Ionene supported peroxodisulfates: Polymeric reagents for the oxidative deprotection of <Emphasis Type=Italic>TMS</Emphasis> and <Emphasis Type=Italic>THP</Emphasis> ethers and oxidative cleavage of the C=N bond in water

Oxidative deprotection of trimethylsilyl and tetrahydropyranyl ethers, and deprotection of phenylhydrazones, semicarbazones, and oximes to their corresponding carbonyl compounds carried out in water at reflux condition using ionene supported peroxodisulfates is reported. The reagents are recyclable and products are obtained in excellent yield under environmentally benign conditions without overoxidation to carboxylic acid. Correspondence: Moslem Mansour Lakouraj, Department of Chemistry, Mazandaran University, Babolsar, Iran.     

Solvent-Free,Efficient, and High Regioselective Conversion of Epoxides to Symmetrical and Unsymmetrical vic-Dihalides Using Chlorodiphenylphosphine and N-Halosuccinimides

Abstract

A new method is described for the efficient and high regioselective conversion of epoxides to symmetrical and unsymmetrical vic-dihalides in high yields using chlorodiphenylphosphine and N-halosuccinimides under solvent-free and neutral conditions and at room temperature.

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GRAPHICAL ABSTRACT      

Flame atomic absorption spectrometry determination of trace amounts of copper after separation and preconcentration onto TDMBAC-treated analcime pyrocatechol-immobilized

A simple and reliable method has been developed for green separation and preconcentration of trace amounts of copper ions in aqueous solutions for subsequent measurement by flame atomic absorption spectrometry (FAAS). The Cu²⁺ ions are adsorbed selectively and quantitatively during the passage of an aqueous solution through TDMBAC-treated analcime pyrocatechol-immobilized. The retained copper ions were desorbed from the column with 5.0 mL of 4 mol L⁻¹ nitric acid solutions as eluent and were determined by FAAS. The linear range was 0.2-75 ng mL⁻¹ in the original solution with a correlation coefficient of 0.9987. In this case we can concentrate 0.1 μg of copper from 1000 mL of solution and the proposed method permits a large enrichment factor (about 200). The detection limit of the proposed method is 0.05 ng mL⁻¹ in the original solution (2σ_bl). Determination of copper in standard alloys showed that the proposed method has good accuracy (recovery was more than 97%). The method was successfully applied for recovery and determination of copper in several water samples.     

Ion Exchange Resin Catalyzed Selective Oxidation of Sulfides to Sulfoxides Using Hydrogen Peroxide

Summary. An efficient method for the selective oxidation of sulfides to sulfoxides under mild and environmentally safe conditions is achieved using hydrogen peroxide in the presence of Amberlyst 15 and Amberlite IR-400 at room temperature. This procedure can be applied for dialkyl and diaryl sulfides with a variety of functional groups. Functional groups such as hydroxyl, methoxy, amino, aldehyde, and olefinic double bonds remain intact.     

Ionene supported peroxodisulfates: Polymeric reagents for the oxidative deprotection of TMS and THP ethers and oxidative cleavage of the C=N bond in water

Oxidative deprotection of trimethylsilyl and tetrahydropyranyl ethers, and deprotection of phenylhydrazones, semicarbazones, and oximes to their corresponding carbonyl compounds carried out in water at reflux condition using ionene supported peroxodisulfates is reported. The reagents are recyclable and products are obtained in excellent yield under environmentally benign conditions without overoxidation to carboxylic acid.     

A facile and convenient method for the conversion of thioamides into amides using pyridinium hydrobromide perbromide

Selective transformation of thioamides to their corresponding carbonyl compounds are performed in high to excellent yields under mild conditions using pyridinium hydrobromide perbromide (PHBP) as a mild and efficient reagent. Correspondence: Moslem M. Lakouraj, Department of Organic Chemistry, Faculty of Chemistry, Mazandaran University, Babolsar 47416, Iran.     

Flame atomic absorption spectrometric determination of trace amounts of nickel after extraction and preconcentration onto natural modified analcime zeolite loaded with 2-(5-bromo-2-pyridylazo)-5-diethylaminophenol

Nickel is a moderately toxic element compared with other transition metals. However, inhalation of nickel and its compounds leads to serious problems, including cancer of the respiratory system and a skin disorder, nickel-eczema. Thus, attention has focused on the toxicity of nickel at low concentrations, and the development of reliable, analytical approaches for the determination of trace amounts of nickel is needed. This paper describes a simple, rapid, and sensitive flame atomic absorption spectrometric method for the determination of trace amounts of nickel in various samples after adsorption of its 2-(5-bromo-2-pyridylazo)-5-diethylaminophenol complex on a modified Analcime column in the pH range of 7.5-10.5. The retained analyte on the Analcime is recovered with 5.0 mL 2 M nitric acid and determined by flame atomic absorption spectrometry. The detection limit is 20 ng/mL, and the calibration curve is linear for analyte concentrations in the range of 0.1-8 microg/mL final solution, with a correlation coefficient of 0.9993. Eight replicate determinations of nickel at 2 microg/mL in the final solution gave an absorbance of 0.1222, with a relative standard deviation (RSD) of +/-1.2%. The interference of a large number of anions and cations was studied, and the proposed method was used for the determination of nickel in various standard reference samples. The accuracy of the proposed method was evaluated by analyzing standard reference samples, and the results were satisfactory (recoveries of >96%; RSD of <3.5%).     

Effect of Functionalized Magnetite Nanoparticles and Diaminoxanthone on the Curing,Thermal Degradation Kinetic and Corrosion Property of Diglycidyl Ether of Bisphenol A-Based Epoxy Resin

To prepare a high-performance epoxy resin with excellent thermal, chemical and corrosion stability, diaminoxanthone（DAX） was used to cure diglycidylether of bisphenol-A（DGEBA）-based epoxy resin and blend of DGEBA with functionalized Fe3O4 nanoparticles. Kinetic parameters of curing and thermal degradation of epoxy resin systems were estimated by differential scanning calorimetry（DSC） and thermogravimetric analysis（TGA）, respectively. The 10% weight loss temperature has been increased from 340 °C to 366 °C and there was an increase in the char yield from 32.6% to 45.3% for the above systems. The corrosion performance of epoxy coated carbon steel was examined by potentiodynamic polarization, along with immersion test in 1.0 mol/L HCl solution. The results showed that epoxy resins cured with DAX had low tendency to corrosion. In addition, the cured epoxy resin containing 10% Fe3O4 had higher anticorrosion activity than bare DGEBA system. The results showed that functionalized Fe3O4 nanoparticles enhanced char formation and improved the thermal stability as well as anticorrosion activity of the resin.     

Convenient Synthesis of Thiol Esters from Acyl Chlorides and Disulfides Using Zn/AlCl3

Summary.  Various thiol esters were prepared by condensation of acyl chlorides with disulfides in the presence of Zn/AlCl₃. The advantages of this method are high yields under relatively mild conditions, simple work-up, lack of toxicity, and low costs. Received July, 20, 2001. Accepted September 24, 2001