高有机可溶性聚酰胺负载磷钨酸(PW_(12)/PA):合成1,3,5-三芳基-2-吡唑啉衍生物的高效催化剂(英文)

A novel compound constructed from polyoxometalate (H3PW12O40,PW12) and poly(amidoamine) (PA) was prepared at room temperature in an aqueous solution by an impregnation method.A series of novel 1,3,5-triaryl-2-pyrazoline derivatives was synthesized by the reaction between chalcone and phenylhydrazine in the presence of the title compound,PW12/PA,in high yields.The structures of the compounds obtained were determined by IR and 1H NMR spectra.     

Determination of Hg(II) in Environmental Water Samples Using DLLME Method Prior to GC-FID

Mercury exists in two forms in environment, inorganic salts and organic compounds. Determination of mercury is very important, due to its health effects. In the present research, diphenylation of mercury using phenylboronic acid as a derivatization reagent was used for the determination of Hg(II) in real water samples. A simple, rapid and cheap method named dispersive liquid–liquid microextraction was used for the extraction of analyte under the following conditions: extraction solvent 16 μL of carbon tetrachloride, disperser solvent 1 mL of ethanol and sample volume 5 mL. Under the optimal conditions, the enrichment factor for diphenylmercury was 931 and the limit of detection calculated on the basis of five replicates was 0.004 μg mL^?1. The repeatability of the method expresses as relative standard deviation was 5.1 (n = 6). The linear range was between 0.01 and 10 μg mL^?1. The performance of the proposed technique was evaluated for the determination of mercury in different environmental water samples.     

Magnetic solid-phase extraction of Zineb by C18-functionalised paramagnetic nanoparticles and determination by first-derivative spectrophotometry

Fe₃O₄-SiO₂-C₁₈ paramagnetic nanoparticles have been synthesised and used as magnetic solid-phase extraction (MSPE) sorbent for the extraction of Zineb from agricultural aqueous samples under ultrasonic condition and quantified through a first-derivative spectrophotometric method. The produced magnetic nanoparticles were characterised by using scanning electron microscopy, X-ray diffraction spectroscopy, Fourier transform infrared spectroscopy and zeta potential reader. The Fe₃O₄-SiO₂-C₁₈ paramagnetic nanoparticles had spherical structures with diameters in the range of 198–201 nm. Further, MSPE was performed by dispersion of Fe₃O₄-SiO₂-C₁₈ paramagnetic nanoparticles in a buffered aqueous solution accompanied by sonication. Next, the sorbents were accumulated by applying an external magnetic field and were washed with 4-(2-pyridylazo) resorcinol-dimethyl sulfoxide solution, for the purpose of desorbing the analyte. The extraction conditions (sample pH, washing and elution solutions, amount of sorbents, time of extraction, sample volume and effect of diverse ions), as well as Zineb-PAR first-order derivative spectra, were also evaluated. The calibration curve of the method was linear in the concentration range of 0.055–24.3 mg L^?1 with a correlation coefficient of 0.991. The limit of detection and limit of quantification values were 0.022 and 0.055 mg L^?1, respectively. The precision of the method for 0.27 mg L^?1 solution of the analyte was found to be less than 3.2%. The recoveries of three different concentrations (0.27, 1.37 and 13.7 mg L^?1) obtained 98.3%, 98.5% and 96.0%, respectively. The proposed Fe₃O₄-SiO₂-C₁₈ paramagnetic nanoparticles were found to have the capability of reusing for 7.0 times.     

Nano catalytic synthesis of flavanone phosphonates using domino Knoevenagel-phospha-Michael route

Abstract

Novel derivatives of diethyl (4-oxo-2-phenylchroman-3-yl) methyl phosphonate have been synthesized under optimal conditions using domino-Knoevenagel-phospha-Michael reaction catalyzed by nano-zinc oxide. The combination of recovery and reusability of catalyst, simple and applicable approach, good reaction time and good yields of products make this method as a suitable route for this purpose. The structures of the products were determined by FT-IR, ¹H-, ¹³C- and ³¹P- Nuclear Magnetic Resonance spectroscopies, and elemental analysis.     

