Synthesis and Properties of Novel pi-Electronic Hydrocarbons Having sigma-pi Interaction

1.环戊二烯-双环烯键合体系的合成以双环[2.2.2]辛烯（简称BCO）为结构单元，合成了具有新性质的pi体系。因此，合成了一系列与两个BCO单元相连的取代环戊二烯基衍生物，并对其氧化还原行为进行了详细的研究。含BCO基团的硅烷和锗环戊二烯的合成。上述硅洞和细菌衍生物是新合成的，并对其光谱性质进行了全面表征。根据紫外数据和MO计算结果，研究了西格玛- π相互作用的存在。与两个BCO单元相连的苯的生成。捕集实验证实了上述苯的生成。该苯还被转化为联苯衍生物，并澄清了其独特的氧化还原行为。四羧基蒽的合成及性质研究。上述蒽衍生物是由BCO二聚体以对苯醌为亲二酚，采用双Diels- Alder反应合成的。利用电化学和有机化学氧化还原反应证明了由于sigma-pi相互作用导致HOMO水平的显著增加。该蒽衍生物成功地生成了稳定的阳离子自由基和阳离子。

1.Synthesis of the Cyclopentadienylpi-System Annelated with Bicyclooctene Frameworks.Bicyclo [2.2.2] octene (abbreviated as BCO) was used as the structural unit for the synthesis of pi-systems having novel properties. Thus, a series of substituted cyclopentadienyl derivatives annelated with two BCO units have been synthesized and their redox behaviors investigated in detail.2.Synthesis of Sila-and Germacyclopentadienes Annelated with BCO Units.The above silole and germole derivatives have been newly synthesized and their spectral properties fully characterized. The presence of sigma-pi interaction has been investigated based on the results of UV data and MO calculations.3.Generation of the Benzyne Annelated with Two BCO Units.The generation of the above mentioned benzyne has been confirmed by trapping experiment. This benzyne has also been converted to the biphenylene derivative and its unique redox behaviors were clarified.4.Synthesis and Properties of the Anthracene Annelated with Four BCO Units.The above mentioned anthracene derivative has been newly synthesized by the use of double Diels- Alder reaction of the BCO dimer with p-benzoquinone as a dienophile. The notable increase in HOMO level owing to the sigma-pi interaction has been demonstrated by the use of electrochemical and organochemical redox reactions. The stable cation radical and dication have successfully been generated from this anthracene derivative.