Study On The Reactions Of [60] Fullerene With Sodium Alkoxides, Phenylhydrazines And Amines

Chemical modification is one of the most important research fields in the fullerene chemistry.Many functionalized fullerene derivatives have been synthesized till now,which have potential applications in material and medicine science.There is great significance in the synthesis of novel fullerene derivatives.While further functionalization of fullerene derivatives is one of the important methods to synthesize new functionized fullerene derivatives.In this dissertation,several new types of fuUerene derivatives were synthesized and further functionalization was successfully carried out.1.The reaction of C₆₀ with freshly prepared sodium alkoxide solution under aerobic condition was well investigated,which provides a facile protocol to synthesize a variety of C₆₀-fused tetrahydrofuran derivatives with oxygen atom directly attached to fullerene cage.The C₆₀-fused tetrahydrofuran derivatives are excellent synthons for further functionalization.While treated with different equiv,of BF₃·OEt₂ at various temperature,several novel functionized fullerene derivatives have been successfully synthesized.2.1,4-Fullerenols C₆₀ArOH were synthesized via the reaction of[60]fullerene with 4-substituted phenylhydrazine hydrochlorides and sodium nitrite under moisture and aerobic conditions.The key and unprecedent intermediate C₆₀Ar(NO₂) was isolated and characterized.A possible mechanism for the formation of 1,4-fullerenols involving C₆₀Ar(NO₂) via a S_N2' pathway was proposed.Further transformations of the 1,4-fullerenols through esterification,etherization,and arylation were also carried out in the presence of p-toluene sulfonic acid.3.Several primary amines are oxidized by PhI(OAc)₂ to generate nitrenes.Then via copper acetate-promoted transfer,they are selectively added to C₆₀ by[2+1] pathway to produce a series of 1,2-aziridino-[60]fullerenes.This is a facile and efficient protocol to synthsize closed 1,2-azabridged aziridinofullerene.4.By PhI(OAc)₂ and Cu(OH)Cl·TMEDA catalyzed reaction of C₆₀ with primary sulonic amins,a new type of C₆₀-fused imidazole derivatives is successfully synthesized.It is the first time to report such fullerene derivatives.