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
收稿日期: 2015-11-17
修回日期: 2015-12-20
网络出版日期: 2016-01-21
基金资助
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)和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.
Syntheses and Dyes Complexation Properties of Multiple-azo Calix[4]arene Derivatives Containing Thiourea Groups
Received date: 2015-11-17
Revised date: 2015-12-20
Online published: 2016-01-21
Supported by
Project supported by the National Natural Science Foundation of China (No. 21406036), the Natural Science Foundation of Fujian Province (No. 2014J01034), the Fujian Province Science and Technology Key Project (No. 2014N0025) and the Program for Innovative Research Team in Science and Technology in Fujian Province University (No. [2012]03).
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105,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.
严祯曦 , 郭红玉 , 杨发福 , 袁锦 . 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[J]. 有机化学, 2016 , 36(5) : 1088 -1093 . DOI: 10.6023/cjoc201511031
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 105 magnitudes for the association constants. The chain-opening structure, more amino groups and more aromatic groups were favorable for the improvement of complexation abilities.
Key words： calix[4]arene; thiourea; synthesis; dye; complexation
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