碗烯独特的曲面结构使其具有特殊的物理化学性质，这些特殊性质的广泛应用价值促使科学界对其进行不断深入的研究。本文对碗烯体系的衍生化进行了研究，发现了一种无金属及氧化剂催化的芳香C?C键断裂开环并同时实现平面芳香体系1,2,4-三唑衍生化的反应；另外，我们合成了一种基于碗烯的Blatter自由基衍生物。

论文的主要工作如下：

1. 研究了1-氨基碗烯与N-苯基肼基氯的反应，证实了此反应在无金属及氧化剂催化条件下发生了碗烯基团的开环并生成一种含有苯并荧蒽平面结构的芳香1,2,4-三唑衍生物，并探索了此反应的机理。反应优化结果表明，1-氨基碗烯与N-苯基肼基氯在甲苯作溶剂的条件下，120 °C反应12小时，能以最高达70%的产率得到开环产物。通过对比平面芳香体系以及氘代1-氨基碗烯等化合物在相同反应条件下的反应结果，我们发现，碗烯的曲面张力是导致其开环的重要驱动力；开环过程发生于N-苯基肼基氯中的-NH进攻1-氨基碗烯中氨基邻位碳的过程中；开环过程中存在两步质子转移反应，开环产物甲基上的两个氢均来自于1-氨基碗烯与N-苯基肼基氯中的活泼氢。这是首次发现无金属无氧化剂催化导致芳香C?C键断裂并产生三唑类化合物的方法。

2. 通过七步合成了一种基于碗烯的Blatter自由基衍生物。利用核磁氢谱，质谱，EPR等表征手段对该自由基进行了表征：核磁氢谱图显示该自由基几乎不出峰；质谱图显示与该自由基分子量一致的峰，可能是自由基失去一个电子的结果；EPR图显示此自由基是典型的N杂自由基七重峰结构。其在空气中可以稳定存在。

The unique curved surface in structure of corannulene (C₂₀H₁₀) provides the chemical special physical and chemical properties, which promptes the scientific community to conduct in-depth exploration on its properties as well as the the application in organic photoelectric materials and biological imaging. In this dissertation, we have studied the coupling reaction of 1-aminocorannulene and hydrazonyl chloride, and found that the catalyst-free reaction can give a direct access to a 1,2,4-triazole-linked benzo[ghi]fluoranthene derivative, providing a unique example of the metal-and oxidant-free C–C bond cleavage in arenes as well as the formation of 1,2,4-triazoles from aromatic amines; in addition, we have synthesized a kind of Blatter free radical derivative from corannulene.

The main work is as follows:

1. The reaction of 1-aminocorannulene and hydrazonoyl chloride was studied. It was found that the ring-opening of the corannulene occurred in the reaction without the catalysis of metals and oxidants; meanwhile, a planar aromatic 1,2,4-triazole derivatives containing benzo[ghi]fluoranthene was formed. The mechanism of this reaction was explored. The results of reaction optimizations showed that the reaction at 120 °C for 12 hours with toluene as the solvent can give the ring-opening product with the highest yield of up to 70%. By comparing the results of the control reactions using planar aromatic system and the deuterated 1-aminocorannulene under the same reaction conditions, we found that the curved surface tension of 1-aminocorannulene provides the driving force for the ring opening. Besides, the C-C cleavage mainly occurs in the process of attacking of the hydrazonoyl chloride -NH nitrogen to the ortho-position carbon adjacent to the amino group in 1-aminocorannulene. The additive two methyl hydrogens of the ring-opening products are all from 1-aminocorannulene and hydrazonoyl chloride. For the first time, this work shows that a C–C bond cleavage in arenes can occor under a metal- and oxidant-free conditions and that 1,2,4-triazoles can be prepared directly from aromatic amines.

        2. A Blatter free radical derivative based on corannulene was synthesized. Starting from 4-bromo-2-chloroaniline and 1-bromocorannulene, the corannulene based Blatter radical was successfully obtained through seven steps. The radical was characterized by NMR, HRMS-ESI, and EPR. The mass of the radical consistents well with its theoretical value. The EPR spectrum shows characteristic peaks of the Blatter free radicals. The radical can exist stably in the air.