手性5-l-(艹孟)氧基丁内酯并[3,4-d]-3-取代基-异(口恶)唑啉类化合物的合成

研究了手性元5-(R)-(l-(艹孟)氧基)-2(5H)-呋喃酮与取代苯甲醛肟以次氯酸钙作为氧化剂进行的区域选择性原位1,3-偶极环加成反应,同步生成两个新的手性中心,得到了一系列光学纯丁内酯并[3,4-d]-3-取代基-异(口恶)唑啉类化合物;应用波谱学手段及X射线单晶衍射法确证了产物的绝对构型,并对产物的核磁共振氢谱规律性加以总结.     

Semi-micro solvent extraction as a rapid and efficient preconcentration technique for the determination of n-alkanes in oil-contaiminated water and soil samples by capillary gas chromatography

Summary In this study, a rapid and efficient semi-micro extraction procedure is presented for the extraction of some higher n-alkanes from water and soil samples. In the case of water samples n-hexane was used as the organic phase in a phase volume ratio (volume of aqueous phase/volume of organic phase) higher than 285, while in the case of soil samples, extraction with n-hexane was carried out in the presence of an excess of 2 M NaCl solution. The extraction rate from soil samples is very high and is better than Soxhlet extraction, comparable with supercritical fluid extraction. High preconcentration factor in water samples allows the limits of detection to be in the ng.mL⁻¹ level with the use of gas chromatographic analysis. Flame ionization detector was used for monitoring the analytes. The obtained recoveries of all studied compounds from both water and soil samples are higher than 90%. This method was successfully used to determine some n-alkanes in municipal wastewater and contaminated soil.     

Application of the semilocalized approach to chemical reactivity of butadiene

The semilocalized approach to chemical reactivity (J. Mol. Struct. (Theochem) 588 (2002) 99; Int. J. Quant. Chem. 94 (2003) 302) is applied to study the addition reaction of an electrophile or nucleophile to the butadiene molecule. In accordance with the classical concept of the reaction center and its neighborhood (substituent), only one of the two H₂C=CH-fragments of butadiene is supposed to be under a direct attack of the reagent, whereas the remaining H₂C=CH-group is assumed to play the role of the substituent and thereby to participate in the process indirectly by exerting certain electron-donating or accepting effect upon the former group and/or the reagent. The main aim of the study consists in revealing the role of the H₂C=CH-substituent in the formation of the known higher reactivity of the terminal carbon atom of the attacked C=C-bond (as compared to the internal atom) irrespective of the nature of the reagent. To this end, we seek to obtain an explicit algebraic representation of the interdependence between the direction and the extent of the total influence of the H₂C=CH-substituent, on the one hand, and the nature of the reagent, on the other hand. The expressions for electron density and bond order redistributions among separate fragments of contacting molecules derived previously in the form of power series are shown to yield the above-anticipated representation. On this basis, it is demonstrated that the electron-donating effect of the initially occupied (bonding) orbital of the substituent and the electron-accepting effect of its initially vacant (antibonding) orbital upon the remaining fragments of the whole reacting system may be considered independently whatever the nature of the reagent. However, a strong interdependence is established between the actual relative extents of these two components of the total effect of the H₂C=CH-group and the electron-donating (accepting) properties of the reagent. Moreover, this group of atoms is shown to manifest itself as an electron-donating (accepting) substituent under influence of an electrophilic (nucleophilic) attack. Using this principal result of the paper, the actual reactivity of butadiene with respect to electrophile (nucleophile) is interpreted by invoking a model system of a substituted ethene containing a simple (one-orbital) electron-donating (accepting) substituent, and a terminal addition easily follows for both types of the reagent.     

Contracted polarization functions for B to Ar

Using optimal exponents for B through Ne given by Dunning and those for Al through Ar by Woon and Dunning, d-type contracted polarization functions (2d/1d), (3d/1d), and (3d/2d) are generated from natural orbitals of atomic single and double excitation configuration interaction (SDCI) calculations, where the numbers before and after the slash are those of the primitive and contracted Gaussian type functions. The resulting contracted functions are tested on N₂ and P₂ molecules by self-consistent field and SDCI calculations, which clarify characteristics of the present polarization functions. Received: 5 June 1997 / Accepted: 20 August 1997     

Copolymerization of butadiene and styrene with a gadolinium tricarboxylate catalyst

Homo- and copolymerizations of butadiene (BD) and styrene (St) were carried out by gadolinium catalysts having various tricarboxylate ligands [Gd(OCOR)₃: R = CH₃, CH₂Cl, CHCl₂, CCl₃, and CF₃], to investigate the effects of ligands and discuss the cis polymerization mechanism. Polymerization of BD with Gd(OCOR)₃—(i—Bu)₃Al—Et₂AlCl catalysts was carried out in hexane at 50°C. By each catalyst, poly(BD) having a high cis content (cis = 97–99%) in 22–85% yields for 2–24 h were obtained. The ligands with low pKa values increased the polymerization activity as follows: R of Gd(OCOR)₃: CF₃ > CCl₃ > CHCl₂ > CH₂Cl ～ CH₃. On the other hand, in the polymerization of St or copolymerization of BD and St under similar conditions, the highest activity was attained by a Gd(OCOCCI₃)₃- based catalyst. The difference in the optimum ligand among the homo- and copolymerization of BD and St was discussed on the basis of energy levels of the catalysts. In the copolymers of BD and St, the cis-1,4 content of the BD unit decreased with increasing St content. Furthermore, according to the diad analysis of copolymers (St content ～ 14.5 mol %) by ¹³C NMR spectroscopy, the low cis value of the BD unit was observed in the St-BD diad (cis/trans/vinyl = 24/53/23), while the high cis value of the BD unit remained in the BD-BD diad (cis/trans/vinyl = 89/10/1). These results suggest that the terminal BD unit is controlled by the cis configuration by the coordination between the penultimate cis vinylene unit and the gadolinium metal catalyst, whereas the presence of the penultimate St unit interferes with cis polymerization of the terminal BD unit. The difference in the coordination mechanism in the course of polymerization between rare earth metal and transition metal catalysts such as the Ni(acac)₂ and Co(acac)₃-based catalyst was also discussed. © 1995 John Wiley & Sons, Inc.     

