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

独特芳香环体系的加成反应及其环转化和摩擦学应用

• 批准号: 12650839
• 负责人: OHNO Masatomi
• 金额: $ 2.37万
• 依托单位: Toyota Technological Institute
• 依托单位国家: 日本
• 项目类别: Grant-in-Aid for Scientific Research (C)
• 财政年份: 2000
• 资助国家: 日本
• 起止时间: 2000 至 2001
• 项目状态: 已结题
• 来源: https://kaken.nii.ac.jp/grant/KAKENHI-PROJECT-12650839/
• 关键词: fullerene; squaric acid; cycloaddition reaction; radical addition; nucleophilic addition; azacyclopentadienone; anti-aromaticity; nitrogen-heterocycle; ラジカル反応; アジ化ナトリウム; 酸素酸化; アザシクロペンタジエノン; 含窒素多環系化合物; [60]フラーレン; 親電子置換反応; ラジカル付加反応; ニトレン中間体

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

独特的芳香环体系具有潜在的物理、化学和生物学特性，因此通过合理的分子设计可以得到各种各样的衍生物。本论文主要研究[60]富勒烯和方酸作为球形π电子离域独特环体系和平面非苯型应变环体系。(1)对于[60]富勒烯，尝试了各种环加成反应，并获得了成功的结果。在1，3-偶极环加成反应中，利用硫代羰基叶立德<60>与含S的五元杂环稠合得到C_衍生物，通过SN 1取代在表面附近引入官能团，一系列研究表明C_<60>核心didi对SN 1反应活性没有实质影响。在无催化剂的条件下，与异腈发生[3+2]环加成反应，但Cu_2O的催化作用更有利于二氢脯氨酸稠合的C_<60>[4+2]环加成反应 ...更多信息 与环辛四烯进行了环加成反应，结果表明该环加成物具有C_<60>基特征。与3，4-稠合吡咯并环丁砜的相同类型的环加成不寻常地提供了源自3，4-二亚甲基吡咯中间体的直接捕获的环加合物，并且这可能反映了[60]富勒烯的高亲自由基性。除了这些环加成，自由基和亲核加成与无机试剂的帮助下进行了尝试。环丙酮甲硅烷基缩醛的反应是用FeCl_3而不是TiCl_4进行的，也表明了上述高亲自由基性。在不可逆条件下，发现无机亲核试剂与C_反应<60>，所需条件是用一定的试剂实现富勒烯阴离子中间体的捕获。(2)对于方酸，研究了环化反应，发现了环丁烯酮环α位上生成的氮烯中间体诱导的重排反应。在这种情况下，产物是多取代的2-氮杂环戊二烯酮，并且其稳定的结构，尽管具有固有的反芳族性质，但归因于双共振。进一步的合成应用是通过与各种单和双亲核试剂的环合进行的，有望形成氮杂环。少

项目成果

H. Ishida, H. Asaji, T. Hida, K. Itoh, and M. Ohno: "SYNTHESIS OF DICARBOXYLIC ACID DERIVATIVES [60]FULLERENE USING DIELS-ALDER REACTION WITH BIS(METHYLENEBUTANEDIOATES"Tetrahedron Lett.. 41. 2153-2156 (2000)

H. Ishida、H. Asaji、T. Hida、K. Itoh 和 M. Ohno：“使用双亚甲基丁二酸酯的狄尔斯-阿尔德反应合成二羧酸衍生物 [60] 富勒烯”Tetrahedron Lett.. 41. 2153-2156

Y.Tsunenishi: "Heterocyclization of [60]Fullerene with Isocyanides"Synlett. 1318-1320 (2000)

Y.Tsunenishi：“[60]富勒烯与异氰化物的杂环化”Synlett。

大野 正富: "フラーレンのラジカル付加:FeCl_3触媒によるシクロプロパノンシリルアセタールとC_<60>との反応"糖鎖物質設計プロジェクト論文集. 51-52 (2002)

Masatomi Ohno：“富勒烯的自由基加成：使用 FeCl_3 催化剂的环丙酮甲硅烷基缩醛和 C_<60> 的反应”聚糖材料设计项目论文 51-52 (2002)。

Y. Tsunenishi, H. Ishida, K. Itoh, and M. Ohno: "HETEROCYCLIZATION OF [60]FULLERENE WITH ISOCYANIDES"Synlett.. 1318-1320 (2000)

Y. Tsunenishi、H. Ishida、K. Itoh 和 M. Ohno：“[60]富勒烯与异氰化物的杂环化”Synlett.. 1318-1320 (2000)

H. Ishida, H. Asaji, K. Itoh, and M. Ohno: "CYCLOADDITION REACTION OF C_60 WITH 2-DIAZO-1,3-DITHIANE AND OXIDATION OF THE CYCLOADDUCT TO SUFOXIDE DERIVATIVES"Heterocyclic Commun.. 7. 223-226 (2001)

H. Ishida、H. Asaji、K. Itoh 和 M. Ohno：“C_60 与 2-重氮-1,3-二噻烷的环加成反应以及环加合物氧化成磺氧化物衍生物”杂环通讯.. 7. 223-226