AROMATIC AND HETEROCYCLIC NITRILES AND THEIR POLYMERS ⅩⅦ. THE POLYMERIZATION KINETICS OF CYANOPYRIDINES AND CHARACTERIZATION OF THE FORMED POLYMER*

The polymerization rates of three cyanopyridines catalyzed by cuprous chloride-zinc system are measured, and the structure of the formed polymer is also determined. Compared with aromatic nitrile, cyanopyridines polymerize faster and form polyconjugated polymer with skeleton—(C=N)—_n instead of triazine structure. This chain-polymer possesses semiconductive property, and can be converted into conductive material by thermal treatment. In addition, the polymerization kinetics of 3-cyanopyridine catalyzed by 3-cyanopyridinium perchlorate is investigated. It is found that the polymerization rate is directly proportional to the concentrations of monomer and catalyst, and the activation energy of the polymerization is 103.1 KJ/mol.     

Synthesis and Crystal Structure of a New Organic-inorganic Hybrid One-dimensional Polymer： [Zn（C8H23N5）]2（Pb3I10）

1 INTRODUCTION Recently, the organic-inorganic hybrid Ⅳa groupmetal halides with low-dimensional structure haveattracted much attention of chemists and physicistsdue to their particular properties and applications.For example, they are akin to “natural quantum-well”architectures and have tunable excitonic propertiesusually governed by the inorganic substructure andorganic component[1]; they have been applied assome technologically important materials, such assemiconductor materials in …     

3-氨基-二氢噻吩-2-酮类Schiff碱的合成和生物活性研究

通过3-氨基-二氢噻吩-2-酮(DL-高半胱氨酸硫内酯)盐酸盐与取代苯甲醛反应, 得到3-氨基-二氢噻吩-2-酮类Schiff碱. 合成了9个化合物, 其中7个为首次报道的新Schiff碱类化合物. 化合物结构经IR, ¹H NMR和元素分析证实, 并对这些化合物进行了室内毒力测试, 结果表明此类化合物具有很好的杀菌、抑菌活性.     

Synthesis of Clarithromycin Using Protective Technique of Total Silylation

Clarithromycin, 6- O-methylerythromycin A (CAM), is a semisynthetic macrolide antibiotic of 6 which exhibits strong antibacterial activity toward a wide range of bacteria inclusive of gram positive bacteria, some gram negative bacteria, anaerobic bacteria, Mycoplasma, Chlamidia and Helicobacter pylori, and because of its high stability in the acidic environment of the stomach, it can be orally administered to treat respiratory organ diseases, and also to prevent recurrence of ulcer when used in a combination with other medicines.     

Conversion of N-Acyl-4-phenyl/benzyl-oxazolidine-2-thiones into Thiol Esters in the Presence of EtSH-K2CO3

N-Acyl-β-hydroxy-4-phenyl-oxazolidinethiones could be rapidly converted into their ethyl thiol esters in high yields by treatment with EtSH at 0 ℃ in CH3CN or 9 ： 1 （V ： V） THF-H2O in the presence of a catalytic amount of K2CO3.     

丙烯环氧化制环氧丙烷Fe-Al-P-O催化剂的研究

用溶胶-凝胶法制得了Fe-Al-P-O催化剂，采用IR、XRD、TEM、BET、TPR和微反等技术研究了催化剂的物化性质和反应性能。实验结果表明，Fe1/2-Al1/2-PO4由10 nm左右 FePO4和AlPO4微晶组合而成，其晶格氧的活泼性大于单纯FePO4，AlPO4在Fe1/2-Al1/2-PO4中起到分散FePO4微晶的作用；Fe1/2-Al1/2-PO4的反应性能与原料气组成密切相关，丙烯与O2的选择氧化产物主要是丙烯醛，原料气中加入H2后，反应产物以环氧丙烷为主，同时还有部分丙烯醛，原料气中引入水蒸气后，可进一步增加环氧丙烷的选择性及减少丙烯醛的产率；在0.1 MPa、200 ℃、C3H6/O2/H2/H2O/N2=1∶1∶1∶1∶6（mol比）和空速1 200 h－1条件下，丙烯的转化率为8.9％，环氧丙烷的选择性为81.0％。     

