Bi2O3/FAp,a sustainable catalyst for synthesis of dihydro-[1,2,4]triazolo[1,5-a]pyrimidine derivatives through green strategy

The bismuth loaded on fluorapatite (Bi₂O₃/FAp) proved to be an excellent catalyst for the synthesis of novel dihydro-[1,2,4]triazolo[1,5-a]pyrimidine derivatives via a three-component reaction involving the mixture of 1H-1,2,4-triazol-5-amine, ethyl cyanoacetate or ethyl acetoacetate, and different benzaldehydes in ethanol at room temperature. The catalyst material was characterized by X-ray diffraction, Brunauer–Emmett–Teller surface area analysis, Fourier-transform infrared, scanning electron microscopy, energy-dispersive X-ray spectroscopy, and transmission electron microscopy techniques. The efficacy of Bi₂O₃/FAp as a heterogeneous catalyst was evaluated with the loading of different wt% of bismuth on FAp. The 2.5% bismuth on FAp performed extremely well as a catalyst with a high yield of products (92%–96%) in a short reaction time (25–35 min). The catalyst was recovered by simple filtration. It showed undiminished activity up to five runs. Simple work-up, room temperature reaction, short reaction time, high yields, no column chromatography, and good reusability of catalyst are the merits of the proposed protocol. In addition, this process offers 100% carbon efficiency and 98% atom economy with noteworthy fiscal and environmental benefits.     

A chalcone showing positional disorder,two related diarylcyclohexenones showing enantiomeric disorder and a related hydroxyterphenyl,all derived from simple carbonyl precursors

Four compounds are reported, all of which lie along a versatile reaction pathway which leads from simple carbonyl compounds to terphenyls. (2E)‐1‐(2,4‐Dichlorophenyl)‐3‐ [4‐(prop‐1‐en‐2‐yl)phenyl]prop‐2‐en‐1‐one, C₁₈H₁₄Cl₂O, (I), prepared from 4‐(prop‐1‐en‐2‐yl)benzaldehyde and 2,4‐dichloroacetophenone, exhibits disorder over two sets of atomic sites having occupancies of 0.664 (6) and 0.336 (6). The related chalcone (2E)‐3‐(4‐chlorophenyl)‐1‐(4‐fluorophenyl)prop‐2‐en‐1‐one reacts with acetone to produce (5RS)‐3‐(4‐chlorophenyl)‐5‐[4‐(propan‐2‐yl)phenyl]cyclohex‐2‐en‐1‐one, C₂₁H₂₁ClO, (II), which exhibits enantiomeric disorder with occupancies at the reference site of 0.662 (4) and 0.338 (4) for the (5R) and (5S) forms; the same chalcone reacts with methyl 3‐oxobutanoate to give methyl (1RS,6SR)‐4‐(4‐chlorophenyl)‐6‐[4‐(propan‐2‐yl)phenyl]‐2‐oxocyclohex‐3‐ene‐1‐carboxylate, C₂₃H₂₃ClO₃, (III), where the reference site contains both (1R,6S) and (1S,6R) forms with occupancies of 0.923 (3) and 0.077 (3), respectively. Oxidation, using 2,3‐dichloro‐5,6‐dicyano‐1,4‐benzoquinone, of ethyl (1RS,6SR)‐6‐(4‐bromophenyl)‐4‐(4‐fluorophenyl)‐2‐oxocyclohex‐3‐ene‐1‐carboxylate, prepared in a similar manner to (II) and (III), produces ethyl 4′′‐bromo‐4‐fluoro‐5′‐hydroxy‐1,1′:3′,1′′‐terphenyl‐4′‐carboxylate, C₂₁H₁₆BrFO₃, (IV), which crystallizes with Z′ = 2 in the space group P. There are no significant intermolecular interactions in the structures of compounds (I) and (II), but for the major disorder component of compound (III), the molecules are linked into sheets by a combination of C—H...O and C—H...π(arene) hydrogen bonds. The two independent molecules of compound (IV) form two different centrosymmetric dimers, one built from inversion‐related pairs of C—H...O hydrogen bonds and the other from inversion‐related pairs of C—H...π(arene) hydrogen bonds. Comparisons are made with related compounds.     

Near‐forward/high‐pressure‐backward Raman study of Zn1 − xBexSe (x ~ 0.5) – evidence for percolation behavior of the long (Zn―Se) bond

The apparently universal 1‐bond → 2‐mode percolation behavior in the Raman spectra of zincblende semiconductor alloys is generally observed for the short bond only, and not for the long one. In this work we perform a combined high‐pressure‐backward/near‐forward Raman study of the leading percolation‐type (Zn,Be)Se alloy (~50 at.% Be), which exhibits a distinct percolation doublet in the spectral range of its short Be―Se bond, in search of a Zn―Se analogue. The high‐pressure‐backward insight is not conclusive per se, but clarifies the perspective behind the near‐forward Raman study. The latter reveals an unique Zn―Se phonon–polariton. Its fair contour modeling depending on the scattering angle is achieved within the linear dielectric approach, based on ellipsometry measurement of the ZnBeSe refractive index. Somewhat surprisingly this reveals that the phonon–polariton in question is a ‘fractional’ one in that it carries only half of the available Zn―Se oscillator strength, as ideally expected in case of a BeSe‐like bimodal Raman behavior of the long Zn―Se bond. Copyright © 2015 John Wiley & Sons, Ltd.     