Configurational and Conformational Properties of 1,3,7,9-Tetraphospha-Cyclododeca-1,2,7,8-tetraene: An Ab Initio Study and NBO Analysis

An investigation employing the ab initio molecular orbital (MO) and density functional theory (DFT) methods to calculate structural optimization and conformational interconversion pathways for the two diastereoisomeric forms, (±) and meso configurations of 1,3,7,9-tetraphospha-cyclododeca-1,2,7,8-tetraene (1) was undertaken. Two axial symmetrical conformations are found for (±)-1 configuration. (±)-1-TB axial symmetrical form is found to be about 0.35 and 0.99 kcal mol^?1 more stable than (±)-1-Crown axial symmetrical conformation, as calculated by HF/6-31G*//HF/6-31G* and B3LYP/6-31G*//HF/6-31G* levels of theory, respectively. The unsymmetrical meso-1-TBCC form is found to be the most stable geometry, among the various conformations of meso-1 configuration. HF/6-31G*//HF/6-31G* and B3LYP/6-31G*//HF/6-31G* results showed that between the two most stable conformations of (±) and meso configurations, (±)-1-TB is more stable than meso-1-TBCC by about 3.35 and 2.43 kcal mol^?1, respectively. In addition, MP2/6-31G* and B3LYP/6-311+G** results showed that the (±)-1-TB form is about 1.10 and 2.36 kcal mol^?1 more stable than the meso-1-TBCC form. Further, NBO results revealed that in the most stable form of meso configuration (meso-1-TBCC), the sum of the π* allenic antibonding orbital occupancies (Σ π *_occupancy) is greater than dl configuration ((±)-1-TB). Also, NBO results indicated that in the (±)-1-TB conformer, the sum of σ and π allenic moieties bonding orbital deviations (Σ σ _dev+Σ π _dev) from their normal values, is lower than in the meso-1-TBCC form.     

Synthesis and characterization of VO–vanillin complex immobilized on MCM-41 and its facile catalytic application in the sulfoxidation reaction,and synthesis of 2,3-dihydroquinazolin-4(1H)-ones and disulfides in green media

In this work, a vanillin complex is immobilized onto MCM-41 and characterized by FT-IR, X-ray diffraction, scanning electron microscopy, energy dispersive spectroscopy, thermogravimetric analysis, and BET techniques. This supported Schiff base complex was found to be an efficient and recoverable catalyst for the chemoselective oxidation of sulfides into sulfoxides and thiols into their corresponding disulfides (using hydrogen peroxide as a green oxidant) and also a suitable catalyst for the preparation of 2,3-dihydroquinazolin-4(1H)-one derivatives in water at 90°C. Using this protocol, we show that a variety of disulfides, sulfoxides, and 2,3-dihydroquinazolin-4(1H)-one derivatives can be synthesized in green conditions. The catalyst can be recovered and recycled for further reactions without appreciable loss of catalytic performance.     

Synthesis of Functionalized Pyrroles by Reaction of 3,4‐Diacetylhexane‐2,5‐dione with Primary Amines in Water

3,4‐Diacetylhexane‐2,5‐dione (tetra‐acetylethane) undergoes a complex reaction with primary amines in boiling water to produce N‐alkyl‐3‐acetyl‐2,5‐dimethylpyrroles, together with small quantities of N‐alkyl‐3,4‐diacetyl‐2,5‐dimethylpyrroles and 2,5‐dimethyl‐1H‐pyrrol‐3‐yl‐vinyl‐acetamides. When the reaction was carried out in methanol at room temperature, the yields of the latter products increased.     

Oxidation of 1,4-Dihydropyridines under Mild and Heterogeneous Conditions

A combination of NaHSO₄.H₂O and NaNO₂ in the presence of wet SiO₂ was used as an effective oxidizing agent for the oxidation of dihydropyridines to their corresponding pyridine derivatives at room temperature with excellent yields.