Micellar Aqueous Oxidation System by Using New Amphiphilic Oxidants

1. 设计并制备了独特的两亲性α-烷氧烷基氢过氧化物（α-AHP），既可作为胶束形成剂，又可作为有机底物的增溶剂和氧化剂。DTA/TG分析表明，α-AHPs在100℃内保持稳定。在MoO_2(acac)_2的催化作用下，用胶束α-AHP法在很温和的条件下，将苄基硫化物在水中有效地氧化为相应的亚砜。这种新型的水氧化系统具有良好的发展前景。烯烃在胶束水溶液中的臭氧分解研究了一系列不溶于水的环戊-1 -苯基苯在水和胶束水溶液中的臭氧分解。这些底物的臭氧分解只产生相应的水参与产物（氧醛）和相应的水不参与产物（次级臭氧化物）。在水中，次生臭氧化物主要在所有底物的臭氧分解中形成。随着底物和表面活性剂的组合，胶束体系中的产物分布发生了巨大的变化。胶束对底物增溶方式的不同似乎是决定产物分布的关键。这些信息将有助于促进这种无害环境的氧化方法在实验室或工业过程中的应用。

1. New Oxidation System in Water by Using Amphiphilic HydroperoxideA unique amphiphilic α-alkoxyalkyl hydroperoxide (α-AHP) to act both as a micellar-forming reagent to solubilize organic substrates and as an oxidizing reagent was designed and prepared. DTA/TG analysis indicated that α-AHPs were stable in neat up to 100 ℃. Effective oxidation of benzyl sulfide to the corresponding sulfoxide in water has been achieved by using micellar α-AHP in the presence of a catalytic amount of MoO_2(acac)_2 under very mild conditions. This new oxidation system in water has a bright prospect of developing the new environmentally benign process.2. Ozonolyses of Alkenes in Micellar Aqueous SolutionsOzonolyses of a series of water-insoluble cyclopent-1 -enylbenzenes were carried out both in water and in micellar aqueous solutions. Ozonolyses of these substrates yielded the corresponding water-participation products (oxoaldehydes) and the corresponding water-nonparticipation products (sec-ozonides) exclusively. In water, secozonides were formed predominantly in the ozonolyses of all substrates. The product distribution in micellar systems drastically varied with the combination of substrate and surfactant. The difference in the solubilizing mode of substrates by micelles seems to be the key in determining the product distribution. This information will contribute to the promotion of application of this environmentally benign oxidation methodology to laboratory or industrial processes.