Polymeric catalysts. IX. Cobalt complexes of polyureas based on bipyridine pyridine and crown ether for aldol condensation

We report herein studies of Co(OAc)₂ and related transition metal compounds which serve as catalysts for aldol condensations when complexed with bipyridine, triphenyl phosphine, and crown ether. A comparison has been made with polymeric complexes of cobalt(II), which serve the same purpose. Cobalt complexes of built-in polyureas based on bipyridine and crown ether as well as those immobilized to polystyrene by triphenylphosphine and poly(4-vinyl pyridine) are also reported.     

Inorganic oxide core, polymer shell nanocomposite as a high K gate dielectric for flexible electronics applications

Organic/inorganic core shell nanoparticles have been synthesized using high K TiO(2) as the core nanoparticle, and polystyrene as the shell. This material is easy to process and forms transparent continuous thin films, which exhibit a dielectric constant enhancement of over 3 times that of bulk polystyrene. This new dielectric material has been incorporated into capacitors and thin film transistors (TFTs). Mobilities approaching 0.2 cm(2)/V.s have been measured for pentacene TFTs incorporating the new TiO(2) polystyrene nanostructured gate dielectric, indicating good surface properties for pentacene film growth. This novel strategy for generating high K flexible gate dielectrics will be of value in improving organic and flexible electronic device performance.     

Studies on polymerization of vinyl acetate using ylide as an initiator and degradative transfer agent

Polymerization of vinyl acetate initiated by β-picolinium p-chlorophenacylide was carried out at 30, 35, and 40°C, using conventional dilatometric technique. The initiator and the monomer exponent values were 0.80 ± 0.15 and unity, respectively. The polymerization was inhibited in the presence of hydroquinone, but was favored by nonpolar solvent and polymerization temperature. The energy of activation was 90.3 KJ mol^?1. An average value of k/k_t for the present system was found to be 0.37 × 10^?2. The results are explained in terms of a radical mode of polymerization with degradative initiator transfer; the principal mode of termination, however, was bimolecular.     

Melt-polymerizable bisimido-bisphthalonitriles containing silicon,fluoro, and ether groups: Synthesis,characterization, and NMR study

Various melt-polymerizable bisimido-bisphthalonitrile polymer precursors were synthesized by the reaction of 4-aminophthalonitrile (4-APN) with bis(3,4-dicarboxyphenyl) dimethylsilane dianhydride (SIDA), 4,4′-hexafluoroisopropylidene diphthalic anhydride (6FDA), bis(3,4-dicarboxyphenyl)ether dianhydride (ODPA), and 3,3′, 4,4′-tetracarboxylichenzophen+ne dianhydride (BTDA) in an aprotic solvent. The synthesized monomers showed crystalline melting at 269 and 271°C. Elemental analysis, differential thermal analysis (DTA), infrared (IR), nuclear magnetic resonance (¹H-NMR) and mass spectral studies were carried out to characterize the synthesized monomers. Thermogravimetric analysis (TGA) of the synthesized monomers showed their thermal stability at 410–400°C. A detailed study and NMR investigation of the first step of condensation reaction was carried out and indicated the formation of a transient charge transfer complex. Thermal cyclization of the formed intermediate, however, gave the required monomers. A preliminary study demonstrated that melt-polymerization of the synthesized monomers gave thermallystable, tough polymers.     

The structure of malabricol

A single crystal X-ray analysis has confirmed the constitution and established the stereochemistry of the triterpene, malabaricol.     

Electrocatalytic activity of binary Palladium Ruthenium anode catalyst on Ni-support for ethanol alkaline fuel cells

In search for a cheaper anode catalyst for the oxidation of ethanol for development of direct alcohol fuel cells, Pd has been considered here as an interesting substitute for Pt in Pt Ru binary electrodeposite. The binary catalyst when co-deposited on nickel support has been found to increase the current density and decrease the anodic overvoltage significantly with respect to pure Pt, Pd and Ni. Its electrocatalytic capability is also comparable with that of the Pt-Ru binary electrocatalyst on Ni-support, when studied in 1 M EtOH containing 1 M NaOH solution. The effect of loading of Pd Ru electrocatalyst on Ni support has also been tested. The electrocatalytic activity of the electrodes for oxidation of ethanol has been explained by studies of cyclic voltammetry, chronopotentiometry, steady-state polarization, and conjugated scanning electron microscopy–energy dispersion X-ray spectroscopy. It has been found that electrode containing the higher amount of deposit are less affected by carbonaceous poisons.     

