金属羰基络合物制备的Pt-Re/Al2O3催化剂的性能Ⅰ.不同方法制备的Pt-Re/Al2O3催化剂上正庚烷的转化

考察了由［Ｐｔ３（ＣＯ）６］５［ＮＥｔ４］２与Ｒｅ２（ＣＯ）１０共浸或分浸制备的一系列催化剂在接近工业运转的压力下的正庚烷转化反应。以羰基金属原子簇化合物作为前身物制备的Ｐｔ－Ｒｅ／Ａｌ２Ｏ３催化剂的活性、芳构化选择性和稳定性等明显地优于常规的以Ｈ２ＰｔＣｌ６与ＨＲｅＯ４溶液共浸制备的催化剂。常规Ｐｔ－Ｒｅ／Ａｌ２Ｏ３催化剂的活性和稳定性比Ｐｔ／Ａｌ２Ｏ３好，但芳构化选择性降低，若引入Ｒｅ２（ＣＯ     

盐酸处理γ—Al2O3的表面性质及其对负载的Pt的表面性质和反应性能的…

本文研究了用盐酸处理γ－Ａｌ２Ｏ３对Ａｌ２Ｏ３的表面性质以及对Ｐｔ／Ａｌ２Ｏ３的表面性质和反应性能的影响。结果表明盐酸处理的γ－Ａｌ２Ｏ３酸中心（强酸和弱酸中心）数目增加，Ｐｔ在Ａｌ２Ｏ３表面的表观分散度或Ｐｔ的低温活性中心数增加，与此同时，Ｐｔ的高温活性中心数也增多，从而使Ｐｔ／Ａｌ２Ｏ３的氢解、异构化和脱氢环化活性都增加。     

盐酸处理γ－Al_2O_3的表面性质及其对负载的Pt的表面性质和反应性能的影响

本文研究了用盐酸处理γ－Ａｌ＿２Ｏ＿３对Ａｌ＿２Ｏ＿３的表面性质以及Ｐｔ／Ａｌ＿Ｏ＿３的表面性质和反应性能的影响。结果表明盐酸处理的γ－Ａｌ＿２Ｏ＿３酸中心（强酸和弱酸中心）数目增加，Ｐｔ在Ａｌ＿２Ｏ＿３表面的表现分散度或Ｐｔ的低温活性中心数增加，与此同时，Ｐｔ的高温活性中心数也增多，从而使Ｐｔ／Ａｌ＿２Ｏ＿３的氢解、异构化和脱氢环化活性都增加。     

K2O对Pt—Sn／Al2O3催化剂表面酸性及MCH脱氢稳定性的影响

利用吡啶吸附－ＩＲ，ＮＨ３吸附－脱附，原位热重积炭，ＤＳＣ等技术并结合甲基环己烷（ＭＣＨ）脱氢活性试验，研究了Ｋ２Ｏ对工业Ｐｔ－Ｓｎ／Ａｌ２Ｏ３催化剂的表面酸性及ＭＣＨ脱氢稳定性的影响，结果表明，Ｋ２Ｏ能有效地调变催化剂的表面酸性，降低其表面酸中心特别是强酸中心的数目；ＭＣＨ脱氢反应的积炭量随Ｋ２Ｏ含量的增加而减少，但催化剂的高温脱氢稳定性与Ｋ２Ｏ含量并不完全呈顺变关系，Ｋ２Ｏ含量应严格控制，当Ｋ     

甲烷部分氧化制合成气Ⅳ．镍铜催化剂的反应性能及影响因素的考察

对镍铜甲烷部分氧化催化剂的制备化学研究表明，在Ａｌ２Ｏ３、ＳｉＯ２、ＭｇＯ、ＴｉＯ２、Ｙ型分子筛等载体中，具有较好氢溢流功能的Ａｌ２Ｏ３所担载的镍铜催化剂，有最佳的反应性能，载体的产物溢流功能对反应中合成气的生成是有利的．对于ＮｉＯ－ＣｕＯ－Ａｌ２Ｏ３催化剂，组分Ｃｕ的最佳含量是Ｃｕ／Ａｌ＝０．２／４（原子比），Ｎｉ／Ａｌ（原子比）在１／４－１．５／４范围内催化剂均保持最佳的反应性能，此时，甲烷转化率为９８．１％，对ＣＯ、Ｈ２的选择性分别达９７％、１００％．制备方法对催化性能影响的结果显示，以（ＮＨ４）２ＣＯ３为沉淀剂的共沉淀法，是制备ＮｉＯ－ＣｕＯ－Ａｌ２Ｏ３催化剂的最佳方法．ＮｉＯ－ＣｕＯ－Ａｌ２Ｏ３催化剂的甲烷部分氧化性能在４００－５００℃间有一突跃，并在７００℃时达到最佳值；过高的反应气空速对ＣＯ、Ｈ２的选择性是不利的     

