Study On The Reaction Of [60]Fullerene With Isocyanates/Isothiocyanates Promoted By Ferric Perchlorate

The functionalization of [60]fullerene (C60) with various organic functional groups is an important subject in fullerene chemistry for further material and medicinal applications. Among a large number of fullerene reactions, the radical reactions of C6o were among the first to be investigated and continue to be important protocols for fullerene functionalization. Recently, the ferric perchlorate (Fe(C104)3·xH20)-mediated radical reactions of C6o have attracted extensive attention and have exhibited remarkable advantages over the traditional peroxide-or light-initiated processes. The main work presented in this dissertation is focused on the Fe(C104)3·xH2O-mediated radical addition reactions of C6o with various isocyanates/isothiocyanates to afford the scarce oxazolidinofullerenes/thaizolidinofullerenes. The direct dissolution method together with the N2protection played a crucial role for the efficient synthesis of oxazolidinofullerenes/thaizolidinofullerenes. Various reaction conditions such as reaction ratio, reaction temperature and reaction time have been systematically screened to obtain the good yield. Additionally, the structures of oxazolidinofullerenes/thaizolidinofullerenes were fully characterized by HR-MS,1H NMR,13C NMR, FT-IR, and UV-vis spectra, and a plausible reaction pathway for the formation of oxazolidinofullerenes/thaizolidinofullerenes was also suggested.Chapter I:Literature reviewAn overview of recent development of novel fullerene chemical reactions at home and aboard, especially the radical addition reactions of C60promoted by various metal salts, was made. In addition, the idea about this research was also provided in this chapter.Chapter II:The synthesis and characterization of oxazolidinofullerenesThe Fe(C104)3-xH20-mediated radical cycloaddition reaction of C60with various isocyanates generated a series of rare oxazolidinofullerenes in good to excellent yields. However, the reaction of C60with4-nitrophenyl isocyanate (1h) bearing the stronger electron-withdrawing NO2group in the presence of Fe(ClO4)3—xH2O gave unexpectedly aziridinofullerene rather than oxazolidinofullerene. The current one-step approach to the preparation of oxazolidinofullerenes was obviously more straightforward and practical than the previously reported protocol.ChapterⅢ:The synthesis and characterization of thaizolidinofullerenesThe facile one-step reaction of C60with a variety of isothiocyanates promoted by Fe(C104)3-xH20afforded a series of unreported mono-addition thiazolidinofullerenes, which will be difficult to prepare by common methods. Nevertheless, the reaction of C6o with benzoyl isothiocyanate linking the stronger electron-withdrawing carbonyl group in the presence of Fe(ClO4)3·H2O was found to produce unexpectedly fullerooxazole instead of thiazolidinofullerene. The reaction pathway for the formation of fullerooxazole was confirmed by some controlled experiments.