Acetylenic derivatives of betulonic acid amide as a new type of compounds possessing spasmolytic activity

Efficient and versatile synthetic procedures towards novel derivatives of betulonic acid via Mannich reaction, Sonogashira cross-coupling, and copper(i)-catalyzed 1,3-dipolar cyclo-additions were developed. Introduction of secondary amines (Mannich reaction) into betulonic acid amides led to derivatives possessing marked spasmolytic activity, which is not characteristic of the triterpene fragment.     

Crystal associates of 18-crown-6 and polyfluoro(het)arylenediamines: structure,properties, and selectivity of formation

The new group of objects in crystal engineering, namely, 1 : 1 associates of polyfluoro(het)arylenediamines and 18-crown-6, being supramolecular 1D assemblies, is considered. Diamine isomerism is shown to serve as a design tool for control of the supramolecular architecture, and the nature of the aromatic framework and location and volume of substituents determine linear dimensions of the elementary unit in an assembly. A linear dependence of the enthalpy of melting of co-crystals on the length of the assembly unit is observed in the series of the meta-(het)arylenediamine and 18-crown-6 associates. The effect of selective co-crystallization of polyfluoroarylenediamines with crown ether is used in practice for the isolation of high-purity compounds from mixtures of products of the non-selective amination of basic polyfluoroarenes.     

Interaction of amorphous and crystalline nickel nanoparticles with hydrogen

Nickel nanoparticles were deposited on the surface of highly oriented pyrolytical graphite by laser electrodispersion and precipitation from a solution of reverse micelles. The particles were studied using scanning tunneling microscopy and spectroscopy as well as Auger spectroscopy. The elemental composition of the nanoparticles and specific features of the electronic structure of their surface were determined. Adsorption of molecular hydrogen was also studied.     

Reaction of 2,3-dibromo-3-nitroacrylates with N-amino-N″-nitroguanidine

Russian Journal of Organic Chemistry -     

Identification of hydroxymethylpyrazines using mass spectrometry

Pyrazines are well‐known natural products that are present in bacterial odours and food flavouring agents and are used as insect pheromones. Recently, a number of hydroxymethylpyrazines have been identified as thynnine wasp pheromones and orchid semiochemicals that are essential for pollination in sexually deceptive plants. These compounds are present in low amounts in complex blends, making GC–MS (including high‐resolution techniques) the method of choice for their structure elucidation. We report the EI mass spectra for 14 representative compounds and have found that based on characteristic fragmentations, it is possible to distinguish between different positional isomers of hydroxymethylpyrazines. The presence or absence of either [M ? 17]⁺, [M ? 18]^+· or [M ? 19]⁺ fragment species provides characteristic information to allow the distinction between the different isomers. Considering the importance of pyrazines as a group of bioactive natural products, and the recent findings of biological activity for hydroxymethylpyrazines, our results presented here will aid the identification of these compounds in other biological systems. Copyright © 2015 John Wiley & Sons, Ltd.     

Studies on the collision‐induced dissociation of adipoR agonists after electrospray ionization and their implementation in sports drug testing

AdipoR agonists are small, orally active molecules capable of mimicking the protein adiponectin, which represents an adipokine with antidiabetic and antiatherogenic effects. Two adiponectin receptors were reported in the literature referred to as adipoR1 and adipoR2. Activation of these receptors stimulates mitochondrial biogenesis and results in an improved oxidative metabolism (via adipoR1) and increased insulin sensitivity (via adipoR2). Hence, adipoR agonists are potentially performance enhancing substances and targets of proactive and preventive anti‐doping measures. In this study, two adipoR agonists termed AdipoRon and 112254 as well as two isotopically labeled internal standards (ISTDs) were synthesized in three‐step reactions. The products were fully characterized by nuclear magnetic resonance spectroscopy (NMR), mass spectrometry (MS) and density functional theory (DFT) computation. Collision‐induced dissociation pathways following electrospray ionization were suggested based on the determined elemental compositions of product ions, comparison to product ions derived from labeled analogs (ISTDs), H/D‐exchange experiments and the results of DFT calculations. The most abundant product ions were found at m/z 174, tentatively assigned to protonated 1‐benzyl‐1,2,3,4‐tetrahydropyridine for AdipoRon, and m/z 207, suggested as protonated 1‐(4‐methoxybenzyl)piperazine, for 112254. Notably, the loss of the heterocyclic ring (i.e. piperazine and piperidine, respectively) in a supposedly intramolecular elimination reaction was observed in both cases. A qualitative determination of both AdipoR agonists in human plasma was established and fully validated for doping control purposes. Validation items such as recovery (86–89%), specificity, linearity, lower limit of detection (1 ng/ml), intraday (3–18%) and interday (5–16%) precision as well as ion suppression or enhancement were determined. Based on these findings adipoR agonists can be implemented in sports drug testing procedures. Copyright © 2015 John Wiley & Sons, Ltd.     

Condensed‐Phase,Halogen‐Bonded CF3I and C2F5I Adducts for Perfluoroalkylation Reactions

A family of practical, liquid trifluoromethylation and pentafluoroethylation reagents is described. We show how halogen bonding can be used to obtain easily handled liquid reagents from gaseous CF₃I and CF₃CF₂I. The synthetic utility of the new reagents is exemplified by a novel direct arene trifluoromethylation reaction as well as adaptations of other perfluoroalkylation reactions.     

Exact solutions to magnetogasdynamic equations in Lagrangian coordinates

The Lie group of point transformations, which leave the equations for a simplified model of one dimensional ideal gas in magnetogasdynamics invariant, are used to obtain some exact solutions for the governing system of hyperbolic partial differential equations (PDEs). Similarity variables which reduces the governing system of PDEs into system of ordinary differential equations (ODEs) are determined through the transformations. The resulting ODEs are solved analytically to obtain some exact solutions that exhibits space-time dependence. Further, we study the propagation of weak discontinuity through a state characterized by one of the solutions.