Chemoselective N-acylation via condensations of N-(benzoyloxy)amines and alpha-ketophosphonic acids under aqueous conditions

A new amide-forming reaction with N-benzoyloxyamines and alpha-ketophosphonic acids was investigated. A mixed solvent of t-BuOH/water (1:1) at 40 degrees C provided the desired amide in high yield (71-96%). Both phosphonic acids ( 9, 12, or 13) and their disodium salts (e.g., 10) were shown to react with the respective N-benzoyloxyamines ( 1b and 4) in excellent yields. The phosphonic acid methyl ester monosodium salt 11 did not react under these conditions. However, compound 11 did provide the desired amide in 22% yield upon addition of 2 equiv of TFA. The N-acylation reaction is highly chemoselective for N-benzoyloxyamines as both aliphatic amines and N-hydroxylamines were shown not to react productively with the alpha-ketophosphonic acids under the conditions tested. Moreover, the alpha-ketophosphonic acids are more selective than the related alpha-ketocarboxylic acid systems, which react with both the N-hydroxylamines and N-benzoyloxyamines. In this regard, this novel phosphonic acid methodology provides a new high-yielding, chemoselective acylating reagent for further study.     

PMMA based protonic polymer gel electrolytes

The paper reports the synthesis of protonic polymer gel electrolytes containing different hydroxy benzoic acids (ortho-, meta- and para-) and aliphatic dicarboxylic acids. Gel electrolytes were prepared by adding polymethylmethacrylate (PMMA) in different weight ratios to the 1M solution of above acids in a ternary solvent mixture of propylene carbonate (PC), ethylene carbonate (EC) and dimethylformamide (DMF) in equal volume ratio. The conductivity of these gel electrolytes has been found to depend upon the amount of PMMA added to the system. A “Breathing Polymeric Chain Model” has been proposed to explain the variation of conductivity with PMMA concentration in these gel electrolytes.     

Hybrid LES–RANS technique based on a one-equation near-wall model

In order to reduce the high computational effort of wall-resolved large-eddy simulations (LES), the present paper suggests a hybrid LES–RANS approach which splits up the simulation into a near-wall RANS part and an outer LES part. Generally, RANS is adequate for attached boundary layers requiring reasonable CPU-time and memory, where LES can also be applied but demands extremely large resources. Contrarily, RANS often fails in flows with massive separation or large-scale vortical structures. Here, LES is without a doubt the best choice. The basic concept of hybrid methods is to combine the advantages of both approaches yielding a prediction method, which, on the one hand, assures reliable results for complex turbulent flows, including large-scale flow phenomena and massive separation, but, on the other hand, consumes much fewer resources than LES, especially for high Reynolds number flows encountered in technical applications. In the present study, a non-zonal hybrid technique is considered (according to the signification retained by the authors concerning the terms zonal and non-zonal), which leads to an approach where the suitable simulation technique is chosen more or less automatically. For this purpose the hybrid approach proposed relies on a unique modeling concept. In the LES mode a subgrid-scale model based on a one-equation model for the subgrid-scale turbulent kinetic energy is applied, where the length scale is defined by the filter width. For the viscosity-affected near-wall RANS mode the one-equation model proposed by Rodi et al. (J Fluids Eng 115:196–205, 1993) is used, which is based on the wall-normal velocity fluctuations as the velocity scale and algebraic relations for the length scales. Although the idea of combined LES–RANS methods is not new, a variety of open questions still has to be answered. This includes, in particular, the demand for appropriate coupling techniques between LES and RANS, adaptive control mechanisms, and proper subgrid-scale and RANS models. Here, in addition to the study on the behavior of the suggested hybrid LES–RANS approach, special emphasis is put on the investigation of suitable interface criteria and the adjustment of the RANS model. To investigate these issues, two different test cases are considered. Besides the standard plane channel flow test case, the flow over a periodic arrangement of hills is studied in detail. This test case includes a pressure-induced flow separation and subsequent reattachment. In comparison with a wall-resolved LES prediction encouraging results are achieved.      

