Synthesis of a novel tetracationic acidic organic salt based on DABCO and its applications as catalyst in the Knoevenagel condensation reactions in water

Synthesis of a novel tetracationic acidic organic salt based on DABCO containing two sulfonic acid groups in the skeleton and four hydrogensulfate groups as counterion is described. Its catalytic efficiency in the Knoevenagel condensation of aldehydes with active cyclic methylene compounds in water is investigated. While 2,2'-(phenylmethylene)bis(3-hydroxy-5,5-dimethylcyclohex-2-enone) derivatives were obtained in 40–98% isolated yields in the reaction of aldehydes with dimedone, the corresponding Knoevenagel adducts were provided in 85–95% yields using 1,3-dimethylbarbituric acid. In addition, a DABCO-based polycationic organic salt polymer was prepared and characterized for the first time.     

The peridynamic differential operator for solving time-fractional partial differential equations

Nonlinear Dynamics - In this paper, the numerical solution of time-fractional convection diffusion equations (TF-CDEs) is considered as a generalization of classical ones, nonexponential relaxation...     

β-Tetra-brominated meso-tetraphenylporphyrin: A conformational study and application to the Mn-porphyrin catalyzed epoxidation of olefins with tetrabutylammonium oxone

X-ray crystallographic studies have shown that the free base β-tetra-brominated meso-tetraphenylporphyrin (H₂TPPBr₄) has a slightly ruffled structure with the dihedral angles of 70.1–79.2° between the phenyl groups and the porphyrin mean plane. The N(pyrrole)–N(pyrrolenine) distance is very similar to that of the standard planar porphyrins. The decreased N–H bond length of H₂TPPBr₄ with respect to that of meso-tetraphenylporphyrin (H₂TPP) seems to be due to the weaker intramolecular hydrogen bond of the former relative to the latter caused by the electron-withdrawing effects of the β-bromine substituents. The large red shifts of the Soret and Q(0,0) bands of H₂TPPBr₄ in comparison with those of H₂TPP, in spite of the nearly planar porphyrin core of the compound, also may be explained on the basis of the electron-withdrawing effects of the bromine atoms. Oxidation of styrene, the para-substituted derivatives and cyclooctene with tetrabutylammonium oxone in the presence of catalytic amounts of β-tetra-brominated meso-tetraphenylporphyrinatomanganese(III) acetate immediately gives the epoxide as the sole product. Terminal double bonds and unconjugated ones are less reactive than the conjugated double bonds and show lower selectivities. Catalytic activity of the electron-deficient Mn(H₂TPPBr₄)OAc dramatically depends on the Co-catalytic activity of the nitrogen donors as the axial base. The best axial bases are the nitrogenous donors with mixed σ- and π-donor ability to the metal centre.     

Poly(<Emphasis Type="Italic">n</Emphasis>-octyl methacrylate) viscosity index improver: Kinetic study via on-line <Superscript>1</Superscript>H-NMR technique

The free radical solution polymerization of n-octyl methacrylate has been studied in benzene-d ₆ in the presence of 2,2′-azobisisobutyronitrile as thermal initiator. An on-line nuclear magnetic resonance spectroscopy was applied to record the reaction data and to determine the monomer conversion at different times during the polymerization reaction. Effect of monomer and initiator concentration as well as reaction temperature on polymerization rate was studied. The order of the reaction with respect to initiator (0.45) was consistent with the classical kinetic rate equation, while the order of reaction with respect to monomer (1.87) was much greater than unity. An overall activation energy (E _a = 53.8 kJ/mol) was obtained over the temperature range 328?338 K. Also, the efficiency of the synthesized poly(n-octyl methacrylate) for improving the viscosity index of the lube oil was investigated.     

