2,3-dibromobicyclo(2.2.2)oct-2-ene | 112439-97-1

• 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: 2,3-dibromobicyclo(2.2.2)oct-2-ene
• 英文别名: 2,3-dibromobicyclo[2.2.2]oct-2-ene；Bicyclo[2.2.2]oct-2-ene, 2,3-dibromo-
• CAS: 112439-97-1
• 化学式: C₈H₁₀Br₂
• 分子量: 265.975
• InChiKey: IOXQMGXGHAMEKU-UHFFFAOYSA-N

物化性质

• 熔点：
  51.5-53 °C(Solv: ethanol (64-17-5))
• 沸点：
  267.5±13.0 °C(Predicted)
• 密度：
  1.886±0.06 g/cm3(Predicted)

计算性质

• 辛醇/水分配系数(LogP)：
  3
• 重原子数：
  10
• 可旋转键数：
  0
• 环数：
  3.0
• 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：

  2,3-dibromobicyclo(2.2.2)oct-2-ene 在 palladium diacetate 六正丁基二锡 、 三苯基膦 作用下， 反应 24.0h， 以100%的产率得到1,2,3,4,5,6,7,8,9,10,11,12-dodecahydro-1,4:5,8:9,12-triethanotriphenylene
  参考文献：
  名称：

  Palladium-catalysed cyclotrimerisation reactions of polycyclic alkenes under the Stille and Grigg coupling conditions

  摘要：

  在钯催化下，预先形成或原位生成的多环溴代烷基烯烃在Stille或Grigg反应条件下，通过三碳-碳偶联反应生成环三聚物加合物。

  DOI：

  10.1039/b006698m
• 作为产物：
  描述：

  2,2,2-双环-2-辛烯 在 potassium tert-butylate 、 溴 作用下， 以 四氢呋喃 、 吡啶 、 四氯化碳 、 氯仿 为溶剂， 反应 3.5h， 生成 2,3-dibromobicyclo(2.2.2)oct-2-ene
  参考文献：
  名称：

  Generation and oligomerization of bicyclo[2.2.2]octyne and properties of tris(bicyclo[2.2.2]octeno)benzene obtained from the linear trimer

  摘要：

  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).

  DOI：

  10.1021/jo00001a039

文献信息

• Chiral Organic Radical Cation and Dication. A Reversible Chiroptical Redox Switch Based on Stepwise Transformation of Optically Active Tetrakis(<i>p</i>-alkoxyphenyl)ethylenes to Radical Cations and Dications
  作者：Tadashi Mori、Yoshihisa Inoue

  DOI：10.1021/jp044917m

  日期：2005.3.1

  visible region, while the radical ion was blue in color and exhibited a weak Cotton effect, with the dication green and giving an intense Cotton effect and a sign opposite that observed for the radical cation, at a longer wavelength. Molecular orbital calculations and X-ray crystallographic studies clearly indicate that the olefinic C=C bond is significantly twisted in the dication to minimize the electrostatic

  发现光学活性的四（对烷氧基苯基）乙烯在氧化还原转化时起可逆的手性开关作用。手性修饰的四芳基乙烯连续的单电子氧化为相应的自由基阳离子，然后再变为指示剂，导致电子吸收和圆二色性（CD）光谱发生了戏剧性的变化。中性物质在可见区域没有显示颜色或CD，而自由基离子的颜色为蓝色，并表现出较弱的Cotton效应，带有绿色指示，并表现出强烈的Cotton效应，并且与自由基阳离子处观察到的符号相反。更长的波长。分子轨道计算和X射线晶体学研究清楚地表明，烯烃C = C键在指示剂中显着扭曲，以最大程度地减少静电和空间排斥。通过降低指示剂的温度，围绕双键的扭曲可以更牢固地固定在P或M手性上，从而产生更强的Cotton效应和更大的各向异性（g）因子。由于光谱变化在多个氧化还原循环中是完全可逆的且可重现的，因此该手性氧化还原系统可用于新型氧化还原驱动的按摩疗法应用，例如分子开关和存储设备，其中信息以三态模式按手性进行
• Novel Synthesis and Structures of Tris-Annelated Benzene Donors for the Electron-Density Elucidation of the Classical Mills−Nixon Effect
  作者：R. Rathore、S. V. Lindeman、A. S. Kumar、J. K. Kochi

  DOI：10.1021/ja980805v

  日期：1998.6.1

  alternation relevant to the Mills−Nixon effect. Most importantly, the efficient synthesis of 1s crystals of extraordinary quality allows us (for the first time) to make precise electron-density measurements of the “banana-type” distortion and the ellipticity (π-character) of the various aromatic C−C bondssufficient to identify the electronic origin of the classical Mills−Nixon effect. The unique electron-donor

