SOME REACTIONS OF ALIPHATIC AMIDES WITH SULFUR AND SODIUM POLYSULFIDES

Abstract

Some reactions of the aliphatic amides, CH₃CONH₂, CH₃CONHCH₃, CH₃CON(CH₃)₂ and CH₃CON(C₂H₅)₂ with elemental S and sodium sulfides, Na₂S _n , n ≥ 1, have been studied. The initial reaction product with elemental sulfur appears to be a substituted polysulfane, CH₃COS _n NR, formed by the insertion of the sulfur chain into the C[sbnd]N bond. This product decomposes on further heating, forming COS as the major gas product. In solutions of Na₂S _n in the amides, the reactive material appears to be elemental S, present in equilibrium with S _n ^?2. In the N-dialkyl substituted amides, CH₃CON(CH₃)₂ and CH₃CON(C₂H₅)₂, the tetrasulfide is uniquely stabilized by solvent coordination so that solutions of Na₂S₄ in these amides are stable for long periods of time at 130°C.     

Integrated Ion Exchange and Liquid-Liquid Extraction Process for the Separation of Platinum Group Metals (PGM)

A process for concentration and separation of platinum group metals (PGM) by a combination of ion exchange and liquid-liquid extraction is presented. First the PGM metals are dissolved by HC1/C1₁ and then passed through an isothiouronium anion exchange resin, where specific absorption occurs. The thiourea eluate from the resin is converted to the chloride complexes. Further hydrolysis (conditioning) yields an aqueous feed to a liquid-liquid extraction step, with Alamine-336. Platinum and palladium are very well extracted, while most of the other PGM are rejected in the aqueous phase. The liquid-liquid extraction can be used by itself, if the level of the base metals does not exceed the concentration of the PGM ions.

Platinum and palladium are now separated from each other by the selective stripping of palladium with thiourea, and platinum with thiocyanate.

The paper discusses the extraction chemistry of all the steps, and provides also experimental pilot-plant results.     

Ligand-supported palladium-catalyzed cross-coupling reactions of (hetero) aryl chlorides

The introduction of electron rich and sterically hindered ligands has made otherwise inert aryl chlorides and hetero aryl chlorides viable coupling partners in palladium-catalyzed Suzuki-Miyaura, Sonogashira, Stille and other types of cross-coupling reactions. This review gives highlights of cross-coupling of aryl chlorides employing in situ generated palladium catalytic systems.     

Practical and Chemoselective Reduction of Acyl Chloride to Alcohol by Borohydride in Aqueous Dichloromethane

A simple methodology for the reduction of acid chlorides to their corresponding alcohols has been developed. Various carboxylic acids were converted to alcohols in excellent yields using NaBH₄-K₂CO₃ in a mixed solvent system of dichloromethane and water (1:1) in the presence of a phase-transfer catalyst at low temperature. The importance of the work is its simplicity, selectivity, excellent yield, and very short reaction time. This new reduction condition has proved to be an excellent chemoselective method for a range of acid chlorides in the presence of various functional groups.     

Microwave-assisted methods for the synthesis of pentacyclo[5.4.0.0.0.0]undecylamines

Efficient methodologies for the preparation of pentacyclo[5.4.0.0^2,6.0^3,10.0^5,9]undecane (PCU) amine derivatives are described via microwave-assisted synthesis. The obtained results revealed that microwave-assisted synthetic procedures under controlled conditions (power, temperature and time) are very convenient, high yielding, efficient and low-cost methods for the preparation of PCU amine derivatives. The new methods show several advantages including operational simplicity, good performance, significant reduction in reaction time, less by-product formation and easier purification.     

Correlation of the Solubilizing Abilities of 1-Butyl-1-methyl-pyrrolidinium Tris(pentafluoroethyl)trifluorophosphate, 1-Butyl-1-methylpyrrolidinium Triflate and 1-Methoxyethyl-1-methylmorpholinium Tris(pentafluoroethyl)trifluorophosphate

