Development of Benign Chemical Processes on Nano-seized Reaction Environments

从环境的角度来看，开发高效、无有害废物的化学过程是一个重要的课题。在我们的项目中，重点开发了水中的有机反应和聚合物固定化催化剂的开发。主要研究结果如下：1.水中有机反应是环境友好化学反应中最有前景的方法之一。此外，水有时对有机反应的反应性和选择性起着有趣的作用。我们对水中的有机反应进行了研究，发现BR-φ酸-表面活性剂组合催化剂通过形成疏水反应环境，在水中的脱水反应中起到了良好的反应促进作用。我们还发现，聚合物负载的BRφnsted酸在水中的几种反应中都是有效的，如脱水反应、醇的脱保护反应等，此外，在水介质中还实现了高对映选择性的Mannich反应和羟甲基化反应。这些结果将启发人们认为水是一种很有前途的溶剂。2.高官能化的有机金属催化剂有时会对人体和环境有害。因此，开发无任何有机金属废物的化学工艺是很重要的。我们小组已经开发了用于固定含金属催化剂的微胶囊方法。在这个项目中，我们重点研究了有用的含金属催化剂、Ru、Pd和Om化合物的固定化。这些试剂被成功地固定在新型聚合物上，并具有良好的回收和重复使用性能。该催化剂还可用于烯烃的歧化、加氢和不对称双羟基化反应，反应效率较高。所获得的结果将有助于清洁化工工艺的发展。

Development of highly efficient chemical processes with no harmful waste is an important subject from an environmental viewpoint. In our project, development of organic reactions in water and development of polymer-immobilized catalysts have been focused. The results obtained are summarized below.1.Organic reaction in water is one of the most promising methods in environmental benign chemical processes. Furthermore, water sometimes plays an interesting role on reactivity and selectivity of organic reactions. We carried out investigations of organic reactions in water, and it was found that a Brφnsted acid-surfactant combined catalyst worked as a good reaction promoter in dehydrating reactions in water by forming hydrophobic reaction environments. We also showed that polymer supported Brφnsted acid is effective in several reactions in water ; for example, dehydrating reactions, deprotecting reactions of alcohols, etc. Moreover, highly enantioselective Mannich-type reactions and hydroxymethylation in aqueous media were also achieved. Those results would inspire that water is a promising solvent.2.Highly functionalized organometallic catalysts were sometimes harmful to human body and environment. Therefore, it is important to develop chemical processes without any organometallic waste. Our group has already developed microencapsulate methods for immobilizing metal-containing catalysts. In this project, we focused immobilization of useful metal-containing catalysts, ruthenium, palladium and osmium compounds. Those reagents were successfully immobilized on novel polymers with perfect recovery and reuse. Those catalysts were also employed in metathesis, hydrogenation, and asymmetric dihydroxylation of olefins with high efficiency. The results obtained would contribute to development of clean chemical processes.