共查询到19条相似文献,搜索用时 109 毫秒
1.
综述了以过氧化氢为氧源,多金属氧酸盐催化烯烃环氧化的研究进展,尤其是针对基于多金属氧酸盐的反应控制相转移催化体系近年来的研究进展进行了详细阐述. 相似文献
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MCM-41固载Co席夫碱配合物的制备及其催化烯烃环氧化的研究 总被引:6,自引:1,他引:6
环氧化合物作为有机合成中间体具有广泛应用,催化烯烃环氧化一直是催化化学中的一个重要课题[1~2].尽管已经报道了以过酸、过氧化氢、烷基过氧化物、或分子氧为氧化剂,以金属配合物(通常为钌、钼、钛的配合物)为催化剂的反应体系,但对环氧化物的选择性却很低[3].另外,除了需探索具有高选择性的催化体系外,应用分子氧或空气作为氧化剂更适宜于经济和安全的要求.目前,在以分子氧作为氧化剂,均相催化烯烃环氧化的研究中,应用醛类化合物作为氧转移试剂是一种有效的和方便的促进烯烃环氧化的方法[4].但是,均相催化剂难于分离和重复使用,因此… 相似文献
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酮-过氧化氢体系对烯烃的环氧化 总被引:2,自引:0,他引:2
过氧化酮是优良的烯烃环氧化试剂,可将烯烃氧化成环氧化物。在这些反应中,所用的氧化剂都是过硫酸氢钾或商品Oxone^[1-6]。用其它氧化剂与酮生成过氧化酮使烯烃环氧化的报道很少^[7,8],只有一例是使用过氧化氢作氧化剂的,但其只研究了一种酮与过氧化氢对烯烃的环氧化^[8]。本文使用价格便宜,且没有污染的过氧化氢取代Oxone,与酮反应形成的过氧化酮使烯烃环氧化,并首次研究了一系列酮化合物与过氧化氢组成的催化体系对烯烃的环氧化反应,考察了各种酮的催化活性。 相似文献
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《分子催化》2012,26(4)
以苯乙烯、环己烯和反式二苯乙烯为烯烃底物,以双氧水、叔丁基过氧化氢和异丙苯过氧化氢为氧化剂,以苯环上对位和邻位氯取代的四苯基金属卟啉为仿生催化剂,对烯烃的催化环氧化反应进行了对比研究.讨论了不同氯取代位的四苯基金属卟啉对烯烃环氧化性能的影响.实验结果表明,在没有助催化剂存在下,邻位氯代的四(2,6-二氯苯基)铁(锰)卟啉对烯烃的环氧化具有优异的催化性能,烯烃底物的转化率和环氧选择性都比对位氯代的四苯基铁(锰)卟啉高,且反应条件温和.其中FeⅢ(TDCPP)Cl的催化性能最好,环氧化选择性最高,催化氧化苯乙烯时,环氧苯乙烷的选择性达到了90.4%.相同金属离子不同配体的金属卟啉传递氧原子的能力为TDCPP〉T(p-Cl)PP〉TPP.氧化剂的结构对环氧化物的选择性有较大影响.过氧键连有吸电子基团的异丙苯过氧化氢对环氧化物的选择性最高.根据实验结果,对金属卟啉催化环氧化机理进行了分析. 相似文献
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苯环上氯取代位对四苯基金属卟啉催化烯烃环氧化性能的影响 总被引:1,自引:1,他引:0
以苯乙烯、环己烯和反式二苯乙烯为烯烃底物,以双氧水、叔丁基过氧化氢和异丙苯过氧化氢为氧化剂,以苯环上对位和邻位氯取代的四苯基金属卟啉为仿生催化剂,对烯烃的催化环氧化反应进行了对比研究.讨论了不同氯取代位的四苯基金属卟啉对烯烃环氧化性能的影响.实验结果表明,在没有助催化剂存在下,邻位氯代的四(2,6-二氯苯基)铁(锰)卟啉对烯烃的环氧化具有优异的催化性能,烯烃底物的转化率和环氧选择性都比对位氯代的四苯基铁(锰)卟啉高,且反应条件温和.其中FeⅢ(TDCPP)Cl的催化性能最好,环氧化选择性最高,催化氧化苯乙烯时,环氧苯乙烷的选择性达到了90.4%.相同金属离子不同配体的金属卟啉传递氧原子的能力为TDCPP>T(p-Cl)PP>TPP.氧化剂的结构对环氧化物的选择性有较大影响.过氧键连有吸电子基团的异丙苯过氧化氢对环氧化物的选择性最高.根据实验结果,对金属卟啉催化环氧化机理进行了分析. 相似文献
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本文介绍近年来国外金属有机化学家报道的烷基及芳基三氧合铼(14e,Ⅶ)络合物RReO3的合成和反应,以及利用该类络合物催化的烯烃歧化、烯烃环氧化和醛与重氮化合物烯烃化反应。 相似文献
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甲烷利用菌催化烯烃环氧化的底物选择性, 细胞失活原因及产物对映体组成 总被引:4,自引:0,他引:4
研究了甲烷利用菌Methylomonas sp. GYJ3, Methylomonas sp. S, Methylomonas sp. Z201,Methylococcus capsulatus IMV3021, Methylosinus trichosporium IMV3011休止细胞催化烯烃环氧化的底物选择性, 细胞失活原因以及产物对映体组成。发生不同菌株和底物的环氧化活性不同。甲烷利用菌只能催化短链烯烃环氧化, 环烯烃和芳香烯烃无反应。对烯丙基型底物而言, 取代基大小和极性影响环氧化活性。丙烯环氧化活性最高, 烯丙醇不能环氧化。细胞失活的主要原因是环氧化产物的细胞毒性和反应体系中辅酶NADH损耗。手性气相色谱揭示甲烷利用菌催化烯烃环氧化形成外消旋产物。 相似文献
9.
