2,3-Bis(3-bromo-2-bicyclo[2.2.2]oct-2-enyl)bicyclo[2.2.2]oct-2-ene | 112439-99-3

• 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-Bis(3-bromo-2-bicyclo[2.2.2]oct-2-enyl)bicyclo[2.2.2]oct-2-ene
• CAS: 112439-99-3
• 化学式: C₂₄H₃₀Br₂
• 分子量: 478.31
• InChiKey: BBEFDROMCARZKS-UHFFFAOYSA-N

物化性质

• 熔点：
  172.5-174 °C(Solv: hexane (110-54-3))
• 沸点：
  518.3±33.0 °C(Predicted)
• 密度：
  1.529±0.06 g/cm3(Predicted)

计算性质

• 辛醇/水分配系数(LogP)：
  6.4
• 重原子数：
  26
• 可旋转键数：
  2
• 环数：
  9.0
• 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-Bis(3-bromo-2-bicyclo[2.2.2]oct-2-enyl)bicyclo[2.2.2]oct-2-ene 在 氟磺酸 、 sodium naphthalenide 作用下， 以 四氢呋喃 为溶剂， 反应 3.5h， 生成
  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：

  2,3-dibromobicyclo(2.2.2)oct-2-ene 在 正丁基锂 作用下， 以 四氢呋喃 、 正己烷 为溶剂， 以18.4%的产率得到2,3-Bis(3-bromo-2-bicyclo[2.2.2]oct-2-enyl)bicyclo[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

• The first silatropylium ion stabilized by rigid σ-frameworks: preparation, properties, and some reactions
  作者：Tohru Nishinaga、Yoshiteru Izukawa、Koichi Komatsu

  DOI：10.1016/s0040-4020(01)00253-8

  日期：2001.4

  demonstrated. When cations 4 and 5 were generated by the use of triphenylmethyl perchlorate instead of triphenylmethyl TPFPB, covalent perchlorate esters 18 and 19 having the O–Si covalent bond were formed instead of ionic salts. By treatment with water, the perchlorate ester 18 was found to undergo a novel rearrangement to give a cyclopentene derivative 20a spiro-connected with bicyclo[2.2.2]octane at the 3-position

  用四（五氟苯基）硼酸酯（TPFPB）作为抗衡阴离子，制备了第一个环状π-共轭硅烷基离子，即在硅原子上带有三个均三甲苯基的三个双环[2.2.2]辛烯单元退火的硅烷基trop离子5在-50°C下通过氢化从相应的硅杂环庚三烯（silepin）中提取2 Cl 2。观察到的阳离子5的1 H，13 C和29 Si NMR化学位移与计算值一致。这些结果和NICS计算表明，阳离子5的芳香性接近对苯二甲基离子的芳香性。阳离子4时在存在两个当量的乙腈的情况下，生成具有甲基而不是均三甲苯基的阳离子和阳离子5，形成具有相当大的共价键特性的乙腈配合物16和17。对于配合物16和17，首次观察到乙腈作为甲硅烷基阳离子的乙腈配合物的交换过程，并且证明了五价硅的中间体。当通过使用高氯酸三苯甲基酯代替三苯基甲基TPFPB生成阳离子4和5时，共价高氯酸酯18和19形成具有O-Si共价键的取代离子盐。通过用水处理，发现高氯酸酯
• Effects of Substituents on Silicon upon the Ring Inversion of Silepins Annelated with Bicyclo[2.2.2]octene Frameworks
  作者：Tohru Nishinaga、Yoshiteru Izukawa、Koichi Komatsu

  DOI：10.1246/cl.1998.269

  日期：1998.3

  The energy barrier for ring inversion of the silepin annelated with bicyclo[2.2.2]octene was found to decrease as the electro-negativity of substituents on silicon increases.

  发现与双环 [2.2.2] 辛烯退火的 silepin 的环反转能垒随着硅上取代基的电负性增加而降低。
• 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
• 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：——
• 1,1-Dimethylsila-, -germa-, and -stannacycloheptatrienes Fully Annelated with Bicyclo[2.2.2]octene: Syntheses, Structures, and Properties
  作者：Tohru Nishinaga、Koichi Komatsu、Nobuyuki Sugita

  DOI：10.1021/jo00110a039

  日期：1995.3

  The titled compounds, i.e., a series of 1,1-dimethyl-2,3:4,5:6,7-tris(bicyclo[2.2.2]octeno)metallacyclo- heptatrienes (metallepins) containing silicon (2a), germanium (2b), and tin (2c), were synthesized by dilithiation of the terminal dibromide of the linear trimer of bicyclo[2.2.2]octene (3) followed by the reaction with (CH3)(2)MCl(2) (M = Si, Ge, Sn). The X-ray structure determination was conducted for the first time for these metallepins containing Group 14 elements and indicated that the central seven-membered ring is in a boat-form for all of 2a-c. As the effective size of the Group 14 metal atom increases, the dihedral angle between the base plane and the stern part of the boat form was found to increase, i.e., the boat structure becomes more deeply folded, for release of the inner angle strain. Variable-temperature NMR measurements indicated that the metallepin ring of 2 is rapidly inverting in solution, and the line-shape analyses gave the activation parameters for ring-inversion at 25 degrees C as follows: 2a, Delta H double dagger = 13.4 +/- 1.3 kcal mol(-1), Delta S double dagger = 3 +/- 5 cal K-1 mol(-1) Delta G double dagger = 12.4 +/- 0.2 kcal mol(-1); 2b, Delta H double dagger = 16.0 +/- 1.8 kcal mol(-1), Delta S double dagger = 7 +/- 6 cal K-1 mol(-1), Delta G double dagger = 14.0 +/- 0.1 kcal mol(-1); 2c, Delta H double dagger = 21.3 +/- 3.1 kcal mol(-1), Delta S double dagger = 10 +/- 9 cal K-1 mol(-1), Delta G double dagger = 18.4 +/- 0.5 kcal mol(-1). Thus, the energy barrier for ring inversion increases as the carbon-metal bond is elongated, reflecting the increasing instability of the planar transition-state structure due to the inner-angle strain. The larger energy barrier for inversion of 2a than that of the corresponding cycloheptatriene 6 implies that the cyclic (p-d)pi delocalization would not be operating in a planar transition-state structure or negligibly small if present. The UV absorption of 2a, 2b, and 2c (lambda(max) in n-hexane. 276, 275, and 268 nm, respectively) did not show much difference from that of the C-unsubstituted metallepins 1a, 1b, and 1c in spite of annelation with three bicyclo[2.2.2]octene units, probably because of the more folded boat structure of the central seven-membered ring and less pi-conjugation in 2a-e than in 1a-c.