Addition Reaction of Unique Aromatic Ring Systems and Their Ring Transformation and Tribological Application

独特的芳环体系具有显示物理、化学和生物特性的潜力，因此通过合理的分子设计来获得各种衍生物是很有吸引力的。在本研究中，我们以[60]富勒烯和方酸作为球形π电子离域唯一环体系和平面非苯类应变环体系。(1)对于[60]富勒烯，尝试了各种环加成反应，并取得了成功的结果。在1，3-偶极环加成反应中，通过与硫代羰基叶立德反应，得到一个与S含五元杂环融合的C_&lt；60&gt；衍生物，通过S_n1取代在近表面引入官能团，一系列研究表明，C_&lt；60&gt；核Didi对S_n1的反应活性没有实质性影响。与异氰酸酯的形式[3+2]环加成反应在没有催化剂的情况下发生，但使用Cu2O更有效地得到了二氢脯氨酸熔融C&gt；60；[4+2]环加成…对环辛四烯进行了更多的研究，结果表明环加成产物具有C_(60)-基的特征。同类型的3，4-稠合吡咯环丁烯与3，4-二甲基吡咯的环加成反应中，通常会生成直接捕获3，4-二甲基吡咯中间体的环加成产物，这可能反映了[60]富勒烯的高亲水性。除了这些环加成反应外，还尝试了无机试剂辅助的自由基加成和亲核加成反应。FeCl3和TiCl4对环丙酮硅基缩醛的反应有一定的影响，表现出较强的亲水性。在不可逆的条件下，发现无机亲核试剂与C&lt；60&gt；发生反应，所需的条件是用一定的试剂捕获富勒烯基阴离子中间体。(2)对于方酸，研究了方酸在环丁烯酮环的α位生成的硝基中间体引起的新的重排反应。在这种情况下，产物是多取代的2-氮杂环戊二烯酮，其稳定的结构，尽管具有内在的抗芳香性，但归因于双重共振。进一步的合成应用是通过与各种单、双亲核试剂环合来进行的，有望形成含氮杂环。较少

Unique Aromatic Ring Systems have potentiality to show physical, chemical and biological characteristics, and therefore they are attractive to obtain various derivatives according to reasonable molecular design. In this study, we focus on [60]fullerene and squaric acid as the spherical π-electron delocalized unique ring system and the planar non-benzenoid strained ring system.(1) As for [60]fullerene, various cycloaddition reactions were tried and successful results were obtained. In 1,3-dipolar cycloaddition, the reaction with thiocarbonyl ylide which gave a C_<60> derivative fused with S-containing five membered heterocycle was utilized for introduction of functional groups near the surface by S_N1 substitution, and a series of studies revealed that C_<60> core didi not affect the S_N1 reactivity substancially. Formal [3+2]cycloaddition with isocyanides was found to occur without catalyst, yet the use of Cu_2O was more effective to give dihydroproline- fused C_<60> [4+2]cycloaddition … More was carried out with cyclooctatetraene, and the cycloadduct was shown to have C_<60>-based characteristics. The same type of cycloaddition with 3,4-fused pyrrolosulfolene unusually afforded a cycloadduct originating from direct trap of 3,4-dimethylenepyrrole intermediate, and this may reflect high radicophilicity of [60]fullerene. Apart from these cycloaddition, radical and nucleophilic additions aided with inorganic reagents were attempted. The reaction of cyclopropanone silyl acetal was effected by the use of FeCl_3 rathan TiCl_4, also indicating high radicophilicity as above. Under irreversible conditions, inorganic nucleophiles were found to react with C_<60>; the required conditions are to realize trapping of a fullerenyl anion intermediate with a certain reagent.(2) As for squaric acid, ring transformation was investigated and novel rearrangement induced by the nitrene inter-mediate which was generated at α-position of the cylobutenone ring was developed. In this case, the product was polysubstituted 2-azacyclopentdienone,and its stable structure, despite of intrinsic anti-aromatic nature, was attributed to double resonace. Further synthetic application was performed by cyclization with various mono- and bi- nucleophilic reagent, promising for the formation of nitrogen-heterocycles. Less