CoPc/Al2O3催化分子氧环氧化环己烯的研究 总被引:1,自引:0,他引:1
常使用均相催化剂[1-4]催化氧化剂对烯烃进行环氧化来制备环氧环己烷,但均相催化剂存在分离回收难,易二聚失活的缺点.近年来对均相催化剂的固载开展了广泛的研究,如郑岩等[5]使用溶胶 -凝胶包容乙酰丙酮镍,M.Salavati-Niasari等[6]用Al2O3固载Mn(Salen)、Mn(en)2和Mn(acac)2金属配合物用于烯烃环氧化,由于Al2O3廉价易得,酞菁具有不易二聚、降解等较稳定的优点[3],本文以酸性Al2O3为载体,固载酞菁钴金属配合物制备CoPc/Al2O3新型环氧化催化剂,并对其结构进行表征,同时以分子氧为氧源,异丁醛为还原剂考察CoPc/Al2O3催化剂对环己烯的催化环氧化活性,探索了环己烯环氧化的较佳工艺参数. 相似文献
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构建了用于催化烯烃与过氧化氢环氧化反应的高效、 绿色催化反应体系. 首先, 通过水热合成法制备了纳米SnO2, 并在320 ℃下煅烧. 随后, 对所有催化剂进行X射线衍射(XRD)、 紫外-可见漫反射光谱(UV-Vis)、 傅里叶变换红外光谱(FTIR)、 扫描电子显微镜(SEM)和透射电子显微镜(TEM)表征. 进一步将催化剂用于以H2O2水溶液为氧化剂环氧化各种官能化烯烃(包括环烯烃, 苯乙烯和直链烯烃)的反应, 以高转化率和高选择性得到了环氧化物. 在相似的反应条件下, 发现合成的纳米SnO2-170催化剂在催化1-甲基环己烯与H2O2的环氧化反应中的活性最佳, 在2 h内1-甲基环己烯的转化率达到100%, 环氧化物选择性达到100%. 相似文献
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Lu Li Hong-Jin Song Xiang-Guang Meng Ren-Qiang Yang Ni Zhang 《Tetrahedron letters》2018,59(25):2436-2439
A highly active iron (II) complex that catalyzed epoxidation of terminal olefins with hydrogen peroxide was described. The catalytic system displayed excellent catalytic ability for the selective oxidation of terminal olefins to epoxides with high selectivity (up to 97.8%) in CH3CN at 25?°C. The catalytic activity of three similarly structural iron (II) complexes was comparatively studied. The effect of various auxiliary ligands on epoxidation was investigated in detail. 相似文献
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LOU JianFang WANG RongMin CAI YongFu WANG YunPu SONG PengFei ZHANG ZhenLin XIA Chungu 《高等学校化学研究》2001,17(3)
The epoxide is a kind of versatile intermediate for manufacture of a wide variety of fine chemicals. The goal of modem efficient catalytic methods is to produce desired compounds with high yield, selectivity, low cost, safety, operational simplicity and more importantly environmentally benign manner. However, there are various oxidants, which are often hazardous or expensive, being used for both laboratory and industrial epoxidation. Hydrogen peroxide (30 wt%) solution is thought as one of the ideal oxidants because water is a sole theoretical side product. Meanwhile the epoxidation of styrene is a typical one among olefins. Here, the performance of styrene epoxidation was studied with hydrogen peroxide solution catalyzed by Co(Ⅱ) phenanthroline complex encapsulated in supercages of MCM-41. 相似文献
15.
