SOME REACTIONS OF 3-AMINO-2-CARBOETHOXY-4,6-DIMETHYLTHIENO[2,3-b]-PYRIDINE. SYNTHESIS OF SOME NEW THIENOPYRIDOPYRIMIDINES

Abstract

Thienopyridine oxazinone (1) has been prepared and explored as a precursor by its reaction with some reagents namely, ammonium acetate, aliphatic amines, aromatic amines, hydrazine hydrate, thiosemicarbazide, and ethyl glycinate to give pyridothienopyrimidines (11-VII). The pyrimidinone compound (11) was converted to the 4-chloro derivative (X) by its reaction with excess POCl₃ Interaction of the 4-chlorocompound (X) with some reagents namely, hydrazine hydrate, methyl amine, aniline, sodium thiophenolate, ethyl glycinate, thiosemicarbazide and thiourea, yielded pyridothieno-pyrimidine derivatives (XI-XVII) substituted at 4-position, respectively.     

SYNTHESIS AND BIOLOGICAL ACTIVITY OF SOME NEW 8-HYDROXYQUINOLINE SULPHONAMIDE DERIVATIVES

Abstract

Some new derivatives containing both 8-hydroxyquinoline and sulphonylamino β-lactams and thiazolidinones have been prepared. These compounds were synthesized from the corresponding 8-hydroxyquinoline sulphonylhydrazide (1) by converting it to hydrazones (2). The latter hydrazones (2) were easily transformed to β-lactams (3) and thiazolidinones (4) by cyclocondensation reaction with chloroacetyl chloride and/or mercaptoacetic acid. Some metal chelates with Fe³⁺. Co²⁺+, Ni²⁺, Cu²⁺ and Cd²⁺ have been prepared for some of the compounds and screened in vitro for their biological activity.     

Synthesis of Novel Semiconducting Aromatic Polyesteramids Containing Pyridine: Characterization of Nanometer-Sized Rod-Like Analogues and their Copper (II) Complexes

In this paper, new thermally stable isomeric unsubstituted polyesteramides have been successfully prepared by condensation of aromatic acids chlorides namely; isophthaloyl, pyridine-3,5-dicarbonyl and pyridine-2,6-pyridine-dicarbonyl dichlorides with the aminophenol isomers in NMP. Conducting the reaction in NMP/H₂O (90/10 v/v) followed by centrifugal separation furnished the desired polymers as rod-like nanoparticles. The morphology of obtained nanoparticles were studied by SEM. Mixing NMP with H₂O was essential for controlling the particles morphology and as a reaction accelerator.

Pyridine-containing polymers exhibit semi-conducting nature as their conductivities increase with increasing temperature, while no variation of the conductivity with the temperature was observed for their corresponding phenylene analogues. Introduction of the nitro group into the polymer backbone led to a red shift in the absorption and the obtained polymers have a bright yellow color, which is unusual with this polymer group. Copper (II) ions were complexed the polyesteramides-containing nitro group in a (1:1) ratio. Complexes of pyridine-containing polymers exhibit semiconducting nature changed to metallic characters on heating and their conductivities increased tens of magnitudes than their corresponding ligands. These new types of polymeric materials and their nano-sized rods may have numerous applications in nanotechnology and their properties can be tuned for specific applications such as conducting adhesives and coating materials.     

Magnetic Polymer Composite Particles Via In situ Inverse Miniemulsion Polymerization Process

We aimed at preparing magnetic iron oxide particles by the oxidation-precipitation method in order to encapsulate these particles in polymer matrices composed of poly(acrylamide-styrene sulfonic acid sodium salt). Nanocomposites were synthesized by the incorporation of surface treated magnetic nanoparticles in the synthesized polymers via in situ inverse mini-emulsion polymerization process. The study parameter was the ionic monomer content in the synthesized polymers. The structure and the morphology of the magnetic nanogels were characterized by Fourier transform infrared spectroscopy (FTIR), X-ray diffraction (XRD), dynamic light scattering (DLS), thermal gravimetric analysis (TGA) and scanning electron microscopy (SEM). FTIR and XRD showed that pure magnetite was formed and successfully encapsulated in the composite nanoparticles. The polymer encapsulation could reduce the susceptibility to leaching and could protect the magnetite particle surfaces from oxidation. The ionic monomer content had a great effect on the magnetization behavior. Magnetite prepared by the oxidation precipitation method, of 50 nm mean particle size, was embedded successfully into the polymer nanogels with a reasonable magnetic response, as proved by vibrating sample magnetometer measurement. Magnetic nanocomposites were proven to be super-ferromagnetic materials.     

