双（三氯甲基）碳酸酯的制备和应用

介绍了近１０年双（三氯甲基）碳酸酯（简称ＢＴＣ）的制备方法及其在有机合成中的应用。ＢＴＣ作为剧毒的光气和双光气在合成中的低毒替代物,在制备一些重要类型有机化合物时,其反应条件温和,选择性好,收率高。     

聚酯基硫脲树脂的合成

首先在N,N-二甲基苯胺的催化下,二（三氯甲基）碳酸酯与1,4-丁-醇或一缩二乙二醇发生光气化反应生成双氯甲酸酯;然后将双氯甲酸酯与硫氰酸钾在相转移催化剂的催化下反应生成二异硫氰酸酯;最后二异硫氰酸酯分别与二乙烯三胺、三乙烯四胺、四乙烯五胺加聚得到聚酯基硫脲树脂。采用红外光谱、元素分析、扫描电镜等方法对树脂进行了表征。     

一锅法合成二硫醚的简便制备过程研究

双（三氯甲基）碳酸酯与三苯基膦反应生成的二氯三苯基膦在三乙胺存在下与 硫酚（醇）反应，合成了一系列收率良好的二硫醚化合物。该过程采用“一锅法” ，操作方便，后处理简单，条件温和，提供了一条合成二硫醚的重要路线。     

双（N,N′—亚烃基—2,2′—（芳亚甲基）二（3,4—二甲基吡咯— …

首次报道了新型Ｓｃｈｉｆｆ碱类配体双（Ｎ，Ｎ′－亚烃基－２，２′－（苯亚甲基）－二（３，４－二甲吡咯－５－醛缩亚胺）和双（Ｎ，Ｎ′－（１，２－亚乙基）－２，２′－（４－甲氧基苯亚甲基）二（３，４－二甲基吡咯－５－醛缩亚胺）及其双锰配合物的合成方法，光谱特征及用配合物催化ＰｈＩＯ单加氧化环己环反应的研究。     

金属化合物催化的1,1′-联二萘酚-4,4′-二乙酸酯和二(2-乙基己醇)碳酸酯的酯交换

芳香族聚碳酸酯性能优良,其中双酚-A型聚碳酸酯是应用广泛的工程塑料,通常采用光气法或酯交换法来制备,但芳香双羟基化合物与二烷基碳酸酯的酯交换反应速度十分缓慢,需要使用催化剂,且反应温度较高,反应过程伴随着复杂的副反应。本文用金属化合物作催化剂进行1,1′-联二萘酚-4,4′-二乙酸酯和二(2-乙基己醇)碳酸酯的酯交换反应,评价了不同金     

国内外碳酸二甲酯酯交换反应催化剂研究进展

碳酸二甲酯（DMC）是一种重要的有机合成原料及中间体，DMC带有-CO、-COOCH3和CH3基团，可进行羰基化、甲基化、甲氧基化和羧甲基化反应，取代传统使用的有毒原料光气、硫酸二甲酯和甲基氯等。因此，1992年DMC在欧洲被登记为绿色无毒化学品，DMC可替代光气合成聚碳酸酯、碳酸二苯酯、异氰酸酯（TDI、MDI、HDI、IPPI）及烯丙基二甘醇碳酸酯（ADC）；也可用于合成氨基甲酸酯类农药（西维因）、苯甲醚、甲基芳胺等；此外，DMC具有高的含氧量（53．3％），可以用做汽油添加剂，能有效提高汽油的辛烷值；还具有与其它溶剂相溶性好，蒸发速度快的特点，适于在特种油漆、药物制造行业使用。因此，碳酸二甲酯是一种有广阔发展前景的化学品。     

N－取代三氯乙酰胺合成N，N″－多亚甲基双［N′－（4－氯苯基）］脲

通过Ｎ－取代三氯乙酰胺与不同的脂肪二胺反应，合成了５种新的Ｎ，Ｎ″－多亚甲基双［Ｎ′－（４－氯苯基）］脲［ＡｒＮＨＣＯＮＨ（ＣＨ２）ｎＮＨＣＯＮＨＡｒ，ｎ＝２～６，Ａｒ＝４－ＣｌＣ６Ｈ４］，其结构经元素分析、１ＨＮＭＲ和ＩＲ证实     

