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。     

有机硅化合物的生物转化

有机硅化合物的研究开发是近来较活跃的研究方向。本文概述了有机硅化合物的生物转化，可能的应用前景及意义．     

具有生物活性的有机硅化合物研究(Ⅺ)——2-(三甲硅基)乙基硫代(N-取代)乙酰胺的研究

研究了2-(三甲硅基)乙基硫代乙酸与(取代)苯胺和脂肪胺直接缩合反应或在五氧化二磷存在下的反应,发现前者收率高于后者。由此合成了17种结构新颖的2-(三甲硅基)乙基硫代(N-取代)乙酰胺类化合物。通过NMR(¹H,¹³C)、IR和MS的研究,确定了这类化合物的结构,并探讨了化合物结构与波谱的关系。经测定,这些化合物的生物活性不甚理想。     

具有生物活性有机硅化合物的研究(XIV)──含硅四配位双(单)硫代磷酸酯化合物的研究

共合成了13个含硅四配位二硫代磷酸酯和2个含硅四配位单硫代磷酸酯的新化合物,经元素分析、IR、¹HNMR、MS确定了新化合物结构,对部分化合物进行了生物活性的测定,结果表明个别化合物有较好的生物活性。     

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。     

有机硅改性环氧树脂的新进展

热固性环氧树脂材料具有良好的物理、化学等诸多优异性能,对于金属和非金属材料的表面都具有优异的粘接强度,可用于浇注、浸渍、层压、粘接剂、涂料等,用途十分广泛。由于环氧树脂材料存在脆性大,抗冲击性差、耐热性差等缺点,科研工作者对环氧树脂进行了大量的改性研究并取得了丰硕的成果。有机硅化合物改性环氧树脂在提高其热氧稳定性、韧性以及耐烧蚀性能等方面具有独特的优势,近年来,研究人员利用功能性有机硅化合物或聚合物在环氧树脂进行改性方面,开展了反应共聚改性、作为交联剂固化改性、与环氧树脂共混/交联改性、增容改性、互穿聚合物网络(IPN)、引入阻燃剂结构改性以及微纳米复合改性等方面的研究,取得了很多新的成果。本文旨在总结上述各种有机硅改性环氧树脂研究的新进展,并预测了有机硅改性环氧树脂材料的潜在应用和发展方向。     

农药用有机硅表面活性剂的研究进展

有机硅表面活性剂是一种新型的农药用表面活性剂，本文对它在农药中的一些应用及其研究进展以及卓越的湿润性、极佳的延展性、气孔渗透率、良好的抗雨冲刷性能等进行了综述。     

Theoretical thermochemistry: Entropies and heat capacities for organosilicon compounds part 3

Ab initio molecular orbital theory was used to compute entropies, heat capacities and other thermochemical properties for a new organosilicon compound H₂SiNaF in the temperature range 300–1500 K. There is currently no information of this kind available about this compound. On the basis of the calculated heat capacities, we have fitted the temperature-dependent functions for heat capacities to the forms (a+bT+cT²) and (a'+b'T+c'T^?2) in the range 300–1500 K. Furthermore, we calculated the equilibrium constants of conversions among the four configurations of this compound. Thus, a new way of determining thermodynamic data theoretically can be derived and is expected to be established.     

Carbofunctional sulfur‐containing organosilicon compounds

This review summarizes literature data and the authors’ own research results from the past 14–15 years relating to practical, valuable organosilicon carbofunctional sulfur‐containing compounds of general formula R_4−n Si(S_x R¹)_n , where R is alkyl, arylalkoxyl, aroxyl or even sylatranyl fragment, R¹ is hydrogen, alkyl, aryl, alkenyl, etc., n = 1–3, x = 1–10, having sulfur functional groups such as thiol, sulfide, di‐ and polysulfide, as well as sulfur heteroatomic groups such as thiocarbamide, dioxothiocarbamide, dithiourethane, thiuramdisulfide, etc. The compounds reviewed have been found to be effective, for example, as ingredients for rubber compositions for non‐flammable, water‐ and wear‐proof tires or as ion‐exchanging and complexing sorbents of heavy and noble metals.     

