Study On The Synthesis Of Novel[60]Fullerene Pyrrolidine/Cyclopentane Derivatives

Chemical modification of fullerenes has been one of the main research fields of fullerene chemistry.Over the past three decades,a large number of novel fullerene derivatives,which may have great potential applications in the fields of photoelectric materials,nanomaterials and biomedicine,have been synthesized and reported.Therefore,the development of new and effective methods for creating scarce and novel fullerene derivatives is still of crucial importance.In this dissertation,two parts of research works on fullerene functionalization were described.At the beginning,the N-alkylation of N-unsubstituted fulleropyrrolidines with ketones/arylboronic acids in the presence of paraformaldehyde and p-toluenesulfonic acid was explored and a series of novel N-alkylated fulleropyrrolidines were prepared.The N-methylation reaction of fulleropyrrolidines with paraformaldehyde and benzyl alcohol promoted by p-toluenesulfonic acid in the absence of ketones/arylboronic acids was also investigated.Plausible reaction mechanisms for the formation of N-alkylation fulleropyrrolidines were proposed.Furthermore,the reaction of[60]fullerenes(C₆₀)with cinnamaldehydes and arylamines promoted by magnesium perchlorate was also studied under mild reaction conditions and a series of scarce cyclopentafullerenes were synthesized.In order to obtain a good yield for the above-mentioned reactions,we screened the reaction conditions including the molar ratio of reactants,reaction temperature,and reaction time.In addition,all products were separated by column chromatography and all of new compounds were unambiguously characterized by their HRMS,¹H NMR,¹³C NMR,UV-vis and FT-IR spectra.Chapter ?:IntroductionIn this chapter,we introduce the discovery,structure,performance and some other properties of fullerene,and provide an overview of the development of functionalized fullerene derivatives at home and aboard in recent years.In addition,the design idear on this research is also proposed.Chapter ?:The synthesis and characterization of N-alkylated fulleropyrrolidinesThe N-alkylation of N-unsubstituted fulleropyrrolidine derivatives in the presence of paraformaldehyde and p-toluenesulfonic acid was systematically studied.With the addition of ketones/arylboronic acids,a series of novel N-alkylated fulleropyrrolidines were obtained.The N-methylation reaction of fulleropyrrolidines with paraformaldehyde and benzyl alcohol promoted by p-toluenesulfonic acid in the absence of ketones/arylboronic acids was also studied.Plausible reaction mechanisms for the formation of all N-alkylated fulleropyrrolidines were proposed.Chapter ?:The synthesis and characterization of cyclopentafullerenesThe reaction of C₆₀ with cinnamaldehydes and arylamines promoted by magnesium perchlorate under air conditions afforded a series of rare cyclopentafullerenes with amino groups.Two isomers(cis/trans)were observed in all cases and were unambiguously assigned by using NOESY spectra.A plausible reaction mechanism was suggested to elucidate the formation of cyclopentafullerenes.