A novel one-pot conversion of amines to homologated esters in poly(ethylene glycol)

The first deaminative homologation of amines (-CH₂NH₂) to esters (-CH₂CH₂COOEt) in one-pot is reported. The reaction proceeds through, formation of an aldehyde from an amine in the presence of Pd/C as catalyst followed by Wittig reaction and catalytic hydrogenation using poly(ethylene glycol) as the solvent in one-pot.     

Mechanism of the oxidation of cycloheptanone by chloramine-T

The oxidation kinetics of cycloheptanone by chloramine-T in alkaline media has been investigated. A mechanism involving the formation of an intermediate by the interaction between the enolic anion of cycloheptanone and chloramine-T in a slow step followed by its interaction with another molecule of chloramine-T in a fast step leading to products has been proposed. The scheme satisfactorily accords with the observed stoichiometry, negligible influence of ionic strength and a positive dielectric effect. Various rate parameters have been computed and 1.2-cycloheptanedione identified as the end product.With 2 Figures     

Cobalt-catalyzed regioselective carbocyclization reaction of o-iodophenyl ketones and aldehydes with alkynes, acrylates, and acrylonitrile: a facile route to indenols and indenes

An efficient cobalt-catalyzed carbocylization for the synthesis of indenols and indenes and a new method for reductive decyanation are described. 2-Iodophenyl ketones and aldehydes 1a-g undergo carbocyclization with various disubstituted alkynes 2a-k in the presence of Co(dppe)I(2) and zinc powder in acetonitrile at 80 degrees C for 3 h to afford the corresponding indenol derivatives 3a-s and4a-m in good to excellent yields. For some unsymmetrical alkynes, the carbocyclization was remarkably regioselective, affording a single regioisomer. The cobalt-catalyzed carbocyclization reaction was successfully extended to the synthesis of indene derivatives. Thus, the reaction of 2-iodophenyl ketones and aldehydes (1) with acrylates H(2)C=CHCO(2)R (7a-d) and acrylonitrile H(2)C=CHCN (7e) proceeds smoothly in the presence of Co(dppe)Cl(2)/dppe and zinc powder in acetonitrile at 80 degrees C for 24 h to afford the corresponding indenes 8a-k and 9a-c in moderate to good yields. Interestingly, when 7e was employed for the carbocylization, reductive decyanation also occurred to give an indene derivative without the cyano functionality. A possible mechanism for this cobalt-catalyzed carbocyclization reaction is also proposed.     

Analytical applications of a differential technique in laser-induced fluorimetry: accurate and precise determination of uranium in concentrates and for designing microchemielectronic devices for on-line determination in processing industries

A novel instrumental technique for the direct, fast, accurate, and precise determination of uranium in concentrates and other U-rich materials (as well as to mineralized rocks) is presented. The proposed technique is an absolute methodology, based on the comparison of the fluorescence of the accurately known standard with a sample of similar but unknown concentration in the low operational range of the instrument (on same sample-dilution basis), by the use of H₃PO₄-NH₄H₂PO₄ as a fluorescence-enhancing reagent. The relative standard deviation of the proposed technique was 0.5-0.9% (n=9) at 18.1, 36.2, 61.2, and 99.6% U₃O₈. The proposed technique is suitable for the determination of uranium in samples arising from exploration projects, ores from mining operations, mill process samples, uranium ore concentrates leading to fuel fabrication as well as samples from environmental monitoring containing up to 100% uranium. The results are in good agreement with those obtained by titrimetric, gravimetric, and TBP extraction-H₂O₂ spectrophotometric methods. The precision of the technique is within the acceptable ‘pure geochemistry’ type of analysis (R.S.D. ∼ 1.0%) and is comparable even those obtained with titrimetric and gravimetric assay. The proposed differential technique coupled with flow injection may open up new advancement in instrumentation leading to design and development of microchemielectronic devices for direct on-line determination, more compatible with the tools of computer age as also to help in handling of radioactive solutions in chemical laboratories in uranium processing industries.