An Ab Initio Study and NBO Analysis of the Stability and Conformational Properties of Hexakis(trimethylelementhyl)benzene (Element = C,Si, Ge,and Sn)

Ab initio molecular orbital and density functional theory were used to investigate energetic and structural properties of the various conformations of hexa-tertbutylbenzene (1), hexakis(trimethylsilyl)benzene (2), hexakis (trimethylgermyl)benzene (3), and hexakis(trimethylstannyl)benzene (4). HF/3-21G//HF/3-21G and B3LYP/3-21G//HF/3-21G results revealed that the Twist-Boat (TB) conformer of compound 1 is more stable than the 1-Chair (C), 1-Boat (B), and 1-Planar (P) conformers. B3LYP/3-21G//HF/3-21G results show that the 1- TB conformer is more stable than 1- C, 1- B, and 1- P conformers of about 1.13, 4.34, and 99.94 kcal mol^?1 , respectively. Contrary to the stability order of compound 1 conformers, the C conformer of compounds 2–4 is more stable than TB, B, and P conformations, as calculated by B3LYP/3-21G//HF/3-21G and HF/3-21G//HF/3-21G levels of theory. The energy gap between the C and P conformers in compounds 1–4 is decreased in the following order: ΔE(4: C, P) < ΔE (3: C, P) < ΔE(2: C, P) < ΔE (1: C, P). This fact can be explained in terms of the increase of C _aromatic -M (M═C, Si, Ge, and Sn) bond lengths and the decrease of steric (van der Waals) repulsions in the previously discussed compounds. For compounds 1–3, the calculations were also performed at the B3LYP/ 6-31G*//HF/3-21G level of theory. However, the comparison showed that the results at B3LYP/3-21G//HF/3-21G methods correlated well with those obtained at the B3LYP/6-31G*// HF/6-31G method. Further, NBO analysis revealed that in compounds 1–4, the resonance energy associated with the σ_M-C1 to σ*_C2-C3 delocalization is 5.20, 9.68, 11.15, and 12.27 kcal mol^?1, respectively. These resonance energy values could explain the easiness of the ring flipping processes of C, B, and TB conformers of compounds 4 to 1. Also, the NBO results showed that by an increase of the σ_M-C1 → σ *_C2-C3 resonance energies in compounds 1–4, the σ_M-C1 bonding orbital occupancies decrease. This fact could fairly explain the increase of the C_aryl-M bond length from compound 1 to 4. The NBO results are also in good agreement with the calculated energy barriers for the ring flipping of the chair conformations in compounds 1–4, as calculated by B3LYP and HF methods.     

Synthesis and Inhibitory Activity Against Epstein-Barr Virus of Some New 1,2,3,4-Tetrahydropyrimidine-2-thiones

1,2,3,4-Tetrahydropyrimidine-2-thiones 4a–n were synthesized through the reaction of aromatic aldehydes 1a–n , ethyl acetoacetate (2) and thiourea ( 3) . The structures of all newly synthesized heterocyclic compounds elucidated by the use of IR, ¹H NMR, mass spectra, and elemental analyses. The inhibitory activity against the Epstein-Barr Virus early antigen (EBA-VA) of all newly synthesized heterocyclic compounds were evaluated.     

A Simple and Highly Efficient One-Pot Procedure for the Synthesis of Amides via Beckmann Rearrangements Using 1-Tosylimidazole (TsIm)

A facile and highly efficient method for one-pot Beckmann rearrangement of ketoximes into N-substituted amides using N-(p-toluenesulfonyl)imidazole (TsIm) is described. In this method, ketoximes are refluxed with TsIm and Cs₂CO₃ in the presence of SiO₂ as a recyclable catalyst in DMF affording the corresponding amides in high yields. This methodology is highly efficient and regioselective for various structurally diverse ketoximes including symmetrical and unsymmetrical as well as cyclic oximes. The results of quantum mechanical studies used to rationalize the experimental outcomes are discussed.     

Impact of Geometric Parameters,Charge, and Lipophilicity on Bioactivity of Armed Quinoxaline,Benzothiaole, and Benzothiazine: Pom Analyses of Antibacterial and Antifungal Activity

Abstract

A series of four different armed heterocyclic candidates; 1-(2-methyl-2,3-dihydro-1,3-benzothiazol-2-yl)acetone (2), 1-(3-methyl-4H-1,4-benzothiazin-2-yl)ethanone (3), 2-[(2-aminophenyl)dithio]aniline (4), and 3-hydroxy-3-methyl-4-(3-methyl-2-quinoxalinyl)-2-butanone (5) have been prepared and their microbial activities were evaluated. A correlation of the structure and activities relationships of these compounds with respect to molecular modeling, Lipinski Rule of Five, drug likeness, toxicity profiles, and other physico-chemical properties of drugs are described and verified experimentally.     

