Why to synthesize vaterite polymorph of calcium carbonate on the cellulose matrix via sonochemistry process?

Vaterite is an important biomedical material due to its features such as high specific surface area, high solubility, high dispersion, and small specific gravity. The purposes of this article were to explore the growth mechanism of vaterite on the cellulose matrix via sonochmistry process. In the work reported herein, the influences of experimental parameters on the polymorph of calcium carbonate were investigated in detail. The calcium carbonate crystals on the cellulose matrix were characterized by means of X-ray diffraction (XRD), Fourier transform infrared spectroscopy (FTIR), and scanning electron microscopy (SEM). Experimental results revealed that all the reactants, solvent, and synthesis method played an important role in the polymorph of calcium carbonate. The pure phase of vaterite polymorph was obtained using Na₂CO₃ as reactant in ethylene glycol on the cellulose matrix via sonochmistry process. Based on the experimental results, one can conclude that the synthesis of vaterite polymorph is a system process.     

CuNaY分子筛的制备及其催化甲醇氧化羰基化

采用多种铜盐溶液与NaY分子筛离子交换制备了CuNaY催化剂,通过加入氨水提高溶液pH值以及高温活化,显著提高了该催化剂对甲醇氧化羰基化合成碳酸二甲酯的反应活性。不同的铜盐水溶液交换制备的CuNaY催化剂催化活性不同,添加氨水将溶液pH值调节为11后,离子交换制备的CuNaY催化剂的催化活性和DMC选择性明显升高且趋于一致。经元素分析、XRD、XPS和H₂-TPR表征可知,加入氨水可促进Cu²⁺离子交换的进行,提高CuNaY催化剂中Cu的交换量,催化剂中约75%的Cu²⁺定位于分子筛的超笼中。     

CONDENSATION REACTION OF 1-OXO-4-CHLOROCARBONYL-1-PHOSPHA-2,6,7-TRIOXABICYCLO[2.2.2]OCTANE WITH N-t-BUTYL-N-BENZOYLHYDRAZINE

Abstract

1-Oxo-4-chlorocarbony1-1-phospha-2,6,7-trioxabicyclo[2.2.2]octane (5) was obtained from phosphorus oxychloride. Benzyl chloroformate was synthesized by the reaction of benzyl alcohol and triphosgene in good yield for the first time. N-r-Butyl-N-benzoylhydrazine(II) was prepared in a new and convenivent procedure with good yield. The reaction of 5 and II proceeded smoothly in the presence of sodium carbonate and afforded the desired compound 13 in good yield, while in the presence of triethylamine, the elimination of butyl was observed and afforded the compound 12.     

Polyethylene Glycol–Enhanced Chemoselective Synthesis of Organic Carbamates from Amines,CO2, and Alkyl Halides

An efficient and environmentally benign method for the synthesis of organic carbamates was developed. Amines, CO₂, and alkyl halides underwent a three-component reaction with the aid of K₂CO₃ and polyethylene glycol (PEG, MW = 400), affording the organic carbamates under ambient conditions. PEG could presumably act as a solvent and phase-transfer catalyst (PTC). Notably, the presence of PEG could also depress the alkylation of both the amine and the carbamate, thus resulting in enhanced selectivity toward the target carbamate.

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Reduced odd–even effects in liquid crystalline carbonate dimers: molecular field analysis

Four liquid crystalline carbonate dimers DCn containing the dimethylbenzalazine mesogen, bis(oxycarbonyloxy)alkane flexible spacers with three to six methylene units and acetate terminal groups were synthesised and their mesogenic behaviour investigated. As compared with the corresponding ester dimers a strong reduction of odd–even fluctuations of nematic–isotropic (N–I) transition entropy is observed. A theoretical analysis of the dimers within the rotational isomeric states (RIS) mean-field approach is also reported. A satisfying agreement between calculated and observed thermodynamic properties is obtained. In fact, the theoretical analysis correctly predicts a significant reduction of the odd–even fluctuations for the core order parameter S as well as for the nematic to isotropic transition entropy △S_NI . The calculated distributions of conformers also show reduced differences between even and odd members. In particular, for even dimers the calculated fraction of linear extended conformers in the nematic phase at the N–I transition is around 27%, which is far below that of the corresponding ester dimers (46%).     

