Synthesis Of Fullerene Pyrrolidine Derivatives

Buckyminiterfullerene is the third allotrope of carbon, fullerene and itsderivatives have widespread and prospective application in chemistry, biology,material and medicine for their particular three-dimensional structures. C60, the mostrepresentative compound, has particular efficacy and bioactivity in anti-HIV,antibacterial, antitumor, inhibition of enzymatic activity, antioxidation,neuroprotective and so on. Lack of soluility in polar solvents and target-specificityhave limit it’s application in medicinal chemistry. It is significant to increase theirwater-soluble and target-specificity by chemical modification C60and to dobioactivity researches on these compounds in the future.In this dissertation, N-substituted glycin was synthesized from benzyl2-bromo-acetate and2-(2-aminoethoxy)ethanol, then,1,3-dipolar cycloaddition of theazomethine ylide generated by condensation of N-substituted glycin withformaldehyde to C60, led to4kinds of di-addition fulleropyrrolidine BFP1～4. Theproducts were characterized by UV-Vis, FT-IR,1H NMR and ESI-MS. All the fourfullerene derivatives can be dissolved in DCM, THF and DMSO. Nanoparticlesuspensions, including BFP1～4, were made successfully by organic solventexchange. The evaporation method was developed to remove the organic solventresident. The characterization of those fullerene nanoparticle suspensions werecharacterized by UV-Vis, DLS and SEM. The results showed that the properties ofthose nanoparticle suspensions were related to the derivatives. In addition, BFP1’sSEM study showed a good shape and well dispersion.Aspartic acid with protected amino and β-carboxyl groups had been used to reactwith the activated hydroxyl group of BFP1under DCC, HOBt and DMAP. Theproduct was characterized by UV-Vis, FT-IR,1H NMR and ESI-MS, its derivativescan be dissolved in THF and DMSO.We connected Wang resin with selective protection amino acids (Dâ†'Gâ†'R) bysolid-phase synthesis, acpuired Wang Resin-Asp(OtBu)-Gly-Arg(Pbf)-NH2, thereaction process was monitored by Ninhydrin test. Then, monoadduct C60aspartic acid coupled with Wang Resin-Asp(OtBu)-Gly-Arg(Pbf)-NH2under DIEA, HBTUand HOBt. The products were deprotected and cracked off resin by TFA/TIS/H2O（95:2:3）, final product was characterized by UV-Vis, FT-IR and ESI-MS.