Spectral and Thermal Studies of Some New Metal Complexes Derived from N-[(Phenylamino)Thioxomethyl] Hydrazinocarbonyl Methyl Pyridinium Chloride (PTHMPC)

New metal complexes derived from the reaction of N-[(phenylamino)thioxomethyl] hydrazino carbonyl methyl pyridinium chloride (H₂L; PTHMPC) with some metal salts of the general formula MX₂ [(X = Cl^? and/or CH₃COO^?; M = Cd(II), UO₂(II), Mn(II) and Zr(IV)] were synthesized and characterized by elemental analyses, spectral analyses (IR, UV-vis., ¹H NMR), thermal analyses (TGA, DTG), and conductance and magnetic measurements. The results showed that the ligand exists in metal complexes either in the keto form or in the enol form. Moreover, the IR spectral data suggest that the acetate ion behaves in a monodentate manner. Semi-empirical calculations ZINDO/1, PM3, and AM1 have been used to study the molecular geometry and the harmonic vibrational spectra of the ligand and its metal complexes with the purpose of assisting the experimental assignment of the complexes. Generally, there is an agreement between the observed and the calculated spectra. Finally, the thermodynamic parameters (ΔE*, ΔH, ΔG, and ΔS) have been calculated from the data of thermal analyses (TGA and DTG).

Supplemental materials are available for this article. Go to the publisher's online edition of Phosphorus, Sulfur, and Silicon and the Related Elements to view the free supplemental file.     

Synthesis and Characterization of Organosoluble Poly(imide-ether)s with Bulky 2,3-Diaryl Imidazole Moiety: Study Physical,Thermal and Optical Properties

Two new symmetrical diamines were designed and synthesized having different functional groups such as a pair of phenyl ether linkages, 2,3-diaryl substituted imidazole rings and CF₃ groups as pendant, and characterized by FT-IR, ¹H and ¹³C-NMR spectroscopy and elemental analysis. A series of new fluorescent poly(imide-ether)s (PIEs) was prepared by polymerization of the diamines with commercial tetracarboxylic dianhydrides such as pyromellitic dianhydride and 3,3′,4,4′-benzophenone tetracarboxylic dianhydride. The resulting PIEs were amorphous and had intrinsic viscosity [η] in the range of 0.42–0.51 dL/g. The weight average molecular weights (Mw) of these polymers were measured by GPC and were in the range of 28658–35595 g/mol with molecular weight distribution (MWD) of 2.12–2.27. These polymers were readily soluble in a variety of organic solvents and formed low-colored and flexible thin films with cut-off wavelength (λ₀) in the range of 385–420 nm, and all PIEs films exhibited high optical transparency. They also possessed good thermal stability with 10% weight loss temperatures (T_10%) in the range 486–537°C in N₂. The glass transition temperatures (T_g) of PIEs are in the range 251–324°C. These polymers showed fluorescence emission in film and in solution at 459–476 nm with the quantum yields in the range 4–12%.     

Chlorine‐Enhanced Surface Mobility of Au(100)

Motivated by experimental studies of two‐dimensional Ostwald ripening on Au(100) electrodes in chlorine‐containing electrolytes, we have studied diffusion processes using density functional theory. We find that chlorine has a propensity to temporary form AuCl complexes, which diffuse significantly faster than gold adatoms. With and without chlorine, the lowest activation energy is found for the exchange mechanism. Chlorine furthermore reduces the activation energy for the detachment from kink sites. Kinetic Monte Carlo simulations were performed on the basis of extensive density functional theory calculations. The island‐decay rate obtained from these Monte Carlo simulations, as well as the decay rate obtained from the theoretical activation energies and frequency factors when inserted into analytical solutions for Ostwald ripening, are in agreement with experimental island‐decay rates in chlorine‐containing electrolytes.     

Efficient imidazolium salts for palladium-catalyzed Mizoroki-Heck and Suzuki-Miyaura cross-coupling reactions

The system, Pd(OAc)2/imidazolium salts (L2), was found as an efficient catalyst in the Heck coupling reaction of olefins with aryl halides and Suzuki reactions of various aryl halides with aryl boronic acids under aerobic condition. This catalytic system demonstrates great tolerance to a wide range of groups on all substrates of aryl halides, alkenes and aryl boronic acids.     

An efficient one-pot multi-component synthesis of 3,4,5-substituted furan-2(5H)-ones catalyzed by tetra-n-butylammonium bisulfate

A facile one-pot synthesis of 3,4,5-substituted furan-2(5H)-one derivatives from a three-component reaction of aniline derivatives, dialkylacetylenedicarboxylates and aromatic aldehydes under mild conditions using tetra-n-butylammonium bisulfate as a catalyst has been developed.     

Determination of Trichloroacetic Acid (TCAA) Using CdO Nanoparticles Modified Carbon Paste Electrode

In this paper, the electrochemical behavior of a carbon paste electrode modified with CdO nanoparticles as a potential electrocatalyst for the reduction of trichloroacetic acid (TCAA) was investigated using cyclic voltammetry and double‐potential step chronoamperometry. The modified electrode showed a great enhancement in cathodic peak current with respect to reduction of TCAA in acidic aqueous solution. Using this increment, a quantitative method was developed for the determination of TCAA in aqueous solution. The detection limit and linear dynamic range of TCAA are 2.3×10^?6 M and 2.3×10^?4–3×10^?6 M, respectively.