CsCuHPVAsMoO杂多化合物对异丁烯选择性氧化反应的催化性能

 用组合法合成了CsCuHPVAsMoO系列杂多化合物催化剂，并采用FT－IR，H2－TPR，NH3－TPD和TG－DTA等方法对催化剂进行了表征．在自制固定床反应器中对异丁烯进行选择性氧化，考察了Cs，Cu和As含量、催化剂焙烧温度及反应条件对催化剂催化性能的影响．结果表明，Cs的引入有利于提高催化剂的选择性；Cu和As的引入在提高催化剂活性的同时，也提高了催化剂的选择性；当焙烧温度为340℃时，催化剂的活性和选择性最高．组成为Cs0．1Cu0．2HxPVAs0．2Mo10Oy的催化剂对异丁烯具有很强的选择性氧化能力，在最佳反应条件下，甲基丙烯酸、甲基丙烯醛和乙酸的收率分别可达52．84％，12．05％和18．21％．     

新型铁锰复合氧化物催化低温脱除NOx

采用溶胶-凝胶法合成了一系列铁锰复合氧化物催化剂,利用X射线衍射(XRD)对催化剂的活性相态进行研究,并考察了铁锰摩尔比及焙烧温度对催化性能的影响.结果表明,该催化剂体系征低温(80-220℃)下选择性催化氨还原NOx反应中显示出优异的活性.其中Fe(0.4)-MnOx(500)(即摩尔比n(Fe)/(n(Fe)+n(Mn))=0.4,焙烧温度500℃)催化剂具有最佳低温催化活性,在空速30000 h-1,温度80℃的条件下,NOx转化效率达到90.6%,N2 选择性达100%.Fe-MnOx复合氧化物催化剂中形成的Fe3Mn3O8晶相有利于促进NO氧化成NO2,从而提高低温选择性催化还原的活性.     

Cr3+取代的磷钒铬三元杂多化合物K13PV12Cr2O42·nH2O催化H2O2分解的研究

在合成一种新的杂多化合物(K13PV12Cr2O42)的基础上,进一步考察了反应温度、过氧化氢起始浓度,以及该杂多化合物作为催化剂时的用量对过氧化氢分解反应的催化作用;并将其与同结构的杂多化合物K7PV12Mo2O42对该反应的催化作用进行了比较。在30～50℃范围内得到了催化反应的速率常数,并由Arrhenius公式计算出反应的活化能约为70.63kJ·mol-1,表明所合成杂多化合物对H2O2分解具有良好的催化性能,也说明Cr3+对V5+的取代有助于改善杂多化合物的催化性能。推导出了H2O2催化分解反应的速率方程。     

新型铁锰复合氧化物催化低温脱除NOx

采用溶胶-凝胶法合成了一系列铁锰复合氧化物催化剂, 利用X射线衍射(XRD)对催化剂的活性相态进行研究, 并考察了铁锰摩尔比及焙烧温度对催化性能的影响. 结果表明, 该催化剂体系在低温(80-220 ℃)下选择性催化氨还原NOx反应中显示出优异的活性. 其中Fe(0.4)-MnOx(500)(即摩尔比n(Fe)/(n(Fe)+n(Mn))=0.4, 焙烧温度500 ℃)催化剂具有最佳低温催化活性, 在空速30000 h-1, 温度80 ℃的条件下, NOx转化效率达到90.6%, N2选择性达100%. Fe-MnOx复合氧化物催化剂中形成的Fe3Mn3O8晶相有利于促进NO氧化成NO2, 从而提高低温选择性催化还原的活性.     

杂多化合物膜催化异丁烯选择氧化反应

 以多孔钛片为支撑体,将组成为HxCu1．2PAs0．6Mo12Oy的杂多化合物与具有氧溢流效应的氧化物Sb2O4制成催化膜,在特制的膜催化反应器中进行异丁烯选择氧化反应．结果表明,杂多化合物－Sb2O4催化膜具有较高的催化活性;在适宜的条件下,甲基丙烯酸收率可达26.3％,甲基丙烯醛收率可达22.4％,液体产物（即可用产物,包括甲基丙烯酸、甲基丙烯醛、乙酸和丙酮）收率可达67.4％．     

分了筛催化合成MTBE的反应性能研究

在开发出催化性能良好的合成ＭＴＢＥ沸石分子筛催化的基础上,详细考察了反应条件：包括温度、压力、空速、醇烯比等操作条件对改性β沸石分子筛催化剂的合成ＭＴＢＥ反应性能的影响。结果表明：反应条件对催化剂活性、ＭＴＢＥ选择性及活性稳定性都有一定影响。在一定范围内反应温度升高,烯烃的转化率增加、ＭＴＢＥ的选择性不变,但反应温度过高,ＭＴＢＥ的选择性和催化剂的稳定性变差;反应压力必须大于系统完全液化压力;醇烯     

