含異咢唑取代雙芳杯衍生物之合成、膠體性質、光反應研究與藉由硫醇烯點擊反應合成芳杯高分子

Abstract

中文摘要

從文獻中可知，凝膠因子通常含有長碳鏈來增加分子間的凡得瓦作用力，而本實驗室蔡佳蓁學姐曾合成一系列異咢唑取代的雙芳杯化合物，其中，以噻吩為橋聯的雙芳杯化合物發表了不含長碳鏈，在特定條件下形成膠體的文章。以此化合物做為延伸，本論文中首先變化雙異咢唑噻吩基橋聯雙芳杯化合物61，將芳杯上緣四組三級丁基修飾為叔辛基與己烷基，利用較長碳鏈增加自組裝時的凡得瓦力，合成了化合物59、60、62及63，其中化合物63能夠於多種醇類溶劑中行成超分子凝膠，其最低膠體形成濃度大約為0.32至0.09 (g/mL × 100%)，我們針對化合物63膠體形成進行一系列測試與討論。 我們亦將學姐合成的系列化合物中，含蒽下緣雙橋聯雙芳杯化合物10與下緣單橋聯雙芳杯化合物14，利用其橋聯蒽的光反應性質嘗試以365 nm紫外光照射，以NMR、吸收與螢光光譜圖解析橋聯蒽所發生的二聚化 (化合物84) 及內過氧化反應 (化合物92)。 此外，本論文中也嘗試了合成1,3交替修飾四個丙烯基的芳杯化合物95為單體、雙硫長鏈化合物49為橋基，利用硫醇烯點擊反應合成高分子96，並以IR、GPC、SEM與TEM探討其生成與形貌。

Abstract

Gelator molecules usually contain long alkyl chains to increase the van der Waals interaction among them. Our previous reseach results by Ms. Tsai have reported a series of isoxazole bridged biscalix[4]arenes without any long alkyl chains. Biscalix[4]arene 61 was found to form gels in certain conditions. To increase the ability of forming gel by compound 61, we started from replacing the tbutyl group on the upperrim of compound 61 with longer alkyl chains, hoping the long chains would provide stronger van der Waals interaction during the aggregation. In this thesis, we successfully synthesize four new bisisoxazolyl thiophene bridged biscalix[4]arene compounds, 59, 60, 62 and 63, with toctyl and nhexyl chains on the upper rim of calix[4]arene. Only compound 63 forms gel in five different solvets and the critical gelation concentrations are between 0.32 and 0.09 (g/mL × 100%). Then we have a series of experiment to discuss the gelation property of compound 63. Moreover, we also studied the photochemistry of mono- and bis-anthracene bridged biscalix[4]arene derivatives 10 and 14. These compounds may undergo photodimerization to get product 84 and form endoperoxide product 92 by photooxidation with singlet oxygen. Photochemical reactions of 10 and 14 were monitored by using 1HNMR, UV, and fluorescence spectrum. Furthermore, by using 1,3alternate calix[4]arene 95 and dithiol 49 as reacting parners, we try to polymerize them through thiolene “click” photoreaction and to give polymer 96. The product were characterized by IR, GPC, SEM and TEM images.