  一种用于高产合成各种三-、双-和单-退火苯（以及环辛四烯）的通用方法是基于 Pd 催化偶联的三个（或四个）由 α,β- 组成的烯基单元二溴烯烃和α'-烯基格氏试剂全部在一个锅中进行。对三（双环戊基）-退火苯的特殊应用产生了高纯度的顺式异构体 1s；X 射线衍射分析证实了与 Mills-Nixon 效应相关的芳香键交替。最重要的是，高质量 1s 晶体的有效合成使我们（第一次）能够对“香蕉型”畸变和各种芳香 C-C 的椭圆度（π 特性）进行精确的电子密度测量。键足以识别经典 Mills-Nixon 效应的电子起源。
• Vicinal-diaryl interactions in stilbenoid hydrocarbons as observed in the through-space charge delocalization of their cation radicals
  作者：Rajendra Rathore、Jay K Kochi

  DOI：10.1139/v99-081

  日期：1999.6.1

  The conformational preference of vicinal or 1,2-phenyl groups is probed in two classes of ring-substituted 1,2-diphenylbicyclooctene (stilbenoid) hydrocarbons 1a-1d and 2a-2c. UV-vis spectroscopy reveals, and X-ray crystallography verifies, the intramolecular (edge-to-face) orientation for the phenyl-phenyl interaction in stilbenoids 1a-1d. Most importantly, when two pairs of ortho-methyl substituents are present, the cofacial phenyl groups in the stilbenoid donors are established by X-ray crystallography and spectrally observed in the cation radicals (2a^+.-2c^+.) by the appearance of new bands with strong absorptions in the near IR with λ_max = 1100-1315 nm, analogous to those previously observed in intermolecular (aromatic) interactions of aromatic cation radicals.Key words: stilbenoid hydrocarbon, cation radical, aryl-aryl interaction.

  在两类环替代的1,2-二苯基双环辛烷（stilbenoid）碳氢化合物1a-1d和2a-2c中，探测了邻位或1,2-苯基的构象偏好。UV-vis光谱揭示了，X射线晶体学证实了，stilbenoid 1a-1d中苯-苯相互作用的分子内（边缘对面）取向。最重要的是，当存在两对邻甲基取代基时，在X射线晶体学中建立了stilbenoid供体中的同面苯基团，并通过在阳离子自由基（2a+. -2c+.）中出现具有强吸收的新带，其λmax = 1100-1315 nm，类似于以前观察到的芳香族阳离子自由基的分子间（芳香族）相互作用。关键词：stilbenoid碳氢化合物，阳离子自由基，芳基-芳基相互作用。
• Synthesis and Properties of Novel Oligothiophenes Surrounded by Bicyclo[2.2.2]octene Frameworks
  作者：Atsushi Wakamiya、Daisuke Yamazaki、Tohru Nishinaga、Toshikazu Kitagawa、Koichi Komatsu

  DOI：10.1021/jo034754i

  日期：2003.10.1

  Novel oligothiophenes surrounded by bicyclo[2.2.2]octene (abbreviated as BCO) frameworks ranging from dimer to hexamer, 1(nT) (n = 2, 3, 4, 6), were prepared, and their structures and electronic properties were investigated. Dimer 1(2T) was synthesized by oxidative coupling of the 2-lithiated monomer generated from 4,5-BCO-annelated 2-bromothiophene 8 with CuCl2 in 76% yield. Trimer 1(3T) and tetramer

  制备了由二聚体到六聚体1（nT）（n = 2、3、4、6）的双环[2.2.2]辛烯（缩写为BCO）构架包围的新型低聚噻吩，并研究了它们的结构和电子性质。二聚体1（2T）是通过将4,5-BCO退火的2-溴噻吩8与CuCl2氧化生成的2-锂化单体以76％的收率合成的。三聚体1（3T）和四聚体1（4T）通过2,5-二溴-3,4-BCO退火的噻吩4和双（3,4-BCO的5,5'-二溴衍生物）的Stille偶联合成（2-噻吩-2-基）10与2-甲锡烷基化的4,5-BCO退火的噻吩9的产率分别为41％和46％。六聚体1（6T）是通过将对噻吩12与BCO单元进行三价退火氧化偶联而合成的，产率为81％。X射线晶体学研究表明，1（2T）和1（3T）中的噻吩环绕环间CC键旋转，其中C = CC = C二面角为-174.3（5）度，为1 （2T）和-149.7（3）度以及1（3T）的34.4（3）度。在1（2T
• An Efficient Venus Flytrap for the Reversible Binding of Nitric Oxide
  作者：Rajendra Rathore、Sergey V. Lindeman、Jay K. Kochi

  DOI：10.1002/(sici)1521-3773(19980619)37:11<1585::aid-anie1585>3.0.co;2-w

  日期：1998.6.19

  Remarkably efficient reversible binding of nitric oxide (NO) by the stilbenoid derivative 1 is observed (K>3×106 M-1 ). This noncovalent interaction is readily controlled by simple oxidation and reduction.

  观察到二苯乙烯类衍生物1对一氧化氮（NO）的显着有效的可逆结合（K＞ 3×10 6 M -1）。这种非共价相互作用很容易通过简单的氧化和还原来控制。