State Key Laboratory of Chemical Resource Engineering, Beijing University of Chemical Technology , Box 266, Beijing 100029, China.
Chem Rev. 2017 May 24;117(10):6929-6983. doi: 10.1021/acs.chemrev.7b00030. Epub 2017 May 1.
Selective oxidation has an important role in environmental and green chemistry (e.g., oxidative desulfurization of fuels and oxidative removal of mercury) as well as chemicals and intermediates chemistry to obtain high-value-added special products (e.g., organic sulfoxides and sulfones, aldehydes, ketones, carboxylic acids, epoxides, esters, and lactones). Due to their unique physical properties such as the nonvolatility, thermal stability, nonexplosion, high polarity, and temperature-dependent miscibility with water, ionic liquids (ILs) have attracted considerable attention as reaction solvents and media for selective oxidations and are considered as green alternatives to volatile organic solvents. Moreover, for easy separation and recyclable utilization, IL catalysts have attracted unprecedented attention as "biphasic catalyst" or "immobilized catalyst" by immobilizing metal- or nonmetal-containing ILs onto mineral or polymer supports to combine the unique properties of ILs (chemical and thermal stability, capacity for extraction of polar substrates and reaction products) with the extended surface of the supports. This review highlights the most recent outcomes on ILs in several important typical oxidation reactions. The contents are arranged in the series of oxidation of sulfides, oxidation of alcohols, epoxidation of alkenes, Baeyer-Villiger oxidation reaction, oxidation of alkanes, and oxidation of other compounds step by step involving ILs as solvents, catalysts, reagents, or their combinations.
选择性氧化在环境和绿色化学(例如燃料的氧化脱硫和汞的氧化去除)以及化学品和中间体化学中具有重要作用,可获得高附加值的特殊产品(例如有机亚砜和砜、醛、酮、羧酸、环氧化物、酯和内酯)。由于离子液体(ILs)具有独特的物理性质,例如非挥发性、热稳定性、非爆炸性、高极性以及与水的温度依赖性混溶性,因此它们作为反应溶剂和介质引起了人们的极大关注,被认为是挥发性有机溶剂的绿色替代品。此外,为了便于分离和可回收利用,通过将含金属或非金属的 IL 固定在矿物或聚合物载体上,将 IL 催化剂作为“两相催化剂”或“固定化催化剂”固定化,将 IL 的独特性质(化学和热稳定性、提取极性底物和反应产物的能力)与载体的扩展表面结合起来,这吸引了前所未有的关注。这篇综述重点介绍了 IL 在几种重要典型氧化反应中的最新研究成果。内容按硫化物氧化、醇氧化、烯烃环氧化、Baeyer-Villiger 氧化反应、烷烃氧化以及涉及 IL 作为溶剂、催化剂、试剂或其组合的其他化合物氧化的顺序逐步排列。