Quadricyclane | 278-06-8

• 分子结构分类: 有机化合物 - 脂质和类脂质分子 - 异戊烯醇脂质
• 英文名称: Quadricyclane
• 英文别名: tetracyclo-[3.2.0.0.^2,7.0^4,6]heptane；tetracyclo[3.2.0.0^2,70^4,6]-heptane
• CAS: 278-06-8
• 化学式: C₇H₈
• 分子量: 92.1405
• InChiKey: DGZUEIPKRRSMGK-BEOVHNCFSA-N

物化性质

• 熔点：
  -45.15°C
• 沸点：
  106.54°C (rough estimate)
• 密度：
  0.8474 (estimate)
• 介电常数：
  2.29

计算性质

• 辛醇/水分配系数(LogP)：
  1.13
• 重原子数：
  7.0
• 可旋转键数：
  0.0
• 环数：
  5.0
• sp3杂化的碳原子比例：
  1.0
• 拓扑面积：
  0.0
• 氢给体数：
  0.0
• 氢受体数：
  0.0

安全信息

• 危险等级：
  3.1
• 海关编码：
  2902199090
• 包装等级：
  II
• 危险类别：
  3.1
• 危险品运输编号：
  UN 1993

反应信息

• 作为反应物：
  描述：

  Quadricyclane 在 tetrasodium (5,10,15,20-tetrakis(4-sulfonatophenyl)porphyrinato)cobalt(II) aluminum oxide 、 4-氨基水杨酸 作用下， 以 正戊烷 为溶剂， 生成 2,5-降冰片二烯
  参考文献：
  名称：

  用于将四环烷转化为降冰片二烯的氧化铝锚定钴卟啉催化剂

  摘要：

  描述了用于制备锚定在涂有聚胺砜-A 的氧化铝珠上的钴 (II) 氘代卟啉和钴 (II) 四（对磺基苯基）卟啉的方法。波长色散 X 射线微量分析表明，钴 (II) 卟啉分布在约 100 微米的催化剂外表面层内。100 微米深度。该催化剂对于四环烷环转化为降冰片二烯具有高活性。使用等温循环反应器的异构化的详细动力学给出了 Langmuir-Hinshelwood 类型的速率表达式。催化剂逐渐失去活性，可通过在真空中将催化剂加热至 200 °C 使其完全再生。

  DOI：

  10.1246/bcsj.61.973
• 作为产物：
  描述：

  exo-3,4-diazotricyclo[4.2.1.0^2,5]nona-3,7-diene 在 Rh(pnen)3⁽³⁺⁾ 作用下， 以 乙腈 为溶剂， 生成 Quadricyclane 、 2,5-降冰片二烯
  参考文献：
  名称：

  Rh(III)-Photosensitized Interconversion of Norbornadiene and Quadricyclane

  摘要：

  The utility of two Rh(III) diimine complexes, Rh(phen)(3)(3+) and Rh(phi)(2)(phen)(3+) (phen = 1,10-phenanthroline, phi = 9,10-phenanthrenequinone diimine), as sensitizers for the interconversion of norbornadiene (N) and quadricyclane (Q) has been investigated using steady-state photochemical and laser flash photolysis (LFP) techniques. Irradiation of acetonitrile solutions of Rh(phen)(3)(3+) and N causes slow conversion to Q. The reaction is reversible; irradiation of Rh(phen)(3)(3+) in the presence of Q leads to N. Irradiation of acetonitrile solutions of Rh(phi)2(phen)3+ and Q yields N. However, this reaction is irreversible; irradiation of the Rh(In) complex in the presence of N fails to afford Q. Irradiation of methanol solutions of either Rh(III) complex in the presence of N or Q affords minor amounts of two methanol-C7 adducts but fails to quench the N-Q interconversion reaction. The results are consistent with N-Q interconversion via an exciplex intermediate. The Rh(III)-sensitized deazatization of two cyclic azoalkane derivatives (Azo-N, Azo-Q) of N and Q was also investigated. Deazatization was achieved by Rh(phen)(3)(3+) but not Rh(phi)(2)(phen)(3+) sensitization. The results are consistent with a mechanism involving triplet energy transfer, but the involvement of exciplex intermediates cannot be ruled out. Bimolecular rate constants for quenching of the Rh(III) excited states by N, Q, Azo-N, and Azo-Q were determined by LFP.

  DOI：

  10.1021/jp972007h

文献信息

• Redox-Photosensitized Aminations of 1,2-Benzo-1,3-cycloalkadienes, Arylcyclopropanes, and Quadricyclane with Ammonia
  作者：Masahide Yasuda、Ryuji Kojima、Hiroshi Tsutsui、Daigo Utsunomiya、Kazuaki Ishii、Koutaro Jinnouchi、Tsutomu Shiragami、Toshiaki Yamashita

  DOI：10.1021/jo030053+

  日期：2003.10.1

  the cation radicals of the sensitizers that were generated by photoinduced electron transfer to the electron acceptors to the substrates. Therefore, it was found that the relationships in oxidation potentials between the sensitizers and the substrates and the positive charge distribution of the cation radicals of the substrates were important factors for the efficient amination.