多孔金属片载杂多化合物膜的催化性能

用组合化学法合成了Ｃｕ１．３Ａｓ０．３ＰＶＭｏ１１高元杂多化合物,并用红外和差热－热重分析技术进行了表征;将高元杂多化合物制成高分子催化膜,用于几种醇的选择性催化氧化反应,结果表明,高元杂多化合物膜具有优异的催化性能,更坦 步探索了多孔金属片载杂多化合物膜催化技术的应用。     

K-Mo基催化剂的表面酸性与其合成醇选择性

对500℃和800℃焙烧制得的氧化态K－MoO3／γ－AlO3，K－MoO3／SiO2及非负载K－Mo催化剂进行硫化后，测试其合成醇活性．结果表明500℃焙烧制得的负载型催化剂显示较高的合成低碳烃活性和较低的合成低磷醇选择性，经800℃焙烧后，合成低磷醇的选择性大幅度提高．500℃焙烧的非负载K－Mo催化剂显示较高的合成醇选择性，经800℃焙烧后，促碳醇的选择性保持不变．用氨的吸附及TPD方法测定了各样品的酸性，并与催化剂活性对照，发现催化剂酸性越强，酸量越大，则其合成醇选择性越低．催化剂上的乙醇分解实验证实，催化剂的酸量大小与它的醇分解活性成正变关系，这些结果说明催化剂酸性对其合成醇性能有直接的影响．     

异丁烷选择氧化制甲基丙烯酸杂多化合物催化剂P1.33-dMo12VaCubSbcAsdK1.5Ox／SiC的研究

采用共沉淀法制备了一系列磷钼体系多组分催化剂P1.33-dMo12VaCubSbcAsdK1.5Ox／SiC（0.0≤a，b，c，d≤0.50）。利用XRD、FTIR、DSC、ESR等方法对催化剂的结构与性质进行了研究。XRD、FTIR的研究结果表明，合成的样品为具有Keggin杂多阴离子结构的磷钼杂多化合物。DSC，ESR测试结果表明催化剂具有较好的稳定性。同时考察了催化剂组分对异丁烷催化氧化性能的影响，结果表明，适量地引入V、As、Cu、Sb都能提高MAA（甲基丙烯酸）的选择性和MAA+MAL（甲基丙烯醛）的收率。催化剂P1.13Mo12V0.25Cu0.25Sb0.25As0.2K1.5Ox／SiC在360 ℃、常压、进料组成异丁烷：空气=1∶2（mol）、空速3 600 h－1条件下，异丁烷转化率10.7％，MAA+MAL的收率为6.8％。     

杂多化合物膜在乙酸乙酯合成中的催化性能

乙酸乙酯是一种重要的有机物,有着广泛应用。杂多酸作催化剂具有催化活性高、选择性好、用量少、产品质量高、对设备无腐蚀、对环境无污染等优点[1-6]。本文从膜催化[7-9]、多相催化的角度、采用多孔钛片载磷钨酸膜研究杂多化合物在乙酸乙酯合成中的催化性能,探讨反应温度、酸醇比对酯收率的影响。1　实验部分1.1　主要仪器与试剂ＧＣ102-Ｎ气相色谱仪(上海分析仪器厂);Ｎ2000色谱数据工作站(浙江大学智能信息工程研究所);ＸＭＴ数显调节仪,ＺＫ-1可控硅电压调整器(联泰仪表有限公司);ＡＢ204电子天平(ＭＥＬＥＲＴＯＬＥＤＯＣＯＭＰＡ…     

α-Amino acid derived enaminones and their application in the synthesis of N-protected methyl 5-substituted-4-hydroxypyrrole-3-carboxylates and other heterocycles

A new and simple synthesis of novel N-protected methyl 5-substituted-4-hydroxypyrrole-3-carboxylates, which exist in equilibrium with their 4-oxo tautomers, has been developed in two steps starting from N-protected α-amino acids. The key intermediates are enaminones, which can also be isolated, characterized, and used for the construction of other functionalized heterocycles, before they spontaneously decompose to pyrrole products. 4-Hydroxypyrroles are prone to partial aerial oxidation but can be efficiently alkylated or reduced to stable polysubstituted pyrrolidine derivatives.     

