超分子抗癌药物双环铂的结构研究

铂类抗癌药物在水中的溶解度和稳定性直接与药物的活性和毒性有关.几十年来,为了改进药物的效能和降低药物的毒性,做了大量的研究.超分子铂类化合物可能具有与众不同的物理化学性质,我们成功设计和合成了一个新型的超分子抗癌药物-双环铂,己证实双环铂对人类的恶性肿瘤有好的治疗效果.用X射线单晶衍射法测定了双环铂的晶体结构,又用电喷雾离子化质谱研究了它在水溶液中的状态.根据实验结果提出了双环铂在水溶液中的结构模型,解释了双环铂在水中好的稳定性和溶解度.     

SYNTHESES OF POLYMER-BOUND RHODIUM COMPLEXES AND THEIR APPLICATION AS CATALYSTS FOR THE HYDROFORMYLATION OF DIISOBUTYLENE (Ⅰ)

Copolymer of styrene-divinylbenzene in bead form (with DVB 8%, average pore radius 3.0×10~2, specific surface area 25m~2/g, particle size 0.2—0.4mm) was made by the suspension polymerization. After chloromethylation, the beads were then reacted with lithium diphenyl phosphine and various amines separately. Two types of polymeric ligands, i.e. polyvinylbenzyl diphenyl phosphine and eight kinds of polyvinylbenzyl amines were thus obtained. In order to prepare the polymer-bound rhodium complexes, the ligands were then reacted with [Rh(CO)_2CI]_2. The initial composition and structure of the polymeric complexes were verified by IR spectra. The complexes synthesized above were used to catalyze the hydroformylation of diisobutylene under conditions of 110℃, 100(120) kg/cm~2 and H_2/CO=1:1. The effects of the donor atoms (N, P) on the activity of the two types of catalysts and the N-substituted groups on the activity 'of polymeric amine-rhodium complexes were examined.     

氯络二羰基邻氨基苯甲酸铑(Ⅰ)的合成与晶体结构及其对丙烯氢甲酰化反应的催化性能

本文合成了化学式为Rh(CO)₂Cl(O—NH₂C₆H₄COOH)的一价铑羰基化合物。用热谱、质谱、红外光谱等方法进行了鉴定和性质的研究。从单晶体结构的X射线分析表明,在此化合物品体中铑为平面四方形配位,除了两个羰基一个氯之外,苯环上的—NH₂直接与铑配位,两个分子中的羧酸以氢键相连,成为二聚体。该络合物对丙烯氢甲酰化反应有良好的催化作用:在110℃,40公斤/厘米²压力下,用三苯基膦为助催化剂时,最高转化率可达92％,醛选择性100％,正构丁醛/异构丁醛比值可达8.8。     

SYNTHESES OF POLYMER-BOUND RHODIUM COMPLEXES AND THEIR APPLICATION AS CATALYSTS FOR THE HYDROFORMYLATION OF DIISOBUTYLENE (Ⅱ)

Five kinds of polymer-anchored aminophosphine-rhodium complexes were synthesizedby ionic and covalent bonding methods. These anehored rhodium complexes synthesizedpossess good catalytic activity and aldehyde-formation selectivity in the hydroformylationof diisobutylene. The complexes anchored via covalent bonds on polymers showedexcellent reproducibility on recycling. After reaction, it indicated that the loss of rhodiumof the catalysts was very small as shown by analysis.     

