anti-benzotris(norbornadiene)

• 分子结构分类: 有机化合物 - 苯类化合物 - 菲及其衍生物
• 英文名称: anti-benzotris(norbornadiene)
• 英文别名: (1S,4R,7S,10S,13R,16R)-heptacyclo[14.2.1.14,7.110,13.02,15.03,8.09,14]henicosa-2,5,8,11,14,17-hexaene
• 化学式: C₂₁H₁₈
• 分子量: 270.374
• InChiKey: OSJYHCRWTHFGIC-ADUPDYIFSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  4.9
• 重原子数：
  21
• 可旋转键数：
  0
• 环数：
  7.0
• sp3杂化的碳原子比例：
  0.43
• 拓扑面积：
  0
• 氢给体数：
  0
• 氢受体数：
  0

反应信息

• 作为产物：
  描述：

  2,5-降冰片二烯 在 正丁基锂 、 噻吩-2-甲酸亚铜(I) 、 potassium tert-butylate 作用下， 以 四氢呋喃 为溶剂， 生成 anti-benzotris(norbornadiene)
  参考文献：
  名称：

  Sumanene的化学。

  摘要：

  Sumanene（C21 H12）是具有C3v对称性的碗形pi共轭分子，由交替的苯环和围绕中心苯环的环戊二烯环组成。该结构对应于富勒烯或碳纳米管末端的结构图案的最小C3v对称片段。三个sp（3）-杂交的苄基位点的存在是苏南烯中最具特征的结构特征之一，它允许与cor喃烯不同的化学性质。自2003年进行首次合成以来，我们一直从事Suanene的研究。本文总结了我们的持续研究，包括合成，结构，动力学，衍生化，与过渡金属的络合，电荷载流子迁移率以及sum双烯的向氮掺杂石墨碳的转化。

  DOI：

  10.1002/tcr.201402078

文献信息

• Sumanene and method for manufacturing the same
  申请人：Hirao Toshikazu

  公开号：US20060142370A1

  公开（公告）日：2006-06-29

  The present invention provides Sumanene, its derivative and a method for manufacturing Sumanene and its derivative. As shown by a below-described scheme, benzotris(norbornadiene) (a below formula (87)) is firstly synthesized from norbornadiene (a below formula (86)). Then, the compound is subjected to a metathesis reaction so as to synthesize hexahydrosumanene (a below formula (88)), and it is dehydrogenized so as to obtain Sumanene (a below formula (84)). Thereby, Sumanene can be mass-synthesized under a moderate condition. In addition, a compound with a structure where a benzyl position of Sumanene is substituted by a N atom or an O atom can be obtained similarly, and various derivatives also can be obtained by further chemical modification of the compound. Sumanene and its derivative are suitable for electronic materials, synthesis raw materials for various kinds of fullerenes and heterofullerenes, and the like. Condition of the Reaction a) BuLi, t-BuOK, BrCH 2 CH 2 Br, THF, −78° C. to −45° C. subsequently CuI, a room temperature b) catalyst quantity of (PCy 3 ) 2 RuCl 2 ═CHPh, CH 2 ═CH 2 , toluene, 0° C. to 80° C. c) DDQ, toluene, 110° C.

  本发明提供了苏曼烯（Sumanene）、其衍生物以及制备苏曼烯及其衍生物的方法。如下所述的方案所示，首先从去氢莰烯（norbornadiene）（下式（86））合成苯三氮莰烯（benzotris(norbornadiene)）（下式（87））。然后，将该化合物经过交换反应，合成六氢苏曼烯（hexahydrosumanene）（下式（88）），并经脱氢处理，从而得到苏曼烯（下式（84））。因此，在适中条件下可以大规模合成苏曼烯。此外，类似地，可以获得一个结构中苏曼烯的苄位被N原子或O原子取代的化合物，并且通过对该化合物的进一步化学修饰也可以获得各种衍生物。苏曼烯及其衍生物适用于电子材料、各种富勒烯和杂原子富勒烯的合成原料等。反应条件如下：a）BuLi、t-BuOK、Br Br、THF、-78°C至-45°C，随后CuI，室温；b）(PCy3)2RuCl2═CHPh催化剂量、CH2═ 、甲苯、0°C至80°C；c）DDQ、甲苯、110°C。
• syn- and anti-Benzotris(norbornadiene)s
  作者：Richard Durr、Ottorino De Lucchi、Sergio Cossu、Vittorio Lucchini

  DOI：10.1039/cc9960002447

  日期：——

  The hitherto unknown syn and anti isomers of benzotris(norbornadiene) 7, the only molecules that include both features known to lead to bond length alternation in benzenes, i.e. bicyclic ring strain and π–π interaction, have been synthesized from 2,3-dibromonorbornadiene using butyllithium and copper(I) iodide.

  我们使用丁锂和碘化铜（I）从 2,3-二溴降冰片二烯合成了迄今未知的苯并三(降冰片二烯)7 的同分异构体和反异构体，它们是唯一包含已知会导致苯键长度交替的两个特征（即双环应变和 π-π 相互作用）的分子。
• Efficient Cyclotrimerization of Bicyclic <i>v</i><i>ic</i>-Bromostannylalkenes Promoted by Copper(I) Thiophen-2-carboxylate
  作者：Giuseppe Borsato、Ottorino De Lucchi、Fabrizio Fabris、Luca Groppo、Vittorio Lucchini、Alfonso Zambon

  DOI：10.1021/jo020396s

  日期：2002.11.1

  Copper(I) thiophen-2-carboxylate was successfully employed in the trimerization of [2.2.1] bicyclic vic-bromotrimethyltin olefins (in their racemic composition), bearing different functionalities, to invariably obtain almost quantitative yields of the syn and anti tris-annelated benzenes. The two isomers come in different ratios, smaller than or equal to the statistical 1:3 ratio, depending on the steric hindrance opposed by the functionalities. In the case of enantiopure (3-bromo-4,7,7-trimethylbicyclo[2.2.1]hept-2-en-2-yl)trimethylstannane, the 1:9 ratio found with Cu(NO3)(2).3H(2)O increases to 1:6.