DSB显著提高羧酸盐驱油体系抗钙镁离子能力的研究

测定了工业品级的天然混合长链烷基羧酸盐(SDC)以及与3-(N,N-二甲基十二烷基胺)-2-羟基-丙磺酸(DSB)复配驱油体系的界面张力(ITFmin), 分别得出其抗钙镁离子的能力为400和5000 mg/L. 选择试剂级十二烷基羧酸钠与DSB复配, 测定了不同配比溶液的表面张力值和临界胶束浓度cmc, 结合长链烷基脂肪酸与钙离子的溶度积Ksp, 分析了对不溶性长链烷基羧酸盐形成的影响. 根据现场驱油体系配方, 计算了两者在溶液中的摩尔配比为4:1时的十二烷基羧酸盐在胶束中的摩尔分数xm1为0.51, 相互作用参数βm值为-3.11, 反映了两者有较强的相互作用. 采用量子化学方法, 对由1个十二烷基羧酸分子、1个DSB分子及1个二价钙离子组成的模型复合物进行了能量计算和电荷分布计算, 得出在长链烷基羧酸盐和DSB两者混合胶束的界面层中存在负电荷空穴, 提出二价金属离子被络合的模型, 合理地解释了实验事实.     

Oxidative cyclization of 2-pyrrolidinyl-acetamide and 2-pyrrolidinyl-propionamide local anaesthetics

2 - Pyrrolidinyl - acetamide and -propionamide local anaesthetics (1a–d) on oxidation with mercuric acetate, potassium hexacyanoferrate(III) and potassium permanganate underwent oxidative cyclization to give new bicyclic compounds, hexahydro - 1H - pyrrolo[1,2 - a]imidazolin - 2 - ones (2a–d). The propionamides (1c–d) yielded mixtures of the two possible diastereoisomers of 2c and 2d. These were separated; in solution and above their melting points they epimerized via ring opening and reclosure between the 7a-carbon and 1-nitrogen atoms.     

Chemical modification of polymer surfaces: a review

The main approaches that have been taken to chemically modify polymer surfaces are introduced and reviewed. These are wet chemical oxidation, plasma treatment, classical organic chemistry, and attachment of polymer chains. The extent to which each of these approaches can produce the specific modifications desired is discussed, and any unwanted effects that commonly occur are cited. Finally, the need for using several methods of surface analysis in concert to obtain adequate surface characterization is described.     

Determination and Differentiation of Two Seemingly Identical Medicinal Herbs by Capillary Electrophoresis with Electrochemical Detection

A high-performance capillary electrophoresis with electrochemical detection (CE-ED) method has been employed for the determination of six bioactive ingredients in traditional Chinese herbs, Herba cepbalanoplosis segeti and Herba cirsii japonici. The effects of several factors such as the acidity and concentration of running buffer, the separation voltage, the applied potential and the injection time on CE-ED were investigated. Under the optimum conditions, the six analytes could be well separated within 21 min in a 75 cm length capillary at the separation voltage of 15 kV in a 50 mmol L^–1 borax running buffer (pH 8.4). A 300 m diameter carbon disk electrode was used as the working electrode positioned carefully opposite the outlet of the capillary in a wall-jet configuration at potential of +950 mV (vs. SCE). Good linear relationship was established between peak current and concentration of analytes over two orders of magnitude with detection limits (S/N=3) ranged from 1.5×10^–7 to 6.0×10^–7 g mL^–1 for all six analytes. This proposed method has been successfully applied for the analysis of traditional Chinese herbs after a relatively simple extraction procedure, further on, for the differentiation of these above two seemingly identical herbs based on their electropherograms or characteristic electrochemical profiles.     

Synthesis, structure, and electrochemical properties of 12,42-dioxo-21,31-diphenyl-7,10,13-trioxa-1,4(3,1)-diquinoxalina-2(2,3),3(3,2)-diindolizinacyclopentadecaphane

The oxidative dehydrocyclization of the 3-(indolizin-2′-yl)-2-oxoquinoxaline monopodand performed either electrochemically or under the action of molecular iodine affords new redox-active heterocyclophane consisting of the redox-switchable biindolizine fragment combined with the polyether-bridged π-deficient quinoxaline systems. The single-crystal X-ray diffraction study showed that the trioxaundecane chain of heterocyclophane adopts an extended conformation, and one of the phenyl substituents of the molecule closes the pseudocavity formed by the spacer from one of the sides. The cyclic voltammetric study of heterocyclophane in MeCN and DMF showed the three-step oxidation of the indolizine fragments accompanied by the single-electron transfer in each step. The first and third steps are reversible, and the second step is irreversible. The oxidation at potentials of the first peak gives rise to stable radical cations detected by the ESR method (g = 2.0024, a _2N = 0.26 mT). Dedicated to Professor E. A. Berdnikov on the occasion of his 70th birthday. Published in Russian in Izvestiya Akademii Nauk. Seriya Khimicheskaya, No. 10, pp. 1991–2003, October, 2007.