Synthesis and Pharmacological Activity of Annelated Pyrimidine Derivatives

A series of 2,3-diglycosylpyrimidine 4, annelated pyrimidine derivatives, pyrazolo-[3,4-d]pyrimidine 8, ditetrazolo[1,5-a; 1′5′]pyrimidine 9, 2,9a,10-triazaanthracene 12, thieno- [2,3-d]pyrimidine 14, 9-thia-1,3,5,7-tetraazafluorene-8-one 15, 7-oxa-9-thia-1,3,5-triazafluorene-8-one 16, and 5-oxa-9-thia-1,3-diazafluorene 21a , b derivatives have been synthesized via a sequence of heterocyclization reactions of suitably functionalized 6-[5-(4-bromophenyl)oxazol-4-yl]-1,2,3,4-tetrahydro-2-thioxo-4-oxopyrimidine-5-carbonitrile (2) with different electrophiles and nucleophiles. The new compounds were prepared with the objective to study their pharmacological properties.     

Studies on the Thermodynamic and Kinetic Properties of the Reactions of Ti+ with Sulfur Transfer Reagent SCO Along the C═S Bond Activation Branch at 200–1200K

Theoretical studies on the thermodynamic and kinetic properties of the reactions of Ti⁺ with sulfur transfer reagent SCO via the C═S bond activation pathway have been carried on using DFT/B3LYP method, general statistical thermodynamics, and Eyring transition state theory with Wigner correction. The relevant reactions include reaction 1 ⁴ Ti⁺+¹SCO → ⁴ IM ₁ → ⁴ TS ₁ → ⁴ IM ₂ → ⁴ TiS⁺+ ¹ CO, and reaction 2 ⁴Ti⁺+¹SCO →⁴IM₁→ CP →²IM₂→²TiS⁺+¹CO in which the spin multiplicity changes from the quartet state to the doublet state in the crossing region. It is concluded that the increase of the temperature is favored to the reaction 1 process, since the equilibrium constants (K) rises from 0.566 × 10[P]-9 at 200 K to 0.109 × 10⁰ at 1200 K, and the reaction rate constant (k) from 0.222 × 10⁰ s[P]-1 at 200 K to 0.540 × 10 ¹¹ s[P]-1 at 1200 K. Moreover, reaction 1 is endothermic, and non-spontaneous in the way the entropy increases, while reaction 2 is exothermic and spontaneous in the way their entropy decreases. The reaction path 2 is the energetically favorable channel, and its thermodynamic data change not largely with the rise of temperature.     

Studies on Poly(Dialkoxyphosphazenes) for the Medical Applications

Abstract

The presence of trace of chlorine in poly(diorganophosphazenes) [-N=P(OR)2-]., where R = C₂H₅, CH₂CF₃, C₂F₅, C₄H₅, C₆H₁₃, C₈H₁₇, C₁₂H₂₅, CH₂C₆H₅ in many cases leads to the substantial changes of their physicochemical properties and limits application possibilities of this class of polymers especial for the medical materials. Despite the optimization of reaction conditions for each nucleophilic alkoxy substituent, the obtained poly(dia1koxyphosphaenes) exhibited some physicochemical anomalies.     

Synthesis,Structures, and Fungitoxicity of Novel Organophosphorus Compounds

Abstract

A series of biologically active organophosphorus compounds have been synthesized by the reactions of O,O-diethylchlorophosphate with Schiff bases derived from 5-(phenyl/substituted phenyl)-2-hydrazino-1,3,4-oxadiazole and salicylaldehyde/2-hydroxyacetophenone. The compounds have been characterized on the basis of analyses and spectral (IR, ¹H, ¹³C NMR) data. Fungicidal activities of these derivatives against Colletotrichum falcatum, Fusarium oxysporum, and Curvularia pallescence have been evaluated. All compounds showed moderate to significant antifungal activity.     

1,2- and 1,3-diphosphetanes from alkylidenephosphines

Abstract

Alkyl- or arylbis(trimethylsilyl)phosphines as well as tris(trimethylsilyl)phosphine and the corresponding arsines react with acyl chlorides to give [1-(trimethylsiloxy)alkylidene]phosphines 1 and -arsines 2; most of their 2,2-dimethylpropylidene derivatives are thermally stable at room temperature. With the same class of phosphines as starting compounds and carbon disulfide [bis(trimethylsilylsulfano)methylidene]phosphines 3 are formed, whereas [(dialkylamino)methylidene]-4 and [diarylmethylidene]phosphines 5 or the corresponding arsines 6 and 7 can be obtained from acyl amides or ketones.¹     

Flame‐retardant and mechanical properties of phenolic foams toughened with polyethylene glycol phosphates

Three kinds of polyethylene glycol phosphates (PEGPs) toughening agents were synthesized by esterification of phosphorus pentoxide (P₂O₅) with polyethylene glycol and characterized by Fourier transform infrared spectra and ³¹P nuclear magnetic resonance. A series of lightweight phenolic foams toughened with different loadings of PEGPs were prepared. Optical microscopy results show that the addition of PEGPs with small molecular weight PEG improves the structural homogeneity of phenolic foams obviously. The flame retardancy of toughened phenolic foams was evaluated by using UL 94, limiting oxygen index, and cone calorimeter. The results indicate that the incorporation of PEGPs not only increases the toughness of phenolic foams but also improves their flame retardancy. Moreover, the thermal stability of PEGPs and the toughened foams was investigated by thermogravimetric analysis. Copyright © 2013 John Wiley & Sons, Ltd.     

