天门冬氨酸催化1,1,1,3,3,3-六甲基二硅氮烷硅烷化羟基为三甲基硅醚(英文)

A wide variety of alcohols and phenols were protected as trimethylsilyl ethers using 1,1,1,3,3,3-hexamethyl disilazane catalyzed by aspartic acid as a non-toxic,metal-free,and green organocatalyst at room temperature in acetonitrile under mild and heterogeneous conditions.The procedure is operationally simple and the silylated product was obtained in high yield and purity.     

Pseudo-Jahn–Teller effect in Si4X4 (X = F,Cl, Br,I) molecules: a theoretical investigation

ABSTRACT

The variability of planar rings in Si₄X₄ (X?=?F, Cl, Br, I) molecules caused by the pseudo-Jahn–Teller impact (PJTE) was evaluated as an original PJTE work. Optimisation and the following frequency calculations in these molecules illustrated that in high-symmetry planar (with D_4h symmetry) geometry, all of these compounds were unstable and their structures were puckered to lower C_2h symmetry stable geometry. Furthermore, the vibronic coupling interaction between ¹A_1g ground and the first ¹E_g excited states through (¹A_1g?+?¹E_g) ? e_g PJTE problem was the cause of non-planarity of the four-member ring and the symmetry breaking phenomenon in those series. The calculated gaps (Δ) between the ground state and the E_g excited state, the vibronic coupling (F) and ground state primary force constant values (k₁) were obtained from the numerical fitting of the ground state adiabatic potential energy surface with the analytical expressions of these molecules. Finally, natural bond analysis (NBO) was used for the design of the strongest interaction and natural atomic charges of these structures.     

Cu(II)–Schiff base complex‐functionalized magnetic Fe3O4 nanoparticles: a heterogeneous catalyst for various oxidation reactions

Cu(II)–Schiff base complex‐functionalized magnetic Fe₃O₄ nanoparticles were prepared and characterized using Fourier transform infrared spectroscopy, thermogravimetric analysis and scanning electron microscopy techniques. This compound acts as a highly active and selective catalyst for the oxidation of sulfides and thiols. These reactions can be carried out in ethanol or solvent‐free conditions in the presence of hydrogen peroxide with complete selectivity and very high conversion under mild reaction conditions. The designed catalytic system prevents effectively the over‐oxidation of sulfides to sulfones. Separation and recycling can also be easily done using a simple magnetic separation process. Copyright © 2015 John Wiley & Sons, Ltd.     

Synthesis of N2-arylaminopyrimidine-5-carbonitrile derivatives via SNAr amination reaction

An efficient and high-yielding synthesis of N~2-arylaminopyrimidine-5-carbonitrile derivatives starting from arylamines and 2-methylthio-pyrimidine-5-carbonitriIe derivatives has been developed in the presence of cesium carbonate as basic reagent.This new protocol showed high chemical tolerance for a range of functional groups,and only the methylthio substituent on C2 of the pyrimidine ring was replaced with arylamine derivatives under the reaction conditions.     

Inside-tube solid-phase microextraction as an interlink between solid-phase microextraction and needle device for n-hexane evaluation in air and urine headspace

Monitoring the trace amount of chemicals in various samples remains a challenge. This study was conducted to develop a new solid-phase microextraction (SPME) system (inside-tube SPME) for trace analysis of n-hexane in air and urine matrix. The inside-tube SPME system was prepared based on the phase separation technique. A mixture of carbon aerogel and polystyrene was loaded inside the needle using methanol as the anti-solvent. The air matrix of n-hexane was prepared in a Tedlar bag, and n-hexane vapor was sampled at a flow rate of 0.1 L/min. Urine samples spiked with n-hexane were used to simulate the sampling method. The limit of detection using the inside-tube SPME was 0.0003 μg/sample with 2.5 mg of adsorbent, whereas that using the packed needle was 0.004 μg/sample with 5 mg of carbon aerogel. For n-hexane analysis, the day-to-day and within-day coefficient variation were lower than 1.37%, with recoveries over 98.41% achieved. The inside-tube SPME is an inter-link device between two sample preparation methods, namely, a needle trap device and an SPME system. The result of this study suggested the use of the inside-tube SPME containing carbon aerogel (adsorbent) as a simple and fast method with low cost for n-hexane evaluation.     