A green non-acid-catalyzed process for direct N=N–C group formation: comprehensive study,modeling, and optimization

The aim of this work is to introduce, model, and optimize a new non-acid-catalyzed system for a direct N\(=\)N–C bond formation. By reacting naphthols or phenol with anilines in the presence of the sodium nitrite as nitrosonium (\(\hbox {NO}^{+})\) source and triethylammonium acetate (TEAA), a N\(=\)N–C group can be formed in non-acid media. Modeling and optimization of the reaction conditions were investigated by response surface method. Sodium nitrite, TEAA, and water were chosen as variables, and reaction yield was also monitored. Analysis of variance indicates that a second-order polynomial model with F value of 35.7, a P value of 0.0001, and regression coefficient of 0.93 is able to predict the response. Based on the model, the optimum process conditions were introduced as 2.2 mmol sodium nitrite, 2.2 mL of TEAA, and 0.5 mL \(\hbox {H}_{2}\hbox {O}\) at room temperature. A quadratic (second-order) polynomial model, by analysis of variance, was able to predict the response for a direct N=N–C group formation. Predicted response values were in good agreement with the experimental values. Electrochemistry studies were done to introduce new Michael acceptor moieties. Broad scope, high yields, short reaction time, and mild conditions are some advantages of the presented method.     

Effect of second monomer and initiator type, mixing method, and stabilizer content on the shape of the particles produced by seeded dispersion polymerization in the presence of saturated hydrocarbon droplets

In this work, the preparation of micron-sized polymer particles with nonspherical shapes via seeded dispersion polymerization of 2-ethylhexyl methacrylate with polystyrene seed particles in the presence of hydrocarbon droplets and evaporation of hydrocarbon after the polymerization under various polymerization conditions was discussed. The effect of second monomer and initiator type, mixing method, and stabilizer content on the shape of the obtained particles was investigated. It was observed that particles with more nonspherical shapes were obtained with increasing the alkyl chain length of ester group of the methacrylate of the second monomer which is because of increasing the absorption amounts of hydrocarbon by second polymer domains. Moreover, the experimental results showed that shape of the particles which was produced by shaking is more nonspherical than the shape of the particles which was obtained from tumbling. Furthermore, particles with different nonspherical shapes were prepared by changing the initiator type and stabilizer content.     

Sonochemical syntheses of a nano-sized copper(II) supramolecule as a precursor for the synthesis of copper(II) oxide nanoparticles

Nanoparticles of a three-dimensional supramolecular, [Cu(L)₂(H₂O)₂] (1), (L⁻ = 1H-1,2,4-triazole-3-carboxylate), have been synthesized by a sonochemical process and characterized by scanning electron microscopy, X-ray powder diffraction, IR spectroscopy and elemental analyses. The thermal stability of compound 1 both its bulk and nano-size has been studied by thermal gravimetric (TG) and differential thermal analyses (DTA) and compared each other. Concentration of initial reagents effects on size and morphology of nano-structured compound 1, have been studied. Calcination of the nano-sized compound 1 at 600 °C under air atmosphere yields CuO nanoparticles.     

Application of Monte Carlo simulation method to polymerization kinetics over Ziegler–Natta catalysts

In the current work, the Monte Carlo simulation method was applied to ethylene polymerization over Ziegler–Natta catalysts. As expected, polymerization over each center of a Ziegler–Natta catalyst leads to a polymer having a Schultz–Flory molecular weight distribution. Notwithstanding, the total molecular weight distribution obtained by all catalyst centers together is at least twice as broad as that of each center. As another interesting finding, the introduction of hydrogen to the reaction deactivates the catalyst active centers and thereby reduces the catalyst activity. Nevertheless, it does not mainly affect the polymerization kinetics. In addition, the polymer molecular weight falls as hydrogen is added to the reaction since it acts as a strong transfer agent. The same effect is seen when cocatalyst concentration increases. Hydrogen also widens the polymer molecular weight distribution. © 2008 Wiley Periodicals, Inc. Int J Chem Kinet 41: 45–56, 2009     

Simulation of styrene free radical polymerization over bi-functional initiators using Monte Carlo simulation method and comparison with mono-functional initiators

In the present study, based on a complete mechanism, a Monte Carlo simulation method is employed to investigate the kinetics of styrene free radical polymerization over bi-functional initiators in a bulk medium. The effects of the concentration of initiator and the monomer, of the temperature on monomer conversion, average molecular weights, polydispersity index, and molecular weight distribution are inspected and compared with mono-functional initiators. According to the simulation results, an increase in either the concentration of initiator or the temperature leads to the rise of the monomer conversion and to the reduction of the average molecular weights, while the increase of the monomer concentration results in the rise of both monomer conversion and molecular weights, which is in accord with predictions of the theory of free-radical polymerization. In addition, application of bi-functional initiators increases both monomer conversion and average molecular weight and results in narrower chain length distributions.