The substitution effect on heavy versions of cyclobutadiene

The structural and electronic characteristics of the M₄R₄ with M = C, Si, Ge and R = H, F, Cl, OH, MgH, BH₂, NH₂ Li are studied by ab initio calculations based on density functional theory using the hybrid B3LYP functional and 6‐311++G* basis set. The results of natural bond orbital analysis (NBO), the analysis of structural parameters (bond lengths and bond angle, dihedral angle), atoms in molecules based theory (AIM) topological parameters such as the characteristics of bond critical points (electron densities and their Laplacians) leads to the conclusion that interamolecular interaction due with OH, MgH₂, and NH₂ substitutions are different from other derivatives. The cyclobutadiene ring and its heavy versions display very different geometrical structures. The cations and anions of C₄R₄, Si₄R₄, and Ge₄R₄ were studied to determine the effect of substitution on structure and stability. It has been shown that substitutions with ability of forming hydrogen bonds, bound to the silicon and germanium atoms are able to change the properties of the four‐member rings more than the other substitutions. Comprehensive analyses of calculated NICS (nucleus‐independent chemical shifts), polarizability, electrophilicity, and electron density are done. © 2009 Wiley Periodicals, Inc. Int J Quantum Chem, 2010     

Anion‐binding properties of two calix[4]arene derivatives containing two ferrocene imine or ferrocene amine units at the upper rim

Calix[4]arene derivatives containing ferrocene units at the upper rim have been synthesized and their anion‐binding and sensing investigated towards anions such as chloride, bromide and hydrogen sulfate by cyclic voltammetry. Electrochemical studies show that these redox‐active ligands electrochemically recognize chloride and bromide anions. These compounds have excellent selectivity for chloride and bromide ions, in the comparison with hydrogen sulfate anion. With ferrocenyl Schiff base calix[4]arene 1 an anodic shift as large as 302 mV is observed on addition of four equivalents of Cl⁻ anion. Also electrochemical and UV–vis spectroscopic titrations ferrocenyl calix[4]arene derivatives 1 with chloride and bromide ions and 2 (only with Cl⁻) indicate a 1:1 binding‐stiochiometry. Copyright © 2011 John Wiley & Sons, Ltd.     

Solvent-Free Synthesis of 2-Amino-3-aryl-5-substituted Thiophenes as Anti-inflammatory Agents using KF-Al2O3 under Microwave Irradiation

The synthesis of 2-amino-3-aryl-5-substituted thiophenes as anti-inflammatory agents catalyzed by KF-Al₂O₃ under microwave irradiation is reported.     

Solvent-free synthesis of penta-substituted pyrroles: one-pot reaction of amine, alkyl acetoacetate, and fumaryl chloride

A novel, convenient, and efficient approach to the synthesis of penta-substituted pyrroles has been reported based on the multicomponent reaction. Solvent-free condition for the formation of enaminones from primary amines and alkyl acetoacetates and it's reaction with fumaryl chloride lead to the formation of pyrroles that have halide, CH₂CO₂H, ester functional groups, and two alkyl substitutions.     

Combined hollow fiber-based liquid-liquid-liquid microextraction and in-situ differential pulse voltammetry to improve selectivity, sensitivity, and interference elimination in electrochemical analysis

In this paper, a combined hollow fiber-based liquid three-phase microextraction and voltammetric method are applied for the first time as a highly selective and sensitive method of electrochemical analysis. Desipramine, used as a model compound was extracted from 8 mL aqueous solution (donor phase, 0.10 mol L⁻¹ NaOH) through a thin phase of propyl benzoate inside the pores of a polypropylene hollow fiber and finally into a 10 μL acidic acceptor solution inside the hollow fiber. Three microelectrodes designed and constructed for the purposes of this study were placed into the two ends of the hollow fiber inside the acceptor solution, and voltammetric analysis was performed in-situ during the extraction. After 15 min, the final stable signal was used for analytical applications. Under the optimized conditions, an enrichment factor of 301 was achieved and the relative standard deviation (R.S.D.) of the method was 6.2% (n = 5). The calibration curve was obtained in the range of 5-5000 nmol L⁻¹ with a reasonable linearity (R² > 0.988) and the limit of detection (LOD) was found to be 0.8 nmol L⁻¹. Finally, the applicability of the proposed method was evaluated by extraction and determination of desipramine in plasma and urine samples without any dilutions.     

Chemical composition of the essential oil of aerial parts of Haussknechtia elymaitica Boiss. from Iran: a good natural source for trans-asaron

The chemical composition of the essential oil of Haussknechtia elymaitica Boiss. was investigated by capillary GC and GC/MS for the first time. Twelve components were identified which accounting for 99.7% of the oil composition. The major compounds were trans-asarone (59.9%), trans-methyl isoeugenol (22.4%), α-zingiberene (7.96%), β-sesquiphellandrene (4.7%) and β-bisabolene (4.3%). The first three compounds considered as the main components of the essential oil were isolated and characterised by spectroscopic techniques.