Specific intramolecular aromatic CH insertion of diazosulfonamides

The chemoselectivity in the intramolecular CH insertion of various diazosulfonamides has been experimentally studied. The results reveal that the aliphatic 1,4-, 1,5-, or 1,6-C(sp³)?H insertions of diazosulfonamides are not accessible, while the aromatic 1,5-C(sp²)?H insertion can be realized specifically by adjusting the diazo-adjacent group. In addition, the general chemoselectivities in the intramolecular CH insertions of diazosulfonyl compounds are summarized. Generally, diazosulfones undergo both aromatic 1,5-C(sp²)?H and aliphatic 1,5- and 1,6-C(sp³)?H insertions, while diazosulfonates undergo aliphatic 1,5- and 1,6-C(sp³)?H insertions. However, diazosulfonamides only undergo aromatic 1,5-C(sp²)?H insertion.     

N-Heterocyclic carbene-palladacyclic complexes: synthesis,characterization and their applications in the C-N coupling and α-arylation of ketones using aryl chlorides

N-Heterocyclic carbene-palladacyclic complexes 3 were successfully achieved in a one-pot procedure under mild conditions. The structure of 3a was unambiguously confirmed by X-ray single crystal diffraction and it was an active catalyst in the Buchwald-Hartwig amination and α-arylation of ketones even at very low catalyst loadings (0.01?mol%).     

Iodine-mediated oxidative Pictet-Spengler reaction using terminal alkyne as the 2-oxoaldehyde surrogate for the synthesis of 1-aroyl-β-carbolines and fused-nitrogen heterocycles

An efficient iodine-mediated oxidative Pictet-Spengler reaction in dimethyl sulphoxide (DMSO) using terminal alkynes as the 2-oxoaldehyde surrogate for the synthesis of aryl (9H-pyrido[3,4-b]indol-1-yl)methanones is described. The scope of the protocol includes the total synthesis of Fascaplysin, Eudistomins Y₁ and Y₂. The methodology is extended for preparing pyrrolo[1,2-a]-quinoxaline and indolo[1,5-a]quinoxaline derivatives. The utility of 1-aroyl-β-carbolines was demonstrated by performing palladium-catalyzed β-carboline directed ortho-C(sp2)-H functionalization of the phenyl ring with thiomethyl (SMe) group using DMSO as source and for accessing 4-aryl-canthin-6-ones.     

Facile synthesis of bicyclic 1-arylpyrazol-5-ones

In this Letter, we described a facile method for constructing fused bicyclic 1-arylpyrazol-5-one ring system. We employed various methylene-containing carboxylic acids as the substrates and proved that the pyrazolone ring closure requires activated methylene group in intermediate II. Accordingly, a series of structurally diversified, fused bicyclic 1-arylpyrazol-5-ones was prepared in moderate to high yields using the requisite substrates.     

Synthesis of pyrrolo[1,2-a]pyrazines and pyrazino[1,2-a]indoles by Curtius reaction in Morita-Baylis-Hillman derivatives

Synthesis of substituted pyrrolo[1,2-a]pyrazines and pyrazino[1,2-a]indoles from the Morita-Baylis-Hillman derivatives of acrylates via saponification followed by Curtius reaction is described.     

正丁胺对激光染料荧光谱影响的研究

用正丁胺作为碳源,采用射频辉光放电制备碳膜,选用激光染料R6G和聚乙二醇混合液作为蒸气源,采用单源热蒸发,在蒸发室与染料同时沉积得到混合膜,用拉曼光谱和红外光谱分析了碳膜的结构和键合方式,分析表明:碳膜中存在胺基团和氢原子.混合膜的荧光谱测量结果表明,认为正丁胺对染料荧光谱的影响是因为胺基和氢原子的存在.     

Cu0-catalysed 1,3-dipolar cycloadditions of α-amino acid derived N,N-cyclic azomethine imines to ynones

A series of 20 CuAIAC reactions between eight 4-acylamino substituted pyrazolidine-3-one-1-azomethine imines and four terminal ynones were performed using Cu⁰ as catalyst. The corresponding fluorescent cycloadducts were obtained in very high yields upon simple workup. Thus, Cu-metal turned out to be a better catalyst than Cu^I in terms of yield and ease of isolation. Availability of azomethine imines, mild reaction conditions, and simple workup enable a “click” access to libraries of densely substituted 2,3-dihydro-1H,5H-pyrazolo[1,2-a]pyrazol-1-ones. Reactivity of differently substituted dipoles was evaluated experimentally and by quantum chemical methods (DFT).     

Synthesis and antioxidative/anti-inflammatory activity of novel fullerene–polyamine conjugates

(E)-4-(Fullerenopyrrolidin-1-yl)-3-methylbut-2-enoic acid and its corresponding succinimidyl ester, readily obtained through Prato-type modification of C₆₀, were used for the selective N-acylation of polyamines. The thus obtained conjugates were evaluated for their antioxidative and anti-inflammatory activity and their cytotoxicity was determined. Members of this family of compounds showed interesting anti-lipid peroxidation, anti-lipoxygenase and anti-inflammatory activity and comparable cytocompatibility to spermidine.