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

独特的芳环体系具有展现物理、化学和生物学特性的潜力，因此通过合理的分子设计获得各种衍生物具有吸引力。在本研究中，我们重点研究了[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张力环体系。(1)对于[60]富勒烯，尝试了各种环加成反应，获得了成功的结果。在1,3-偶极环加成反应中，利用硫代羰基与含s的五元杂环融合得到C_<60>的衍生物，通过S_N1取代在表面附近引入官能团，一系列研究表明，C_<60>核心对S_N1的反应活性没有实质性影响。在没有催化剂的情况下，异氰酸酯可以形成[3+2]正环加成反应，而用Cu_2O可以更有效地得到二氢脯氨酸-熔合C_<60>[4+2]环加成反应。与3,4-融合的吡咯基亚砜发生相同类型的环加成反应，产生了由3,4-二亚甲基吡咯中间体直接捕获的环加合物，这可能反映了[60]富勒烯具有较高的亲自由基性。除了这些环加成外，还尝试了用无机试剂辅助的自由基和亲核加成。用FeCl_3而不是TiCl_4来影响环丙酮硅基缩醛的反应，也显示出较高的亲根性。在不可逆条件下，无机亲核试剂与C_<60>反应；所需要的条件是用一定的试剂实现富勒烯基阴离子中间体的捕获。(2)对方酸进行了环转化研究，发现环丁烯酮环α-位置产生的亚硝基中间体诱导了新的重排。在本实验中，产物为多取代2-氮杂环戊二烯酮，其结构稳定，尽管具有固有的抗芳香族性质，但归因于双共振。进一步的合成应用是用各种亲核试剂和双亲核试剂进行环化，有望形成氮杂环。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