具有生物活性的有机硅化合物的研究 Ⅴ. N-烃基-N-三甲(三乙氧)硅基-2-呋喃甲酰胺类化合物的合成及生物活性研究

目前生物有机硅化学已经形成了有机硅化学的一个新的研究领域,已发现大批具有较高和某些专门的生物活性的有机硅化合物。我们对一些酰氧基类型有机硅化合物的毒性进行了研究,总结了毒性和结构关系,发现其毒性一般都比相应的不含硅的母体化合物低;研究了某些有机硅的取代苯氧乙酸酯的生物活性及水杨酰替苯胺类型的有机硅化合物。本文合成了一系列新的2-呋喃甲酰胺类型的有机硅化合物,研究了它们对一些植物病原菌的抗菌活性,探讨了其结构与抗菌活性的关系.     

几种新型有机硅冠醚的合成

有机硅王冠化合物包括带有冠醚结构单元的有机硅化合物和将硅原子引入大环中的化合物,迄今已知的为数不多。作者合成了七种新的前一类有机硅王冠化合物。     

有机硅金属试剂在碳硅交叉偶联应用研究进展

有机硅化合物因其特殊的性质广泛应用于合成化学、医药、农药和材料等领域.有机硅化合物通常由亲核取代、烯烃硅氢化和碳氢键直接硅化等方法制备.近年来,交叉偶联构建碳硅键,特别是构建C(sp~3)—Si键取得突破性进展,引起广泛关注和兴趣,成为有机硅化合物合成研究热点.从极性反转的硅亲核试剂即有机硅金属试剂角度,总结近些年来有机硅金属试剂参与交叉偶联合成有机硅烷研究进展.有机硅硼试剂、有机硅镁试剂、有机硅锌试剂、联硅试剂、有机硅铝试剂和有机硅锂试剂等六方面总结各类金属试剂在碳硅键偶联的进展.     

具有生物活性的有机硅化合物研究近况

生物有机硅化合物的研究进展迅速,而且越来越受到人们的重视。实际上,它是有机硅化学的一个新的分支。本文对有机硅化合物的毒理学、有机硅药物化学以及有机硅农药作了简要的论述。     

有机硅化合物和有机硼化合物在有机半导体材料中的应用

有机硅化合物和有机硼化合物是有机化学中2类非常重要的化合物,它们在有机合成化学和材料化学等领域都有着广泛的应用。有机半导体材料是一个新兴的研究领域,这2类化合物在这个新兴领域中也有着独特的贡献。简单介绍了有机硅化合物和有机硼化合物在有机半导体材料中的应用。     

五苯基苯基硅化合物及其原料苯乙炔基硅化合物的合成

近年来,我们从事多苯基芳基类有机硅化合物的合成。并发现这类化合物对有机硅高聚物的热稳定性有一定的影响^[1.2]。本文研究了五苯基苯基硅化合物的合成。其主要方法是以苯乙炔基有机硅化合物与四苯基环戊二烯酮为原料,通过Diels-Alder反应来合成的。有的文献认为苯乙炔基硅烷由于电子效应与位阻关系,除苯乙炔基三甲基硅烷外,一般不容易与四苯基环戊二烯酮进行缩合^[3]。根据我们的实验却得到了较好产率的各种五苯基苯基有机硅化合物,而且产物也易于分离。同时我们还对原料苯乙炔基甲基二乙氧基硅烷的合成进行了研究。     

有机硅化合物的色谱—质谱—计算机联用仪的定性分析

有机硅化合物定性对有机硅合成工艺研究是一个重要环节。通常的定性方法有色谱法,或采用制备色谱制取纯样结合核磁共振、红外等手段确定化合物结构等。但上述方法对于复杂的有机硅混合物系统不相适应。本文采用色谱—质谱—计算机联用系统对一甲基三氯硅烷连续醇解尾气组成和二甲基二氯硅烷水解连续裂解物组成,及三甲基一氯硅烷连续水解物组成等进行定性研究。     

硅亲电试剂参与碳硅交叉偶联反应研究进展

有机硅化合物因其特殊的性质而广泛应用于合成化学、材料、药物和农药化学等领域.有机硅化合物通常由亲核取代、烯烃硅氢化和碳氢键直接硅化等方法制备.近年来,通过交叉偶联构建碳硅键合成有机硅烷取得突破性进展,引起合成化学领域研究者的广泛关注和兴趣,成为有机硅化合物合成研究热点.主要从硅亲电试剂参与的Heck反应、Negishi...     

