trans-2,3-dibromobicyclo<2.2.2>octane | 72444-00-9

• 分子结构分类: 有机化合物 - 有机卤素化合物 - 有机溴化物
• 英文名称: trans-2,3-dibromobicyclo<2.2.2>octane
• 英文别名: trans-2,3-Dibrom-bicyclo<2.2.2>octan；(2R,3R)-2,3-dibromobicyclo[2.2.2]octane
• CAS: 72444-00-9；90085-73-7；130985-93-2
• 化学式: C₈H₁₂Br₂
• 分子量: 267.991
• InChiKey: IEXHWZUHQJMMGV-DWYQZRHDSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  3.4
• 重原子数：
  10
• 可旋转键数：
  0
• 环数：
  3.0
• sp3杂化的碳原子比例：
  1.0
• 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：

  trans-2,3-dibromobicyclo<2.2.2>octane 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 4.0h， 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 溴 作用下， 以 吡啶 、 氯仿 为溶剂， 以72.3%的产率得到trans-2,3-dibromobicyclo<2.2.2>octane
  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

• 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).