Synthesis of 1-[3-methyl-2(3H)-benzazolon-5- or 6-yl]-4-{4-[cis-2-(2,4-dichlorophenyl)-2-(1H-imidazol-1-yl-methyl)-1,3-dioxolan-4-yl]methyleneoxyphenyl}piperazines

Reactions of 3-methyl-6-[4-(4-hydroxyphenyl)-1-piperazinyl]-2(3H)-benzoxazolone, 3-methyl-6-[4-(4-hydroxy-phenyl)-1-piperazinyl]-2(3H)-benzothiazolone and 1,3-dimethyl-5-[4-(4-hydroxyphenyl)-1-piperazinyl]-2(3H)-benzimidazolone with cis-{[2-(2,4-dichlorophenyl) -2-(1H-imidazol-1-ylmethyl)]-1,3-dioxolan-4-yl}methyl meth-anesulfonate in the presence of sodium hydride furnish the title compounds.     

Deterministic version of Wigner's semicircle law for the distribution of matrix eigenvalues

It is proved that Wigner's semicircle law for the distribution of eigenvalues of random matrices, which is important in the statistical theory of energy levels of heavy nuclei, possesses the following completely deterministic version. Let A_n=(a_ij), 1?i, ?n, be the nth section of an infinite Hermitian matrix, {λ⁽ⁿ⁾}_1?k?n its eigenvalues, and {u_k⁽ⁿ⁾}_1?k?n the corresponding (orthonormalized column) eigenvectors. Let $\text{v}{}^1{}_{\mathrm{n}}\text{=(a}{}_{\mathrm{n1}}\text{,a}{}_{\mathrm{n2}}\text{,?,a}{}_{\mathrm{n,n?1}}\text{)}$, put

$\text{X}{}_{\mathrm{n}}\text{(t)=[n(n-1)]}{}^{\mathrm{<mtext>-1</mtext><mtext>2</mtext>}}\text{∑}\text{k=1}\text{[(n-1)t]}\text{|v}{}_{\mathrm{n}}{}^1\text{u}{}_{\mathrm{f}}{}^{\mathrm{(n-1)}}\text{|}{}^2\text{,}\text{0?t?1}$

(bookeeping function for the length of the projections of the new row v¹_n of A_n onto the eigenvectors of the preceding matrix A_n?1), and let finally

$\text{F}{}_{\mathrm{n}}\text{(x)=n}{}^{-1}\text{(}\text{number of}\text{λ}{}_{\mathrm{k}}{}^{\mathrm{(n)}}\text{?x}\text{n}\text{,1?k?n)}$

(empirical distribution function of the eigenvalues of $\text{A}{}_{\mathrm{n}}\text{n}$. Suppose (i) $\text{lim}{}_{\mathrm{n}}\text{a}{}_{\mathrm{nn}}\text{n}\text{=0}$, (ii) lim_nX_n(t)=Ct(0<C<∞,0?t?1). Then

$\text{F}{}_{\mathrm{n}}\text{?W(·,C)}\text{(n→∞)}$

,where W is absolutely continuous with (semicircle) density

$\text{w(x,C)=}\text{(2Cπ)}{}^{-1}\text{(4C-x}{}^2{}^{\mathrm{<mtext>1</mtext><mtext>2</mtext>}}\text{for}\text{|x|?2}\text{C}\text{0}\text{for}\text{|x|?2}\text{C}$

     

Comparison of Force Fields on the Basis of Various Model Approaches—How To Design the Best Model for the [CnMIM][NTf2] Family of Ionic Liquids

In this contribution, we present two new united‐atom force fields (UA‐FFs) for 1‐alkyl‐3‐methylimidazolium bis(trifluoromethylsulfonyl)imide [C_nMIM][NTf₂] (n=1, 2, 4, 6, 8) ionic liquids (ILs). One is parametrized manually, and the other is developed with the gradient‐based optimization workflow (GROW). By doing so, we wanted to perform a hard test to determine how researchers could benefit from semiautomated optimization procedures. As with our already published all‐atom force field (AA‐FF) for [C_nMIM][NTf₂] (T. Köddermann, D. Paschek, R. Ludwig, ChemPhysChem­ 2007, 8, 2464 ), the new force fields were derived to fit experimental densities, self‐diffusion coefficients, and NMR rotational correlation times for the IL cation and for water molecules dissolved in [C₂MIM][NTf₂]. In the manual force field, the alkyl chains of the cation and the CF₃ groups of the anion were treated as united atoms. In the GROW force field, only the alkyl chains of the cation were united. All other parts of the structures of the ions remained unchanged to prevent any loss of physical information. Structural, dynamic, and thermodynamic properties such as viscosity, cation rotational correlation times, and heats of vaporization calculated with the new force fields were compared with values simulated with the previous AA‐FF and the experimental data. All simulated properties were in excellent agreement with the experimental values. Altogether, the UA‐FFs are slightly superior for speed‐up reasons. The UA‐FF speeds up the simulation by about 100 % and reduces the demanded disk space by about 78 %. More importantly, real time and efforts to generate force fields could be significantly reduced by utilizing GROW. The real time for the GROW parametrization in this work was 2 months. Manual parametrization, in contrast, may take up to 12 months, and this is, therefore, a significant increase in speed, though it is difficult to estimate the duration of manual parametrization.     

