Sulfamic Acid–Catalyzed One‐Pot Synthesis of 3‐(4,6‐Dimethyl‐oxazolo[4,5‐c]quinolin‐2‐yl)‐chromen‐2‐ones using the Conventional Method and Microwave Irradiation

A rapid and efficient method for the preparation of 3‐(4,6‐dimethyl‐oxazolo[4,5‐c]quinolin‐2‐yl)‐chromen‐2‐ones by the reaction between 3‐amino‐2,8‐dimethyl‐quinolin‐4‐ol and 2‐oxo‐2H‐chromen‐3‐carboxylic acid using sulfamic acid as a acid catalyst and dimethyl formamide as a solvent using the conventional method and microwave irradiation is reported.     

Proton transfer and N(+)-H...S(-) hydrogen bonds in the crystal structure of 4-aminothiophenol

4-Aminothiophenol exists as 4-ammonio-1-benzenethiolate in the solid and liquid state. The crystal structure is characterised by a tetrahedral beta-As type network which is the driving force for the proton transfer.     

Biclustering Three-Dimensional Data Arrays With Plaid Models

Three-dimensional data arrays (collections of individual data matrices) are increasingly prevalent in modern data and pose unique challenges to pattern extraction and visualization. This article introduces a biclustering technique for exploration and pattern detection in such complex structured data. The proposed framework couples the popular plaid model together with tools from functional data analysis to guide the estimation of bicluster responses over the array. We present an efficient algorithm that first detects biclusters that exhibit strong deviations for some data matrices, and then estimates their responses over the entire data array. Altogether, the framework is useful to home in on and display underlying structure and its evolution over conditions/time. The methods are scalable to large datasets, and can accommodate a variety of dynamic patterns. The proposed techniques are illustrated on gene expression data and bilateral trade networks. Supplementary materials are available online.     

An ab initio study of ground state, electronic and thermodynamical properties of GaP and Ga2P

In the present paper, we report an ab initio calculation of the ground state, electronic and thermodynamical properties like constant volume lattice specific heat, vibrational energy, internal energy, and entropy for GaP and Ga₂P is presented. These properties are obtained after calculating the phonon spectrum over the entire Brillouin zone. The calculations were performed using the ABINIT program package, which is based on density functional theory (DFT) method and the use of pseudopotentials and plane wave expansion. Difference in the ground state properties such as electronic structure and thermodynamical properties are discussed. The thermodynamical properties follow the expected trend. There is a good agreement between present theoretical and limited available experimental data in the case of ground state such as lattice constant and bulk modulus and electronic properties. With the increase of Ga atoms in the unit cell the semiconducting nature of Ga₂P turns to metallic. There is a noticeable difference in the thermodynamical properties in the case of both gallium compounds.     

Preparation and characterization of aromatic copolyesters containing the o,o′-biphenylene ring system

Poly[oxy-2,2′-diphenyleneoxyisophthaloyl-b-oxy(2-methyl-1,3-phenylene)oxyterephthaloyl] I, poly[oxy-2,2′-diphenyleneoxyterephthaloyl-b-oxy(2-methyl-1,3-phenylene)oxyterephthaloyl] II, poly(oxy-2,2′-diphenyleneoxyisophthaloyl-b-oxy-2,2′-diphenyleneoxyterephthaloyl) III, poly[oxy-2,2′-diphenyleneoxyterephthaloyl-b-oxy(2-methyl-1,4-phenylene)oxyterephthaloyl] IV, poly[oxy2,2′-diphenyleneoxyterephthaloyl-b-oxy(2-chloro-1,4-phenylene)oxyterephthaloyl] V, poly[oxy-2,2′-diphenyleneoxyterephthaloyl-co-oxy(2-chloro-1,4-phenylene)oxyterephthaloyl] VI, and poly[oxy-2,2′-diphenyleneoxyterephthaloyl-co-oxy(2-methyl-1,4-phenylene)oxyterephthaloyl] VII have been synthesized and characterized. Random copolyester VI appears to form a birefringent fluid phase above the melting temperature.     

First principles lattice dynamical calculation of semiboride Be2B and its ternary alloys XBeB (X=Na, Mg, Al)

We present results of first principles total energy calculations of the structure, electronic and lattice dynamics for beryllium semiboride and its three ternary alloys using generalized gradient and local density approximations under the framework of density functional theory. The generalized gradient approximation is used for all compounds except MgBeB using the Perdew-Burke-Ernzehorf exchange correlation functional while local density approximations use the Perdew-Zunger ultrasoft exchange correlation functional. The calculated ground state structural parameters are in good agreement with those of experimental and previous theoretical studies. The electronic band structure calculations show that Be₂B may transform to a semiconductor after Al substitution. A linear response approach to density functional theory is used to calculate phonon dispersion curves and vibrational density of states. The phonon dispersion curves of Be₂B and AlBeB are positive indicating a dynamical stablility of the structure for these compounds. The phonon dispersion curves of NaBeB and MgBeB show the imaginary phonons throughout the Brillouin zone, which confirms dynamical instability as indicated in band structures for these alloys. We also present the partial phonon density of states for different species of Be₂B and AlBeB to bring out the details of the participation of different atoms in the total phonon density of state, particularly the role played by Al atom. The first time calculated phonon properties are clearly able to bring out the significant effect of isoelectronic substitution in Be₂B.     

Zn(OTf)2 catalyzed addition-cyclization reaction of allenylphosphine oxides with propargyl alcohol-unexpected formation of 2,5-dimethylenetetrahydrofurans and 2-substituted furans

A novel synthesis of 2,5-dimethylenetetrahydrofurans, 2-substituted furans and a β,ω-diketophosphonate in good to excellent yields has been achieved by the reaction of allenylphosphine oxides/allenylphosphonate with propargyl alcohol using zinc triflate/triethylamine combination.     

Two metals are better than one in the gold catalyzed oxidative heteroarylation of alkenes

We present a detailed study of the mechanism for oxidative heteroarylation, based on DFT calculations and experimental observations. We propose binuclear Au(II)-Au(II) complexes to be key intermediates in the mechanism for gold catalyzed oxidative heteroarylation. The reaction is thought to proceed via a gold redox cycle involving initial oxidation of Au(I) to binuclear Au(II)-Au(II) complexes by Selectfluor, followed by heteroauration and reductive elimination. While it is tempting to invoke a transmetalation/reductive elimination mechanism similar to that proposed for other transition metal complexes, experimental and DFT studies suggest that the key C-C bond forming reaction occurs via a bimolecular reductive elimination process (devoid of transmetalation). In addition, the stereochemistry of the elimination step was determined experimentally to proceed with complete retention. Ligand and halide effects played an important role in the development and optimization of the catalyst; our data provides an explanation for the ligand effects observed experimentally, useful for future catalyst development. Cyclic voltammetry data is presented that supports redox synergy of the Au···Au aurophilic interaction. The monometallic reductive elimination from mononuclear Au(III) complexes is also studied from which we can predict a ~15 kcal/mol advantage for bimetallic reductive elimination.