间苯二酚杯[4]芳烃穴状物胺类衍生物的合成与金属配位分析
Synthesis and Metal Coordination Analysis of Resorcinolcalix[4]arene Cavitands Amine Derivatives

首先合成了带有不同侧链的四甲基间苯二酚杯[4]芳烃，并用四甲基间苯二酚杯[4]芳烃作为原料加入溴氯甲烷试剂合成了两种四甲基穴状物。用N-溴代琥珀酰亚胺对C-2位的甲基进行溴代，合成了四溴甲基穴状物(3c、3d)。随后通过胺基及3,5-二甲基吡唑修饰，合成了四胺甲基间苯二酚杯[4]芳烃穴状物(4a、4b、5a、5b、6a、6b、7a、7b)和3,5-二甲基吡唑间苯二酚杯[4]芳烃穴状物12a。对上述化合物通过红外、核磁氢谱及元素分析进行表征。通过紫外光谱法探索了二硫代氨基配体对过渡金属离子的识别作用及吡唑配体与过渡金属离子的配位情况。结果表明：红外光谱特征峰、核磁氢谱峰与化合物结构相符合；二硫代氨基穴状物配体对Mn²⁺、Cu²⁺、Zn²⁺、Mg²⁺、Cd²⁺和Pb²⁺有明显的识别作用，对Ca²⁺的识别作用较差。3,5-二甲基吡唑甲基穴状物配体对二价过渡金属离子有明显的配位的作用，其中对Cu²⁺，Mn²⁺，Mg²⁺和Hg²⁺的识别作用较好，对Zn²⁺的识别作用较差。
Tetramethylresorcinol calix[4]arenes with different side chains were synthesized firstly, with tetramethylresorcinol calix[4]arene as the substrates, two types of tetramethyl cavitands were synthesized by adding bromochloromethane reagents and a tetrabromomethyl cavitands (3c, 3d) were synthesized by brominating the methyl group at the C-2 position with N-bromosuccinimide. Subsequently, tetraaminomethylresorcinol calix[4]arene cavitands (4a, 4b, 5a, 5b, 6a, 6b, 7a, 7b) and 3,5-dimethylpyrazole resorcinol calix[4]arene cavitand 12a were synthesized through modification with amine groups and 3,5-dimethylpyrazole. The above compounds were characterized by FT-IR, ¹H NMR and elemental analysis. The recognition effect of dithioamino ligands on transition metal ions and the coordination between pyrazole ligands and transition metal ions were explored through UV-Vis spectroscopy. The results showed that the characteristic infrared peaks signal and 1H NMR spectroscopy are consistent with the molecular structures of the compounds; The dithioamino cavitand like ligand has a significant recognition effect on Mn²⁺, Cu²⁺, Zn²⁺, Mg²⁺, Cd²⁺, and Pb²⁺, but its recognition effect on Ca²⁺ is poor; The 3,5-dimethylpyrazole methyl cavitand ligand has a significant coordination effect on divalent transition metal ions, with good recognition for Cu²⁺, Mn²⁺, Mg²⁺, and Hg²⁺, but poor recognition for Zn²⁺.