Synthesis of Some New Triphenylphosphanylidenes,Alkylphosphonates, and Heterocycles of Pyrazole Derivatives and Their Antimicrobial Activity

Abstract

The reaction of 5(4H)-pyrazolone with phosphorus ylides afforded new triphenylphosphanylidene alkanone derivatives. Moreover, its benzylidene derivative reacted with Wittig–Horner reagents to give the corresponding dialkoxyphosphoryl, alkyl phosphonate, and heterocyclic products. Treatment of pyrazole-4-carbaldehyde with Wittig–Horner reagents and trialkyl phosphites gave the respective alkyl phosphonate adducts. Mechanisms accounting for the formation of the new products are discussed. The biological activity of some of the newly synthesized compounds was also examined.     

Air‐assisted liquid–liquid extraction coupled with dispersive liquid–liquid microextraction and a drying step for extraction and preconcentration of some phthalate esters from edible oils prior to their determination by GC

In this work, a new, cheap, simple, fast, and low organic solvent consuming procedure is proposed for isolation, enrichment, and gas chromatographic determination of some phthalate esters in edible oils. The method is based on a combination of air‐assisted liquid–liquid extraction and dispersive liquid–liquid microextraction followed by a drying step under N₂ gas. Several experimental parameters affecting both extraction and preconcentration steps were investigated and optimized. Under the optimum conditions for the proposed method, wide linear ranges (0.05–800 μg/L) and low detection limits (0.007–0.023 μg/L) were observed. The ranges of enrichment factors and extraction recoveries were 68–340 and 14–68%, respectively. Eventually, the target analytes were successfully determined in different edible oils using the proposed method.     

Synthesis of Thio Analogues of Quinolone Antibacterials

A facile and rapid synthesis of thio compounds, analogues to ciprofloxacin, and norfloxacin is described.     

Simple and Efficient Procedure for the Friedel–Crafts Acylation of Aromatic Compounds with Carboxylic Acids in the Presence of P2O5/AL2O3 Under Heterogeneous Conditions

An efficient and chemoselective method for the Friedel–Crafts acylation of aromatic compounds using P₂O₅/Al₂O₃ and carboxylic acids. Both aromatic and aliphatic carboxylic acids reacted easily to afford the corresponding aromatic ketones in good yields.     

The first suberate lanthanum(III) complex without uncoordinated water

catena‐Poly­[[aqua­lanthanum(III)]‐μ‐(8‐carboxy­octanoato)‐μ‐octanedioato], [La(C₈H₁₂O₄)(C₈H₁₃O₄)(H₂O)]_n, is, to our knowledge, the first reported rare‐earth complex containing a flexible long‐chain ligand that crystallizes without water of crystallization. The layered polymeric structure is built from infinite chains of one‐edge‐sharing LaO₈(H₂O) polyhedra, connected through the carbon backbone chains of the ligands. The two chemically different ligands act in the same coordination modes, exhibiting chelating bonds and μ‐1,1‐bridging monodentate linkage, and adopting the same extended conformation. In the relatively limited hydrogen‐bonding network, a very strong hydrogen bond between the deprotonated and protonated ligand ends stabilizes the framework.     

Reaction of N‐(phenyl and methyl)‐C‐arylnitrones with DMAD in ionic liquid: Efficient synthesis of Δ4‐isoxazolines

Facile synthesis of N‐(methyl and phenyl)‐Δ⁴‐isoxazolines via the reaction of (Z)‐N‐(methyl and phenyl)‐C‐arylnitrones with dimethyl acethylenedicarboxylate, DMAD, in ionic liquid is described. (Z)‐N‐methyl‐C‐arylnitrones afforded the high yield of N‐methyl‐Δ⁴‐isoxazolines 4a , 4b , 4c , 4d , 4e in ionic liquid, [bmim]BF₄, at room temperature. However, the reaction of (Z)‐N‐phenyl‐C‐arylnitrones with DMAD afforded the mixtures of cis and trans isomers of related N‐phenyl‐Δ⁴‐isoxazolines ( 5a , 5b , 5c , 5d , 5e , 5f , 5g , 5h , 5i , 5j , 6a , 6b , 6c , 6d , 6e , 6f , 6g , 6h , 6i , 6j ) under these conditions. J. Heterocyclic Chem., (2012).     

