Investigation On Cycloaddition Reactions Of Fullerene

Chemical modification is one of the most important research fields in the fullerene chemistry. Many functional fullerene derivatives have been synthesized to this day, and have potential applications in material and medicinal science. In this dissertation, we synthesized three types of new fullerene derivatives and investigated the regioselectivity of the mono-addition reactions of C₇₀.1. The thermal reaction of C₆₀ with the carbonyl ylides generated in situ from epoxides to give a new type of C₆₀-fused tetrahydrofuran derivatives has been investigated. There was a strong stereoselectivity in this reaction. The reaction of C₆₀ with trans-2-benzoy1-3-aryl oxiranes afforded cis-products, while the reaction of C₆₀ with 2-cyano-2-ethoxycarbonyl-3-aryl oxiranes gave only cis-isomer or a mixture of cis-and trans-isomers, for which the isomer distribution was drastically affected by the substituent on the phenyl ring.synthesized2. The hetero-Diels-Alder reaction of C₆₀ with 1,2-diaza-1,3-butadienes generated in situ by the thermal extrusion of SO₂ from 2,5-dihydro-1,2,3-thiadiazole-1,1-dioxides has been realized for the first time, and led to the formation of a new type of stable C₆₀-fused tetrahydropyridazine derivatives. We also investigated the influence of the substituted groups.3. Mn(OAc)₃·2H₂O has been successfully utilized in the radical reactions of C₆₀ with β-enamino carbonyl compounds to give C₆₀-fused pyrroline derivatives, of which the nitrogen atom is directly connected to fullerene cage. It was a brand-new method for the synthesis of 4,5-dihydropyrrole compounds.4. The reaction of C₆₀ with the nitrile ylides generated in situ from two kinds of N-substituted-4-nitro-benzimidoyl chlorides gave two types of [6,6]-closed C₆₀-fused 1,2-dihydropyrrole derivatives, respectively. There was not [6,5]-opened isomer formed at all. We also explored the influence of reaction temperature to the distribution of the two isomers.5. We investigated the regioselectivity of the mono-addition reactions of C₇₀ through the reactions of different substrates with C₇₀ and characterization of the structures and distributions of the isomers. We proved that the [6,5]-bond on the C7-C8 but not the [6,6]-bond on the C7-C21 is the most active site besides for C1-C2 double bond and C5-C6 double bond.