Kräutler B, Müller T, Duarte-Ruiz A
Institute of Organic Chemistry, University of Innsbruck, Austria.
Chemistry. 2001 Aug 3;7(15):3223-35. doi: 10.1002/1521-3765(20010803)7:15<3223::aid-chem3223>3.0.co;2-b.
The efficient preparation of monoadducts of [60]fullerene and seven anthracenes (anthracene, 1-methylanthracene, 2-methylanthracene, 9-methylanthracene, 9,10-dimethylanthracene, 2,3,6,7-tetramethylanthracene, and 2,6-di-tert-butylanthracene) by cycloaddition in solution is described. The seven mono-adducts of [60]fullerene and the anthracenes were characterized spectroscopically and were obtained in good yields as crystalline solids. The monoadducts of [60]fullerene and anthracene, 1-methylanthracene, 2-methylanthracene and 9,10-dimethylanthracene crystallized directly from the reaction mixture. The thermolytic decomposition at 180 degrees C of the crystalline monoadducts of [60]fullerene and anthracene, 1-methylanthracene, 9-methylanthracene and 9,10-dimethylanthracene all gave rise to the specific formation of a roughly 1:1 mixture of [60]fullerene and the corresponding antipodal bisadducts ("trans-1"-bisadducts) of [60]fullerene and the anthracenes. In contrast, the crystalline monoadducts of [60]fullerene and the anthracene derivatives 2-methylanthracene, 2,3,6,7-tetramethylanthracene and 2,6-di-tert-butylanthracene all decomposed to [60]fullerene and anthracenes (without detectable formation of bisadducts) upon heating in the solid state to temperatures of 180 to 240 degrees C. The formation of the antipodal bisadducts from thermolytic decomposition of crystalline samples of the monoadducts was rationalized by topochemical control.
本文描述了通过溶液中环加成反应高效制备[60]富勒烯与七种蒽（蒽、1-甲基蒽、2-甲基蒽、9-甲基蒽、9,10-二甲基蒽、2,3,6,7-四甲基蒽和2,6-二叔丁基蒽）的单加合物的方法。通过光谱对[60]富勒烯与蒽的七种单加合物进行了表征，并以良好的产率获得了结晶固体。[60]富勒烯与蒽、1-甲基蒽、2-甲基蒽和9,10-二甲基蒽的单加合物直接从反应混合物中结晶出来。[60]富勒烯与蒽、1-甲基蒽、9-甲基蒽和9,10-二甲基蒽的结晶单加合物在180℃下的热解均导致[60]富勒烯与相应的[60]富勒烯和蒽的对映体双加合物（“反式-1”-双加合物）形成大致1:1的混合物。相比之下，[60]富勒烯与蒽衍生物2-甲基蒽、2,3,6,7-四甲基蒽和2,6-二叔丁基蒽的结晶单加合物在固态下加热至180至240℃时均分解为[60]富勒烯和蒽（未检测到双加合物的形成）。通过拓扑化学控制对单加合物结晶样品热解形成对映体双加合物的现象进行了合理解释。