Understanding guest and pressure‐induced porosity through structural transition in flexible interpenetrated MOF by Raman spectroscopy

Interpenetrating metal organic frameworks are interesting functional materials exhibiting exceptional framework properties. Uptake or exclusion of guest molecules can induce sliding in the framework making it porous or non‐porous. To understand this dynamic nature and how framework interaction changes during sliding, metal organic framework (MOF) 508 {Zn(BDC)( 4,4′‐Bipy)_0.5 · DMF(H₂O)_0.5} was selected for study. We have investigated structural transformation in MOF‐508 under variable conditions of temperature, pressure and gas loading using Raman spectroscopy and substantiated it with IR studies and density functional theory (DFT) calculations. Conformational changes in the organic linkers leading to the sliding of the framework result in changes in Raman spectra. These changes in the organic linkers are measured as a function of high pressure and low temperature, suggesting that the dynamism in MOF‐508 framework is driven by ligand conformation change and inter‐linker interactions. The presence of Raman signatures of adsorbed CO₂ and its librational mode at 149 cm⁻¹ suggests cooperative adsorption of CO₂ in the MOF‐508 framework, which is also confirmed from DFT calculations that give a binding energy of 34 kJ/mol. Copyright © 2015 John Wiley & Sons, Ltd.     

An experimental investigation of separating flow on a convex surface

The mean and turbulent characteristics of an incompressible turbulent boundary layer developing on a convex surface under the influence of an adverse pressure gradient are presented in this paper.The turbulence quantities measured include all the components of Reynolds stresses, auto-correlation functions and power spectra of the three components of turbulence. The results indicate the comparative influence of the convex curvature and adverse pressure gradient which are simultaneously acting on the flow. The investigation provides extensive experimental information which is much needed for a better understanding of turbulent shear flows.Nomenclature a, b constants in equation for velocity defect profile (Fig. 6) - c _f skin-friction coefficient (= _w/F _1/2 U ₁ ² ) - E(k ₁) one-dimensional wave number spectra - f frequency in Hz - G Clauser's equilibrium parameter = (H–1)/H(c _f /2) - H shape parameter (= ₁/ ₂) - k ₁ wave number (=2f/U) - L _u, L _v, L _w length scales of u, v and w fluctuations - p _s static pressure on the measurement surface - p _w reference tunnel wall static pressure - q ² total turbulent kinetic energy - R radius of curvature of the convex surface - R() auto-correlation function - T _u, T _v, T _w time scales of u, v and w fluctuations - U local mean velocity - U ₁ local free stream velocity - U _* friction velocity - u, v, w velocity fluctuations in x, y and z directions respectively - X streamwise coordinate measured along the surface from A (Fig. 1b) - x streamwise coordinate measured along the surface reckoned from station 9 - y coordinate normal to the surface - z spanwise coordinate - ₁/ _w · dp/dx - - boundary layer thickness - ₁ displacement thickness - ₂ momentum thickness - ₃ energy thickness - kinematic viscosity - density - time delay - _w wall shear stress     

Stress memory polymers

Like shape memory polymers, a novel phenomenon of stress memory was shown in which the stress of a material can respond to an external stimulus. This concept was further enlightened by a switch‐spring‐frame model that would eliminate the limitation of existing models which overlooked the stimulus responsive nature of such polymers. The discovery being reported in this article was stemmed from a real case study into shape memory polymer fibers in compression stocking for varicose veins. The breakthrough of stress memory enabled researchers to develop applications needing stimuli‐responsive forces, which can broaden the horizon of such smart polymers in emerging smart products in many multidisciplinary fields such as sensors, stress garments, and massage devices, electronic skins, and artificial muscles. © 2015 Wiley Periodicals, Inc. J. Polym. Sci., Part B: Polym. Phys. 2015 , 53, 893–898     

A Short New Synthesis of Ethyl trans-Chrysanthemate

The discovery of synthetic pyrethroids with increased insecticidal activity and low mammalian toxicity led to abundance of new synthetic results in the chemistry of pyrethroids¹ . Many of these methods adopted on an industrial scale make use of sigmatropic rearrangement, radical addition and nucleophilic ring closer with carbanions. Herein we report a simple and stereospecific route for the synthesis of ethyl trans-chrysanthernate (1) by utilizing carbonyl stabilized sulphuranes. Although the use of Sulphurane was demonstrated at a much earlier stage for the synthesis of methyl trans-chrysanthe-mate², the present approach makes use of simple reagents and offers some operational advantages.     

Bromination of Alkenes Using a Mixture of Sodium Bromide and Sodium Perborate

Bromination of alkenes with sodium bromide in the presence sodium perborate provides a simple, high yield route to dibromoalkanes.