Aminomethyl Transfer (Mannich) Reactions Between an O-Triethylsilylated Hemiaminal and Anilines,RnC6H5−nNH2 Leading to New Diamines,Triamines, Imines,or 1,3,5-Triazines Dependent upon Substituent R

The reactions of the Mannich reagent Et₃SiOCH₂NMe₂ ( 1 ) with a variety of anilines (mono-substituted RC₆H₄NH₂, R=H, 4-CN, 4-NO₂, 4-Ph, 4-Me, 4-MeO, 4-Me₂N; di-substituted R₂C₆H₃NH₂, R₂=3,5-(CH₃)₂, 3,5-(CF₃)₂; tri-substituted R₃C₆H₂NH₂, R₃=3,5-Me₂-4-Br and a “super bulky” aniline (Ar*NH₂) [Ar*=2,6-bis(diphenylmethyl)-4-tert-butylphenyl]) led to the formation of a range of products dependent upon the substituent. With electron-withdrawing substituents, previously unknown diamines, RC₆H₄NH(CH₂NMe₂) [R=CN ( 2 a ), NO₂ ( 2 b )] and R₂C₆H₃NH(CH₂NMe₂) [R₂=3,5-(CF₃)₂ ( 2 c) ] were formed. Further reaction of 2 a , b , c with 1 yielded the corresponding triamines RC₆H₄N(CH₂NMe₂)₂ (R=CN ( 3 a ), NO₂ ( 3 b ) and R₂C₆H₃N(CH₂NMe₂)₂, R₂=3,5-(CF₃)₂ ( 3 c ). The new polyamines were characterized by NMR spectroscopy, and for 2 a , 2 c _, and 3 c , by single crystal XRD. In the case of electron-donating groups, R=4-OMe, 4-NMe₂, 4-Me, 3,5-Me₂, 3,5-Me₂-4-Br, and for R=4-Ph, the reactions with 1 immediately led to the formation of the related 1,3,5-triazines, R=4-MeO ( 5 a ), 4-Me₂N ( 5 b ), 4-Me ( 5 c ), 3,5-Me₂ ( 5 d ), 3,5-Me₂-4-Br ( 5 e ), 4-Ph ( 5 f ), 4-Cl ( 5 g ). The “super bulky” aniline rapidly produced a single product, namely the corresponding imine Ar*N=CH₂ ( 4 ) which was also characterized by single crystal XRD. Imine 4 is both thermally and oxidatively stable. All reactions are very fast, thus based upon the presence of Si we are tempted to denote the reactions of 1 as examples of “Silick” chemistry.     

Validated ecofriendly chromatographic method for quantitative determination of anti‐migraine quaternary mixture

A novel ecofriendly, cost and time saving high‐performance thin‐layer chromatographic method was developed and validated for simultaneous determination of metoclopramide, ergotamine, caffeine, and paracetamol in bulk and pharmaceutical formulation. The separation was carried out on silica gel plates, using ethyl acetate:ethanol:ammonia (9:1:0.1, v/v/v) as a developing system. Ultraviolet detection was carried out at 272 nm. The resulting retention times were 0.15, 0.36, 0.49, and 0.74 min for metoclopramide, ergotamine, caffeine, and paracetamol, respectively. The greenness profile assessment was achieved to the proposed method to evaluate its greenness characters to the environment with acceptable results. Validation parameters were checked according to International Conference of Harmonization guidelines to achieve the international requirements for quality control analysis of the proposed drugs.     

Offline estimation of 2D crystal lattice parameters by processing the electron diffraction image

Electron diffraction provides useful information about the internal composition of materials and has been in the use of material scientists for more than fifty years. In order to extract useful information from offline diffraction images, they are manually analyzed by using some photometric technique. Manual analysis is however a cumbersome, laborious and difficult task. To reduce the labors of material scientists one can employ image processing techniques to perform automated analysis, due to the well established popularity and clear evidence of widely used image processing techniques. In this work an image processing technique is being proposed for the extraction of 2D unit cell information from diffraction images on one hand and finding the 2D point group contained by the lattices on the other. The technique employs a morphological shrinking operation to find the center of each spot in the underlying preprocessed diffraction image. This is followed by the extraction of eight points with reference to the spot produced by the transmitted electron beam. The resultant nine points, i.e. the extracted eight plus the reference spot generated by the transmitted electron beam, are then subjected to symmetry operations, rotation symmetry and mirror symmetry, in polar coordinate system, to classify the point group of the lattice produced by the electron diffraction. One of the difficult task, even in manual analysis, is to ascertain the exact spot where the transmitted electron beam hit the sample at the time of realization of the image. This has been accurately and intuitively done by employing the notion that the transmitted spot must have greater number of pixels, with the highest gray value, among the diffracted spots. The proposed strategy has been applied to a sample set of various images and the results shows that the technique is efficient in determining the unit cell in 2D and classify the point group with good accuracy.     

Complexes of Low Oxidized 99Tc and Re with Thiosalicylic Acid and Their Characterization in Solution with Some CNDO-MO Calculations

Complexation of technetium-99 and rhenium in low oxidized forms with thiosalicylic acid (TSA) were investigated by uv.-vis. spectrophotometry and HPL-chromatography.

