【作者】 邹家浩；

【导师】 郑文杰；

【作者基本信息】 暨南大学 ， 无机化学， 2004， 硕士

【摘要】 硒（Ⅳ）与某些芳香邻二胺类化合物能定量、快速反应生成1，2，5-硒二唑类化合物（俗称苤硒脑化合物），在分析、合成及药物化学中占有十分重要的地位。 本论文工作主要开展了包括BS、MBS、BBS、DBBS、NS、SPb、SPc、SPO、SPDO和AS等10种1，2，5-硒二唑类化合物的以下5个方面的研究： 1．固相合成 在室温下，固相合成了7个硒二唑类化合物，并用XRD，IR，EA对其过程和产物进行了表征。结果表明：与液相反应法合成相比，固相反应合成法的粗产物纯，产率高。 2．IR，UV-Vis，¹H NMR 对硒二唑类化合物的IR吸收峰进行了归类与指认，讨论了SPO、SPDO的异构体的分子结构；探讨了UV-Vis、吸收波长和摩尔吸光系数与分子结构的相对应关系，以及紫外吸收光谱性质在分析化学上的应用价值和溶液的pH值引起SPO、SPDO的结构变化。最后研究了SPO、SPDO的¹H NMR，通过计算确定了它们的结构。 3．GC／MS 用气相色谱—质谱联用仪对硒二唑化合物进行研究，发现部分硒二唑化合物具有挥发性，在气相色谱中有较好的响应；CH₃—与Br—两种取代基影响硒二唑化合物于气相色谱中的保留时间与它们的分子量成比例；同分异构体因极性和熔沸点不同，于气相色谱中保留时间完全不一样；含硒化合物在质谱裂解图中有特征分子离子或离子峰簇，其主要峰M：（M-2）约为2：1，完全不使用标准样品，也可以辨别含硒化合物。同时，对硒二唑类化合物的质谱裂解作了初步的探讨。 4．电化学性质 探讨了硒二唑化合物的循环伏安性质。硒二唑化合物的溶液体系中，电极过程主受吸附控制，为硒二二唑化合物的自组装提供了参考。 5．白组装及其单分子膜的表征与电化学性质 讨论了硒二唑化合物形成自组装膜的自组条件、自组装的表征和自组装膜的电化学性质。结果表明：自组装时，浓度以为10^-3mol／L数量级为佳；硒二唑化合物自组装膜的电化学信号与其溶液相似，在-600mV左右有一还原峰。更多还原

【Abstract】 Se(IV) react with ortho aromatic diamine leads to 1,2,5-selenadiazole compounds fast and quantificationally. The selenadia- zoles have an very important role in chemistry including analysis, synthesis and medical.The five aspects of research for BS, MBS, BBS, DBBS, NS, SPb, SPc, SPO, SPDO and AS that were done in this thesis are as follows:1. Solid phase synthesis At room temperature, seven selenadiazoles were synthesized in solid phase, inspected and characterized with XRD, IR, EA. The results showed that the synthetical yield in solid-phase synthesis is higher than that in liquid-phase.2. IR, UV-Vis, 1H NMR The IR, UV-Vis and 1H NMR of selenadiazoles were investigated. Their IR peaks were classified as the corresponding groups or bonds; The relation of their structure with the conjugative effects, absorbtion wavelength and molar absorb coefficients were discussed with the UV-Vis. The value of selenadiazoles in analytical chemistry and the varieties of structure with the pH were discussed. 1H NMR of SPO and SPDO were studied, and their structures were identified by the calculation.3. GC/MS The selenadiazoles were investigated with GC/MS. In GC, some of selenadiazoles could be separated which is volatile, the effects of retention time were in direct relation in their molecular weights by the group CH3- and Br-. The retention times of isomer was different such as SPb and SPc, SPDO has two different peaks which were regarded as the isomers of SPDO. In MS, the Se-containing compounds had the characterized molecular or ion clusters, and the M: (M-2) is about 2:1 in the clusters. As the characterized molecular or ion clusters, the Se-containing compounds can be identified without the standard samples. The possible cleavage ways of selenadiazoles were discussed.4. Electrochemical property The cyclic voltammetry of selenadiazoles were investigated, the results showed that the process of electrode was mainly dominated by adsorption. These properties provided evidence for self-assemble.5. The characterization and electrochemical properties for self-assemble and its monolayer The results showed that the best concentration of selenadiazoles is about 10-3mol/L. The monolayers had reductive peaks at about -600mV which was consistent with the selenadiazoles in solution.更多还原