Design of Catalytic Ionic Liquids for Oxidation Catalysis

本项目的重点是设计用于氧化催化的新型催化离子液体。催化离子液体不仅是一种具有惰性阳离子和阴离子的溶剂，而且还含有催化活性阳离子或催化活性阴离子。这种方法意味着离子液体离子对以可重复的周期性方式改变其化学性质，即在催化循环的一次周转内。由于许多氧化过程的典型副产物水会抑制催化剂或降低催化剂的选择性和翻转数，因此设计相应的高疏水性非催化长链五烷基胍阳离子或新型全氟酰胺和-亚胺洋葱用于双相催化。新型离子液体含有催化氧化酸盐阴离子[Cu4OCl10]-将应用于2,3,5-三甲基苯酚的有氧氧化成2,3,5-三甲基醌，这是工业合成维生素E的关键中间体，其他离子液体含有[Br]-， [Br3]和[过氧化物酸盐]的混合物，将用于溴/ ROOH对烯烃和芳烃的溴化试验。最后，研究了含铜、银、金离子[L-M-L]+的新型CIL在甲醇和苯酚双相氧化羰基化制有机碳酸盐过程中的液晶相行为和催化活性。

The project focuses on the design of novel catalytic ionic liquids (CIL) for the use in oxidation catalysis. Catalytic ionic liquids are not just a solvent with inert cation and anion, but they contain either a catalytically active cation or a catalytically active anion. This approach implies that the ionic liquid ion pair changes its chemical nature in a reproducible periodic manner, namely within one turnover of the catalytic cycle. As water, the typical byproduct of many oxidation processes, is inhibiting the catalyst or lowering its selectivity and turn over number, strategies will be followed to design new corresponding highly hydrophobic non-catalytic long-chain pentaalkyl-guanidinium cations or novel perfluoramide and -imide onions for biphasic catalysis. Novel ionic liquids containing the catalytic oxocuprate anion [Cu4OCl10]- will be applied in the aerobic oxidation of 2,3,5-trimethylphenol to 2,3,5-trimethylquinone, a key intermediate of industrial vitamin E synthesis, others with a mixture of [Br]-, [Br3]-and [peroxometallate]- will be tested in the bromination of olefins and aromatics by bromide / ROOH. Finally novel CIL with cupronium, argentonium and auronium cations [L-M-L]+ will be investigated for their liquid crystalline phase behavior and catalytic activity in the biphasic oxidative carbonylation of methanol and phenol to organocarbonates.