含硫脲基的多重氮杂杯[4]芳烃衍生物的合成与有机染料配合性能  

Syntheses and Dyes Complexation Properties of Multiple-azo Calix[4]arene Derivatives Containing Thiourea Groups

作　　者：严祯曦 郭红玉[1] 杨发福[1,2] 袁锦[1] 

机构地区：[1]福建师范大学化学与化工学院,福州350007 [2]福建省高分子材料重点实验室,福州350007

出　　处：《有机化学》2016年第5期1088-1093,共6页Chinese Journal of Organic Chemistry

基　　金：国家自然科学基金(No.21406036);福建省自然科学基金(No.2014J01034);福建省科技重点项目(No.2014N0025);福建省高校科技创新团队支持计划(No.闽教科[2012]03号)资助项目~~

摘　　要：以杯[4]芳烃为平台,构筑结构与识别性能独特的杯[4]芳烃衍生物是有机超分子化学的重要研究领域.本文中,杯[4]二芳胺基衍生物3与异硫氰酸苯酯反应得到开链的二硫脲基杯[4]衍生物4,产率为95%.化合物3与等物质的量对二异硫氰酸苯酯反应得到二硫脲基桥连杯[4]衍生物5,产率为80%.与过量的对二异硫氰酸苯酯反应则以产率为82%得到化合物6.化合物6进一步与水杨酰肼反应得到含硫脲基的多重氮杂杯[4]衍生物7,产率为75%.紫外光谱配合实验表明新主体分子4-7对测试的4种有机染料分子（橙黄Ⅰ、茜绿素、维多利亚蓝和亚甲基蓝）均显示出较强的配合能力,配合常数的数量级达10^5,配合比为1∶1.开链结构与多重胺基和芳基结构更有利于配位包合能力的提高.By using calix[4]arene as platform, the construction of calix[4]arene derivatives with unique structures and binding properties is the important research field in organic supramolecular chemistry. In this paper, the chain-opening calix[4]arene bi-thiourea derivative 4 was synthesized by reacting calix[4]arene bi-aromatic amino derivative 3 with phenyl isothiocyanate in yield of 95%. Treating compound 3 with p-phenylene diisothiocyanate（molar ratio=1∶1） gave bridging calix[4]arene bi-thiourea derivative 5 in yield of 80%. Treating compound 3 with excess p-phenylene diisothiocyanate afforded calix[4]arene thiourea derivative 6 in yield of 82% and was further converted to multiple-azo calix[4]arene derivative 7 by reacting compound 6 with salicylyl hydrazine in yield of 75%. The experiments of UV titration spectra for four tested dyes（orange Ⅰ, alizarin green, victorial blue and methylene blue） showed that compounds 4-7 possessed excellent complexation abilities with 1∶1 ratios for complexation and 10-5 magnitudes for the association constants. The chain-opening structure, more amino groups and more aromatic groups were favorable for the improvement of complexation abilities.

关 键 词：杯[4]芳烃 硫脲 合成 染料 配合 

分 类 号：O641.4[理学—物理化学]