部分甲基取代改性瓜环的合成、表征及其性质研究

【作者】 林景祥；

【导师】 陶朱；

【作者基本信息】 贵州大学 ， 物理化学， 2007， 硕士

【摘要】 普通瓜环因为溶解性比较差，所以限制了对它的研究及应用，为了得到性能更好的瓜环，国内外研究者合成了一系列取代苷脲，进而合成带有不同官能团的改性瓜环。近年来，一系列的含取代基的改性瓜环已见报道。贵州大学应用化学研究所合成了一系列的瓜环，并在合成改性瓜环方面做了很多基础性工作，这为进一步改性瓜环的研究工作提供了良好的基础，而其意义不仅在于获得了溶解性得到改善的新型瓜环，提供了一种新的合成瓜环途径，更重要的是建立了一种可在瓜环指定位置上引入特定基团的方法，为进一步合成以瓜环为单元结构的纳米管以及功能高分子材料提供有用的原料，以及将瓜环应用于药物缓释剂等，以拓宽瓜环的研究领域和应用范围。本文首先以丙酮醛为原料合成得到单甲基取代苷脲，再以此为原料合成部分甲基取代的改性瓜环。利用重结晶的方法，得到了部分甲基取代五元瓜环；加入客体1，4-二氧六环，分离得到部分甲基取代六元瓜环；并经分步结晶和重结晶的方法，进一步提纯所合成部分甲基取代瓜环。在分离过程中得到部分甲基取代五元瓜环的单晶，并用单晶X-射线衍射测定其结构；在分步结晶和重结晶分离六元瓜环的过程中，得到了部分甲基取代六元瓜环的晶体，并用单晶X-射线衍射测定其结构。利用~1HNMR，MS等检测方法对所合成分离得到的部分甲基取代瓜环进行进一步的结构表征。本文还测定了所合成的部分甲基取代改性瓜环在多种常见溶剂中的溶解度，实验数据表明，部分甲基取代瓜环在水中的溶解性比普通瓜环的有较大改善，还可溶于部分有机溶剂。本文还做了部分甲基取代瓜环在主客体相互作用方面的初步研究。更多还原

【Abstract】 Q[n]s have poor solubility in commonly used solvent which hamper the development of Q[n]s. Many research group seek to synthesize substituted Q[n]s which with good solubility. Recently, a number of substituted Q[n]s have been reported. Institute of Applied Chemistry of Guizhou University has Synthesized a number of substituted Q[n]s and Q[n], and has done a lot of basal work. These offer a very good opportunity for further study of substituted Q[n] that its importance not only achieves a new substituted Q[n] with ready solubility, but also gives a new route to substituted Q[n]. The most important facet is the way that adds specific group in certain location of Q[n]’s. Then we may bring cucurbiturils into practical application.Firstly, synthesis of a unsymmetrical methylsubstituted cucurbit[5,6]uril （PMeQ[5] and HMeQ[6]） has been achieved by using the monomethylsubstituted glycoluril. By crystallizing again and again, partially methylsubstituted cucurbit[5]uril （PMeQ[5]） have been achieved; partially methylsubstituted cucurbit[6]uril （HMeQ[6]） have also been isolated by adding dioxane to the complex solution. During the course of separation, crystal of PMeQ[5] and the crystal of interaction compound of HMeQ[6] and dioxane has been achieved, this crystal is analyzed by single crystal X-ray diffraction.Secondly, different kind of detective techniques have been employed including ¹HNMR,¹³CNMR and MS for characterize PMeQ[5] and HMeQ[6]’s structure.Furthermore ,we measured the PMeQ[5] and HMeQ[6]’s solubility in commonly used solvents, the study show that PMeQ[5] and HMeQ[6] both have good solubility in aqua, and reasonable solubility in some organic solvents. Investigation into interactive chemical between HMeQ[6] and some organic guest molecules has been carried out更多还原