By CNDO-MO calculations of the proper structure of TSA, the charge densities, ionization potential, electron affinity and its dipole moment were studied. The violet solútions of the Tc and Re complexes exhibit characteristic bands in the visible at 420,590 nm and 410,570 nm respectively. Comparative HPLC studies using MeOH/H₂O as a mobile phase indicate the Re-TSA complex to be less stable than the Tc-TSA complex.     

Ethylene Glycol as New Mobile Phase for Resolution of Two-Component Mixture of Cationic Surfactants on Alumina Surface

Aqueous ethylene glycol (ethane 1,2 diol) as a green mobile phase has been used for thin layer chromatographic (TLC) studies of cationic surfactants on alumina layers. Nineteen solvent systems were used to examine the mobility of the surfactants and to discover the best TLC system for the selective separation of dodecyl trimethylammonium bromide (DTAB) from multi-component mixture of other surfactants. Among the TLC systems studied, M₃ (ethylene glycol: water, 8:2) was best for achieving the selective separation of DTAB from multi-component mixture of other surfactants because in this mobile phase mobility of all surfactants except DTAB were insignificant. Effect of organic additives in aqueous ethylene glycol mobile phase on the mobility of surfactants was examined. The results obtained on laboratory made alumina TLC plates and commercially available precoated alumina HPTLC plates were compared. The lower limits of detection of DTAB, CPC, CTAB, HDTAC, and TTAB were 0.02, 0.05, 0.04, 0.06, or 0.08 µg per zone respectively. The resolution of mixture of cationic surfactants was also examined in the presence metal cations as an impurity in the analyzed sample.     

Oxazoline‐Based Organocatalyst for Enantioselective Strecker Reactions: A Protocol for the Synthesis of Levamisole

A chiral oxazoline‐based organocatalyst has been found to efficiently catalyze asymmetric Strecker reactions of various aromatic and aliphatic N‐benzhydrylimines with trimethylsilyl cyanide (TMSCN) as a cyanide source at ?20 °C to give α‐aminonitriles in high yield (96 %) with excellent chiral induction (up to 98 % ee). DFT calculations have been performed to rationalize the enantioselective formation of the product with the organocatalyst in these reactions. The organocatalyst has been characterized by single‐crystal X‐ray diffraction analysis, as well as by other analytical methods. This protocol has been extended to the synthesis of the pharmaceutically important drug molecule levamisole in high yield and with high enantioselectivity.     

Penultimate Approximations in Statistics of Extremes and Reliability of Large Coherent Systems

In reliability theory any coherent system can be represented as either a series-parallel or a parallel-series system. Its lifetime can thus be written as the minimum of maxima or the maximum of minima. For large-scale coherent systems it is sensible to assume that the number of system components goes to infinity. Then, the possible non-degenerate extreme value laws either for maxima or for minima are eligible candidates for the system reliability or at least for the finding of adequate lower and upper bounds for the reliability. The identification of the possible limit laws for the system reliability of homogeneous series-parallel (or parallel-series) systems has already been done under different frameworks. However, it is well-known that in most situations such non-degenerate limit laws are better approximated by an adequate penultimate distribution. Dealing with regular and homogeneous parallel-series systems, we assess both theoretically and through Monte-Carlo simulations the gain in accuracy when a penultimate approximation is used instead of the ultimate one.     

Densities,Refractive Indices,Ultrasonic Speeds and Excess Properties of Acetonitrile + Poly(ethylene glycol) Binary Mixtures at Temperatures from 298.15 to 313.15 K

The densities, ρ, refractive indices, n _D, and ultrasonic speeds, u, of binary mixtures of acetonitrile (AN) with poly(ethylene glycol) 200 (PEG200), poly(ethylene glycol) 300 (PEG300) and poly(ethylene glycol) 400 (PEG400) were measured over the entire composition range at temperatures (298.15, 303.15, 308.15 and 313.15) K and at atmospheric pressure. From the experimental data, the excess molar volumes, \( V_{\text{m}}^{\text{E}} \) , deviations in refractive indices, \( \Delta n_{\text{D}} \) , excess molar isentropic compressibility, \( K_{{s , {\text{m}}}}^{\text{E}} \) , excess intermolecular free length, \( L_{\text{f}}^{\text{E}} \) , and excess acoustic impedance, Z ^E, have been evaluated. The partial molar volumes, \( \overline{V}_{\text{m,1}} \) and \( \overline{V}_{\text{m,2}} \) , partial molar isentropic compressibilities, \( \overline{K}_{{s , {\text{m,1}}}} \) and \( \overline{K}_{{s , {\text{m,2}}}} \) , and their excess values over whole composition range and at infinite dilution have also been calculated. The variations of these properties with composition and temperature are discussed in terms of intermolecular interactions in these mixtures. The results indicate the presence of specific interactions among the AN and PEG molecules, which follow the order PEG200 < PEG300 < PEG400.     

Determination of Lambda-Cyhalothrin and Malathion Residues in Locust by Gas Chromatography with Electron Capture Detection

Journal of Analytical Chemistry - A reliable, easy, and reproducible method was developed for the quantification of λ-cyhalothrin and malathion residues in desert locust. For the extraction, a...     

Preparation and dispersion stability of aqueous metal oxide nanofluids for potential heat transfer applications: a review of experimental studies

Journal of Thermal Analysis and Calorimetry - Nanofluids have recently attracted attention of many researchers due to their growing potential applications in heat transfer devices. They possess...