Investigation On The Nucleophilic Cycloaddition Reactions Of [60] Fullerene

Chemical modification is one of the most important research fields in the fullerene chemistry.Many functionalized fullerene derivatives have been synthesized hitherto,and have potential applications in material and medicine science.Among these various functionalization methods,nucleophilic reactions are among the pioneering reactions investigated in fullerene chemistry.In this dissertation,we synthesized several new types of fullerene derivatives through four new types of nucleophilic cycloaddition reactions.1.It was found that the novel reaction of C₆₀with diethyl aminomalonate hydrochloride and CS₂ in the presence of Et₃N afforded C₆₀-fused thiopyrrolidone derivative with high yield.The C=S group in the heterocycle fused to C₆₀could easily be hydrolyzed to C=O group.And the derivative with the C=S group could react with halides to give thioethers or amides with high yields under basic condition.2.Nucleophilic cycloaddition of thiocyanates with C₆₀in the presence of DBU afforded C₆₀-fused 3-imino-thiophene derivatives and methanofullerenes.The product distributions were highly sensitive to the employed substrates.And the products were further manipulated by hydrolysis and acetylation to give more stable 3-oxo-thiophene derivatives and 3-acetamido-thiophene derivatives.The possible reaction mechanism for the formation of products was also proposed.3.The novel multicomponent cycloaddition reaction of C₆₀with 1,4-dipolar reagents generated from DMAD and isoquinoline,quinolines or substituted quinolines giving a new type of C₆₀-fused isoquinoline or quinoline derivatives was investigated.And the isoquinoline had higher activity than quinoline in this reaction.4.The solvent-free cycloadditions of alkylidene malononitrile derivatives with C₆₀ were realized in the presence of Et₃N or DMAP under the HSVM conditions, which led to the formation of C₆₀-fused cyclohexadiene derivatives.