| [60]Fullerene derivatives have received widespread attention from scientists because of their unique spatial skeleton structures,which have been effectively applied in chemistry,materials and medicine.Therefore,it is necessary to study the reactions of functionalizing fullerene.In this thesis,we mainly studied the synthesis ofthreetypesoffullerenederivatives.Firstly,[60]fullerene-fused-3,4-dihydropyrimido[1,6-a]indol-1（2H）-ones are directly synthesized by the N-H/C-H fusion of C60 with N-alkoxy-1（H）-indolecarboxamides under the synergetic promotion of di-tert-butyl hydroperoxide（DTBP）,iodine（I2）,and succinimide;Secondly,under the co-promotion of p-toluenesulfonic acid monohydrate（Ts OH·H2O）,light,and heat,C60 reacts with various cinnamaldehydes and oxygen to afford scarce dioxygenated[60]fullerene derivatives;Thirdly,fullerene-fused cyclopropanedicarboxylic acid ester derivatives are generated by the reaction of C60 with iodonium ylides under heating conditions.The mono-addition products can be further converted into multi-addition products,and fullerene-fused cyclopropanedicarboxylic acids can be obtained by hydrolysis of the corresponding fullerene-fused cyclopropanedicarboxylic acid esters with the aid of Ts OH·H2O.All products were separated by column chromatography,and their structures were confirmed using various analytical methods.Chapter I:IntroductionThis chapter briefly describes the discovery of[60]fullerenes and the domestic and international research on fullerene chemistry in recent years.On this basis,the research on this topic is carried out.ChapterⅡ:Cyclization reaction of[60]fullerene with indole carboxamides promoted by DTBP/I2Inthischapter,westudiedthesynthesisof fullerene-fused-3,4-dihydropyrimido[1,6-a]indol-1（2H）-ones by the N-H/C-H fusion of C60 with N-alkoxy-1（H）-indolecarboxamides under the synergetic promotion of di-tert-butyl hydroperoxide（DTBP）,iodine（I2）,and succinimide.Reaction conditions were systematically optimized to improve the product yields.The synthesis of fullerene-fused-3,4-dihydropyrimido[1,6-a]indol-1（2H）-ones has the advantages of moderate to excellent yields,high chemoselectivity and functional group tolerance without the use of valuable metals.In addition,the structure of the product are stable,which are favourable to expand its application in other fields.Finally,a possible reaction mechanism is proposed based on mechanistic experiments as well as reported in the relevant literature.ChapterⅢ:Cyclization reaction of[60]fullerene with cinnamaldehydes and oxygen promoted by heat and lightIn this chapter,a series of scarce dioxygenated[60]fullerene derivatives were prepared by the reaction of C60 with different cinnamaldehydes and oxygen under the co-promotion of Ts OH·H2O,light,and heat.The structures of these products were fully characterized by various spectroscopic methods.Compared with other fullerene derivatives,dioxygenated[60]fullerene derivatives show novel and stable structures.In addition,the raw materials for the reaction are cheap and readily available,the synthesis steps are relatively simple,and no valuable metals are used.ChapterⅣ:Thermal reactions of[60]fullerene with iodonium ylidesIn this chapter,a series of fullerene-fused cyclopropanedicarboxylic acid esters were obtained by the thermal reaction of C60 with different iodonium ylides.The structures of these products were fully characterized by various spectroscopic methods.In addition,fullerene-fused cyclopropanedicarboxylic acid ester derivatives with diaddition,triaddition and tetraaddition can also be obtained by gradient addition of monoaddition products.Furthermore,fullerene-fused cyclopropanedicarboxylic acid esters can be quantitatively converted to the corresponding fullerene-fused cyclopropanedicarboxylic acids by hydrolysis in the presence of Ts OH·H2O.These products have stable structure and good water solubility,which are of great significance for expanding their application in other fields. |
