Interactions of polar hydrogen bond donor solvents with ions: a theoretical study

Structural Chemistry - Intermolecular interactions between molecules of protic solvents (water, methanol, formic acid, formamide, methylamine and ammonia) and monatomic ions (Li+, Na+, K+,...     

Copper Causes Regiospecific Formation of C4F8‐Containing Six‐Membered Rings and their Defluorination/Aromatization to C4F4‐Containing Rings in Triphenylene/1,4‐C4F8I2 Reactions

The presence of Cu in reactions of triphenylene (TRPH) and 1,4‐C₄F₈I₂ at 360 °C led to regiospecific substitution of TRPH ortho C(β) atoms to form C₄F₈‐containing rings, completely suppressing substitution on C(α) atoms. In addition, Cu caused selective reductive‐defluorination/aromatization (RD/A) to form C₄F₄‐containing aromatic rings. Without Cu, the reactions of TRPH and 1,4‐C₄F₈I₂ were not regiospecific and no RD/A was observed. These results, supported by DFT calculations, are the first examples of Cu‐promoted 1) regiospecific perfluoroannulation, 2) preparative C?F activation, and 3) RD/A. HPLC‐purified products were characterized by X‐ray diffraction, low‐temperature PES, and ¹H/¹⁹F NMR.     

Influence of inert components on the formation of conducting channels in ion-exchange membranes

In this work, the results of investigation of the influence of inert binder and reinforcing fabric on structural organization and mechanism of current transfer in homogeneous and heterogeneous ion-exchange membranes are presented by theoretical analysis of parameters of the extended three-wire conductivity model. It was established that analogy in reorganization of the current paths takes place in the course of inclusion of the reinforcing fabric in perfluorinated membranes and addition of polyethylene and nylon 6 to ion-exchange resins during preparation of heterogeneous membranes. In comparison with perfluorinated membranes, the essential difference in conducting properties of heterogeneous membranes is the opportunity for the current transfer via the channel filled with equilibrium solution. The size of this channel decreases with increase in the volume fraction of the inert component inside the membrane.     

Evolution of synthetic routes towards homochiral Tapentadol

Analysis of the literature shows that the development of synthetic approaches to Tapentadol, an agonist of the μ-opioid receptor and norepinephrine reuptake inhibitor, has followed four, partially overlapping, phases. The most advanced approaches, based on stereoselective syntheses, appeared only after 2010. The majority of the chemistry examples presented in this review come from patent applications and as such have not been subjected to rigorous peer review, but may serve well as an inspiration to organic chemists for solving analogous synthetic problems.     

A comparison of numerical and analytical radiative-transfer solutions for plane albedo of natural waters

Several numerical and analytical solutions of the radiative transfer equation (RTE) were compared for plane albedo in a problem of solar light reflection by sea water. The study incorporated the simplest case—a semi-infinite one-dimensional plane—parallel absorbing and scattering homogeneous layer illuminated by a monodirectional light beam. Inelastic processes (such as Raman scattering and fluorescence), polarization and air-water surface refraction-reflection effects, were not considered. Algorithms were based on the invariant imbedding method and two different variants of the discrete ordinate method (DOM). Calculations were performed using parameters across all possible ranges (single-scattering albedo ω₀ and refracted solar zenith angle θ₁), but with a special emphasis on natural waters. All computations were made for two scattering phase functions, which included an almost isotropic Rayleigh phase function and strongly anisotropic double-peaked Fournier-Forand-Mobley phase function. Models were validated using quasi-single-scattering (QSSA) and exponential approximations, which represent the extreme cases of ω₀→0 and ω₀→1, respectively. All methods yielded relative differences within 1.8% for modeled natural waters. An analysis of plane albedo behavior resulted in the development of a new extended QSSA approximation, which when applied in conjunction with the extended Hapke approximation developed earlier, resulted in a maximum relative error of 2.7%. The study results demonstrated that for practical applications, the estimation of inherent optical properties from observed reflectance can best be achieved using an extended Hapke approximation.     

Novel Effectively Carbonaceous and Sulfurated Hydrogen Corrosion Inhibitors on the Basis of Organosulfurphosphorus Compounds

Abstract

Novel ammonium salts of O,O-dialkyl dithiophosphoric acids were obtained by one-pot synthesis from white phosphorus, elemental sulfur, industrial alcohols or phenols, and amines. Long-chain S-alkyl O,O-dialkyldithiophosphonates were prepared by the reaction of red phosphorus with elemental sulfur, alcohols, and the cheap industrial fractions of С₁₆–С₁₈ and С₂₀–С₂₆ of higher α-olefins in the presence of Lewis acid catalyst. The dithiophosphates obtained possess the high anticorrosion activities toward mild steel.     

Study of “Racemic Compound-Like” Behavior of Diastereomeric Mixture of Pinanyl Sulfoxides by X-Ray Diffraction,IR Spectroscopy,and DFT Calculations

Abstract

The oxidation of a β-hydroxysulfide in the pinane series by use of m-chloroperbenzoic acid resulted in the formation of the corresponding β-hydroxysulfoxide as a mixture of two diastereomers in 4:5 ratio. According to single-crystal X-ray diffraction (XRD) results, it is established that the diastereomeric mixture of sulfoxides crystallizes in the “racemic compound-like” manner under formation of asymmetric dimers through S=O··H–O interactions. This asymmetric dimer formed from diastereomeric molecules is a structural unit in both crystal modifications, the triclinic and the monoclinic one. The behavior of the diastereomeric mixture of pinane derived sulfoxides in crystals, melts and in tetrachloromethane solutions was studied by IR spectroscopy. The density functional theory (DFT) method with 6-31G (d, p) basis set was used to calculate the optimized geometrical parameters and vibrational frequencies of different associates in solutions. The calculated vibrational frequencies are compared with experimental IR spectra.