Yin G Buchalova M Danby AM Perkins CM Kitko D Carter JD Scheper WM Busch DH 《Journal of the American Chemical Society》2005,127(49):17170-17171
The reactive intermediates and mechanisms of oxygenation of olefins by manganese complexes were investigated by treating olefins with newly synthesized [MnIV(Me2EBC)(OH)2](PF6)2 in the presence and absence of peroxide and by studying its catalytic epoxidation reaction in normal aqueous solution and, individually, with isotopically labeled H218O, 18O2, and H218O2. The manganese oxo species is not the reactive intermediate for the oxygen transfer process mediated by this manganese complex. A novel manganese(IV) peroxide intermediate, MnIV(Me2EBC)(O)(OOH)+, was captured by mass spectrometry and is proposed as the intermediate that oxygenates olefins in this catalytic system. 相似文献
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Phase-transfer catalytic epoxidation of olefins under liquid-liquid biphasic conditions 总被引:1,自引:0,他引:1
The phase transfer catalytic epoxidation of various olefins in the presence of cocatalysts (sodium tungstate and phosphoric
acid) and an oxidant (hydrogen peroxide) in an organic/aqueous two-phase medium was investigated. The different conversions
and selectivities casued by olefins of different carbon-carbon double bonds are discussed.
This revised version was published online in August 2006 with corrections to the Cover Date. 相似文献
17.
Maria Louloudi Chrisavgi Kolokytha Nick Hadjiliadis 《Journal of molecular catalysis. A, Chemical》2002,180(1-2):19-24
Binuclear manganese(II) complexes with macrocyclic ligands have been synthesized by template Schiff base condensation of diethylenetriamine and pentane-2,4-dione or 1,3-diphenyl-propane-1,3-dione. Catalytic epoxidation of simple olefins with hydrogen peroxide and t-BHP were studied using the above manganese complexes in the presence of a base. The influence of reaction temperature, the additive methanol and the cocatalyst had been investigated. The major products of the oxidations were the epoxides. The new manganese complexes showed significant catalytic activities for the epoxidation of alkenes using hydrogen peroxide as oxidant and ammonium acetate as cocatalyst. 相似文献
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Kamata K Kotani M Yamaguchi K Hikichi S Mizuno N 《Chemistry (Weinheim an der Bergstrasse, Germany)》2007,13(2):639-648
The tetra-n-butylammonium (TBA) salt of the divacant Keggin-type polyoxometalate [TBA](4)[gamma-SiW(10)O(34)(H(2)O)(2)] (I) catalyzes the oxygen-transfer reactions of olefins, allylic alcohols, and sulfides with 30 % aqueous hydrogen peroxide. The negative Hammett rho(+) (-0.99) for the competitive oxidation of p-substituted styrenes and the low value of (nucleophilic oxidation)/(total oxidation), X(SO)=0.04, for I-catalyzed oxidation of thianthrene 5-oxide (SSO) reveals that a strongly electrophilic oxidant species is formed on I. The preferential formation of trans-epoxide during epoxidation of 3-methyl-1-cyclohexene demonstrates the steric constraints of the active site of I. The I-catalyzed epoxidation proceeds with an induction period that disappears upon treatment of I with hydrogen peroxide. (29)Si and (183)W NMR spectroscopy and CSI mass spectrometry show that reaction of I with excess hydrogen peroxide leads to fast formation of a diperoxo species, [TBA](4)[gamma-SiW(10)O(32)(O(2))(2)] (II), with retention of a gamma-Keggin type structure. Whereas the isolated compound II is inactive for stoichiometric epoxidation of cyclooctene, epoxidation with II does proceed in the presence of hydrogen peroxide. The reaction of II with hydrogen peroxide would form a reactive species (III), and this step corresponds to the induction period observed in the catalytic epoxidation. The steric and electronic characters of III are the same as those for the catalytic epoxidation by I. Kinetic, spectroscopic, and mechanistic investigations show that the present epoxidation proceeds via III. 相似文献