Non-phosgene route to unsymmetrical ureas from N-Cbz-α-amino acid amides

A convenient method toward the synthesis of α-amino acid-derived unsymmetrical ureas 2 is described herein. This route involves an interesting rearrangement of amides of N-Cbz-α-amino acids 1, which presumably entails the intermediacy of hydantoins that is followed by hydrolysis to afford unsymmetrical ureas 2 in quantitative yields and high purity.     

Agglomerative hierarchical clustering analysis of twenty-six rice samples analysed by instrumental neutron activation analysis and other techniques

As part of the ongoing work on the safety and security of foods grown locally and imported into Jamaica, twenty five rice brands available on the Jamaican market and one sample of locally grown brown rice were collected and analysed for 36 elements using a combination of instrumental neutron activation analysis, total reflection X-ray fluorescence, flame atomic absorption spectrometry and inductively coupled plasma optical emission spectrometry. Quality control for each of the techniques was provided by analysis of reference materials and inter-comparisons of common elements. Agglomerative hierarchical clustering analysis performed on the raw data set identified white, parboiled and brown rice as the major clusters. The element and cluster median concentration in μg/g (for polished, parboiled and brown respectively) for each of the three clusters were Al (8.7, 11.3, 14.9), As (0.20, 0.21, 0.15), Br (12.1, 0.9, 3.4), Ca (60.4, 409.1, 112.5), Co (0.1, 0.09, 0.11), Cr (0.11, 0.10, 0.11), Cs (0.012, 0.004, 0.018), Eu (0.004, 0.004, 0.003), Cu (2.2,2.7, 3.6), Fe (13, 17, 20), K (894,1,815,2,538), La (0.009, 0.014, 0.015), Mg (340, 504, 1,303), Mn (9.7, 14.9, 28.5), Mo (0.7, 1.1, 0.8), Na (5.1, 9.9, 16.9), P (936, 2,328, 3,670), Rb (4.5, 6.1, 7.3), S (1,088,1,308, 1,321), Sb (0.004, 0.006, 0.005), Sc (0.001, 0.002, 0.002), Se (0.09, 0.17, 0.16), Sm (0.001, 0.003, 0.001), Sr (2.0, 1.9, 2.9), V (0.036, 0.041, 0.058), Zn (17.9, 15.3, 22.8). The use of agglomerative hierarchical clustering has proven to be a rapid method for the analysis of the dataset, correctly clustering rice by process that is, polished, parboiled and brown, with sub-clusters that further identified location, cultivars and an adulterated sample. The data validated here has been used to estimate the elemental contribution of rice to the Jamaican diet.     

The Kinetics and Mechanism of the Reaction of Onium Cyclopentadienylides with Tetrahalo-p-Benzoquinones

Abstract

The reaction of triphenylphosphonium cyclopentadienylide (1) with halogen-substituted p-benzoquinones (4) is shown to give a new class of dipolar (zwitterionic) dyes (5) containing phosphorus. The general structure of these molecules has been investigated by a combination of mass spectrometry and multinuclear (¹H, ^l3C and 3l^P) nmr using the specialist techniques of DEPT spectroscopy, homonuclear (COSY) and heteronuclear, 2-D nmr. In addition, stopped-flow (uv/vis) techniques have been used to study the kinetics of the reactions and hence demonsrate that the rate-limiting step is nucleophilic addition of the ylid to the quinone, followed by a rapid loss of halide ion. The mechanism follows the classical pattern associated with nucleophilic aromatic substitution in activated aryl halides.     

Synthesis of 5‐Aminotetrazole‐1 N‐oxide and Its Azo Derivative: A Key Step in the Development of New Energetic Materials

1‐Hydroxy‐5‐aminotetrazole ( 1 ), which is a long‐desired starting material for the synthesis of hundreds of new energetic materials, was synthesized for the first time by the reaction of aqueous hydroxylamine with cyanogen azide. The use of this unique precursor was demonstrated by the preparation of several energetic compounds with equal or higher performance than that of commonly used explosives, such as hexogen (RDX). The prepared compounds, including energetic salts of 1‐hydroxy‐5‐aminotetrazole (hydroxylammonium ( 2 , two polymorphs) and ammonium ( 3 )), azo‐coupled derivatives (potassium ( 5 ), hydroxylammonium ( 6 ), ammonium ( 7 ), and hydrazinium 5,5′‐azo‐bis(1‐N‐oxidotetrazolate ( 8 , two polymorphs)), as well as neutral compounds 5,5′‐azo‐bis(1‐oxidotetrazole) ( 4 ) and 5,5′‐bis(1‐oxidotetrazole)hydrazine ( 9 ), were intensively characterized by low‐temperature X‐ray diffraction, IR, Raman, and multinuclear NMR spectroscopy, elemental analysis, and DSC. The calculated energetic performance, by using the EXPLO5 code, based on the calculated (CBS‐4M) heats of formation and X‐ray densities confirm the high energetic performance of tetrazole‐N‐oxides as energetic materials. Last but not least, their sensitivity towards impact, friction, and electrostatic discharge were explored. 5,5′‐Azo‐bis(1‐N‐oxidotetrazole) deflagrates close to the DDT (deflagration‐to‐detonation transition) faster than all compounds that have been investigated in our research group to date.     

