Efficient Synthesis of 4H-Pyran and Spiro-Oxindole Derivatives Based on Al2O3/V2O5 Nanocomposite as Catalyst

Russian Journal of Organic Chemistry - A simple and eco-friendly catalytic alternative has been proposed for one-pot three-component synthesis of 4H-pyrane and spiro-oxindole derivatives, as two...     

A new molecularly imprinted polymer for selective extraction and pre‐concentration of guaifenesin in different samples: Adsorption studies and kinetic modeling

This paper describes the synthesis of a molecularly imprinted polymer by chemical oxidation of pyrrole as the functional monomer, and at the presence of guaifenesin as the template. The prepared polymer was used as adsorbent in molecularly imprinted solid‐phase extraction followed by spectrophotometric determination. Different parameters in the solid‐phase extraction including sample pH, adsorbent weight, washing solution, and elution solvent were studied to determine optimum conditions for isolation and enrichment of guaifenesin. The results showed guaifenesin was quantitatively adsorbed on the molecularly imprinted polymer at pH 6.0 and completely eluted with an ethanol–water solution (50% v/v). An enrichment factor of four with satisfactory recoveries (87.0–95.0%) was obtained. The solid‐phase extraction columns could be used for up to six consecutive elution‐loading cycles without significant decreases in the analyte recoveries. The method had a dynamic range of 3.0 × 10^?6–1.5 × 10^?4 mol/L with a limit of detection and limit of quantification of 1.4×10^?6 and 4.5×10^?6 mol/L, respectively. The proposed procedure was used for the extraction and determination of guaifenesin in different pharmaceutical formulations, with satisfying results being achieved.     

Reinvestigation of intramolecular hydrogen bond in malonaldehyde derivatives: An ab initio,AIM and NBO study

The RAHB systems in malonaldehyde and its derivatives at MP2/ 6‐311++G(d,p) level of theory were studied and their intramolecular hydrogen bond energies by using the related rotamers method was obtained. The topological properties of electron density distribution in O? H···O intramolecular hydrogen bond have been analyzed in term of quantum theory of atoms in molecules (QTAIM). Correlations between the H‐bond strength and topological parameters are probed. The results of QTAIM clearly showed that the linear correlation between the electron density distribution at HB critical point and RAHB ring critical point with the corresponding hydrogen bond energies was obtained. Moreover, it was found a linear correlation between the electronic potential energy density, V(r_cp), and hydrogen bond energy which can be used as a simple equation for evaluation of HB energy in complex RAHB systems. Finally, the similar linear treatment between the geometrical parameters, such as O···O or O? H distance, and Lp(O)→σ*_OH charge transfer energy with the intramolecular hydrogen bond energy is observed. © 2010 Wiley Periodicals, Inc., Int J Quantum Chem, 2011     

N?H···S and S?H···N intramolecular hydrogen bond in β‐thioaminoacrolein: A quantum chemical study

The conformational study of β‐thioaminoacrolein was performed at various theoretical levels, HF, B3LYP, and MP2 with 6‐311++G(d,p) basis set, and the equilibrium conformations were determined. To have more reliable energies, the total energies of all conformers were recomputed at high‐level ab initio methods, G2MP2, G3, and CBS‐QB3. According to these calculations, the intramolecular hydrogen bond is accepted as the origin of conformational preference in thialamine (TAA) and thiolimine groups. The hydrogen bond strength in various resonance‐assisted hydrogen bond systems was evaluated by HB energy, geometrical parameters, topological parameters, and charge transfers corresponding to orbital interactions. Furthermore, our results reveal that the TAA tautomer has extra stability with respect to the other tautomers. The population analyses of the possible conformations by NBO predict that the origin of this preference is mainly due to the π‐electron delocalization in framework of TAA forms, especially usual π_C?C → π*_C?S and Lp (N) → π*_C?C charge transfers. © 2010 Wiley Periodicals, Inc. Int J Quantum Chem, 2011     

Online system identification using fractional-order Hammerstein model with noise cancellation

Slow convergence and low accuracy are two main drawbacks in nonlinear system identification methods. It becomes more complicated when time delay and noises are considered. In this paper, considering a fractional-order Hammerstein model, an online identification method is proposed. A combination of an evolutionary optimization method and recursive least square algorithm is used to estimate the system parameters and orders in the presence of unknown noises. Finally, simulation results are taken to prove the effectiveness of the proposed algorithm.

     

Phase transition and thermodynamic stability in extended phase space and charged Hořava–Lifshitz black holes

For charged black holes in Ho?ava–Lifshitz gravity, a second order phase transition takes place in extended phase space where the cosmological constant is taken as thermodynamic pressure. We relate the second order nature of phase transition to the fact that the phase transition occurs at a sharp temperature and not over a temperature interval. Once we know the continuity of the first derivatives of the Gibbs free energy, we show that all the Ehrenfest equations are readily satisfied. We study the effect of the perturbation of the cosmological constant as well as the perturbation of the electric charge on thermodynamic stability of Ho?ava–Lifshitz black hole. We also use thermodynamic geometry to study phase transition in extended phase space. We investigate the behavior of scalar curvature of Weinhold, Ruppeiner, and Quevedo metric in extended phase space of charged Ho?ava–Lifshitz black holes. It is checked if these curvatures could reproduce the result of specific heat for the phase transition.     

Identification of Damping Characteristic of a Structural Adhesive by Extended Modal Based Direct Model Updating Method

In order to identify damping characteristics (loss factors in bending and shear modes versus frequency) of an adhesive material, modal based direct model updating method used in previous paper (Jahani and Nobari, Exp Mech, 48:2008) is modified here. Two approaches adopted in the identification process. In the first one, the pre identified moduli from undamped model were used in identification of loss factors and in the second approach loss factors and moduli are identified simultaneously. The loss factors of a typical adhesive were identified using both approaches leading to acceptable results in both cases. The results show that loss factors and Young’s and shear moduli of adhesive are frequency dependent. All experiments and subsequent identifications are conducted both in bending and shear modes. The repeatability and consistency of method is proved by repeating the identification process for several times.     

TBHP/R4N+X– promoted hydroaroylation of dialkyl azodicarboxylates with methyl arenes,aldehydes, aryl methanols and arylmethyl chlorides

Efficient TBHP/R₄N⁺X^– promoted hydroaroylations of dialkyl azo-1,2-dicarboxylates with methyl arenes, aldehydes, aryl methanols and arylmethyl chlorides are described. These oxidation/oxygenation and hydroaroylation processes were carried out by tert-butyl hydroperoxide as terminal oxidant/oxygen source, and were catalyzed by tetrabutylammonium bromide and tricaprylmethylammonium chloride as the driving force. During this investigation, all these hydroaroylating sources were found to be highly efficient reagents without the need of any transition-metal.     

One‐pot synthesis of highly functionalized benzo [1,3] thiazine from isocyanides,aniline, and heterocumulene via Cu‐catalyzed intramolecular C‐H activation reactions

A one‐pot synthesis of functionalized benzo thiazine derivatives via a Cu‐catalyzed, multicomponent reaction of isocyanides, aniline, and heterocumulenes in acetonitrile at room temperature was developed. Transition metal‐catalyzed activation of C‐H bonds under mild copper‐catalytic reaction conditions, using simple and available starting materials, also obtaining a pure product with high yield without applying column chromatography are the major advantages of the applied method among the other ones used for this purpose. The structures are confirmed spectroscopically (¹H‐ and ¹³C‐NMR, IR, and EI‐MS) and through elemental analyses.