Synthesis,polymerization, and thermal properties of benzoxazine based on bisphenol‐S and allylamine

A bifunctional benzoxazine monomer, 6,6′‐bis(3‐allyl‐3,4‐dihydro‐2H‐benzo[e][1,3]oxazinyl) sulfone (BS‐ala), was synthesized from bisphenol‐S, allylamine and formaldehyde via a solution method. The chemical structure of BS‐ala was confirmed by ¹H and ¹³C nuclear magnetic resonance (NMR) spectroscopy, Fourier transform infrared (FTIR) spectroscopy, and elemental analysis. The polymerization behavior of BS‐ala was investigated by FTIR, solid‐state ¹³C NMR, and differential scanning calorimetry (DSC). The oxazine ring opening polymerization is prior to the addition polymerization of allyl group, and the exothermic peaks corresponding to the two reactions appear partially overlapped in the DSC curve. The storage modulus of the resultant polybenzoxazine at 25°C is about 3.9 GPa, and the glass transition temperature is 254°C. The 5% and 10% weight loss temperatures of the polybenzoxazine are about 335°C and 361°C in both air and nitrogen, respectively. The char yield is about 58% at 800°C in nitrogen, whereas almost no residue is remained at 700°C in air. Copyright © 2012 John Wiley & Sons, Ltd.     

Mechanical and anti‐stabbing properties of modified thermoplastic polymers impregnated multiaxial p‐aramid fabrics

New forms of hybrid multiaxial nanocomposites with enhanced mechanical and stab resisting properties are presented. This study is motivated by the lack of knowledge in the study of the multiaxial fabric nanocomposites with two modified thermoplastic matrices for antiballistic protection. Introduction of 5 wt.% silica nanoparticles in the composite of polyurethane/p‐aramid/poly (vinyl butyral) leads to significant improvement in mechanical properties, and the addition of silane as a coupling agents and glutaraldehyde as a crosslinking agents yielded maximal values of storage modulus, tensile modulus and anti‐stabbing properties for hybrid nanocomposites. Ballistic resistance testing and penetration depth of the hybrid nanocomposites were visualized using image analysis. Copyright © 2013 John Wiley & Sons, Ltd.     

Novel toughened automotive clearcoats modified by a polyester‐amide hyperbranched polymer: structural and mechanical aspects

The present work attempts to study the mechanical properties and toughness behavior of a typical acrylic melamine clearcoat modified by a polyester‐amide hyperbranched polymer (HBP). Formulations were such that 0, 5, 10, 25 and 50% (molar percent) of total acrylic hydroxyl groups were stoichiometrically substituted by those of HBP. Bulk and surface of the clearcoats were studied by various mechanical techniques including hardness, tensile, dynamic mechanical thermal analysis (DMTA), nano‐indentation and scratch tests. In addition a scanning electron microscope (SEM) was utilized to observe the morphology of the fractured films. The bulk mechanical properties showed that a low loading (5 molar %) of HBP was sufficient to considerably increase the bulk hardness, cross‐linking density and toughness. DMTA and SEM results proved the occurrence of a single‐phase blend and that the shear deformation was the main toughening mechanism of HBP modified clearcoats. In general, it was revealed that the HBP not only could act as an excellent compatible toughening agent, but also maintained the clarity of the clearcoat and increased its scratch resistance. Copyright © 2013 John Wiley & Sons, Ltd.     

Effect of cholesteric liquid crystalline elastomer with binaphthalene crosslinkings on thermal and optical properties of a liquid crystal that show smectic A‐cholesteric phase transition

A side‐chain polysiloxane cholesteric liquid crystalline elastomer (ChLCE) with binaphthalene derivate as crosslinkings and cholesterol derivate as liquid crystalline monomers was designed and synthesized. A binaphthyl chiral dopant (CD) was synthesized as well. The chemical structures and liquid crystalline properties of the ChLCE and the CD were characterized by Fourier transform infrared spectroscopy, proton nuclear magnetic resonance spectroscopy, element analyses, differential scanning calorimetry and polarizing optical microscopy measurements. The helical twisting power of the ChLCE exhibited a turning point with changing temperature and was smaller than that of the CD. In addition, the effect of the ChLCE on phase transition temperatures and thermal‐optical properties of a liquid crystal that show smectic A (SmA)‐cholesteric (Ch) phase transition was studied. Worthily, the testing of the reflection wavelength with changing temperature suggested that the adding of the ChLCE in liquid crystals that show SmA‐Ch phase transition can expedite their SmA‐Ch transition. In addition, the network structure of the ChLCE may play a significant role in the accelerating of the transition. These properties provided theoretical and experimental foundations for applying ChLCE in thermally sensitive liquid crystal devices requiring fast response, such as thermally controllable windows, materials and displays. Copyright © 2012 John Wiley & Sons, Ltd.