Model reduction and clustering techniques for crash simulations

Model reduction in car crash simulations is a fairly new research field. In this paper, a possible workflow is presented: Since nonlinear behavior can occur, parts with linear and nonlinear behavior need to be separated with clustering methods such as k-means or spectral clustering. For the latter, a nonlinear reduction technique such as POD-DEIM needs to be applied. A longitudinal chassis beam of a 2001 Ford Taurus is used to examine the different clustering methods. (© 2015 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim)     

Potential flow simulations of Peregrine-type deep water surface gravity wave packets

Applying a higher order spectral method for potential flow we numerically determine the time evolution of non-linear deep water wave packets originating from initial conditions derived from the Peregrine breather solution of the non-linear Schrödinger equation (NLS). The spatio-temporal evolution of the wave packets qualitatively agrees well with what would be expected from lowest order weakly nonlinear estimates (NLS). Some quantitative discrepancies do, however, exist: The maximum wave envelope amplification appears retarded with respect to the NLS predictions. The amplification factor slightly exceeds the factor known from the NLS solution. (© 2015 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim)     

Ochraceopyronide,a Rare α-Pyrone-C-lyxofuranoside from a Soil-Derived Fungus Aspergillus ochraceopetaliformis

The fungal strain was isolated from a soil sample collected in Giza province, Egypt, and was identified as Aspergillus ochraceopetaliformis based on phenotypic and genotypic data. The ethyl acetate extract of the fungal strain exhibited promising activity levels against several pathogenic test organisms and through a series of ¹H NMR guided chromatographic separations, a new α-pyrone-C-lyxofuranoside (1) along with four known compounds (2–5) were isolated. The planar structure of the new metabolite was elucidated by detailed analysis of its 1D/2D NMR and HRMS/IR/UV spectroscopic data, while the relative configuration of the sugar moiety was determined by a combined study of NOESY and coupling constants data, with the aid of theoretical calculations. The structures of the known compounds—isolated for the first time from A. ochraceopetaliformis—were established by comparison of their spectroscopic data with those in the literature. All isolated fungal metabolites were evaluated for their antibacterial and antifungal activities against six Gram-positive and Gram-negative bacteria as well as against three human pathogenic fungi.     

A tiling proof of Euler’s Pentagonal Number Theorem and generalizations

The Ramanujan Journal - In two papers, Little and Sellers introduced an exciting new combinatorial method for proving partition identities which is not directly bijective. Instead, they consider...     

EASY-GOING deconvolution: combining accurate simulation and evolutionary algorithms for fast deconvolution of solid-state quadrupolar NMR spectra

A fast and accurate fit program is presented for deconvolution of one-dimensional solid-state quadrupolar NMR spectra of powdered materials. Computational costs of the synthesis of theoretical spectra are reduced by the use of libraries containing simulated time/frequency domain data. These libraries are calculated once and with the use of second-party simulation software readily available in the NMR community, to ensure a maximum flexibility and accuracy with respect to experimental conditions. EASY-GOING deconvolution (EGdeconv) is equipped with evolutionary algorithms that provide robust many-parameter fitting and offers efficient parallellised computing. The program supports quantification of relative chemical site abundances and (dis)order in the solid-state by incorporation of (extended) Czjzek and order parameter models. To illustrate EGdeconv's current capabilities, we provide three case studies. Given the program's simple concept it allows a straightforward extension to include other NMR interactions. The program is available as is for 64-bit Linux operating systems.     

Further consideration of the correlation of the rates of solvolytic displacement of chloride ion from phosphorus (V)

Specific rates of solvolysis of diphenyl ( 1 ) and bis(2,4‐dichlorophenyl) ( 3 ) phosphorochloridate (chlorophosphate) have been determined by a conductivity technique. The available specific rates together with those determined earlier for bis(4‐chlorophenyl) phosphorochloridate ( 2 ) have been analyzed in terms of the extended (two‐term) Grunwald–Winstein equation. It is found that rather poor overall correlations found earlier for 1 and 2 and now for 3 are considerably improved when data points for 2,2,2‐trifluoroethanol–ethanol and acetone–water mixtures are excluded. The large sensitivities toward changes in solvent nucleophilicity are consistent with a bimolecular process. The differences in nucleophilicity of an acetone–water mixture for attack at carbon or at phosphorus are discussed. Copyright © 2010 John Wiley & Sons, Ltd.