微秒脉冲下极性效应对碳酸丙烯酯击穿场强的影响

通过对比碳酸丙烯酯在针板电极间距分别为0.5、1.0和2.0 mm下的击穿电压大小的实验,研究碳酸丙烯酯的极性效应.实验设备包含一个充电时间在5～20毫秒的电容储能型脉冲型脉冲功率源和一个内置针板电极的击穿试件. 每一组的击穿电压通过示波器显示记录. 三组不同间距下的击穿实验数据表明碳酸丙烯酯的正电极击穿场强高于负电极击穿场强,并且击穿场强随着电极间距的增大而增 大. 对碳酸丙烯酯针板电极的击穿进行了仿真模拟实验. 基于实验结果对碳酸丙烯酯的极性效应给出了相应的解释.     

Phase‐controlled crystallization of amorphous calcium carbonate in ethanol‐water binary solvents

The evolution of amorphous calcium carbonate (ACC) into crystals in ethanol/water binary solvents under ambient temperature was investigated, and it was found to depend on the volume ratio of ethanol to water (R). Calcite remained dominant when the amount of water was high (R = 1/3). A slight change in the amount of ethanol (R = 3/1) could lead to a dramatic change in the polymorph from calcite to aragonite. However, when poly (allylamine hydrochloride) (PAH) was added at R = 3/1, almost pure vaterite could be obtained, which has a specific morphological variation (from hollow microspheres to cloud‐like). This study provides an alternative polymorphic route for the CaCO₃ mineral by using the evolution of ACC in different solvent environments, which provides some useful clues for understanding the importance of kinetic control of the morphologies and polymorphs of a wide range of inorganic materials. In addition, this simple mild phase‐controlled synthetic method could be scaled up as a green chemistry route for the industrial production of different polymorphs of CaCO₃.     

Influence of ion-exchange and impregnation modification of zeolite X on its catalytic properties in the alkylation of toluene with methanol

The dependence of the activity and selectivity of ion-exchanged forms of zeolite X with incorporated cesium process in alkylation of toluene with methanol in the side chain on the nature of the ion-exchanged cations (Na⁺, Cs⁺, Mg²⁺, Zn²⁺) has been established. It is shown that introduction of Mg²⁺ and Zn²⁺ in combination with Cs₂CO₃ significantly increased the yields of ethylbenzene and styrene in comparison with their yields on alkali forms of zeolite X. __________ Translated from Teoreticheskaya i éksperimental’naya Khimiya, Vol. 42, No. 1, pp. 33–38, January–February, 2006.     

Rare earth‐doped calcium‐based magnetic catalysts for transesterification of glycerol to glycerol carbonate

Several rare earth‐doped, calcium‐based magnetic catalysts were prepared for the synthesis of glycerol carbonate. The basicity and basic strength analysis of the catalysts showed that the doping of rare earth improved the basicity of the catalysts, and the doping of lanthanum maximized it. In addition, with the doping of lanthanum, the particle size of the catalyst became smaller to promote the organic reactants near the active sites of catalysts, thereby effectively improving the performance. NiFe₂O₄@[CaO‐La₂O₃] shows better catalytic performance with 99.0% yield of glycerol carbonate compared to the other catalysts. The NiFe₂O₄@(CaO‐La₂O₃) could be reused in six cycles without significant loss in activity.     

Synthesis of Polyanionic Cellulose Carbamates by Homogeneous Aminolysis in an Ionic Liquid/DMF Medium

Polyanionic cellulose carbamates were synthesized by rapid and efficient homogeneous aminolysis of cellulose carbonate half-esters in an ionic liquid/DMF medium. Cellulose bis-2,3-O-(3,5-dimethylphenyl carbamate), as a model compound, reacted with different chloroformates to cellulose carbonates. These intermediates were subjected to aminolysis, for which both the reactivity of different chloroformates towards C6-OH and the reactivity/suitability of the respective carbonate half-ester in the aminolysis were comprehensively studied. Phenyl chloroformate and 4-chlorophenyl chloroformate readily reacted with C6-OH of the model cellulose derivative, while 4-nitrophenyl chloroformate did not. The intermediate 4-chlorophenyl carbonate derivative with the highest DS (1.05) was then used to evaluate different aminolysis pathways, applying three different amines (propargyl amine, β-alanine, and taurine) as reactants. The latter two zwitterionic compounds are only sparingly soluble in pure DMF as the typical reaction medium for aminolysis; therefore, several alternative procedures were suggested, carefully evaluated, and critically compared. Solubility problems with β-alanine and taurine were overcome by the binary solvent system DMF/[EMIM]OAc (1:1, v/v), which was shown to be a promising medium for rapid and efficient homogeneous aminolysis and for the preparation of the corresponding cellulose carbamate derivatives or other compounds that are not accessible by conventional isocyanate chemistry. The zwitterionic cellulose carbamate derivatives presented in this work could be promising chiral cation exchangers for HPLC enantiomer separations.