臺灣博碩士論文加值系統

碳 60 的研究近年來蓬勃發展, 為了瞭解碳 60 的化學, 合成具有部份
碳 60 結構的碳氫化合物是有用的且具挑戰性的. 關於此方面的研究, 目
前只有碗狀結構的 corannulene 被合成出. 故此篇論文中,我們嘗試合
成 circumfulvalene, 其為一 fulvalene 分子, 周圍以苯環環繞的結構.
合成的關鍵步驟, 在於連續的生成碳-碳鍵以得到稠合苯環化合物.首先
將 45a 進行照光反應, 以碘為氧化劑, 可使其生成碳1-碳1'鍵.之後, 嘗
試利用鈀/活性碳試劑, 使 56 進行脫氫反應以期生成碳8-碳8'鍵, 但是
並未得到任何的脫氫化產物.除此之外, 並對 45a, 56 進行變溫 1H NMR
實驗, 其活化能分別為 17.4 及 12.6 仟卡/莫耳, 此乃是醚鏈架橋交錯
運動的能量.

Whereas the chemistry of buckminesterfullerenes is so pro-
sperous, the synthetic appproaches towards various hydrocarbon
molecules having partial fullerene skeletons are highly
intrigu- ing and useful for understanding chemistry of
fullerenes. Among these investigations, only bowl-like
structure corannulene has been syntheisized. In this thesis, we
attempted to synthesze circumfulvalene, a fulvalene moiety
surrounded by fused benzene ring. The key steps for the
formation of circumfulvalene are the sequential carbon-carbon
bond formation leading to fused aromatic products. In the
beginnning of this work, 45a was irradiated in the presence of
iodine, the carbon 1-carbon1' bond can be formed. Palladium/
charcoal is supposedly a good reagent for dehydroge- nation.
Attempts to form the carbon 8-carbon 8' of 56 by these
procedures yield no dehydrogenation products at all. Various
temperature 1H NMR experiments for 45a,56 were also reported.
The barriers were found to be 17.4 and 12.6 Kcal/mole,
respectively, whick correspond to the twisting motion of the
ethylene bridge.