Syntheses and structural characterization of New Tl + and K + complexes of 3,5-dinitrobenzoic acid (HDNB), [Tl(μ-DNB)] n and [K(μ-DNB)(μ-HDNB)] n

Two new Tl⁺ and K⁺ complexes of 3,5-dinitrobenzoic acid (HDNB), [Tl(μ-DNB)] _n and [K(μ-DNB)(μ-HDNB)] _n have been synthesized and characterized by elemental analysis, IR, ¹H NMR and ¹³C NMR spectroscopy. Determination of the structure of the [K(μ-DNB)(μ-HDNB)] _n and [Tl(μ-DNB)] _n by X-ray crystallography shows that there are nine coordinate K atoms (KO₉) and eight coordinate Tl atoms (TlO₈). The [Tl(μ-DNB)] _n and [K(μ-DNB)(μ-HDNB)] _n complexes are 2D and 3D coordination polymers, respectively.     

An active and selective heterogeneous catalytic system for Michael addition

Potassium fluoride doped natural zeolite was found to be an efficient and selective solid base catalyst for 1,4-Michael addition. The catalyst is easily prepared and the workup procedure simplified by simple filtration.All products were obtained in high yields as well as short reaction times.     

GRAFT COPOLYMERIZATION OF METHYL ACRYLATE ONTO CHITOSAN INITIATED BY POTASSIUM DIPERIODATONICKELATE (IV)

ABSTRACT

A novel redox system, potassium diperiodatonickelate [Ni (IV)]‐chitosan, was employed to initiate the graft copolymerization of methyl acrylate (MA) onto chitosan in alkali aqueous solution. The effects of reaction variables such as monomer concentration, initiator concentration, reaction time, pH and temperature were determined. By means of a series of copolymerization, the grafting conditions were optimized. The maximum grafting percentage obtained was 404.1% when 0.3 g chitosan was copolymerized with 1.8 mL monomer at 35°C for 5 hours with [Ni (IV)]=9.4×10^?4 M and the total volume was 20 mL. Ni (IV)-chitosan system is found to be an efficient redox initiator for this graft copolymerization. A single electron transfer mechanism is proposed to explain the formation of radicals and the initiation. The grafted copolymers were characterized by IR and X-ray diffraction diagrams. The thermal stability of chitosan and chitosan-g-PMA was studied by thermogravimetric analysis (TGA).     

Kinetic Study on Models of the Noncatalyzed Reaction Between α, ω -Dicarboxypolyamide-11 and α, ω -Dihydroxypolyoxyalkylenes

The kinetics of the noncatalyzed reaction between α, ω -dicarboxypoly-amide-11 and α, ω -dihydroxypolyoxyalkylenes is investigated by using the reactions of 11-dodecylamidoundecanoic acid with 1-dodecanol, 2-tridecanol, α-dodecyl-ω-hydroxypolyoxyethylene or α-dodecyl-ω;-hydroxypolyoxypropylene as models. Kinetic data fit a 3rd overall order (2 in acid and 1 in alcohol). Rate constants and activation parameters are determined and compared.     

Biparametric potentiometric analytical microsystem for nitrate and potassium monitoring in water recycling processes for manned space missions

The construction and evaluation of a Low Temperature Co-fired Ceramics (LTCC)-based continuous flow potentiometric microanalyzer prototype to simultaneously monitor the presence of two ions (potassium and nitrate) in samples from the water recycling process for future manned space missions is presented. The microsystem integrates microfluidics and the detection system in a single substrate and it is smaller than a credit card. The detection system is based on two ion-selective electrodes (ISEs), which are built using all-solid state nitrate and potassium polymeric membranes, and a screen-printed Ag/AgCl reference electrode. The obtained analytical features after the optimization of the microfluidic design and hydrodynamics are a linear range from 10 to 1000 mg L⁻¹ and from 1.9 to 155 mg L⁻¹ and a detection limit of 9.56 mg L⁻¹ and 0.81 mg L⁻¹ for nitrate and potassium ions respectively.     

Oxidation of Benzylic Alcohols to Carbonyl Compounds with Potassium Permanganate in Ionic Liquids

Abstract

The selective oxidation of primary and secondary benzylic alcohols with potassium permanganate in ionic liquids to give corresponding aldehydes and ketones in 83–97% yields has been described.     

An environmentally benign synthesis of isoxazolines and isoxazoles mediated by potassium chloride in water

An effective and environmentally benign procedure for the synthesis of isoxazolines and isoxazoles has been developed by a cycloaddition of nitrile oxides with alkenes or alkynes in water. In this approach, potassium chloride is first oxidized into chlorine in water by the environmentally friendly oxidant Oxone®, then aldoximes are oxidized into nitrile oxides by the in situ generated hypochlorous acid, finally a 1,3-dipolar cycloaddition between nitrile oxides and alkenes or alkynes occurs to provide the corresponding isoxazolines and isoxazoles in good yields.     

Catalyst free,base free microwave irradiated synthesis of aryl nitrites from potassium aryltrifluoroborates and bismuth nitrate

A mixture of bismuth nitrate pentahydrate and potassium aryltrifluoroborate in toluene under microwave heating at 120 °C for 20 min provides an interesting and mild reaction protocol for the synthesis of aryl nitrite. The conversion to aryl nitrites from aryltrifluoroborates without transition metal catalyst and base in high yields is remarkable.     

Catalyzation of 1,4-additions of arylboronic acids to α,β-unsaturated substrates using nickel(I) complexes

Nickel(I) complexes were generated in situ from Ni (PPh₃)₂Cl₂ using activated iron and the complexes combined with N,N′-bis(4-fluorobenzylidene) ethane-1,2-diamine (BFBED) were then used as a catalyst for the 1,4-addition reaction of arylboronic acids to α,β-unsaturated substrates. The reaction proceeded to completion and did not require the addition of a base but the addition of potassium iodide is crucial to this cross-coupling reaction. Moreover, experimental observations suggested a possible Ni(I)–Ni(III) catalytic cycle mechanism.     

Molecular Dynamics in 1- and 2-D Confinement as Studied for the Case of Poly(Cis-1,4-Isoprene)

Broadband Dielectric Spectroscopy (BDS) is used to probe the molecular dynamics of Type A polymer, poly(cis-1,4-isoprene), when confined in the 1-dimensional (1D) exploring space of thin layers and the 2-dimensional (2D) constraining geometry of unidirectional anodic aluminum oxide (AAO) nanopores. For both cases, it was observed that the structural relaxation remains bulk-like in its mean relaxation rate, although the distribution of its relaxation times is broadened in 2D confinement. Furthermore, the fluctuation of the end-to-end vector is interrupted, with the 1D case being relatively less pronounced. By this clear-cut comparison, it is demonstrated that the effects of confinement on molecular dynamics depend, inter alia, on the dimensionality of the restricting space.