Synthesis and Characterization of Organosoluble Poly(imide-ether)s with Bulky 2,3-Diaryl Imidazole Moiety: Study Physical,Thermal and Optical Properties

Two new symmetrical diamines were designed and synthesized having different functional groups such as a pair of phenyl ether linkages, 2,3-diaryl substituted imidazole rings and CF₃ groups as pendant, and characterized by FT-IR, ¹H and ¹³C-NMR spectroscopy and elemental analysis. A series of new fluorescent poly(imide-ether)s (PIEs) was prepared by polymerization of the diamines with commercial tetracarboxylic dianhydrides such as pyromellitic dianhydride and 3,3′,4,4′-benzophenone tetracarboxylic dianhydride. The resulting PIEs were amorphous and had intrinsic viscosity [η] in the range of 0.42–0.51 dL/g. The weight average molecular weights (Mw) of these polymers were measured by GPC and were in the range of 28658–35595 g/mol with molecular weight distribution (MWD) of 2.12–2.27. These polymers were readily soluble in a variety of organic solvents and formed low-colored and flexible thin films with cut-off wavelength (λ₀) in the range of 385–420 nm, and all PIEs films exhibited high optical transparency. They also possessed good thermal stability with 10% weight loss temperatures (T_10%) in the range 486–537°C in N₂. The glass transition temperatures (T_g) of PIEs are in the range 251–324°C. These polymers showed fluorescence emission in film and in solution at 459–476 nm with the quantum yields in the range 4–12%.     

New Coordination Polymers of 1,4-Bis(2″-Hydroxyphenylazomethine) Phenylene

Coordination polymers of 1,4-bis(2′-hydroxyphenylazomethine) phenylene have been prepared with the metal ions Ti(III), Cr(III), Fe(III), Mn(II), Ni(II), and Cu(II). They were characterized by elemental analysis, IR, and electronic spectra. The metal contents in all polymers were found to be consistent with a 1:1 (metal:ligand) stoichiometry. The thermal behavior of these coordination polymers has been studied by thermogravimetric analysis in air up to 750°C, and the data showed that they are thermally stable up to 200°C. Physical properties such as the solubility and viscosity of the polymer complexes were also determined. Electrical conductivity measurements of the synthesized polychelated polymers showed that they are insulators except for the Ni(II) complex which shows a semiconducting character. Mössbauer data clearly establish the 3 + oxidation state for the iron complex polymer.     

Synthesis,characterisation and supramolecular interaction of Rh-biphenylic-imidazole-phenanthroline with antibiotics

A novel rhodium biphenylic imidazole phenanthroline metal-organic complex (BIP-MC) has been synthesised and characterised as a stable supramolecule. The structure of compound was established on the basis ESI, ¹H NMR and UV–vis spectroscopic data. The selectivity of BIP-MC as a new fluorescent chemosensor for various antibiotics has been explored. The supramolecular interaction of amoxicillin with BIP-MC enhanced the fluorescence activity of BIP-MC. A linear response of the sensor was observed in the measuring ranges of excitation 240–298 nm and emission 290–360 nm with detection limits of up to 10 μg/ml at an optimum pH 8.0. Based on the observations made here, a new quantitative method for the determination of this drug in synthetic samples without the use of separation of matrix is developed. It is also inferred that the possible fluorescence enhancement is due to the formation of exciplex between the BIP-MC and amoxicillin. These finding will thus help in pharmacokinetics studies of drugs. The sensor was used for the direct assay of amoxicillin antibiotic in commercial pharmaceutical preparations.     