四苯基苯基五苯基苯基二乙氧基硅烷的分离制备和鉴定

杜作栋等先后合成了四苯基苯基有机硅化合物和五苯基苯基有机硅化合物,并用溶剂沉淀法和重结晶法纯化产物后进行结构分析,在此基础上陈剑华等又合成了双多苯基苯基有机硅化合物,此类化合物具有更好的耐高温性能,可制成耐高温树脂、耐高温橡胶、耐高温粘合剂和耐高温涂料。     

不对称催化构建硅立体中心化合物的新反应体系研究进展

过去二十年以来,硅立体中心手性有机硅化合物在有机合成、材料科学和药物设计等领域引起了广泛关注.然而,有机硅化合物的来源局限性大大限制了其在这些领域的应用拓展.因此,发展高效、高选择性的不对称催化合成方法以获得硅立体中心手性有机硅化合物是亟需解决的挑战性难题.主要综述了2011年以来通过不对称催化合成硅立体中心手性有机硅化合物的最新研究进展.     

Agostic bonds in cyclometalation

Cyclometalation reactions proceed very easily with one step reaction between metal compounds and substrates having a heteroatom such as O, S, N, P and As. However, under mild reaction conditions, many agostic compounds which are intermediates in these cyclometalation reactions, can be isolated. The metal compounds used for the formation of these agostic intermediates are both transition metal and main group metal compounds. The substrates are nitrogen-containing compounds, phosphorus-containing compounds, oxygen-containing compounds and sulfur-containing compounds. These agostic intermediates are mainly δ-C-H agostic compounds, some are γ-C-H agostic compounds and very few are ?-C-H-agostic compounds. The agostic intermediates are prepared, usually, under mild reaction conditions in the cyclometalation reaction. These agostic compounds are also prepared from cyclometalation reaction products, e.g., by the protonation, irradiation, and elimination of ligand molecules by vacuum, inert gas current, dehydration with a molecular sieves 4A, etc. Some agostic compounds are utilized for preparation of stable catalysts, e.g., hydrogenation catalysts.     

白石湖煤液化粗油加氢精制过程硫、氮化合物转化规律

采用实沸点蒸馏仪对白石湖煤液化油进行馏分切割,切取<170℃液化粗油进行加氢精制脱除其中硫、氮化合物,采用硫化学发光气相色谱仪（GC-SCD）、氮化学发光气相色谱仪（GC-NCD）对液化粗油和精制油中硫、氮化合物进行分析表征,研究加氢精制过程硫、氮化合物的转化规律。结果表明,液化粗油中含硫化合物主要是噻吩类化合物和硫醇,经过加氢精制后基本消失,苯并噻酚类化合物脱除比例要低于噻吩类化合物,属于较难脱除含硫化合物。液化粗油中含氮化合物主要是苯胺类化合物,其次是吲哚类化合物,经过加氢精制吲哚类化合物全被脱除,苯胺和喹啉类化合物属于碱性含氮化合物,是精制油中残留的主要含氮化合物,含量达1.61 mg/kg。     

某些结构受阻氧鎓盐的吸收和荧光

A series of pyrylium compounds with different structures have been synthesized. The photophysical behavior of these compounds has also been measured. Results show that the structures of compounds and the polarities of solvents make great effects on the photophysical behaviors of compounds, especially when the structures of compounds are hindered. It indicats that the intramolecular rotation relaxation of compounds in excited state in closely related to the fluorescence quantum yields of compounds.     