Chromatographic retention data were measured for a wide range of organic solutes on 1-butyl-1-methylpyrolidinium tris(pentafluoroethyl)trifluorophosphate ([BMPyrr]⁺[FAP]^?), 1-butyl-1-methylpyrrolidinium triflate, ([BMPyrr]⁺[Trif]^?), and 1-methoxyethyl-1-methylmorpholinium tris(pentafluoroethyl)trifluorophosphate, ([MeoeMMorp]⁺[FAP]^?), stationary phases at (323, 353 and 383) K. The measured retention factors were combined with published infinite dilution activity coefficient and gas-to-water partition coefficient data to yield gas-to-anhydrous ionic liquid (IL) and water-to-anhydrous IL partition coefficients. The three sets of partition coefficients were analyzed using the Abraham model. The derived Abraham model correlations describe the observed gas-to-IL (log₁₀ K) and water-to-IL (log₁₀ P) partition coefficient data to within average standard deviations of about 0.11 and 0.15 log₁₀ units, respectively.     

Protein-Polysaccharide Interactions for Stabilization of Food Emulsions

Proteins, polysaccharides and their blends, as examples of natural biopolymers, are surface active materials. Biopolymers may be considered as amphiphilic macromolecules that play an essential role in stabilizing food formulations (foams, emulsions and dispersions). Under specific conditions (such as protein-to-polysaccharide ratio, pH, ionic strength, temperature, mixing processing), it has been stated that proteins and polysaccharides form hybrids (complexes) with enhanced functional properties in comparison to the proteins and polysaccharides alone. Different protein-polysaccharide pairs are reviewed with particular attention to the emulsification capability of their mixtures. In the case of uncomplexed blends of biopolymers, competitive adsorption onto hydrophobic surfaces is generally reported. Conversely, electrostatic complexation between oppositely charged proteins and polysaccharides allows better anchoring of the new-formed macro-molecular amphiphile onto oil-water interfaces. Moreover, improved thermal stability and increased resistance to external treatment (high pressure) involved in food processing are obtained. This review presents basic and applied knowledge on protein-polysaccharide interactions in aqueous medium and at the oil-water interface in food emulsion systems. Electrostatic interactions and thermodynamic incompatibility in mixed biopolymer solutions are correlated to the functional properties (rheology, surface hydrophobiciry, emulsification power) of these interesting blends. Basic and industrial selected systems of different families of hydrocolloids (as gum Arabic, galactomannans, pectins) and protein (caseins, whey, soya, gelatin) mixtures are reviewed.     

Crystallization of Celecoxib in Microemulsion Media

Celecoxib belongs to a new NSAID family specifically inhibiting cyclooxygenase‐2 (COX‐2). The present formulations require high dosage since the transmembrane transport fluctuates and is very difficult to control. We solubilized celecoxib in micelles of nonionic microemulsions and hydrophilic surfactant. The supersaturated solubilized drug was precipitated from the nano‐droplets to form a new solid structure with improved dissolution properties. The selected microemulsion systems loaded with celecoxib were characterized by SAXS, SD‐NMR, viscosity, and electrical conductivity techniques. Precipitation was conducted from W/O as well as from O/W U‐type microemulsions. The crystals obtained by the precipitation were characterized by x‐ray powder scattering, differential scanning calorimetry, FTIR measurements, and microscopic scans.     

Advances in RNA Interference Technology and Its Impact on Nutritional Improvement, Disease and Insect Control in Plants

This review highlights the advances in the knowledge of RNA interference (RNAi) and discusses recent progress on the functionality of different components RNAi machinery operating in the organisms. The silencing of genes by RNA interference has become the technology of choice for investigation of gene functions in different organisms. The refinement in the knowledge of the endogenous RNAi pathways in plants along with the development of new strategies and applications for the improvement of nutritional value of important agricultural crops through suppression of genes in different plants have opened new vistas for nutritional security. The improvement in the nutritional status of the plants and reduction in the level of toxins or antinutrients was desired for long, but the available technology was not completely successful in achieving the tissue specific regulation of some genes. In the recent years, a number of economically important crop plants have been tested successfully for improving plant nutritional value through metabolic engineering using RNAi. The implications of this technology for crop improvement programs, including nutritional enrichment, reduction of antinutrients, disease, and insect control have been successfully tested in variety of crops with commercial considerations. The enhancement of the nutraceutical traits for the desired health benefits in common crop plants through manipulation of gene expression has been elaborated in this article. The tremendous potential with RNAi technology is expected to revolutionize the modern agriculture for meeting the growing challenges is discussed.