基于质谱技术的有机反应中间体分析研究

Research on the organic reactive intermediates has important significance for the elucidation of organic reaction mechanisms and exploring more efficient organic synthesis routes. Reactive intermediates are extremely active and have short lifetime, which are difficult to be isolated and studied by conventional methods. In recent years, the rapid development and application of mass spectrometry technique has opened up a new way for organic reactive intermediate research. But the use of mass spectrometry techniques to study organic reactive intermediates is still in the initial stage, some established methods are not universal, and the practical application is very limited. Therefore, this project studies various reactive intermediates in organic reactions involving metal or free radical. Focusing on detection method improvement and mass spectrometer innovation, we will build a series of efficient, universal and practical new mass spectrometric methods for organic reactive intermediate research, including: increasing the detection efficiency of trace intermediates by improving the ionization efficiency, ion injection efficiency, and ion transmission efficiency; improving the detection efficiency of transient reactive intermediates by applying the in-situ reaction and low temperature ultrasonic spray technology; studying the neutral reactive intermediates by applying the charge-tagged method, supermolecule capture, and new ionization technique. In addition, the newly-established mass spectrometric technologies will be used to develop novel method for gas-phase synthesis of reactive intermediates, which can provide new and effective ways for the structure characterization and reactivity evaluation of these reactive intermediates. The research results on organic reactive intermediates based on mass spectrometry may further guide the design and optimization of related organic reactions and provide new ideas for the development of synthetic organic chemistry.

有机反应的活性中间体研究对于阐明有机反应机理和探索高效的合成路径具有重要的意义。常规方法分离分析痕量、瞬态中间体存在诸多困难。现代质谱技术的快速发展为有机活性中间体的分析研究提供了新途径，但相关研究还十分有限，方法的普适性和实用性不足，更缺乏深入系统的活性分析研究。本项目拟从金属和自由基参与的两类有机反应中形成的各类活性中间体着手，立足于技术和仪器创新，通过改进离子化、离子进样和离子传输过程的效率来增加痕量中间体的检测效率；通过原位反应、低温超声喷雾等技术来提高瞬态活性中间体的检测效率；通过电荷标记、超分子捕获、新的电离方法等研究中性的活性中间体，构建高效、普适和实用的有机活性中间体分析研究新方法；通过发展多路气相离子-分子和离子-离子反应的质谱技术，为这些中间体的结构和反应活性研究提供新的手段。应用这些研究成果指导相关液相有机反应的设计和优化，有望为有机合成化学的发展提供新思路。

有机反应的活性中间体由于其痕量、瞬态的特性，给传统的分析方法带来了极大的挑战。质谱在分析化学中扮演着至关重要的角色。现代质谱技术的快速发展为有机活性中间体的分析研究提供了新途径，但相关研究还十分有限，方法的普适性和实用性不足，更缺乏深入系统的活性分析研究。本项目从金属和自由基参与的两类有机反应中形成的各类活性中间体着手，立足于技术和仪器创新，构建与发展了一系列可方便检测活性中间体的新技术新方法。应用构建的新技术，通过电荷标记、超分子捕获、新的电离方法等研究中性的活性中间体，构建高效、普适和实用的有机活性中间体分析研究新方法，并开展了反应中间体的结构表征和活性研究；发展了多路气相离子-分子和离子-离子反应的质谱技术和新颖的活性中间体的气相合成方法，为活性中间体的结构和反应活性研究提供新的手段；研究了基于质谱技术的气相反应机理，并拓展到液相有机反应中间体的研究，对于阐明有机反应机理和探索高效的合成路径具有重要的意义。应用这些研究成果指导相关有机反应的设计和优化，有望为有机合成化学的发展提供新思路。.关键词：现代质谱技术；有机反应中间体；分析检测；反应活性研究；反应机理