Lead validation and SAR development via chemical similarity searching; application to compounds targeting the pY+3 site of the SH2 domain of p56lck

Compound selection based on chemical similarity has been used to validate active "parent" compounds identified via database searching as viable lead compounds and to obtain initial structure-activity relationships for those leads. Twelve parent compounds that have inhibitory activity against the SH2 domain of the p56 T-cell tyrosine kinase (Lck) are the focus of this study. Lck is involved in the T-cell mediated immune response, and inhibitors of Lck protein-protein interactions could potentially be used to develop novel immunosuppressants. Similarity searches for each parent compound were performed using 2D structural fingerprints on a database containing 1,300,000 commercially available compounds. The inhibitory activity of the selected compounds was assessed using enzyme immunoassay (EIA). In general, the most active parent compounds yield the most high activity similar compounds; however, in two cases low activity parent compounds (i.e. inhibitory activity < 25% at 100 microM) yielded multiple similar compounds with activities > 60%. Such compounds may, therefore, be considered as viable lead compounds for optimization. Structure-activity relationships were explored by examining both ligand structures and their computed bound conformations to the protein. Functional groups common to the active compounds as well as key amino acid residues that form hydrogen bonds with the active compounds were identified. This information will act as the basis for the rational optimization of the lead compounds.     

某些结构受阻氧鎓盐的吸收和荧光

氧锅盐是一类带正电行的杂环化合物，作为一种合成中间体，氧锅盐在有机合成方面已得到广泛的应用［’］近年来人们对其发光和光谱性质的研究也给予足够的注意．这是由于很多氧锅盐化合物有着很强的荧光发射【’J，并且其中有些已被用作激光染料出或Q一开关材料卜1由于氧钠盐强烈的亲电特性，因而它在聚乙烯咋哇电照相体系中也受到特殊的注意，即通过它来捕获电子和诱导分子内正空穴向负电极方向迁移问染料分子的刚性化对激发分子的弛豫过程往往会带来巨大的影响，如非刚性化分子会通过分子内自由旋转使分子在激发态的弛豫过程中形成不同的…     

含氧、氮、硫杂螺环结构的光致变色化合物研究进展

有机螺环光致变色化合物具有较好的化学稳定性、光敏性和抗光疲劳性, 可应用于光过滤器及光学记录存储. 为了获得性能优良的螺环光致变色化合物, 新的设计合成一直是该领域研究的热点. 总结了对含氧、氮、硫杂螺环结构的光致变色化合物的研究进展, 描述了螺环化合物的结构特征和部分化合物的合成过程, 展望了螺环光致变色化合物的发展前景.     

多功能光致变色化合物

有机光致变色化合物是一种新型有机功能化合物,可广泛应用于光存储、光开关和光转换器件等领域,本文综述近几年来双光致变色化合物体系及具有荧光性能、磁性能等多功能光致变色化合物体系的研究进展,并对有机光致变色化合物的研究应用做了展望。     

Synthesis, Chemistry, and Applications of Heterocyclic Cage Compounds (V)

The synthesis and chemistry of polycyclic of cage compounds have attracted considerable attention in recent years. The vast majority of the work reported in this area has dealt with carbocylic cage compounds. On the other hand, the synthesis and chemistry of heterocyclic cage compounds have received less attention. Recently, we envisioned that studies on the synthesis and chemistry of heterocyclic cage compounds can greatly expand the scopes and utilities of cage compounds.1 As part of a program that involves the synthesis, chemistry, and application of heterocyclic cage compounds, we report here the synthesis of new thia-oxa-cage compounds and the chemical nature of these thia-cages.     

Data shaving: a focused screening approach

The number of compounds available for evaluation as part of the drug discovery process continues to increase. These compounds may exist physically or be stored electronically allowing screening by either actual or virtual means. This growing number of compounds has generated an increasing need for effective strategies to direct screening efforts. Initial efforts toward this goal led to the development of methods to select diverse sets of compounds for screening, methods to cluster actives into related groups of compounds, and tools to select compounds similar to actives of interest for further screening. In this work we extend these earlier efforts to exploit information about inactive compounds to help make rational decisions about which sets of compounds to include as part of a continuing screening campaign, or as part of a focused follow-up effort. This method uses the information from inactive compounds to "shave" off or deprioritize compounds similar to inactives from further consideration. This methodology can be used in two ways: first, to provide a rational means of deciding when sufficient compounds containing certain structural features have been tested and second as a tool to enhance similarity searching around known actives. Similarity searching is improved by deprioritizing compounds predicted to be inactive, due to the presence of structural features associated with inactivity.