溶胶-凝胶制备技术与新型催化材料Ⅲ.溶胶粒子表面修饰方法制备催化膜

提出用溶胶粒子表面修饰方法，结合溶胶－凝胶技术制备无机催化膜，该方法的基本原理是利用合适的金属配合物在胶粒表面吸附作用，经溶胶－凝胶过程，将活性组分结合到无机膜中，实验测定结果表明：（ＮｉＥＤＴＡ）＾２－，ＶＯ＾－３，ＭｏＯ＾２－４，（Ｐｄ（ＮＨ３）４＾２＋，ＰｄＣｌ＾２－４，ＰｔＣｌ＾２－６和ＲｈＣｌ＾３－６可用来修饰ＡｌＯＯＨ溶胶，以Ｐｄ／γ－Ａｌ２Ｏ３催化膜的制备为例，经三次溶胶－凝胶过程，     

甲烷部分氧化制合成气反应Pt/Al_2O_3和Pt/CeO2/Al_2O_3催化剂的研究(英文)

研究了Ｐｔ／Ａｌ２Ｏ３和Ｐｔ／ＣｅＯ２／Ａｌ２Ｏ３催化剂对甲烷部分氧化制合成气反应的催化活性，发现Ｐｔ／ＣｅＯ２／Ａｌ２Ｏ３显示了比Ｐｔ／Ａｌ２Ｏ３更高的甲烷转化率和合成气选择性。用Ｈ２ＴＰＲ，Ｈ２ＴＰＤ，ＳＥＭ和ＸＲＤ等手段和技术对催化剂进行了表征。ＣｅＯ２与Ｐｔ之间存在较强的相互作用（ＳＭＳＩ），这种作用促进了Ｐｔ在催化剂表面的分散，抑制了Ｐｔ在催化剂表面的迁移，大大降低了催化剂在反应中的完全燃烧活性，提高了催化剂的部分氧化活性和选择性，避免了因催化剂床层局部温度过高而导致催化剂活性下降或失活，提高了催化剂的稳定性。同时，在反应过程中，ＣｅＯ２通过促进水蒸气变换反应（ＷＧＳＲ）的进行使反应体系迅速达到平衡，提高了催化剂对Ｈ２的选择性。     

超高比表面炭载钼煤气甲烷化催化剂

以沥青中间相为原料，氢氧化钾直接活化，获得了比表面达２３６３ｍ￣２／ｇ的超高比表面炭分子筛（ＣＭＳ）。分别以ＣＭＳ、ＳｉＯ＿２、活性炭和θ－Ａｌ＿２Ｏ＿３为担体，制备了负载钼催化剂，并研究其加压甲烷化反应性能，发现活性依下面顺序增加：θ－Ａｌ＿２Ｏ＿３＜ＳｉＯ＿２＜活性炭（ＡＣ）＜ＣＭＳ。还分别以钼酸铵和磷钼酸（ＨＰＭｏ）为前驱体，制备了ＣＭＳ负载钼催化剂，并考察了其煤气甲烷化活性，发现不同的催化剂前驱体对催化剂反应活性影响很大。根据产物中ＣＨ＿４／ＣＯ＿２的变化，推测ＣＯ在钼催化剂上的甲烷化反应包括如下两个步骤：（１）３Ｈ＿２＋ＣＯ→ＣＨ＿４＋Ｈ＿２Ｏ，（２）ＣＯ＋Ｈ＿２Ｏ→ＣＯ＿２＋Ｈ＿２。     

CrO3.CH3NH2.HCl／Al2O3的制备及其对苯偶姻体系的氧化反应

ＣｒＯ３·ＣＨ３ＮＨ２·ＨＣｌ／Ａｌ２Ｏ３的制备及其对苯偶姻体系的氧化反应张贵生＊石启增陈密峰蔡昆（河南师范大学化学系新乡４５３００２）关键词ＣｒＯ３·ＣＨ３ＮＨ２·ＨＣｌ／Ａｌ２Ｏ３，苯偶姻，苯偶酰，氧化１９９６－０８－１８收稿，１９９６－１１－０...     

溶胶-凝胶制备技术与新型催化材料Ⅲ.溶胶粒子表面修饰方法制备催化膜

提出用溶胶粒子表面修饰方法，结合溶胶凝胶技术制备无机催化膜．该方法的基本原理是利用合适的金属配合物在胶粒表面的吸附作用，经溶胶凝胶过程，将活性组分结合到无机膜中．实验测定结果表明：（ＮｉＥＤＴＡ）２－，ＶＯ－３，ＭｏＯ２－４，（Ｐｄ（ＮＨ３）４）２＋，ＰｄＣｌ２－４，ＰｔＣｌ２－６和ＲｈＣｌ３－６可用来修饰ＡｌＯＯＨ溶胶．以Ｐｄ／γＡｌ２Ｏ３催化膜的制备为例，经三次溶胶凝胶过程，可制得无裂缺的厚度为９μｍ的Ｐｄ／γＡｌ２Ｏ３催化膜，膜材料的平均孔直径为６ｎｍ，Ｐｄ被均匀地分布在膜的顶层，其平均粒径为２３ｎｍ．     

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.