Study On The Synthesis Of [60]Fulleropyrrolidines Based On Aldehydes And Amines

Since the macroscopic manufacturing of[60]fullerene(C₆₀)and other fullerene series in1990 by Kr?tschmer et al.,chemical modification has become one of the important methods for studying fullerene chemistry.Over the past decades,a large number of novel fullerene derivatives have been synthesized and reported,and they have been applied in physics,biological,chemistry,and so on.Therefore,the derivatization of fullerene is still a very important and meaningful research work.In this paper,we mainly describe the 1,3-dipolar cycloaddition reaction of C₆₀ with aromatic aldehydes and inactive primary amines without the addition of metal salts as well as the reaction of C₆₀ with aromatic aldehydes and triethylamine/diethylamine in the absence or presence of manganese（Ⅲ）acetate to obtain a rare 2-aryl-5-alkyl-fulleropyrrolidines and N-ethyl-2-arylvinyl-5-methyl fulleropyrrolidines derivatives,respectively.In addition,all of new compounds were unambiguously characterized.Finally,plausible reaction mechanisms for the reaction process of all the above fullerene derivatives were also suggested.Chapter Ⅰ:IntroductionIn this chapter,we introduce the discovery and history,crystal structure,specific performance and some other properties of C₆₀,and provide an overview of the development of fullerene derivatives at home and aboard in recent years.In addition,the design philosophy and synthetic method about this research is also proposed.Chapter Ⅱ:The synthesis and characterization of 2-aryl-5-alkyl-fulleropyrrolidinesA series of scarce 2-aryl-5-alkyl-fulleropyrrolidines can be prepared by the 1,3-dipolar cycloaddition reaction of C₆₀ with aromatic aldehydes and inactive primary amines without the addition of metal salts.However,the obtained 2-aryl-5-alkyl-fulleropyrrolidine derivatives as a mixture of cis and trans isomers could be easily separated and purified by a silica gel column,with the cis isomers as major products.Finally,we propose a reasonable reaction mechanism for the formation of fulleropyrrolidines.Chapter Ⅲ:The synthesis and characterization of N-ethyl-2-arylvinyl-5-methyl fulleropyrrolidinesA series of novel N-ethyl-2-arylvinyl-5-methyl fulleropyrrolidines are synthesized by the reaction of C₆₀ with aromatic aldehydes and triethylamine/diethylamine in the absence or presence of manganese（Ⅲ）acetate.Depending on the reaction conditions,both cis and trans isomers of fulleropyrrolidines could be selectively synthesized.Cis isomers as major products could be obtained by reacting with triethylamine at 160℃ without the addition of manganese（Ⅲ）acetate,while trans isomers as major products,with rare exceptions,could be observed via the reaction with diethylamine at 120℃ under the assistance of manganese（Ⅲ）acetate.Moreover,the in situ generated arylvinyl aldehydes displayed higher reactivity towards diethylamine as compared with aryl aldehydes,leading to the formation of arylvinyl-substituted fulleropyrrolidines.Finally,we propose a reasonable reaction mechanism.