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Construction of Safer Oxidation Systems

构建更安全的氧化系统

基本信息

批准号：
14550809
负责人：
MASUYAMA Araki
金额：
$ 2.3万
依托单位：
Osaka University
依托单位国家：
日本
项目类别：
Grant-in-Aid for Scientific Research (C)
财政年份：
2002
资助国家：
日本
起止时间：
2002 至 2003
项目状态：
已结题

项目摘要

1. New Protocol for Oxidation in Water : Micellar Oxidation Systems Composed of α-AHPA series of novel amphiphilic hydroperoxides, α-alkoxyalkyl hydroperoxides (α-AHP) and their related hydroperoxides, were prepared with the intention of developing new oxidizing agents bearing a micelle-forming character in water. Both oxidation of benzyl sulfide and epoxidation of geraniol promoted by these hydroperoxides were investigated in detail under various conditions. Because the conversion of each substrate in the micellar systems was higher than that in nonmicellar media, the solubilization of substrates into micelles was certainly effective in promoting oxidations of insoluble substrates in aqueous media.2. Safer Oxidation Systems Composed of Oxone and Amphiphilic Ketones in WaterNew nonionic surfactant bearing a carbonyl group at the terminal position of hydrophilic moiety were prepared and were applied to newly designed micellar aqueous oxidation systems composed of Oxone (2KHSO_5-KHSO_4・K_2S0_4) as an oxidizing agent. Both solubilization of substrates by micelles of these surfactants and active peroxo species generated by the reaction of these surfactants with Oxone in situ were the keys in promoting effective epoxidation of various alkenes in water.3. Radical Cyclization Initiated by the Reaction of Allylic Hydroperoxides with FeSO_4 in Aqueous MediaTreatment of 1-methyl-2-methylene-1-cyclohexane with a mixture of FeSO_4/CuCl_2 in aqueous media yielded 1-(1-chlorocyclohexyl)ethanones as the major product consistent with 6-endo-trig cyclization of the intermediate alkyl radical. This strategy was extended to the ring enlargement of a series of 1 -isopropylcycloalkyl hydroperoxides. Regioselective 7-or 8-endo-trig cyclization reactions could be achieved by treatment of the corresponding cyclopentyl or cyclohexyl hydroperoxides with a mixture of FeSO_4/CuCl_2 in aqueous media.

1.水中氧化新方法：为了开发在水中具有胶束形成特性的新型氧化剂，合成了一系列新型两亲性过氧化氢化合物--α-烷氧烷基过氧化氢氧化物(α-α)及其相关的过氧化氢化合物组成的胶束氧化体系。在不同条件下，考察了它们对苯硫醚氧化和香叶醇环氧化的促进作用。由于各底物在胶束体系中的转化率高于在非胶束介质中的转化率，因此底物在胶束中的增溶作用对不溶底物在水介质中的氧化具有一定的促进作用。合成了由氧酮和两亲酮组成的新型非离子表面活性剂，并将其应用于氧酮(2KHSO5-KHSO4·K2SO4)胶束水溶液氧化体系。这些表面活性剂胶束对底物的增溶作用以及这些表面活性剂与氧酮原位反应产生的活性过氧基物种都是促进各种烯烃在水中有效环氧化的关键。1-甲基-2-亚甲基-1-环己烷在水介质中与FeSO_4/CuCl2的混合物在水介质中发生自由基环化反应，主要产物为1-(1-氯环己基)乙酮，与中间体烷基自由基的6-内切环化反应一致。这一策略被扩展到一系列1-异丙基环烷基氢过氧化氢的扩环反应。在水介质中，用FeSO4/CuCl2的混合物处理相应的环戊基或环己基过氧化氢，可以实现区域选择性的7-或8-内切环化反应。