MoO3—SiO2表面复合物金属催化剂载体的制备与表征

采用ＭｏＯＣｌ４的盐酸溶液负载于ＳｉＯ２的表面反应法，制备了负载型和键联型两种ＭｏＯ３－ＳｉＯ２（ＭｏＳＯ）表面复合物载体。利用红外光谱法研究了ＭｏＳＯ的表面构造及其化学吸附性能；并利用ＴＰＲ技术考察了该表面复合物载体对负载金属Ｐｄ，Ｃｕ氧化物还原过程的影响。     

Trends in lipase-catalyzed asymmetric access to enantiomerically pure/enriched compounds

Over the last few years, there has been a dramatic increase in the number of publications in the field of lipase-catalyzed reactions performed in common organic solvents, ionic liquids or even non-conventional solvents. A fairly large percentage of these publications have emerged from organic chemists who have recognized the potential of biocatalysis as a viable and popular technique in organic synthesis. Considerable research has shown that reactions catalyzed by enzymes are more selective and efficiently performed than many of their analogues in the organic chemistry laboratory. This review article focuses on some of the recent developments in the rapidly growing field of lipase-catalyzed asymmetric access to enantiomerically pure/enriched compounds. The literature search is dated back to the last five years and covers some comprehensive examples.     

离子液体相转移催化环己醇氧化制备环己酮

以不同种类的离子液体作为相转移催化剂,用双氧水作为氧化剂,Na2WO4·2H2O为催化剂,在适当的反应条件下,能有效进行相转移催化环己醇氧化制备环己酮.实验结果表明,采用酸性离子液体[C16mim]HSO4和[C14mim]HSO4相转移催化合成环己酮,可提高环己酮的产率,具有反应条件温和、操作简便、需用时间短、相转移催化剂可以循环使用等优点.在反应温度为90℃,反应时间为50min条件下,环己醇的转化率高达100%,选择性99%以上.     

Adaptation of Cu/ZnO/Al_2O_3 to Temperature Change in Methanol Synthesis from CO_2 Hydrogenation

The induction behavior in CO2 hydrogenation was studied by varying the reaction temperature to investigate the adaptation of the Cu/ZnO/Al2O3 catalyst to the temperature change. The results indicated that a used catalyst had a tendency to keep the last running state in new reaction conditions for MeOH formation, and that this tendency was related to the difference in Cu/Cun+ ratio caused by CO2 and CO produced at different reaction temperatures. However, the reverse water-gas shift reaction (RWGS) induced at four temperatures was completely different from that of methanol synthesis. It implied that the two so-called competitive reactions in CO2+H2, RWGS and methanol synthesis, have different active centers.     

高质量AlPO4-5分子筛单晶的螯合剂法合成与表征

考察了几种螯合剂对AlPO4-5分子筛单晶合成的影响，结果表明，用邻苯二酚，乙酰丙酮，水杨醛为螯合剂可以得到高质量的，尺寸较大的分子筛单晶，其作用机理可能与它们加入到分子筛合成体系中，改变了溶胶中铝的配位数或产生了铝的螯合物有关。     

THE REACTION OF AROMATIC ALDEHYDES WITH p-NITROBENZYLLIBUTYLTELLURONIUM BROMIDE BY PHASE TRANSFER CATALYSIS

Under the condition of solid-liquid phase transfer catalysis,olefins were obtained by the reaction of p-nitrobenzyldibutyltelluroniumbromide with aromatic aldehyde.Under the condition of liquid-liquid phasetransfer catalysis,however,different products were obtained due to thereactivity of different bases or aldehydes.     

应用扫描电化学显微镜研究电子在室温离子液体与1,2-二氯乙烷混合溶液/水相界面上的转移反应

应用扫描电化学显微镜研究了室温离子液体(Omim·Tf2N)与1,2-二氯乙烷(DCE)混合溶液/水界面上的电子转移反应. 在保持共同离子(Tf2N-)的浓度比恒定及异相电子转移反应由界面电势差所决定的条件下, 研究了离子液体和DCE混合溶液中二茂铁(Fc)与水相中亚铁氰化钾[K4Fe(CN)6]之间异相电子转移反应. 探讨了混合溶液中离子液体的体积分数(xRTIL)的变化对混合溶液/水界面上电子转移反应的影响. 结果表明, 随着xRTIL的减小(从1减小到0.1), Fc在混合溶液中的扩散系数单调递增(从2.730×10-7 cm2·s-1增加到9.131×10-6 cm2·s-1); 而异相电子转移反应速率常数(k)则先逐渐减小(从8.0 mol-1·cm·s-1减小到0.32 mol-1·cm·s-1), 之后又略有增大(从0.32 mol-1·cm·s-1增大到0.48 mol-1·cm·s-1). 对这种现象可能的原因进行了较详细探讨.     

N,N,N′′-三取代氨基甲酰脲类化合物的合成

N，N－二取代脲和取代三氯乙酰胺反应合成了10种未见文献报道的标题化合物，产物结构经元素分析、IR和^1H NMR确证。初步生物活性测定表明多数化合物具有明显的除草活性。     

Steroids as chiral model compounds for selective reactions with metals

Our own work on steroid compounds with defined conformation as chiral model compounds for investigations of chemo-, regio- and stereoselectivity of metal-mediated new reactions is reviewed. Reactions with nickelacycles, (π-allyl)zirconoxycarbene complexes, iron tricarbonyl complexes of dienes and 1-azadienes, the Ru-catalyzed synthesis of 1,3-dihydropyrrol-2-ones from 1-azadienes, the Pd-catalyzed cyclopropanation of 1-azadienes, syntheses with cuprio steroids, copper complexes of amino alcohol derivatives and the copper-mediated hydroxylation of nonactivated C-H bonds with molecular oxygen are discussed.