2-bromobicyclo<2.2.2>oct-2-ene | 90002-37-2

• 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: 2-bromobicyclo<2.2.2>oct-2-ene
• 英文别名: 2-bromobicyclo[2.2.2]octene；Bicyclo[2.2.2]oct-2-ene, 2-bromo-；2-bromobicyclo[2.2.2]oct-2-ene
• CAS: 90002-37-2
• 化学式: C₈H₁₁Br
• 分子量: 187.079
• InChiKey: XBDJDMNKFWMRKU-UHFFFAOYSA-N

物化性质

• 沸点：
  64-65 °C(Press: 6 Torr)
• 密度：
  1.454±0.06 g/cm3(Predicted)

计算性质

• 辛醇/水分配系数(LogP)：
  2.9
• 重原子数：
  9
• 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-bromobicyclo<2.2.2>oct-2-ene 在 正丁基锂 、 potassium tert-butylate 、 溴 作用下， 以 四氢呋喃 、 四氯化碳 、 正己烷 为溶剂， 反应 2.0h， 生成 3,10-diphenyl-17-oxapentacyclo[10.2.2.13,10.02,11.04,9]heptadeca-2(11),4,6,8-tetraene
  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
• 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 、 氯仿 为溶剂， 反应 2.0h， 生成 2-bromobicyclo<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

• Nickel‐Catalyzed Conversion of Enol Triflates into Alkenyl Halides
  作者：Julie L. Hofstra、Kelsey E. Poremba、Alex M. Shimozono、Sarah E. Reisman

  DOI：10.1002/anie.201906815

  日期：2019.10.14

  A Ni-catalyzed halogenation of enol triflates was developed and it enables the synthesis of a broad range of alkenyl iodides, bromides, and chlorides under mild reaction conditions. The reaction utilizes inexpensive, bench-stable Ni(OAc)2 ⋅4 H2 O as a precatalyst and proceeds at room temperature in the presence of sub-stoichiometric Zn and either 1,5-cyclooctadiene or 4-(N,N-dimethylamino)pyridine

  开发了镍催化的烯醇三氟甲磺酸酯卤化反应，能够在温和的反应条件下合成多种烯基碘化物、溴化物和氯化物。该反应使用廉价、实验室稳定的 Ni(OAc)2·4 H2 O 作为预催化剂，并在亚化学计量的 Zn 和 1,5-环辛二烯或 4-(N,N-二甲基氨基) 存在下在室温下进行吡啶。
• Synthesis, Structure, and Dynamic Behavior of Cyclopentadienyl-Lithium, -Sodium, and -Potassium Annelated with Bicyclo[2.2.2]octene Units:  A Systematic Study on Site Exchange of Alkali Metals on a Cyclopentadienyl Ring in Tetrahydrofuran
  作者：Tohru Nishinaga、Daisuke Yamazaki、Helmut Stahr、Atsushi Wakamiya、Koichi Komatsu

  DOI：10.1021/ja0346431

  日期：2003.6.1

  kcal mol(-)(1) for M = Na; 115.4 kcal mol(-)(1) for M = K). These values should be compensated for by a decrease in the solvation energies for the metal ions with increasing size, as exemplified by the calculated solvation energy for M(+)(Me(2)O)(4), which serves as a model for metal ions solvated with four molecules of THF (-122.9 kcal mol(-)(1) for M = Li; -94.7 kcal mol(-)(1) for M = Na; -67.7 kcal

  新型环戊二烯基 (Cp)-碱金属配合物 1-M 和 2-M (M = Li, Na, K)，其中 Cp 环与两个双环 [2.2.2] 辛烯单元退火并被苯基取代合成了 1 和 2 的叔丁基，并通过 X 射线晶体学、动态 (13)C 核磁共振和 DFT 计算研究了它们的结构和动力学行为。X 射线晶体学结果表明，1-Li、1-Na 和 2-Na 与三个与金属原子配位的 THF 分子形成单体接触离子对 (CIP)。此外，在 THF-d(8) 中，所有 1-M 和 2-M 都在基态形成单体 CIP。然而，在 THF-d(8) 中 1-M 和 2-M 的变温 (13) C NMR 测量显示了动态行为，其中金属离子在 Cp 环的上下表面之间交换位置。从动态行为的浓度依赖性研究中，发现交换主要作为浓度范围低于 0.2 M 的分子内过程进行。实验观察到的所有 1-M 和 2-M 分子内交换过程的 deltaG
• 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：——
• 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).