Further Study On The Reaction Of [60]Fullerene With Azomethine Ylides And Ethyl Azidoformate

Chemical modification is one of the most important research fields in the fullerene chemistry. Among these various functionalization methods, the Prato's reaction is one of the most effective and convenient one and has been widely used to synthesize many functionalized fullerene derivatives. Besides, theoretical studies on fullerenes should be important to the experimental investigation of fullerenes. In this thesis, we investigated Prato's reaction deeply on stereochemistry and selectivity of the products. We also explored the mechanism of the reaction of [60]fullerene with ethyl azidoformate.We studied the reactions of C60 with a series of azomethine ylides in situ generated from variousα-amino acid derivatives and different aldehydes and obtained some N-unsubstituted fulleropyrrolidine derivatives. The stereo-selectivity of the products was unambiguously assigned based on MS, NMR, IR, UV-vis, and NOESY spectra. Therefore, we concluded that Wilson's structure assignments were incorrect based on our results. From further investigation on these reactions we found that the ratio of cis-isomer and trans-isomer could be influenced by the reaction conditions, such as temperature and reaction time. We also found the interconversion between the two isomers under some conditions. Finally, we proposed a reasonable mechanism for this interconversion.The reaction of C60 with ethyl azidoformate in refluxing 1,1,2,2-tetrachloroethane afforded [5,6] annulene, [6,6] aziridine and oxazoline derivative. We explored the mechanism of the reaction using the B3LYP/6-31G**//AM1 method and found it was consistent with the experimental results.