三亚甲基环碳酸酯及2,2-二甲基三亚甲基环碳酸酯开环均聚合*

生物降解聚合物聚三亚甲基环碳酸酯（PTMC）及聚2,2-二甲基三亚甲基环碳酸酯（PDTC）在药物控释载体及其它生物医学技术领域有着良好的应用前景。与脂肪族聚酯不同,PTMC、PDTC降解时,不会产生有害的酸性化合物。PTMC、PDTC主要由三亚甲基环碳酸酯（TMC）及2,2-二甲基三亚甲基环碳酸酯（DTC）开环均聚合制备。本文总结了催化TMC、DTC开环均聚合的不同催化剂及其聚合机理,综述了近年来国内外在TMC、DTC均聚合催化剂开发上的研究进展,并对生物相容性催化剂如稀土催化剂、Ca、Mg、Zn、Fe催化剂以及酶催化剂催化TMC、DTC开环聚合的优缺点进行了比较。     

某些有机硅及2—三丁基锡二茂铁衍生物的合成及表征

由Ｎ，Ｎ－二甲氨甲基二茂铁（Ｉ）单锂化后与三甲基氯硅烷（Ｍｅ３ＳｉＣｌ）反应，合成了２－（三甲硅基）二甲氨甲基二茂铁（Ⅱ）；Ⅱ再单锂化后与Ｍｅ３ＳｉＣｌ反应得到了２，５－二（三甲硅基）二甲氨甲基二茂铁（Ⅲ）；单锂化的Ｉ与Ｍｅ２ＳｉＣｌ２反是得到了双－（２－（二甲氨甲基）二茂铁基）二甲基硅烷（Ⅳ）双锂化Ｉ与二倍量的Ｍｅ３ＳｉＣｌ反应得到了２，１′－二（三甲硅基）二甲氨甲基二茂铁（Ｖ），由碘化（２－（     

Nafion-聚[N′,N″-(1,3-丙二亚甲基)双(1,2-苯二氨基)-N,N′,N″,N]合镍修饰微电极用于测定一氧化氮的研究

详细报道了Ｎａｆｉｏｎ－聚［Ｎ′，Ｎ″－（１，３－丙二亚甲基）双（１，２－苯二氨基）－Ｎ，Ｎ′，Ｎ″，Ｎ］合镍［ＰｏｌｙＮｉ（Ⅱ）Ｌ］修饰微铂电极的制备及性质．实验表明，该修饰电极对ＮＯ有较高的灵敏度和选择性．当ＮＯ的浓度在２．０×１０－７～１．６×１０－５ｍｏｌ／Ｌ范围内峰电流与ＮＯ的浓度呈线性关系，相关系数ｒ＝０．９９４．用于血液中ＮＯ的检测，效果良好．     

A study of the effect of network angle of fabrics on kinetics of impregnation upon molding of articles made from carbon plastics

The permittivity coefficient, volume, and porosity of an elementary cell of fabric filler have been calculated. Two types of fabric structures have been considered using the example of carbon fabric: standard, in which filament yarn is cylindrical, and spread, it which it has a rectangular shape. A reflector of a mirror space antenna has been considered characterized by the presence of doubly curved surfaces is used as the object of study. Modeling of the kinetics of impregnation of reflector for two types of fabric structures has been carried out using the RAM–RTM program. In the work, the effect of the network angle on the duration of impregnation process has also been investigated. Based on the results of calculation, reflector samples have been made and their quality has been evaluated. Theoretical and experimental results have been compared.     

贵金属Au冷却过程中结构及能量变化的分子动力学计算机模拟

通过分子动力学方法,研究了不同冷速下贵金属Au在温度2000～300K的冷却过程中微观结构的变化特点。结果发现,冷却速度对Au的微观结构产生重要影响。采用偶关联函数和键对分析技术对原子局域团簇结构进行分析,并考察了冷却过程中原子势能随温度的变化,比较了Au的微观结构转变与能量变化的对应关系,从能量转化的角度对冷却过程中Au的结构变化进行了说明。     

Synthesis and studies of structure and biological properties of D-homoanalogs of steroid estrogens

In order to estimate the potential of steroid estrogens modification, three D-homoanalogs of estrogens have been prepared; their structures and biological properties have been studied. The expansion of D-ring in such compounds has lead to strong decrease if the uterotropic action, however, the unfavorable hypertriglyceridemic effect has been retained. The latter has been eliminated by combined action of the studied steroids and ursolic acid; therewith the hypocholesterolemic activity has been retained.     

