新型ABNO修饰电极的制备及其电催化合成腈类化合物性能

With stable structure, small steric hindrance and high electrocatalytic property, 9-azabicyclo[3,3,1]nonane N-oxyl (ABNO) is employed as a green oxidation catalyst. This project intends to synthesize novel monomers of pyrrole and thiophene containing ABNO side chain. Then ABNO-modified polypyrrole and polythiophene electrodes will be prepared by in situ electropolymerization on matrix electrodes respectively. Thus ABNO can be reused in the form of modified electrode, and the separation of reaction products can be greatly simplified. The electrocatalytic activities of ABNO-modified electrodes will be studied with some aldehydes and alcohols as the substrates to synthesis nitrile compounds using different nitrogen sources, such as ammonium acetate and ammonium carbonate. The dynamics models of electrocatalytic reaction of ABNO-modified electrodes will be built and the methodological study will be carried out under the optimized reaction conditions. Finally, electrochemical technologies with in situ FTIR and in situ Raman spectroscopy will be used to analysis electrocatalytic oxidation reaction mechanism of ABNO-modified electrodes. Therefore, a green and economic system for synthesis of nitrile compounds can be constructed with the above researches. It will also provide theoretical guidance to enlarge the applicable area of ABNO-modified electrodes.

9-氮杂双环[3.3.1]壬烷氮氧自由基（ABNO）具有结构稳定、空间位阻小、电催化性能高等优点，是一绿色的氧化催化剂。本项目拟合成侧链含有ABNO的新型吡咯单体和噻吩单体，通过电聚合作用，分别在电极表面原位聚合得到ABNO修饰聚吡咯电极和聚噻吩电极，以修饰电极的形式，实现ABNO的重复利用，简化反应产物的分离步骤；以醛和醇为反应底物，以醋酸铵、碳酸铵等为氮源，研究ABNO修饰电极电催化合成腈类化合物的性能，构建其电催化反应动力学模型，并在优化的反应条件下，进行方法学研究；采用电化学原位红外光谱和原位拉曼光谱技术，研究分析其电催化氧化反应机理。通过对这一新型电催化氧化体系的系统研究，构建适用于腈类化合物的经济的、环境友好的合成体系，同时为进一步扩展ABNO修饰电极的应用提供的科学理论指导。

9-氮杂双环[3.3.1]壬烷氮氧自由基（9-azabicyclo[3.3.1]nonane-N-oxyl, ABNO）具有结构稳定、空间位阻小、电催化性能高等优点，是一绿色的电氧化催化剂。本项目合成了3-(2-(噻吩-3-基))乙酰氧基-9-氮杂双环[3.3.1]壬烷-氮氧自由基、N-(9-氮杂双环[3.3.1]-壬-3-基)-3-(1H-吡咯-1-基)丙酰胺、3-(9-己酰氧基咔唑)-9-氮杂双环[3.3.1]壬烷-N-氧基自由基等系列侧链含有ABNO的单体，通过电化学聚合作用，分别在电极表面原位聚合制备得到对应的ABNO修饰聚合物电极。研究了ABNO修饰聚合物电极电催化合成腈类化合物的性能；采用原位光谱技术，研究分析其电催化氧化反应机理。项目还研究了ABNO修饰电极电催化氧化醇的活性，并将研究内容拓展到4-(2,5-双(2-噻吩基)-1H-吡咯)苯甲酰氧基-2,2,6,6-四甲基哌啶氮氧自由基、4-(2-(2,5-双(2-噻吩基))噻吩-3-基)乙酰氧基-2,2,6,6-四甲基哌啶氮氧基自由基、4-(4-二苯氨基)苯甲酰氧基-2,2,6,6-四甲基哌啶氮氧基自由基、4-(2-(9H-咔唑-9-基))乙酰氧基-2,2,6,6-四甲基哌啶氮氧基自由基、4-(4-(9H-咔唑-9-基))丁酰氧基-2,2,6,6-四甲基哌啶氮氧基自由基、4-(6-(9H-咔唑-9-基))丁酰氧基-2,2,6,6-四甲基哌啶氮氧基自由基和2-(噻吩-3-基)丙二酸双(2,2,6,6-四甲基哌啶氮氧自由基-4-醇)酯等其它新型氮氧自由基聚合体系，和其它电化学氧化体系如电氧化亚磷酸三烷基酯和芳基硫醇合成硫代磷酸酯、以富电子芳烃和芳基硫醇为原料电氧化合成芳基硫化物、3-巯基吲哚类化合物的电氧化合成、碘化钾催化芳基硫醇与香豆素的电氧化反应等的研究中。