Solanopubamine,a rare steroidal alkaloid from Solanum schimperianum: Synthesis of some new alkyl and acyl derivatives,their anticancer and antimicrobial evaluation

Solanopubamine (3β-amino-5α, 22αH, 25βH-solanidan-23β-ol), a steroidal alkaloid was isolated from the alkaloidal fraction of Solanum schimperianum in significant yield. Its structure was established by IR, positive ESI-MS, 1D and 2D NMR. The presence of -3β-NH₂ and -23β-OH groups was achieved through methylation, acetylation or coupling with octadecanoic and undec-11-enoic acids to produce six derivatives (2–7). Their structures were confirmed by spectroscopic analyses. Solanopubamine and semi-synthetic analogs are investigated for their in vitro cytotoxicity against a panel of human cancer cell lines and anti-microbial activity. Solanopubamine showed good antifungal activity only against Candida albicans and C. tenuis with MIC of 12.5 μg/mL. Semi-synthesized compounds (2–7) have failed to show anti-tumor and anti-microbial activities.     

Preparation of activated carbon filled epoxy nanocomposites

Activated carbon derived from oil palm empty fruit bunch (AC-EFB), bamboo stem (AC-BS), and coconut shells (AC-CNS) were obtained by pyrolysis of agricultural wastes using two chemical reagents (H₃PO₄ or KOH). The AC-EFB, AC-BS and AC-CNS were used as filler in preparation of epoxy nanocomposites. Epoxy nanocomposites prepared at 1, 5 and 10 % activated carbons filler loading using KOH and H₃PO₄ chemical agents. Transmission electron microscopy confirms better dispersion of the nano-activated carbons in the epoxy matrix at 5 % activated carbon. The presence of 5 % AC-CNS in the epoxy matrix using H₃PO₄ chemical reagent resulted in an improvement of the thermal stability of epoxy matrix. KOH treated AC filled epoxy nanocomposites were slightly better in thermal stability as compared to H₃PO₄ treated AC filled epoxy nanocomposites, may be due to better interaction of filler with epoxy matrix. Thermal analysis results showed that thermal stability of the activated carbon filled epoxy nanocomposites improved as compared to the neat epoxy matrix. The degree of crystallinity of epoxy matrix was improved by adding the activated carbon due to interfacial interaction between AC and epoxy matrix rather than loading of AC alone. Developed nanocomposites from biomass (agricultural wastes) materials will help to reduce the overall cost of the materials for its demanding applications as insulating material.     

Organically modified montmorillonite and chitosan–phosphotungstic acid complex nanocomposites as high performance membranes for fuel cell applications

Nanocomposite membranes based on polyelectrolyte complex (PEC) of chitosan/phosphotungstic acid (PWA) and different types of montmorillonite (MMT) were prepared as alternative membranes to Nafion for direct methanol fuel cell (DMFC) applications. Fourier transform infrared spectroscopy (FTIR) revealed an electrostatically fixed PWA within the PEC membranes, which avoids a decrease in proton conductivity at practical condition. Various amounts of pristine as well as organically modified MMT (OMMT) (MMT: Cloisite Na, OMMT: Cloisite 15A, and Cloisite 30B) were introduced to the PEC membranes to decrease in methanol permeability and, thus, enhance efficiency and power density of the cells. X-ray diffraction patterns of the nanocomposite membranes proved that MMT (or OMMT) layers were exfoliated in the membranes at loading weights of lower than 3 wt.%. Moreover, the proton conductivity and the methanol permeability as well as the water uptake behavior of the manufactured nanocomposite membranes were studied. According to the selectivity parameter, ratio of proton conductivity to methanol permeability, the PEC/2 wt.% MMT 30B was identified as the optimum composition. The DMFC performance tests were carried out at 70 °C and 5 M methanol feed and the optimum membrane showed higher maximum power density as well as acceptable durability compared to Nafion 117. The obtained results indicated that owing to the relatively high selectivity and power density, the optimum nanocomposite membrane could be considered as a promising polyelectrolyte membrane (PEM) for DMFC applications.