Nitrites-participated Synthesis Of [60] Fulleroisoxazolines Derivatives

Functionalization of fullerenes is an important subject of fullerene chemistry and syhthetic chemistry.Chemical functionanlization can tune their physical and chemical properties and prepare numerous fullerene derivertives with wide applications in nano materials,photoelectric materials,supramolecular chemistry and biomedicine,etc.Therefore,the exploration and development of new methods and strategies to achieve the efficient synthesis and construction of new structures of fullerene derivertives plays an important role in enriching the diversity of fullerene derivatives and expanding their applications.In this dissertation,the main work presented is focused on the functionalization of fullerenes,involving nitrites-participated synthesis of fulleroisoxazolines.A novel reaction for the direct construction of fulleroisoxazoline derivertives has been developed utilizing nitrites as a NO source from simple hydrocarbons via C-H functionalization.The optimal reaction conditions were determined by screening different NO source,additive,solvent,reaction temperature and time.Based on the optimal conditions,we extended a wide range of substrates with different substituents,discussed the effects of substrate electronic effect,steric hindrance on the reaction.At the same time,the radical reaction mechanism for the formation of fulleroisoxazoline derivertives ws also proposed.In addition,the electrochemical properties of new-obtained fulleroisoxazoline derivertives were investigated by cyclic voltammetry.The results show that they can be used as acceptor materials in charge transfer chemistry.In conclusion,we have developed a novel reaction for the preparation of fulleroisoxazolines via the direct NO transfer and C-H functionalization.Readily available starting materials,high atomic economy,broad substrate scope,good functional group compatibility,simple operation as well as scale-up synthesis are merits of this reaction.The present transformation provides a new and pratical route to fulleroisoxazoline derivatives.