Synthesis Of [60] Fulleroisoxazolines And Fullerene-fused Dibenzothiophene/benzothiophene And Dibenzofuran Derivatives

Due to the unique structure and photoelectric properties,fullerene derivatives exhibit extensive application in material science,biomedicine,supramolecular chemistry and so on.The functionalization of fullerenes has become an important research topic in recent years.On the one hand,the introduction of different organic functionalization on the carbon cage can effectively improve their physical properties and chemical properties,such as solubility,electron affinity and so on.On the other hand,the development of new reaction provides more opportunities for expansion the potential applications in the related field of functional materials.In this dissertation,the main work focus on Ag NO₂-mediated the synthesis of fulleroisoxazolines derivatives and DDQ-mediated the synthesis of[60]fullerene-fused benzothiophene,dibenzothiophene and dibenzofuran derivatives.1.Ag NO₂-mediated the synthesis of fulleroisoxazolines derivativesWe have developed a Ag NO₂-mediated novel transformation of sulfonylhydrazones with[60]fullerene to various fulleroisoxazolines,involving the cleavage of the N–N bond and oxygen transfer.The optimum reaction conditions were determined by screening the different catalysts,acids,bases and temperature.Under the optimized conditions,the substrate scope and functional group compatibility were investigated,and a series of control experiments were performed to shed light on the mechanism of the reaction.2.DDQ-mediated the synthesis of[60]fullerene-fused dibenzothiophene,benzothiophene and dibenzofuran derivatives.We have developed a DDQ-promoted 2,5-dimethyl-3-p-methoxybenzylthiophene,3-methyl-2-p-methoxybenzylbenzothiophene/benzofuranwithfullereneviaatransition-metal-freeoxidative dehydrogenative coupling reaction for the direct construction of novel C₆₀-fused dibenzothiophenes,benzothiophenes and dibenzofurans.By screening the oxidants,solvents,reaction time and so on,the best reaction conditions were obtained.The scope of substrate and the compatibility of functional groups were investigated under the optimum conditions,and the possible reaction mechanism was proposed.