四苯基卟啉质子化结构变化的理论研究（Ⅱ）－－五氟苯基及吡咯环上氟的取代基效应

卟啉的衍生物在DNA螺旋中的嵌入并堆积具有高选择性。为考察5，10，15，20－四（五氟苯基）卟啉（TF5PPH2）和2，3，7，8，12，13，17，18－八氟－5，10，15，20－四（五氟苯基）卟啉（F28TPPH2）中F取代基对质子化卟啉结构的影响，在四苯基卟啉研究的基础上，用半经验的AM1 MO方法，并进行合理的对称性限制，计算了TF5PPH2和F28TPPH2及其质子化二酸（TF5PHH4^2 ）和（F28TPPH4^2＋）的几种可能的构型。结果表明，由于F取代基的影响，质子化过程中的结构、键电荷布居和前线分子轨道均有明显的变化，二者的质子化二酸与溶液质子的快速交换作用也都变得更加困难。     

Synthesis and Structure of Dimolybdenum Carbonyl Thiolate Compound [Et4N]2[Mo2（CO）8（SC6H4—CH3—m）2]

1 INTRODUCTION In 1984, thiolate ligand was successfully introduced into molybdenum carbonyl compound by the reaction of Mo(CO)6 with [Et4N]SR( R = C6H5, But) in a moderate condition[1]. From then on, a series of dinuclear molybdenum(0) carbonyl thiolate compounds have been synthesized and characterized by using a variety of thiolate ligands in our research group. It was found that a planar Mo2S2 unit is in the compound [Et4N]2[Mo2(CO)8(SC6H4-CH_3-p)2][2] (2) and a "butterfly" t…     

N，N′—1，2—丙水杨酰胺合铜（Ⅱ）酸根的双核Cu（Ⅱ）配合物的合成与磁性

合成了一类新的金属配合物[Cu(sampn)CuL](sampn^4-:N，N′－1，2－丙水杨酰胺根离子；L：2，2－联吡啶或1，10－菲绕啉），经元素分析、IR、电子光谱等手段推定配合物具有酚氧桥结构，Cu（Ⅱ）离子和配位环境为畸变四方构型，测定了配合物的变温磁化率，其数值用量二乘法与修正的Bleaney-Bowers方程拟合，从中得到较大的θ值，表明双核分子间有较大的分子间相互作用。     

E，E—1，4—二[2′,2^〃—（苯并恶唑基乙烯基）]苯及衍生物的合成和光性能

合成了E，E－1，4－二[2′,2^〃-（苯并恶唑基乙烯基）]苯及衍生物共14种，测定了它们的熔点、红外光谱、核磁共振氢谱、紫外吸收光谱和荧光发射光谱、荧光量子产率及激光性能。     

Novel Chiral Aminophosphine Ligand:Synthesis and Application in Saymmetric Catalytic Hydrogenation Reaction

A new chiral aminophosphine ligand 6,6′-dimethoxy-2,2′-bis(diphenylphosphinoamino)biphenyl(DMBDPPABP) was prepared and its rhodium complex was found to be an effective catalyst for the asymmetric hydrogenation of amidoacrylic acid and its dervatives.The effects of solvent and reaction temperature on enantioselectivity were also studied.     

Sesquiterpene Lactone Glycosides from Carpesium macrocephalum

Two new sesquiterpene lactone glycosides were isolated from the seeds of Carpesium meacrocephalum. Their structures were elucidated as 2α-O-β-D-glucopyranosy-5α,11αH-eudesma-4(15)-en-12,8β-olide and 2α-O-β-D-glucopyranosy-5αH-eudesma-4(15),11(13)-dien-12,8β-olide by spectral methods (HRMS,1D and 2D NMR).     

Two New C—21 Steroidal Glycosides from Cynanchum aurichulatum

Two new C-21 steroidal glycosides, cynanauriculoside I and cynanauriculoside Ⅱ, were isolated from the roots of Cynanchum aurichulatum. Their structures were established using spectroscopic methods including one and two-dimensional NMR.     

SELECTIVE SEPARATION OF WATER—ETHANOL MIXTURE THROUGH COPOLYMERIC MEMBRANES.Ⅱ.ACRYLONITRILE AND MALEIC ANHYDRIDE COPOLYMERIC MEMBRANES

Acrylonitrile(AN) and maleic anhydride(MA) copolymer has been synthesized by radical polymerization using ammonium persulfate and sodium bisulfite as initiator.The pervaporation properties of the copolymeric membranes prepared have been investigated for the first time. The dependences of pervaporation characteristics on coplymer composition,feed concentration and operating temperature have been studied.In order to improve the separation properties of the copolymeric membranes,the membranes were hydrolyzed with 10 wt% soldium hydroxide or potassium hydroxide aqueous solution.The hydrolyzed membranes containing more than 0.069MA mol fraction showed higher tensile strength and separation properties than the original membranes.     

叔醇脱水成烯反应的溶剂化能力与介电常数的关系

我们用Fe_2(SO_4)_3·xH_2O为催化剂,对2-甲基-2-已醇脱水生成烯烃反应的溶剂化能力及其动力学做了研究,测定了20种不同溶剂中的反应速率常数和以丙至辛6种直链醇为溶剂于不同温度下反应的速率常数,确定了溶剂化能力与溶剂介电常数之间的线性关系。这方面工作尚未见报道。     

微波技术在有机化学反应中的应用

本文介绍了微波技术在干法有机反应、加速有机合成速率及合成短寿命放射性药剂中的应用,概述了微波技术中影响反应速率的因素等,说明了微波特有的能量及快速加热能力在化学反应研究中具有广泛的实际意义。