Copper-Catalyzed Aerobic Oxidative Reaction of C60 with Aliphatic Primary Amines and CS2

A novel type of fullerene derivatives, [60]­fullerothiazolidinethiones (2), were obtained from the copper-catalyzed aerobic oxidative reaction of C60 with aliphatic primary amines and CS2 in 4:1 v/v DMF and o-DCB. The obtained products were fully characterized with the X-ray single-crystal diffraction and spectroscopic methods. Control experiment with maleic anhydride, an analogue to C60, also afforded thiazolidinethione product, but via a mechanism different from that of C60 judging from the structure difference between the two types of thiazolidinethione compounds, demonstrating the unique reactivity of C60.本研究通过铜催化有氧氧化反应，以体积比4:1的N,N-二甲基甲酰胺(DMF)与邻二氯苯(o-DCB)为混合溶剂，使C₆₀与脂肪族伯胺、二硫化碳(CS₂)发生反应，得到一类新型富勒烯衍生物——[60]富勒烯噻唑烷二硫酮(2)。所获产物通过X射线单晶衍射(X-ray single-crystal diffraction)与光谱学方法完成了全面表征。以与C₆₀结构类似的马来酸酐(maleic anhydride)作为对照底物开展实验，同样得到了噻唑烷二硫酮类产物，但结合两类噻唑烷二硫酮化合物的结构差异可判断，其反应机理与C₆₀参与的反应截然不同，这证实了C₆₀独特的反应活性。