Reactions of N-(vinylimonophosphoranes) : Synthesis and properties of new aromatic compounds

[（甘菊环-2-基）亚氨基]正膦和[（1-氮杂甘菊环基）亚氨基]正膦的制备及其与2-溴代托品酮的热反应得到6-氮杂-和6，7-二氮杂甘菊环并[1，2-a]甘菊环。通过NMR和电子光谱研究，包括PPP型分子轨道计算，发现化合物中几乎没有18-π共轭的贡献，而是由两个甘菊环型π体系组成。研究了这两种化合物在酸性介质中以阳离子和双阳离子形式存在的情况。与这些研究相关，还通过2 H-环庚并[B]-呋喃-2-酮与2-（1-吡咯烷基）-3（2，4，6-环庚三烯基）丙烯的热反应和随后的氢化物夺取-去质子化过程制备了甘菊环-[1，2-a]甘菊环。光谱数据也表明该化合物由两个甘菊环型π-体系组成，与理论预测一致。此外，二苯基膦基托酮亚胺与烯醇化物反应，得到1-氮杂氮杂环烯衍生物。进一步的研究正在我们的实验室进行，以探索该方法的scope和通用性。

Preparation and thermal reactions of [(azulen-2-yl) imino] phosphorane and [(1-azaazulenyl) imino] phosphorane with 2-bromotropone afforded 6-aza-and 6,7-diazaazuleno [1,2-a] azulenes. The NMR and electronic spectral studies including PPP-type MO calculations of the compounds revealed that there are litle contribbution of peropheral 18-pi conjugation, but there are rather composed of two azulene-type pi-systems. The both compounds existing as cationic and dicationic species in acidic media were also studied. In relation to the studies, azuleno-[1,2-a] azulene was also prepared through the thermal reaction of 2H-cyclohepta [b]-furan-2-one with 2-(1-pyrrolidinyl)-3(2,4,6-cycloheptatrienlylpropene and subsequent hydride abstraction-deprotonation processes. The spectral data revealed also that the compound are composed of two azulene-type pi-systems, are agreeable with the theoretical predictions.Furthermore, diphenylphosphinyltroponeimine reacted with enolates to give 1-azaazalene derivatives. Furthear studies are underway in our laboratory to explore the scompe and generality of the methodology.