Study On The Synthesis Of New Type Of [60] Fullerene Heterocyclic Compounds

In fullerene chemistry,chemical modification of fullerenes to produce various fullerene derivatives with different structural motifs have attracted extensive attention over the past thirty years because functionalized fullerenes may have great potential applications in mendicinal chemistry,material science,and nanotechnology.Accordingly,the development of new methods for functionalizing fullerene is of great significance.The radical reactions of C₆₀ were among the first to be investigated and continue to be important protocols for fullerene functionalization.Recently,the ferric perchlorate（Fe（ClO₄）₃·xH₂O）-mediated radical reactions of C₆₀ have received increasing attention and have exhibited remarkable advantages over the the radical additions of parent fullerenes induced by traditional peroxide or light,which tend to result in the generation of multi-addition fullerene products extremely difficult to separate and characterize.This work is focused on the Fe（ClO₄）₃·xH₂O-mediated radical addition reactions of C₆₀ with primary amides and diols to afford the scarce fullerooxazoles and fullerene-fused dioxanes/dioxepanes.We have screened a plenty of reaction conditions such as reaction time,reaction temperature,and reaction ratio to obtain the good yields.In addition,new compounds were unambiguously characterized by their HRMS,1H NMR,13C NMR,FT-IR,and UV-vis spectra.At last,we also propose a possible formation mechanism for all the above fullerene derivatives.Chapter Ⅰ:Literature review An overview of recent development of novel fullerene chemical reactions at home and aboard,especially the radical addition reactions of C₆₀ promoted by various metal salts,was made.In addition,the idea about this research was also provided in this chapter.Chapter Ⅱ:The synthesis and characterization of fullerooxazoles The Fe（ClO₄）₃·xH₂O-mediated radical cycloaddition reaction of C₆₀ with a plenty of primary amides generated a series of rare fullerooxazoles.The current one-step approach to the preparation of fullerooxazoles was obviously more straightforward and practical than the previously reported protocols.In addition,we also propose a possible formation mechanism for fullerooxazoles.Chapter Ⅲ:The synthesis and characterization of fullerene-fused dioxanes/dioxepanesThe Fe（ClO₄）₃·xH₂O-mediated one-step cycloaddition reaction of C₆₀ with a plenty of diols generated a series of rare fullerene-fused dioxanes/dioxepanes.In addition,triethylene glycol,diethylene glycol,and tripropylene glycol were also chosen to react with C₆₀ in the presence of Fe（ClO₄）₃,which provided the second route to the preparation of fullerene-fused dioxanes.At last,we also propose a possible formation mechanism for fullerene-fused dioxanes/dioxepanes.