Synthesis and characterization of active ester-functionalized polypyrrole-silica nanoparticles: application to the covalent attachment of proteins

Novel ester-functionalized polypyrrole-silica nanocomposite particles were prepared by oxidative copolymerization of pyrrole and N-succinimidyl ester pyrrole (50/50% initial concentrations), using FeCl3 in the presence of ultrafine silica nanoparticles (20 nm diameter). The N-succinimidyl ester pyrrole monomer was prepared in aqueous solution using 1-(2-carboxyethylpyrrole) and N-hydroxysuccinimide in the presence of 1-ethyl-3-(3-dimethylaminopropyl) carbodiimide. The resulting nanocomposites (N-succinimidyl ester polypyrrole-silica) are raspberry-shaped agglomerates of silica sol particles "glued" together by the insoluble poly(pyrrole-co-N-succinimidyl pyrrole). The N-succinimidyl ester polypyrrole-silica particles were characterized in terms of their size, density, copolymer content, and polydispersity. Scanning electron microscopy and disk centrifuge sedimentometry confirmed that the nanocomposite particles had narrow size distributions. X-ray photoelectron spectroscopy analysis indicated a silica-rich surface and a high surface concentration of N-succinimidyl ester groups. These nanoparticles exhibited good long-term dispersion stability. The chemical stability of the ester functions in aqueous media after several weeks of storage was monitored by FTIR spectroscopy. The functionalized nanocomposites were tested as bioadsorbents of human serum albumin (HSA). The very high amount of immobilized HSA determined by UV-visible spectroscopy is believed to be due to covalent binding. Incubation of the HSA-grafted nanocomposite with anti-HSA resulted in immediate flocculation, an indication that they are alternative candidates for visual diagnostic assays.     

Novel long chain unsaturated diisocyanate from fatty acid: Synthesis,characterization, and application in bio‐based polyurethane

A novel long chain linear unsaturated terminal diisocyanate, 1,16‐diisocyanatohexadec‐8‐ene (HDEDI) was synthesized from oleic acid via Curtius rearrangement. Its chemical structure was identified by FTIR, ¹H NMR, ¹³C NMR, and HRMS. This diisocyanate was used as a starting material for the preparation of entirely bio‐based polyurethanes (PUs) by reacting it with canola diol and canola polyol, respectively. The physical properties and crystalline structure of the PUs prepared from this diisocyanate were compared to their counterparts prepared from similar fatty acid‐derived diisocyanate, 1,7‐heptamethylene diisocyanate (HPMDI). The HDEDI based PUs demonstrated various different properties compared to those of HPMDI based PUs. For example, HDEDI based PUs exhibited a triclinic crystal form; whereas HPMDI based PUs exhibited a hexagonal crystal lattice. In addition, canola polyol‐HDEDI PU demonstrated a higher tensile strength at break than that of canola polyol‐HPMDI, attributed to the higher degree of hydrogen bonding associated with the former sample. Nevertheless, lower Young's modulus and higher elongation in canola polyol‐HDEDI PU were obtained because of the flexibility of the long chain introduced by the HDEDI diisocyanate. © 2010 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 48: 3302–3310, 2010     

A simple and rapid dispersive liquid-liquid microextraction method followed by GC-FID for determination of N-methylpyrrolidine in cefepime

A simple, rapid and efficient sample preparation technique, dispersive liquid-liquid microextraction, coupled with gas chromatography-flame ionization detection has been developed to determine N-methylpyrrolidine in cefepime. The effect of various experimental factors on the preparation procedure, such as the nature and volume of extraction and disperser solvents, extraction time, the nature of buffer and its pH, and salt effect, was investigated, optimized and the following results were obtained: extraction solvent, chloroform; dispersive solvent and solvent for dissolving cefepime, a mixture of methanol/water (88:12, v/v); salting out agent, NaCl; and buffer, carbonate/bicarbonate (C=0.5?M, pH=12). The optimized conditions were applied to the real sample (cefepime) for the extraction and determination of N-methylpyrrolidine. The calibration graph is linear from 0.02 to 850?mg/L with the square of correlation coefficient 0.999. LOD and LOQ are 6.4 and 21.2?μg/L in solution, respectively, and 0.2 (2×10(-5) ) and 0.6 (6×10(-5) ) μg/g (%, w/w) in cefepime powder, respectively, using sample size 50?mg. Repeatability of the method is good and RSD% for six repeated experiments (C=170?mg/L) is 6.35%.     

Protic ionic liquid [TMG][Ac] as an efficient,homogeneous and recyclable catalyst for Boc protection of amines

An efficient and practical protocol for the chemoselective N-Boc protection of various structurally different aryl, aliphatic and heterocyclic amines was carried out with (Boc)₂O using protic 1, 1, 3, 3-tetra-methylguanidinium acetate (10 mol%) as recyclable catalyst under solvent free condition at ambient temperature. No competitive side reactions (isocyanate, urea and N, N-di-Boc) were observed. α-Amino alcohols afforded the N-Boc-derivative without oxazolidinone formation.