几种含氮聚合物配体键联羰基氯铑络合物的合成及其对二异丁烯的氢甲酰化反应的催化性能

铑膦均相络合物用于低级烯烃的氢甲酰化已经取得了工业规模的应用.但均相络合物存在着稳定性差、贵金属铑容易流失、催化剂回收及再生工艺复杂、腐蚀设备、污染产品以及不能用于高级烯烃的连续化羰基合成等缺点.如以不溶性功能聚合物作为配位体而制得的聚合物给合催化剂,一方面保持了络合催化的实质,另一方面又保持了多相催化剂     

聚合物配位体络铑催化剂的合成及对二异丁烯氢甲酰化反应的催化性能研究

本文用含有多胺、多(胺基膦)和单齿的胺基膦、亚磷酸酯等配位基团的功能基化交联聚苯乙烯与二氯四羰基二铑反应得到了10种聚合物配位体络铑催化剂。用这些催化剂进行了二异丁烯的催化氢甲酰化反应(反应条件:110℃;100,80,60kg/cm~2;H_2/CO=1:1;6h;苯为溶剂),大多数催化剂表现出了良好的催化性能。催化剂的红外光谱证明了聚合物多胺配位体与铑活性中心之间具有多齿配位结构。文中还对催化过程的铑脱落现象进行了研究,讨论了配位体结构与铑脱落量及催化活性的关系,测定了铑脱落量与催化剂使用次数关系的曲线,考察了反应条件及外添加试剂对铑脱落的影响,并提出了催化剂可能的铑脱落机制。     

SYNTHESES OF POLYMERIC LIGAND-BOUND RHODIUM COMPLEXES AND THEIR CATALYTIC APPLICATION FOR THE HYDROFORMYLATION OF DIISOBUTYLENE

Ten polymeric ligand bound rhodium complexes were synthesized by the reaction ofRh_2(CO)_4Cl_2 and functional cross-linked poly-styrene consisting of amine, aminophosphine andphosphite groups. These polymeric catalysts were used for hydroformylation of diisobuty-lene at a temperature of 110℃, under pressures of 100, 80, 60 kg/cm~2 and H_2/CO = 1: 1 for 6h, benzene being used as the solvent. Most of the catalysts prepared showed good catalyticproperties. IR spectral analysis indicates that the polymeric amine bound rhodium catalystspossess a polydentatc structure. The rhodium elution of the catalysts was examined. Therelationship between the structure of ligands, the rhodium elution and catalytic activity wasdiscussed. A curve of rhodium elution v.s. the number of catalytic application cycles wasinvestigated. The influence of reaction conditions and additives on the loss of rhodium wasalso studied. The possible mechanism of rhodium elution of the polymeric catalysts wassuggested.     

聚合物键铑络合物的合成及其在催化二异丁烯氢甲酰化反应中的应用

苯乙烯、二乙烯基苯经悬浮共聚制成珠状、大孔共聚体(交联度8％,孔径r=3.0×10~2,比表面积25M~2/g,粒度0.2—0.4mm),再经氯甲基化、膦化或胺化等功能基反应制成聚乙烯苄基二苯基膦和八种聚乙烯苄胺树脂。用这些聚合物配位体和二-μ-氯四羰基二铑[Rh_2(CO)_4Cl_2]反应,制成九种聚合物键铑催化剂。测定了二-μ-氯四羰基二铑、九种聚合物配位体和聚合物键铑催化剂的红外光谱。比较了聚合物膦、胺二类配体催化剂的活性及N-取代基对聚合物苄胺-铑催化剂活性的影响。     

聚合物键铑络合物的合成及其在催化二异丁烯氢甲酰化反应中的应用(Ⅱ)

本文用离子键键合法和共价键键合法合成了五种聚合物胺基膦配体键联的铑络合物催化剂,它们对二异丁烯的氢甲酰化反应有良好的催化活性和成醛选择性。用共价键键合法制得的聚合物催化剂有着良好的重复使用性能,反应后溶液中铑含量分析结果表明催化剂只有轻微的铑脱落。     

一种抗癌药的新构思

本文概述了现今抗癌药物的开发现状，总结了癌症药物治疗的作用机制，以及主要的致癌因素。以众多学科基本原理为依据，并结合临床试验，阐述了安托可金──一种新的抗癌药物的设计构思及其成功性。最后指出了今后癌症治疗中需解决的主要问题。