Al-Mn-Ce quasicrystalline composites: Phase formation and mechanical properties

Aluminium-based composites with quasicrystalline particles as reinforcements were synthesized via the powder metallurgy processing route. In order to obtain bulk samples with a nanoscale microstructure most equivalent to that resulting from rapid solidification, powders of Al-Mn-Ce alloys were prepared by pulverization of melt-spun ribbons using a planetary ball mill. Significant differences in the phase formation upon quenching, composite microstructure and thermal stability of the microstructure were found for different alloy compositions. Severe grain growth during the subsequent consolidation by hot extrusion caused the formation of a micrometre-scale composite instead of the nanoscale phase mixture initially existing after rapid solidification. After hot extrusion, the specimens were deformed by compression at a constant compression rate at room temperature. With an ultimate strength of up to 975 MPa and a ductility of more than 4% the material yields excellent properties compared with conventionally produced aluminium-based alloys.     

Synthesis,Crystal Structure,and Selected Properties of [Au(S2CNH2)2]SCN: A Precursor for Gold Macro-Needles Consisting of Gold Nanoparticles Glued by Graphitic Carbon Nitride

A new preparation route is developed for the synthesis of needle-like crystals of [Au(S₂CNH₂)₂]SCN, which avoids disproportionation of the Au^I salt used as a starting material. In the crystal structure, the two crystallographically independent Au^III centers are in a square-planar environment of two S₂CNH₂ ligands. The Hirshfeld surface analysis reveals the presence of noncovalent intermolecular S⋅⋅⋅S interactions, which are essential for the spatial arrangement of the molecules. Density functional theory (DFT) calculations including dispersion and damping corrections result in a unit cell volume very close to the value determined experimentally. Thermal decomposition in an inert atmosphere generates black needles with lengths of up to 500 μm. X-ray powder diffraction and pair distribution function analyses demonstrate that the needles are composed of nanosized crystals with a volume-weighted average domain size of 20(1) nm. According to results of X-ray photoemission experiments, the black needles are covered by a nitrogen-rich carbon nitride with composition near (CN)₂N. ¹³C solid-state NMR investigations indicate that two different carbon species are present, with signals corresponding well to heptazine units as in melon and triazine units as in poly(triazin imide) type compounds. Scanning transmission electron microscopy tomography evidences that the needles are composed of slightly elongated nanoparticles.     

A mixed hp FEM for the approximation of fourth‐order singularly perturbed problems on smooth domains

We consider fourth‐order singularly perturbed problems posed on smooth domains and the approximation of their solution by a mixed Finite Element Method on the so‐called Spectral Boundary Layer Mesh. We show that the method converges uniformly, with respect to the singular perturbation parameter, at an exponential rate when the error is measured in the energy norm. Numerical examples illustrate our theoretical findings.     

Magnetomechanical training of single crystalline Ni-Mn-Ga alloy

A 5M Ni-Mn-Ga single crystal was investigated, supplied by Adaptamat Ltd, Finland. Especially low temperature magnetic actuation as well as cyclic tensile-compression tests revealed promising properties, which provide useful insights for training concepts in polycrystalline materials. Successive compressions lead to a significant reduction of the twinning stress by a factor of two.     

ORGANISCHE PHOSPHORVERBINDUNGEN 80 HERSTELLUNG VON TRIAZOLYLMETHYL-PHOSPHONATEN UND VON TRIAZOLYL-METHYLPHOSPHONIUMSALZEN UND DEREN VERWENDUNG IN DER WITTIG-HORNER REAKTION

Abstract

Attempts to prepare 1H-1,2,4-triazol-1-ylmethylphosphonates (4 and 5) by a Mannichtype reaction or by transesterification of 1-hydroxymethyl-1H-1,2,4-triazol 1 with tertiary phosphites failed. On the other hand 4 and 5 are obtained by a Michaelis-Becker reaction from 1-chloromethyl-1H-1,2,4-triazol 3 and sodium phosphites in high yield. The Michaelis-Arbuzov reaction is less suited for the preparation of 4 and 5. 3 is obtained in good yield as a water clear liquid, b.p. 52–54°C/0.2 torr, from the interaction of 1 with thionyl chloride followed by treatment with a base. On standing at 0° or 20°C it decomposes within hours and yields the unsymmetrical methylen-bis(triazol) 3a in addition to other products. However an acetonitrile solution of 3 is stable for months. Heating this solution with tertiary phosphines gives triazolylsubstituted phosphoniumsalts 6 to 8. The Wittig-Horner reaction with 4 to 6 gives the olefinically substituted triazols 9–12 as a Z/E mixture in high yield. Alkylation of 4 with methyl-and ethyl iodide gives the corresponding alkylated diethyl-1H-1,2,4-triazol-1-yl-ethyl-1-and-propyl-1-phosphonates 14 and 15 which on hydrolysis with HCI yield 1H-1,2,4-triazol-1-yl-ethyl-1-and propyl-1-phosphonic acids 17 and 18, respectively. Hydrolysis of 4 gives the unsubstituted 1H-1,2,4-triazol-1-ylmethyl-phosphonic acid, 16.