Syntheses and Properties of Allene・Cumulene Compounds Connecting with Non-benzenoid Aromatics

本课题的目的是合成与环庚二烯、环戊二烯或环丙烯等非苯芳烃具有共轭体系的累积化合物，并研究这些新型共轭化合物的化学和物理性质。为此，合成了芳基环庚三烯乙烯，发现这些化合物很容易形成三种不同的二聚体，并对其性质进行了研究。一些环戊二烯已被报道，但其热不稳定性不允许进行详细的研究。我们发现，在C-1位置氢原子被溴原子取代，使得该体系稳定，并得到了一些环戊二烯-乙烯。研究了环戊二烯类化合物的几种物理性质和热二聚化反应，包括一些芳烯衍生物。建立了二聚化机理。环丙烯衍生物的合成尚未成功。将在专题上作进一步的尝试。对二苯基环丙烯与肼的反应进行了进一步的研究，并探索了该体系通过肉桂酰肼和苯基甲酰胺衍生物得到吡唑衍生物的多重反应性。合成了几种芘衍生物和苯并[a]茚并[1,2,3-cd]偶氮烯衍生物，并研究了它们的化学性质，作为络合物形成和芳烯烯衍生物合成的新材料。

The purpose of our project is to synthesize cumulated compounds which possess conjugate system with non-benzenoid aromatics such as cycloheptatrienylidene, cyclopentadienylidene or cyclopropenylidenes, and to investigate chemical and physical properties of those novel conjugate compounds.For this, arylcycloheptatrienylidene-ethenes were synthesized and it was found that those compounds readily gave three different kinds of dimer which properties were also investigated.Some cyclopentadienylideneethenes have been reported, but their thermal unstability did not allow detailed studies. We found that substitution of hydrogen atom at the C-1 position by bromine atom makes those system stable and some cyclopentadienylidene-ethenes were obtained. Several physical properties and thermal dimerization reactions of the cyclopentadienylidenes including some arylallene derivatives were investigated. As the results, the dimerization mechanisms are established.Syntheses of cyclopropenylidene derivatives have not been succeeded yet. Further attempts will be made in feature. Additional research has been done about reactions of diphenylcyclopropenone with hydrazines and multiple reactivities of this system has been explored to give pyrazole derivatives via cinnamhydrazides and also styrilformazan derivatives.Several pyrene derivatives and benz[a]indeno[1,2,3-cd]azulene derivatives were synthesized and their chemical properties were investigated as new materials for complex formation and for arylallene derivatives' syntheses.