• KOMATSU, KOICHI;AONUMA, SHUJI;JINBU, YASUHISA;TSUJI, RYOTARO;HIROSAWA, CH+, J. ORG. CHEM., 56,(1991) N, C. 195-203
  作者：KOMATSU, KOICHI、AONUMA, SHUJI、JINBU, YASUHISA、TSUJI, RYOTARO、HIROSAWA, CH+

  DOI：——

  日期：——
• 1,2:3,4:5,6-Tris(bicyclo[2.2.2]octeno)tropylium ion: an all-hydrocarbon carbocation with extraordinary stability
  作者：Koichi. Komatsu、Hidekazu. Akamatsu、Yasuhisa. Jinbu、Kunio. Okamoto

  DOI：10.1021/ja00210a072

  日期：1988.1