含有羧基配体的蝎型钒氧配合物的合成、结构及其热分解动力学

设计合成了两种新型的以聚吡唑硼酸盐、氨基酸为配体的钒氧配合物VO[phCH2CH(NH2)COO][HB(pz)3](1)和VO(3,5-Me2pz)[HB(3,5-Me2pz)3](CH3COO)(2). 通过元素分析、红外光谱对配合物进行了表征, 并利用单晶X射线衍射技术解析了它们的结构. 非等温热分解动力学研究表明, 配合物1和2的热分解反应都是分两步进行的. 通过计算, 配合物1热分解的第一步反应的可能机理为成核与生长(n=1/4); 第二步反应的可能机理为化学反应. 其非等温动力学方程分别为, dα/dT=(A/β)e-E/RT(1/4)(1-α)[-ln(1-α)]-3 和dα/dT=(A/β)e-E/RT(1-α)2. 分解反应的表观活化能分别是223.52 和331.94 kJ·mol-1; 指前因子ln(A/s-1)分别是49.67 和57.50. 配合物2 热分解的第一步反应的可能机理为化学反应; 第二步反应的可能机理为成核与生长(n=1/2). 其非等温动力学方程分别为, dα/dT=(A/β)e-E/RT(1-α)2, 和dα/dT=(A/β)e-E/RT(1/2)(1-α)[-ln(1-α)]-1. 分解反应的表观活化能分别是300.56 和444.72 kJ·mol-1; 指前因子ln(A/s-1)分别是75.53 和92.50.     

新型介孔分子筛KIT-1加氢脱硫催化剂的研究

制备了新型的结构排列无序的介孔分子筛KIT-1和负载Ni, Mo的KIT-1加氢脱硫催化剂。实验结果表明MoO3较易分散在KIT-1的表面,而NiO则容易在其表面形成小晶粒。与以MCM-41和NaY分子筛为载体的Ni, Mo催化剂相比, KIT-1负载催化剂具有较高的加氢脱硫催化活性,因为KIT-1载体具有相互交错的三维孔道结构, 有利于反应物和产物的扩散, 而不容易受孔道堵塞的影响。     

高稳定性CaO-ZrO2固体碱催化剂的表征和催化性能

用共沉淀法经高温焙烧制备了CaO摩尔分数从10%至50%的CaO-ZrO₂系列催化剂, 将其应用于碳酸丙烯酯和甲醇酯交换合成碳酸二甲酯过程, 并通过XRD, FT-IR, BET, ICP, CO₂-TPD, XPS等表征手段研究了催化剂的物性及其催化性能随组成变化的的规律. 结果表明, 当CaO摩尔分数高于30%时, 表面出现游离的CaO, 虽然具有强碱性和高活性, 但是稳定性差; 而当CaO摩尔分数低于30%时, Ca^2＋进入ZrO₂晶格, CaO与ZrO₂形成连续固溶体, 并且随着CaO含量的增加, 晶格氧的电荷密度增加, 催化剂的碱性增强, 使得CaO-ZrO₂催化剂在碳酸丙烯酯和甲醇酯交换合成碳酸二甲酯过程中获得了高活性和高稳定性.     

二价金属离子萃取速率常数与软硬酸碱规则

用上升液滴法测定了２－乙基己基膦酸单（２－乙基己基）酯－正辛烷从硝酸介质中萃取镁、钙、锌、镍、铜和铅等二价金属离子的正向初始速率，建立了速率方程，计算出正向萃取反应的速率常数、活化能及活化熵，首次将软硬酸碱规则与金属溶萃取速率常数关联。结果表明，在萃取机理相同时，萃取速率常数的大小与金属离子的软硬酸碱标度一致，即萃取过程中，作为酸的被萃取金属离子，其硬度越大，萃取速率常数亦越大，萃取反应的活化能…