Cooperative Catalysis of Ru(III)-Porphyrin in CO2-Involved Synthesis of Oxazolidinones

CO₂-transformations into high value-added products have become a fascinating area in green chemistry. Herein, a Ru(III)-porphyrin catalyst (RuCl₃ ⋅ 3H₂O−H₂TPP) was found highly efficient in the three-component reaction of CO₂, aliphatic amines and dichloroethane (or its derivative) for synthesis of oxazolidinones in the yields of 71∼91%. It was indicated by means of the control experiments and UV-vis spectra that CO₂ was stoichiometrically activated by the involved aliphatic amine substrates to form a stable carbamate salt while 1,2-dichloroethane (or its derivative) was independently activated by the involved Ru(III)-porphyrin catalyst. The combination of CO₂-activation by aliphatic amines with 1,2-dichloroethane activation by Ru(III)-porphyrin catalyst cooperatively contributed to this successful transformation.     

Electro‐induced oxidative polymerization of N‐vinylcarbazole

In this study, a novel procedure to increase the yield of the non‐crosslinked, photoconductive, white form of linear poly(N‐vinylcarbazole) (LPVCz) is reported. The yield of LPVCz is increased (up to 53%) by the addition of catalytic amounts of ceric ammonium nitrate as an oxidant during the electrochemical polymerization of N‐vinylcarbazole in a divided electrochemical cell. The concentration of Ce(IV) remained constant during the polymerization since Ce(III) is readily oxidized to Ce(IV) electrochemically. Since the electrochemical oxidation of Ce(III) to Ce(IV) took place simultaneously at the anode, the deposition of dark green crosslinked polyvinylcarbazole on the electrode surface, which hinders the formation of white LPVCz, can be prevented. The Fourier transform infrared, ultraviolet–visible and fluorescence spectra of white LPVCz showed that the structures of polymers are the same as those produced by conventional polymerization. Copyright © 1999 John Wiley & Sons, Ltd.     

水相中3,5-二芳基异噁唑衍生物的微波辐射合成

微波辐射下,以芳香醛和芳香酮为起始原料合成2,4,6-三芳基吡喃盐,在NaOH水溶液中与盐酸羟胺发生开环、缩环和脱苯甲酰基反应,一步生成3,5-二芳基异噁唑衍生物。考察了微波辐射功率和辐射时间对目标产物收率的影响,2,4,6-三芳基吡喃盐与盐酸羟胺反应生成3,5-二芳基异噁唑衍生物的最佳微波辐射功率为600W,辐射时间为8min,最大收率为83%。该法不仅避免了使用高氯酸造成的环境污染,而且以水作为反应介质,使后处理简便。该工艺具有操作安全、反应条件温和和产率高等优点,是一种环境友好的合成工艺。产物经元素分析、1HNMR和MS测试技术表征了其结构。     

Types of saltwater intrusion of the Changjiang Estuary

The Changjiang Estuary is characterized by multi-order bifurcations, unsteady submerged sandbars, mid-channel sandbars, creeks and riffles. The following four types of saltwater intrusion are found: (1) direct intrusion from the sea; (2) intrusion during tidal flooding; (3) intrusion from tidal flats overflow; and (4) salt water coming upstream through other waterways. These result in a complicated temporal and spatial salinity distribution. A high chlorinity concentration zone exists from the Liuhekou to the Sidongkou along the South Branch. The salinity during neap tide or ordinary tide is higher than during spring tide.     

A polymer imidazole salt as phase-transfer catalyst in halex fluorination irradiated by microwave

A new imidazole polymer salt was synthesized in order to develop a high efficiency phase-transfer catalyst for multi-phase reactions. The polymer salt was prepared easily by co-polymerization of 1-1′-(1,4-butamethylene)bis(imidazole) and 1,2-dibromoethane, and has the properties of excellent chemical and thermal stability and high ionic conductivity. It was applied as phase-transfer catalyst in the fluorination of chloronitrobenzenes under the irradiation of microwave and gave excellent yields of corresponding fluoronitrobenzenes. In addition, the enhanced mechanism of microwave was studied and found “non-thermal” effect was a great factor.     

熔盐法合成LiNi0.5Mn1.5O4及电化学性能

以一定比例的LiCl-LiNO_3为低熔点共混物,采用熔盐法合成了电化学性能良好的LiNi_(0.5)Mn_(1.5)O_4,XRD表征结果显示产物为单一尖晶石相,SEM表征显示出材料良好的晶形,充放电测试结果显示出材料在4.7V平台附近有较大的可逆容量,在4.1V平台附近仅有较少的可逆容量。文章讨论了影响产物晶形和性能的各种因素,建议通过退火、改变合成气氛来消除4.1V平台的产生;研究结果还显示,容量的损失主要发生在第一次放电过程中在高电位区时的电解液的氧化分解.建议通过更换适合在高电位条件下工作的电解液来克服此问题;同时,通过调整低熔点共混物的配比、气氛、反应时间等条件可以实现对产物的结晶形态和大小进行适当的控制,显示了该方法在制备LiNi_(0.5)Mn_(1.5)O_4材料中的应用前景.     

The influence of ionic medium on the kinetics of ligand replacement in the Ptdient H2O2+ complex in an aqueous solution

The influence of the ion background (NaClO₄, LiClO₄, and HClO₄) on the kinetics of the reaction PtdientH₂O²⁺+X⁻→PtdientX⁺+H₂O(X=Cl, Br, I, SCN, and N₃) was studied at 25°C by spectrophotometry. Changes in the rate constant with increase in the ionic strength are described by the Debye-Hückel and Gosh-Bjerrum equations. The reaction PtdienCl⁺+H₂O→PtdientH₂O²⁺+Cl⁻ was studied by potentiometry and its rate constant was established to depend weakly on variations of the medium. Translated fromIzvestiya Akademii Nauk. Seriya Khimicheskaya, No. 10, pp. 1918–1921, October, 1998.     

Analysis of polar compounds on PEG-40M/KF glass capillary columns

The chromatographic properties of potassium fluoride as an additive to the polyethylene glycol stationary phase were investigated. This unique base in organic chemistry was shown to succeed in yielding good results for the analysis of polar compounds, including the primary amines. Glass capillary columns of high selectivity for primary and secondary aliphatic amines were obtained by the “hexane plug” procedure by which a thin layer of KF is deposited on the inner surface of glass capillary columns. Some possible types of donor-acceptor interactions occuring within the system PEG/KF/solute were considered.     

Treating ion distribution with Gaussian‐based smooth dielectric function in DelPhi

The standard treatment of ions in the framework of the Poisson–Boltzmann equation relies on molecular surfaces, which are commonly constructed along with the Stern layer. The molecular surface determines where ions can be present. In the Gaussian‐based smooth dielectric function in DelPhi, smooth boundaries between the solute and solvent take the place of molecular surface. Therefore, this invokes the question of how to model mobile ions in the water phase without a definite solute‐solvent boundary. This article reports a natural extension of the Gaussian‐based smooth dielectric function approach that treats mobile ions via Boltzmann distribution with an added desolvation penalty. Thus, ion concentration near macromolecules is governed by the local electrostatic potential and the desolvation penalty (from being partially desolvated). The approach is tested against the experimental salt dependence of binding free energy on 7 protein–protein complexes and 12 DNA–protein complexes, resulting in Pearson correlations of 0.95 and 0.88, respectively. © 2017 Wiley Periodicals, Inc.