A spectroscopic resolution of the structure of Zn(CN)2

Two different cubic structures of the negative thermal expansion (NTE) material zinc cyanide have been reported in the literature: one, an ordered structure (space group P4 3m) in which the ZnC₄ tetrahedra are linked to neighbouring ZnN₄ tetrahedra with CN bonds and vice versa, and the other, a disordered structure (space group Pn4 3m) where N and C sites are indistinguishable. Here, we present group theoretical analyses to classify the phonons of different symmetries in the two structures and report Raman and infrared spectroscopic studies to resolve the ambiguity about the structure. On the basis of the number of Raman and IR modes expected and observed, we conclude that the compound exists in a disordered structure. Copyright © 2006 John Wiley & Sons, Ltd.     

Synthesis and anticonvulsant activity of 3-[3-[(dimethylamino)-methyl]-5-methyl-4H-1,2,4-triazol-4-yl]-4-(o-chlorobenzoyl)pyridine

Wolff-Kishner reduction of 3-amino-4-(o-chlorobenzoyl)pyridine ( 3 ) afforded 3-amino-4-(o-chlorobenzyl)pyridine ( 5 ), which on subsequent reaction with triethyl orthoformate and then acetyl hydrazide yielded 1-acetyl-2-[N-[4-(o-chlorobenzyl)pyridin-3-yl]formimidoyl]hydrazone ( 7 ). Cyclization of hydrazone 7 gave 3-(3-methyl-4H-1,2,4-triazol-4-yl)-4-(o-chlorobenzyl)pyridine ( 8 ), which on Jones oxidation yielded 3-(3-methyl-4H-1,2,4-triazol-4-yl)-4-(o-chlorobenzyl)pyridine ( 9 ). The Mannick reaction of 3-(3-methyl-4H-l,2,4-triazol-4-yl)-4-(o-chlorobenzyl)pyridine ( 9 ) with aqueous formalin and dimethylamine hydrochloride afforded 3-[3-[(dimethylamino)methyl]-5-methyl-4H-1,2,4-triazol-4-yl]-4-(o-chlorobenzoyl)-pyridine ( 10 ). 3-[3-[(Dimethylamino)methyl]-5-methyl-4H-1,2,4-triazol-4-yl]-4-(o-chlorobenzoyl)pyridine ( 10 ) exhibited good anticonvulsant activity in the subcutaneous pentylenetetrazole anticonvulsant screen indi cating that an appropriately substituted-pyridine ring moiety can serve as a bioisostere of a chlorobenzene ring with respect to anticonvulsant activity.     

PVT and CVT Growth and Characterization of SnSxSe2-x (0 ≤ x ≤ 2) Single Crystals

Single crystals of solid solutions of tin sulphoselenide have been grown in the same ampoule. Specific conditions for growing single crystals of SnSSe have also been identified. A study of microstructures on the growth surfaces responds to the mechanism of growth of these crystals. The dependence of electrical resistivity, Hall mobility and carrier concentration with the values of the configuration parameter 2 has been studied.     

Microstructures on Zirconium Trisulphide Single Crystals

Physical vapour transport grown single crystals of zirconium trisulphide have been examined by optical microscope, and the study of growth patterns on their finished surfaces reveal the screw dislocation mechanism by which the crystals have grown.     

Cu(II) ion based 1D coordination polymer: Its thermal,fluorescence properties,Hirshfeld surface analysis and theoretical calculations

In this investigation, the reaction of [Cu(2,2′-bpy)(H₂O)₄][ClO₄]₂ with thiosemicarbazide (tsc) yielded [Cu(2,2′-bpy)(NCS)₂]_n frameworks, which has crystallized in noncentrosymmetric space group (Cc). The complex has been characterized by elemental analyses, FT-IR spectrum, powder X-ray diffraction analysis and single-crystal diffraction analysis. This complex is 1D polymer with high thermal stability and showing positive cotton effect. These results have provided some interesting insights into its nonlinear optical applications. Solid state fluorescence spectrum shows broad photoluminescence emission bands, which are assigned as the bands of intra-ligand charge transfer and MLCT (metal to ligand charge transfer) transitions. During investigation of various intermolecular interactions, both single crystal X-ray diffraction and Hirshfeld surface analysis give comparable results.