耐蚀合金Au3 Cu高温冷却过程中能量及结构转变的分子动力学模拟

用分子动力学模拟方法对液态Au3Cu冷却过程进行了研究,考察了不同冷却速度下Au3Cu结构变化特点,原子间相互作用势采用F-S多体势,结构分析采用键取向序和对分析技术.计算结果表明,冷却速度对液态Au3Cu能量及结构转变有重要影响,给出了不同冷却速度下液态Au3Cu结构转变的微观信息.     

Accurate theoretical prediction of optical properties of BODIPY dyes

Boron-dipyrromethene dyes (BODIPY) are of great interest nowadays mostly due to their valuable optical properties. Nevertheless, no systematic research of the optical property dependence on the structure of dyes has been performed yet. In this work, analysis of the available quantum-chemical methods for BODIPY optical property calculations has been carried out. The accuracy of eight DFT functionals has been studied. The solvation effects upon excitation have been considered within two schemes. The methods that predict the absorption and emission spectra of BODIPY derivatives with high accuracy have been proposed. Using the suggested methods, the influence of nature of substituents and their position in the BODIPY core on the optical spectra of the dyes has been studied. A complex pattern of red- and blue-shifts in optical spectra in dependence of nature and position of substituents has been revealed. The results of this work provide the way for efficient design of BODIPY derivatives with desired optical properties.     

Research of Fluorination Process of Rutile Concentrate

The brief review of industrial technologies of titanium-containing concentrates processing has been carried out. Drawbacks of the existing titanium manufacture schemes are shown and the necessity of the essentially new fluoride technologies development has been proved. The reactions proceeding during the fluorination of rutile concentrate with element fluoride are described in the given work. The thermodynamic research of the process has been carried using ASTRA software. Dependence of mass concentration change of titanium tetrafluoride has been investigated in products of reaction on the temperature of the process, and the choice of optimum excess of fluoride has been proved.     

Kinetics of oxidation of some disaccharides in ammoniacal medium

Kinetics of oxidation of lactose, maltose, cellobiose and melibiose has been studied by hexacyanoferrate(III) in the presence of ammonia. A general mechanism involving the formation of intermediate enodiol anion has been suggested. The effects of dielectric constant and salts have been studied in detail. The oxidation products have been characterised by descending paper chromatography. Compensation effects have been observed.     

Investigation of the extraction equilibrium of ion-association complexes of molybdenum (VI) with some polyphenols and thiazolyl blue. extraction-spectrophotometric determination of molybdenum

The extraction process of ternary ion-association complexes of molybdenum (VI) with some polyphenols (4-nitrocatechol, 2,3-dihydroxy naphthalene) and thiazolyl blue has been investigated by using an extraction-spectrophotometric method. The optimum conditions for their quantitative preparation in aqueous medium and subsequent extraction into an organic solvent have been found. The extraction, distribution and association constants, and the recovery factors have been calculated. The composition of the complexes has been determined. A precise, sensitive and simple extraction-spectrophotometric method for determination of molybdenum in products from ferrous metallurgy has been developed.     

MNDO study of reaction paths: Hydroboration of methyl cyanide

The hydroboration reaction of methyl cyanide has been investigated by the MNDO method. It has been shown that the reaction requires an activation energy of 25.3 kcal/mol and involves a four-center-like transition state in the rate-determining step. This reaction has been compared with the corresponding reaction of hydrogen cyanide, and the effect of methyl substitution on the reaction has been discussed. The charge-transfer effects accompanying the reaction have also been studied.     

Effect of the composition of polyacrylimide-forming copolymers on their processing

Thermomechanical studies of thermosetting copolymers of acrylonitrile with methacrylic acid and acrylamide with acrylic acid that form similar polyacrylimide foam plastics during curing have been performed. The dependence of the glass-transition temperatures of the copolymers on the degrees of intramolecular imidization has been calculated and confirmed experimentally. Procedures to control the curing rate have been proposed. The influence of plasticizing additives on the glass-transition temperatures, imidization, and foaming of foam-forming compositions has been studied. Plasticized powdered foam-forming compositions with delayed imidization have been developed, and temperature conditions for their processing have been determined.