Ring opening polymerization of cyclic organosilicon compounds: Recent progress

A novel initiator, i.e. trimethylsilylmethyllithium has been successfully used for the ring opening polymerization of cyclosiloxanes in toluene, in the presence of the cryptand [211]. Suitable conditions have been found in which monomodal distributions of molecular weights of polysiloxanes are observed by GPC, even in the case of D₄ and 1,3,5,7-tetramethyl-1,3,5,7-tetravinyl cyclotetra siloxane (D₄Vi) polymerizations. Moreover, kinetics of propagation and of formation of cyclosiloxanes can be followed by ²⁹Si or ¹³C NMR spectroscopy on living polymer solutions. The rate of propagation of hexaethylcyclotrisiloxane is 120 times lower than that of the corresponding dimethylated analog D₃, under the same conditions.     

Asymmetric allylation of aldehydes and alkylation using "carbon-centered" chiral organosilicon compounds

The effects of the chiral substituents attached to silicon on the stereoselectivity of the reactions of C-centered chiral silicon compounds was examined. The investigation was focused on the asymmetric C-C bond formation reaction of chiral allylsilanes and α-silylallyl anions with aldehydes. The functionalities of the substituents on silicon can be manipulated to improve the stereoselectivities of the reactions remote from silicon atom.     

Comparative study of the biological activity of organosilicon and organogermanium compounds

The literature data and the results of our own investigations on the comparative study of the biological activity of isostructural organogermanium and organosilicon compounds have been summarized. It has been shown that the series of organogermanium and organosilicon compounds is more active than the carbon analogues, the majority of organogermanium compounds are less toxic than the sila analogues, the biological activity of the compounds under study appears to be similar but can dramatically differ in the degree of activity, and, moreover, in some particular cases sila and germa analogues exhibit the opposite biological effects.     

Novel organosilicon betaines

The structure of organosilicon betaines R₃P⁺CMe₂SiMe₂S^– (R = Ph and Me₂N) was determined by X-ray diffraction analysis.Translated fromIzvestiya Akademii Nauk. Seriya Khimicheskaya, No. 2, pp. 339–340, February, 1994.     

腈基功能化有机硅基电解液在4.4V钴酸锂/石墨锂离子电池中的性能研究

研究了3-丙基腈-甲氧基乙氧基-二甲基硅烷(SN1)作为电解液共溶剂对高电压钴酸锂/石墨全电池电化学性能的影响.在商业烷基碳酸酯电解液里掺入30%SN1(体积分数),钴酸锂/石墨全电池在4.4 V截止电压下仍表现出良好的循环稳定性和倍率性能:以0.5 C充放电,首次放电比容量为154 mA h/g,循环150周后,容量保持率为92.9%;当放电倍率增加到1和1.5 C时,放电容量分别为143和133 mA h/g.电化学阻抗谱、扫描电镜和傅里叶红外光谱的结果表明,耐高电压腈基功能化有机硅化合物的引入有效抑制了共溶剂电解液在正极材料表面的分解,压制了循环过程中电极极化的增长,为电极/电解液界面的Li+扩散和电荷转移提供了有利的动力学条件.     

Catalysis of hydrosilylation of carbon-carbon multiple bonds: Recent progress

Recent progress in the catalytic hydrosilylation of organic and organosilicon compounds containing carbon-carbon multiple bonds is reviewed. Related to this, dehydrogenative silylation is also discussed. During the last decade new hydrosilylation catalysts, predominantly homogenous and heterogenous transition methal complexes, have been developed. These catalysts offer not only increased efficiency and turnover rate but also improved regioselectivity and stereoselectivity; moreover, there has been development in the mechanistic rationale behind these improvements. Application and extension of these basic chemical advances are found in many areas including polyorganosiloxane curing, hydrosilylation polymerization, polysiloxane functionalization, and silicon-containing dendrimer development.