Densities and Viscosities for Binary and Ternary Mixtures of 2-Methylbutan-2-ol (1) + Trichloroethylene (2) + Acetonitrile (3) at 298.15 K and at Ambient Pressure (81.5 kPa)

Densities (ρ) and viscosities (η) of ternary mixtures of 2-methylbutan-2-ol (1) + trichloroethylene (2) + acetonitrile (3) and the related binary mixtures of {2-methylbutan-2-ol (1) + trichloroethylene (2)}, {2-methylbutan-2-ol (1) + acetonitrile (3)}, and {trichloroethylene (2) + acetonitrile (3)} have been measured over the whole composition range at 298.15 K and at ambient pressure (81.5 kPa). Excess molar volumes $ V_{\text{m}}^{\text{E}} $ , viscosity deviations Δη, and excess Gibbs energies of activation ΔG ^*E were derived from the experimental data. The binary and ternary data of $ V_{\text{m}}^{\text{E}} $ , Δη, and ΔG ^*E for the binary and ternary mixtures were correlated as functions of the mole fraction by using the Redlich–Kister and the Cibulka equations. Kinematic viscosities of the binary mixtures were correlated by means of several semi-empirical equations to determine the fitting parameters and the SDs. The experimental results are analyzed to discuss the nature and strength of intermolecular interactions in these mixtures.     

Efficient One‐Pot Synthesis of Bis(4‐hydroxycoumarin)methanes in the Presence of Sulfonic Acid Functionalized Nanoporous Silica (SBA‐Pr‐SO3H)

An efficient and simple method for the synthesis of bis(4‐hydroxycoumarin)methanes has been achieved through a one‐pot condensation of aryl aldehydes and 4‐hydroxycoumarin in the presence of nanoporous solid acid catalyst of SBA‐Pr‐SO₃H with pore size of 6 nm. Excellent yields, short reaction times, reusability of the catalyst and simple workup are advantages of this synthetic procedure.     

Determination of monocyclic aromatic amines using headspace solid‐phase microextraction based on sol–gel technique prior to GC

In this research, the headspace solid‐phase microextraction (SPME) coupled with GC flame ionization detector was applied for the determination of some monocyclic aromatic amines in real water and urine samples. A sol–gel technique was applied for the preparation of the SPME fibers. Two different sol–gel coatings, (PEG and poly(ethylene glycol) modified with multi‐walled carbon nanotubes [PEG/CNTs]), were prepared and compared. Extraction efficiency of PEG/CNTs was better than PEG fiber in the same conditions. To obtain maximum extraction efficiency, some parameters such as desorption temperature and time, temperature and time of extraction, salt effect, pH, and stirring speed were investigated and optimized for PEG/CNTs fiber. Under optimized conditions, the LODs (S/N = 3) were in the range of 0.5–50 ng/L and limits of quantification (S/N = 10) were between 1 and 500 ng/L. Repeatability (n = 5) was in the range of 3.2–9.1% and reproducibility (n = 3) was obtained from 5.5 to 12.0%. The method was successfully applied to the analysis of real water and urine samples with recoveries from 63.7 to 97.0%.     

Synthesis and characterization of Si-Zr-Mo nanocomposite as a rapid and efficient catalyst for aromatization of Hantzsch 1,4-dihydropyridines

Nanocomposite of Silica-zirconia-molybdate designated as Si-Zr-Mo was prepared via the reaction of the in situ generated zirconium-tetra octanoxide [Zr(Oct)₄] through condensation of zirconium-tetra-n-butoxide and 1-octanol in a sol–gel method with sulfuric acid and tetraethylorthosilicate (TEOS) followed by grafting of MoO₄^2? on modified silico zirconia nanocomposite under reflux conditions. The prepared nanocomposite was characterized using inductively coupled plasma (ICP), N₂ sorption isotherms, transmission electron microscopy (TEM), and FT-IR spectroscopy. The as prepared nanocomposite had a surface area and pore dimension of 140 m²/g and 1.48 nm, respectively. The morphology of sulphated silico zirconia nanocomposite after immobilization MoO₄^2? has been changed from nanoparticles to nanaorods. It was found that the synthesized nanocomposite successfully catalyze the oxidative dehydrogenation of 1,4-dihydropyridines (1,4-DHPs) with 92–100% conversion and 80–100% selectivity toward the desired products.