氟原子和含氟基团迁移反应的质谱学研究

The project aims to explore, study and summarize the unique mass spectrometric behaviors of organic fluorinated compounds and complexes by developing and applying suitable mass spectrometry technologies. After some preliminary studies in recent years, we found that the fluorine-atom and fluorinated moiety migration/rearrangement reactions were the typical mass spectrometric behaviors of organic fluorinated compounds, reflecting the changing of the chemical nature and reactivity of the compounds after the introduction of one or more fluorine atom or fluorine-containing groups. However, the related researches about gas phase fluorine migration are rarely reported and have not been carefully studied. Meanwhile, in some fluorination reactions, the fluorine or fluorinated moiety migration step of the key reactive intermediates was key step of generating a new C-F bond in the final fluorinated product and the related mass spectrometric studies were important to elucidate the reaction mechanism and the discovery of novel fluorination reaction. Thus,this project focused on studying the fluorine atom or fluorine-containing group migration reactions as the key scientific issues and systematic studies would be carried out according to the following two specific areas: (1) the studying for the structural characterization methods and gas phase reaction behaviors of the organic fluorinated compounds and complexes by mass spectrometry; (2) investigation for the interception strategy and technology of the key reactive intermediates in some novel fluorination reactions by mass spectrometry.

本项目旨在发展和应用质谱学技术, 探索、研究和总结含氟有机物与复合物独特的质谱行为。经过一些前期研究,申请人发现气相氟原子和含氟基团的迁移或重排, 是含氟有机物和复合物最显著的质谱学特性，体现了氟原子和含氟基团引入后所引发的化合物性质的变化。而这些特殊的化学历程以前鲜有深入的研究和报道。同时在一些氟化反应中，关键活性复合物或反应中间体的氟原子和含氟基团的迁移和重排反应，也是构建新C-F键和生成最终含氟产物的关键步骤，相关的质谱学研究对阐明这些氟化反应机理和发现新型氟化反应有重要意义。本项目拟针对氟原子和含氟基团的迁移反应这一关键科学问题，从两个方面入手来开展系统性的质谱学研究:(1)含氟化合物及复合物的质谱学结构表征方法和特征的质谱学行为研究；(2)一些新型氟化反应中关键活泼含氟中间体的质谱学表征策略和技术的研究。

本项目发展了多种离子化技术，并将这些技术用于有机质谱学和有机氟化学的研究中，解决了一系列有机氟化学问题，发现并总结了一些有代表性的氟化反应中氟原子和含氟基团迁移和成键的活性特点。经过近四年系统的研究，申请人发现气相氟原子和含氟基团的迁移或重排是含氟有机物和复合物最显著的质谱学特性，体现了氟原子和含氟基团引入后所引发的化合物性质的变化。而这些特殊的化学历程在以前鲜有深入的研究和报道。同时研究了一系列新发展出来的氟化反应，我们发现关键活性复合物或反应中间体的氟原子和含氟基团的迁移和重排反应，也是构建新C-F键和生成最终含氟产物的关键步骤，相关的质谱学研究对阐明这些氟化反应机理和发现新型氟化反应有重要意义。本项目在以下两个方面都取得了研究进展(1)含氟化合物及复合物特殊的质谱学行为和其中化学机理；(2)一些新型氟化反应中关键活泼含氟中间体的质谱学表征结果和反应活性的研究。