  1,2,4-三苯苯和2,2'-亚甲基二氧基-1,1'-联萘在存在下用氨和伯胺成功地光敏化1,2-苯并-1,3-环链二烯，芳基环丙烷和四环烷的胺化间-或对-二氰基苯，得到4-氨基-1,2-苯并环烯烃，3-氨基-1-芳基丙烷和7-氨基-5-（对氰基苯基）双环[2.2.1] hept-2 -ene。光敏胺化的关键途径是空穴从敏化剂的阳离子自由基的转移，该阳离子自由基是由光诱导的电子转移到电子受体转移到基体而产生的。因此，发现敏化剂与基材之间的氧化电势与基材的阳离子自由基的正电荷分布之间的关系是有效胺化的重要因素。
• The synthesis of rigid norbornylogs for the purpose of studying orbital interactions through bonds
  作者：Michael N. Paddon-Row、Evangelo Cotsaris、Harish K. Patney

  DOI：10.1016/s0040-4020(01)87597-9

  日期：1986.1

  metal catalyzed (2+2) cycloaddition of DMAD and (2+2+2)cydoaddition of quadricyclane to ene substrates(Scheme).The photoelectron spectra of some of the dienes are discussed in terms of through bond orbital interactions.

  刚性双发色降冰片原木系列4-8的成员的合成进行了描述。二烯图4a和b是根据方案1的还原decolorination合成26-28（方案2），得到二烯5B-d分别。如方案3中所述，使用四氯二甲氧基-环戊二烯，苯使适当的烯底物脱核，得到二苯并化合物6a-c。用适当的二烯捕获二溴喹二甲烷​​中间体49，得到双萘酚化合物7a-c。扩展的降冰原木8a和b 结合了金属催化的DMAD的（2 + 2）环加成和四环烷（2 + 2 + 2）的环加成到烯基上的合成（方案）。通过直键轨道讨论了某些二烯的光电子能谱互动。
• A Simple Entry to Fused <i>N</i>-Aryl 1,2-Thiazetidine-<i>S</i>-Oxides: Thermal Isomerisation to 1,4-Thiazine-<i>S</i>-Oxides and Nucleophilic Ring-Opening with Alcohols and Amines
  作者：Ronald Warrener、Ananda Amarasekara

  DOI：10.1055/s-1997-737

  日期：1997.2

  We show that fused 1,2-thiazetidine-S-oxides can be produced in one step from readily available aryl sulfonylamines by cycloaddition with quadricyclane; these adducts undergo smooth rearrangement to fused 1,4-thiazines-S-oxides on heating, and can be ring-opened with alcohols to form cis-1,2-arylamino sulfinic esters and cis-1,2-arylamino sulfinamides on treatment with amines.

  我们表明，融合的1,2-噻唑烷-S-氧化物可以通过与四环烯的环加成反应，从易得的芳基磺酰胺一次性合成；这些加合物在加热时会顺利重排形成融合的1,4-噻嗪-S-氧化物，并且可以通过醇进行开环反应，生成顺式-1,2-芳基氨基 sulfinic 酯和顺式-1,2-芳基氨基 sulfinamide。
• Synthesis and structural characterization of a novel pair of rigid diastereomeric triads
  作者：James M. Lawson、Donald C. Craig、Anna M. Oliver、Michael N. Paddon-Row

  DOI：10.1016/0040-4020(95)00107-j

  日期：1995.3

  A method is described for constructing totally rigid triad (nichromophoric) systems, D2-B1-D1-B2-A, in which the chromophores D2 (= dimethylaniline), D1 (= 1,4-dimethoxynaphthalene), and A (= dicyanovinyl) are fused to rigid hydrocarbon bridges, B1 and B2, comprising linearly fused norbornane and bicyclo[2.2.0]hexane units.

  描述了一种用于构建完全刚性的三联体（发色团）系统D 2 -B 1 -D 1 -B 2 -A的方法，其中发色团D 2（=二甲基苯胺），D 1（= 1,4-二甲氧基萘），和A（＝二氰基ovyl）稠合到刚性烃桥B 1和B 2，其包括线性稠合的降冰片烷和双环[2.2.0]己烷单元。
• Structure–reactivity factors for exciplex isomerization of quadricyclene and related compounds
  作者：Guilford Jones、Sheau-Hwa Chiang、William G. Becker、Don P. Greenberg

  DOI：10.1039/c39800000681

  日期：——

  The quadricyclenes (1) and (3) are equally effective in exciplex isomerization although other cage hydrocarbons do not undergo efficient reaction when sensitized by aromatic fluorophores; irradiation of charge-transfer complexes of (1) and (3) and electron-deficient alkenes results in efficient valence but not geometrical isomerization.

  四环（1）和（3）在激基异构化中同样有效，尽管当被芳香族荧光团敏化时，其他笼型碳氢化合物并没有发生有效的反应。辐射（1）和（3）的电荷转移络合物以及缺电子的烯烃会导致有效价态，但不会导致几何异构化。