核磁共振波谱和红外光谱在研究离子液体催化CO<sub>2</sub>与邻氨基苯腈反应机理的应用及进展

doi:10.3964/j.issn.1000-0593(2025)10-2711-09

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摘要：核磁共振波谱(NMR)和红外光谱(IR)是两种常用的谱学检测方法，不仅可以用于物质含量分析和分子结构鉴定，而且还能通过其吸收峰的强度与位置，从分子层面来表征分子间相互作用位点、类型和强度等重要微观信息，已被拓展应用于研究化学反应机理。CO₂资源化利用是当前绿色化学研究热点之一。离子液体(ILs)具有蒸汽压低、热稳定性高和结构与性质可调的特点，作为一种新型、绿色的催化剂广泛应用于CO₂与邻氨基苯腈反应，能同时活化CO₂和邻氨基苯腈，在无金属、温和条件下使常压CO₂高效化学转化为具有生物活性的喹唑啉-2,4(¹H, ³H)-二酮及衍生物，显示出了优异催化性能和潜在应用价值。因此，其化学反应机理引起了广大研究者的浓厚兴趣。掌握化学反应机理是有效调控反应的前提，而借助正确、合适的检测方法来表征ILs与反应底物之间的相互作用信息，是研究化学反应机理的有效途径和关键步骤。为此，为了更好地了解和掌握NMR和IR等谱学方法在研究ILs催化CO₂与邻氨基苯腈反应机理中的应用及进展，在简述ILs催化CO₂与邻氨基苯腈反应发展的基础上，首先介绍了NMR和IR技术的自身特点及其在研究该反应机理中所发挥的作用；其次，重点聚焦¹H NMR、¹³C NMR、¹⁵N NMR、¹⁸³W NMR、FTIR和in-situ FTIR等手段在表征ILs与CO₂或邻氨基苯腈相互作用机制、反应过程中新形成(消失)的基团和形成可能的反应中间体等方面所取得的应用进展，结合文献调研详细分析了NMR和IR技术在研究化学反应机理中的独特优势与存在的问题，并提出了可能的解决思路和方案；最后，为进一步推广NMR和IR技术应用于化学反应机理研究提出了合理建议，即利用二维NMR和IR光谱获得更精细的分子结构和相互作用信息，进一步确定催化剂与底物的相互作用位点与类型，再结合DFT计算和分子动力学模拟等理论方法获得的反应过程中底物的电子结构和体系的能量变化，准确地获取反应中间体和过渡态的结构信息，从而更加清晰地阐明反应机理，这将迎来NMR和IR在研究化学反应机理的新发展。

关键词：核磁共振；红外光谱；离子液体；二氧化碳转化；反应机理

Abstract：Nuclear magnetic resonance (NMR) and infrared (IR) spectra are two commonly used spectroscopic methods, which can not only be used for the analysis of substance content and identification of molecular structure, but also characterize important microscopic information such as intermolecular interaction sites, types and strengths at the molecular level through the intensity and position of the absorption peaks, and have been expanded to be used in the study of chemical reaction mechanisms. The resourceful utilization of CO₂ is one of the current hotspots in green chemistry research. Ionic liquids (ILs), with low vapor pressure, high thermal stability and adjustable structure and property, are widely used as a new type of green catalysts for the reaction of CO₂ with 2-aminobenzonitrile, which can simultaneously activate CO₂ and 2-aminobenzonitrile, and efficiently convert atmospheric CO₂ into biologically active quinazoline-2,4(¹H, ³H)-dione and its derivatives under metal-free and mild conditions, showing excellent catalytic performance and potential application value. Therefore, its chemical reaction mechanism has garnered significant interest from a diverse range of researchers. Understanding the chemical reaction mechanism is a prerequisite for effective regulation of the reaction. Characterizing the interaction information between ILs and reaction substrates, aided by suitable detection methods, is an effective way and a key step in studying the chemical reaction mechanism. For this reason, to better understand the application and progress of NMR and IR spectroscopic methods in the study of the mechanism of IL-catalyzed reaction of CO₂ with 2-aminobenzonitrile, based on briefly description of the history and current development of the reaction between CO₂ and 2-aminobenzonitrile, we firstly introduce the characteristics of NMR and IR techniques and their roles in the study of this reaction mechanism. Secondly, we focus on ¹H NMR, ¹³C NMR, ¹⁵N NMR, ¹⁸³W NMR, FTIR and in-situ FTIR in the characterization of the interaction of ILs with CO₂ or 2-aminobenzonitrile, the newly formed (disappeared) groups and the formation of possible reaction intermediates, etc., and combined with the results of the literature, and then the unique advantages and problems of the NMR and IR techniques in the study of the intermolecular interactions and the mechanism of chemical reactions are analyzed, and possible solutions are proposed. Finally, reasonable suggestions are put forward for the further promotion of the application of NMR and IR spectra in the study of chemical reaction mechanisms, namely, using two-dimensional NMR and IR spectra to obtain more refined molecular structure and interaction information, further determining the interaction sites and types between catalysts and substrates, and combining theoretical methods such as DFT calculation and molecular dynamics simulation to obtain the electronic structure of substrates and energy changes of the system during the reaction process, accurately obtaining the structural information of reaction intermediates and transition states, and thus clarifying the reaction mechanism more clearly. This will usher in new developments in NMR and IR spectra in the study of chemical reaction mechanisms.

Key words：NMR; IR; Ionic liquid; CO₂ conversion; Reaction mechanism

收稿日期: 2025-02-11 修订日期: 2025-07-27

中图分类号:

O657.61

基金资助: 浙江省科技计划项目(2024C03108)，国家自然科学基金项目(21978172)资助

通讯作者: 许映杰 E-mail: xuyj@usx.edu.cn

作者简介: 孙中远，2000年生，绍兴文理学院化学化工学院硕士研究生 e-mail: 1633660403@qq.com

引用本文:

孙中远，郭昱君，许映杰. 核磁共振波谱和红外光谱在研究离子液体催化CO₂与邻氨基苯腈反应机理的应用及进展[J]. 光谱学与光谱分析, 2025, 45(10): 2711-2719.
SUN Zhong-yuan, GUO Yu-jun, XU Ying-jie. Application and Progress of Nuclear Magnetic Resonance and Infrared Spectra in the Study of the Mechanism of Ionic Liquid-Catalyzed Reaction of CO₂ With 2-Aminobenzonitrile. SPECTROSCOPY AND SPECTRAL ANALYSIS, 2025, 45(10): 2711-2719.

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