Development of High-performance Oxidation Systems in Water by Use of Inorganic Oxidants

1. 制备了一种亲水性部分末端含有羰基的新型非离子型两亲性试剂，并将其应用于以氧酮为氧化剂的新型胶束水氧化体系。有机底物对表面活性剂胶束的增溶作用以及两亲性酮与氧酮原位反应产生的活性过氧物质是促进烯烃在水中环氧化的关键。通过萃取-柱层析的方法，可以定量地从反应混合物中回收两亲酮。设计并制备了以氧酮为水反应位的两亲性功能树脂基质氧化体系，目的是开发一种简单有效的氧酮在水中氧化体系。这些接枝聚合物在水中的溶胀特性和羰基的存在是促进烯烃与氧酮在水介质中环氧化的重要因素。这些两亲性树脂可以很容易地通过过滤回收。这些树脂在第三次回收后仍保持其有效性。在以过硼酸钠（SPB）为氧化剂的胶束水溶液中，研究了几种不溶于水的苯基硫化物的氧化。采用阴离子十二烷基硫酸钠（SDS）、阳离子十二烷基三甲基溴化铵（DTAB）和非离子庚（乙二醇）单十二烷基醚（C_<12>E_7）三种常规表面活性剂作为胶束形成剂，对底物进行了增溶。碱性条件下DTAB胶束和酸性条件下SDS胶束能有效促进水中SPB的氧化。提出了简单易行的分离氧化产物的工序。这些氧化系统的优点是烯烃的环氧化或硫化物的s氧化可以在不可燃和无害的水中安全有效地进行。因此，这些方法将对现代绿色和可持续化学做出重大贡献。少

1. New aqueous micellar oxidation system promoted by the combination of Oxone and an amphiphilic ketoneA new nonionic amphiphile bearing a carbonyl group at the terminal position of hydrophilic moiety was prepared and was applied to a newly designed micellar aqueous oxidation system containing Oxone as an oxidant. Both solubilization of organic substrates into the surfactant micelles and the active peroxo species generated by the reaction of this amphiphilic ketone with Oxone in situ were the keys in promoting epoxidation of alkenes in water. The amphiphilic ketone could be recovered quantitatively from the reaction mixture by extraction followed by column chromatography.2. New oxidation system with Oxone in the Matrices of amphiphilic functional resins as the reaction sites in waterTerminal functionalized PEG-polystyrene graft polymer resins were designed and prepared with the intention of developing the simple and an effective oxidation systems with Oxone in water. Both swelling char … More acteristic of these graft polymers in water and the presence of carbonyl groups in the polymer were substantial factors to promote the epoxidation of alkenes with Oxone in the aqueous medium. These amphiphilic resins could be easily recovered by filtration. The effectiveness of these resins was maintained after the third recycling.3. Oxidation using sodium perborate in aqueous micellar solutionsOxidation of a couple of water-insoluble phenylsulfides was explored in the aqueous micellar solutions containing sodium perborate (SPB) as an oxidant. Three kinds of conventional surfactants, anionic sodium dodecylsulfate (SDS), cationic dodecyltrimethylammonium bromide (DTAB) and nonionic hepta (ethylene glycol) monododecyl ether (C_<12>E_7), were used as micellar forming reagents to solubilize substrates. The SPB oxidation in water was effectively promoted by DTAB micelles under alkaline conditions and by SDS micelles under acidic conditions. Simple and easy work-up procedures to isolate the oxidation products were proposed.The merit of these oxidation systems is the epoxidation of alkenes or the S-oxidation of sulfides can be carried out in a safe and effective manner in nonflammable and harmless water. So these methodologies will make a significant contribution to the modern Green and Sustainable Chemistry. Less