三蝶烯衍生物之合成策略改進探討與自組裝行為研究

Abstract

第一部分我們嘗試合成三蝶烯衍生化杯[6]芳烴40，期待能在化合物40上接以辨識基團使其可以對陰離子或中性小分子客體分子進行辨識。我們遵循文獻中所報導之合成路徑時發現其難以達到量產化合物40並加以應用之目的，為此我們希望可以另闢路徑，以較簡單、產率較高之合成路徑取得化合物40。我們從可以在蒽醌上行羥 甲基化之Marschalk 反應為起點，設計一系列之合成路徑試圖保護羥甲基再以狄爾斯–阿爾德反應合成三蝶烯，經由進一步去保護期望可以快速地得到羥甲基三蝶烯分子39。經過多方嘗試，我們最終以苄基作為保護基，待得到三蝶烯分子76之後，再以鈀碳催化試劑與1,4-環己二烯進行去保護，方可得到羥甲基三蝶烯39。我們所設計之合成路徑較原始文獻之方法為短、產率則更高，因此也更適合用來量產三蝶烯衍生化杯[6]芳烴40。 第二部分則為我們嘗試以羥甲基三蝶烯39接以特殊官能基團，期待可以合成出以三蝶烯為骨架之新型超分子凝膠分子。我們設計並合成了含有醯基脲之三蝶烯85，但是將化合物85與各種溶劑進行膠體測試卻未發現膠體之形成。雖然化合物85無法形成膠體，我們從SEM與TEM中依然觀察到化合物85在特定溶劑中會產生自組裝之特殊形貌，因此我們針對化合物85在不同溶劑中的自組裝現象進行了一系列的探討。

In the first part of our work, we tried to synthesize triptycene-derived calix[6]arene 40 as a sensor toward anions or neutral small molecules by modifying it with sort of functional groups. By following the synthetic scheme from literature, we found it difficult to reach our expectation. Thus we tried to explore a new approach to compound 40 with more convenient synthesis and higher yield. Inspiring by hydroxymethyl group formation via Marschalk reaction, we found a possible way to easily get hydroxymethyl group attached to triptycene molecule with fewer steps. We tested a series of reagent and found benzyl group to be suitable as protecting group of hydroxymethyl group as it is stable under various reaction conditions. After protecting the hydroxymethyl group, we synthesized benzyl-substituted triptycene via Diels-Alder cycloaddition, followed by deprotection with Pd/C and 1,4-cyclohexadiene to give hydroxymethyl triptycene 39. With this new synthetic strategy we could obtain compound 39 in a shorter synthetic scheme with higher yield, making the application of triptycene-derived calix[6]arene more achievable. While we made hydroxymethyl triptycene 39 easily accessible, we wished to know if it is possible for triptycene to become an ideal backbone structure for supramolecular gelator. Thus we synthesized triazole and N-acylurea substituted triptycene 85 to see if it’s a potential gelator. Unfortunately, no gel was found after compound 85 was dissolved in various different solvents. Compound 85 was later submitted to SEM and TEM, surprisingly some self-assembly phenomenon was found. It showed different morphology from types of solvent, indicating that triptycene derivatives are potential supramolecular gelator and worthy of studying .