5- And 6-exocyclic products, cis-2,3,5-trisubstituted tetrahydrofurans, and cis-2,3,6-trisubstituted tetrahydropyrans via Prins-type cyclization

Exocyclic products having cis-2,5 and cis-2,6 substitution were synthesized from terminally substituted alkynyl alcohols with various aldehydes via Prins-type cyclization in good yields. It is of interest that synthesized 5- and 6-exocyclic vinyl cations generated as a result of Prins-type cyclization could be trapped as a vinyl triflate in CH2Cl2 to give 3-furanylidenes and 3-pyranylidenes. Those 3-furanylidenes and 3-pyranylidenes underwent hydrolysis to give the corresponding 3-acyl-substituted products having all-cis-configured isomers, such as 2,3,5-trisubstituted tetrahydrofurans and 2,3,6-trisubstituted tetrahydropyrans.     

Determination of linezolid in pharmaceutical dosage forms by liquid chromatography and ultraviolet spectroscopy

A liquid chromatographic (LC) method and a UV spectrophotometric method were developed and validated for quantitative determination of linezolid in tablets and injection. The isocratic LC analyses were performed on an RP18 column using a mobile phase composed of methanol-water-acetonitrile (40 + 40 + 20, v/v/v) at a flow rate of 1.0 mL/min. The UV spectrophotometric method was performed at 251 nm. The analytical methods were validated according to International Conference on Harmonization guidelines. The calibration graphs were linear (correlation coefficient > 0.999) in the studied concentration ranges of 0.1 to 10 microg/mL for LC and 2 to 16 microg/mL for UV spectrophotometry. The relative standard deviation values for intraday and interday precision studies were <2%, and the accuracy was >98% for both methods. The specificity of the LC method was proved using forced degradation. Statistical analysis showed no significant difference between the results obtained by the 2 methods. The proposed methods are precise and accurate and can be applied directly to the oral and parenteral pharmaceutical preparations of linezolid.     

Palladium-catalysed regioselective addition reaction of ethyl phenylphosphinate with terminal acetylenes: ligand- and solvent-dependent regioselectivity

Palladium-1,2-bis(diphenylphosphino)ethane complex catalyses regioselective Markovnikov addition of ethyl phenylphosphinate to terminal alkynes in toluene, while the use of tri-tert-butylphosphine as the ligand or ethanol as the solvent leads to regioselectivity reversal.     

Instability of confined thin liquid film trilayers

The instability of a system in which three stratified thin liquid films are confined in a channel with parallel walls and the interior film is subject to van der Waals-driven breakup is examined in this work. We derive a model based on lubrication theory and consisting of a pair of nonlinear partial differential equations describing the position of the two liquid interfaces. A linear stability analysis is carried out to show that the effects of varying the boundary film thicknesses can be understood in terms of several known limits, including a supported monolayer, confined bilayer, and supported bilayer. Variation of the boundary film viscosities is shown in many cases to eliminate the supported-bilayer limit. The parameter regimes in which squeezing and bending modes dominate the initial growth are determined, and nonlinear simulations are used to show that the mode always switches to squeezing near rupture. It is also found that a multi-modal dispersion relation may be created by asymmetries in thickness ratio, but not viscosity ratio, even in the absence of asymmetric interfacial tensions. The results of this study are expected to be relevant to multiphase microfluidic systems and the lithographic printing process.     

Structure elucidation of thermal degradation products of amlodipine

Thermal degradation of amlodipine base causes intramolecular reactions affording three cyclic products, referred to as AMLDEG-I, AMLDEG-II, and AMLDEG-III, respectively. AMLDEG-I is a cyclized product formed by intramolecular elimination of ammonia from amlodipine. AMLDEG-II is a positional isomer of AMLDEG-I. AMLDEG-III is also intramolecular cyclisation product. The three degradation products were isolated by column chromatography and characterized by FT-IR and 1H and 13C NMR spectroscopy data. The AMLDEG-III was crystallized and its structure was solved by single crystal X-ray diffraction (SXRD).     

Kinetics and mechanism of the oxidation of lower oxyacids of phosphorus by hexamethylenetetramine bromine

The oxidation of lower oxyacids of phosphorus by hexamethylenetetramine bromine (HABR) in glacial acetic acid resulted in the formation of corresponding oxyacids with phosphorus in a higher oxidation state. The reaction exhibited 2:1 stoichiometry. The reaction is first order with respect to HABR. Michaelis–Menten‐type kinetics were observed with respect to the acids. The formation constant of the phenylphosphinic acid–HABR complex also has been determined spectrophotometrically. The thermodynamic parameters for the complex formation and the activation parameters for their decomposition were calculated. The reaction showed the presence of a substantial kinetic isotope effect. It is proposed that the HABR itself is the reactive oxidizing species. It has been shown that the pentacoordinated tautomer of the phosphorus oxyacid is the reactive reductant. A suitable mechanism has been proposed. © 2000 John Wiley & Sons, Inc. Int J Chem Kinet 32: 165–170, 2000     

Synthesis and characterization of poly(benzobisthiazole) with tetramethylbiphenyl moiety in the main chain

Poly(benzobisthiazole)s containing an ortho-tetramethyl substituted biphenyl moiety were synthesized via the polycondensation of 2,5-diamino-1,4-benzenedithiol dihydrochloride with 2,2′,6,6′-tetramethylbiphenyl-4,4′-dicarboxylic acid in poly(phosphoric acid) (PPA). The intrinsic viscosities of the tetramethylbiphenyl poly-(benzobisthiazole)s in chlorosulfonic acid at 30°C were in the range of 6.9–13.4 dL/g. Copolycondensation of 2,5-diamino-1,4-benzenedithiol dihydrochloride with terephthalic acid and 2,2′,6,6′-tetramethylbiphenyl-4,4′-dicarboxylic acid was carried out as well by varying the ratio of the two dicarboxylic acid monomers in the reactant mixture. The homopolymers and copolymers were characterized by Fourier transform infrared spectroscopy (FTIR) and ¹³C solid-state nuclear magnetic resonance spectroscopy (NMR). Thermal stability of the polymers was evaluated by thermogravimetric analysis (TGA) and thermogravimetric mass spectrum analysis (TG-MS). The tetramethylbiphenyl poly(benzobisthiazole)s were found to be more stable at elevated temperatures than the parent poly(p-phenylene benzobisthiazole) (PBZT). © 1998 John Wiley & Sons, Inc. J Polym Sci A: Polym Chem 36: 1407–1416, 1998     

Thermoelectric properties of Fe-substituted layered compound,LiCo<Subscript>1−<Emphasis Type="Italic">x</Emphasis></Subscript>Fe<Subscript><Emphasis Type="Italic">x</Emphasis></Subscript>O<Subscript>2</Subscript>

The layered compound LiCoO₂ belonging to the ABO₂ class exhibits a variety of interesting behaviors, and substitution adds a twist to the properties. Hence, the effect of partial substitution of Co⁺³ with Fe⁺³ on the high-temperature thermoelectric properties has been studied in detail. The X-ray diffraction patterns together with Rietveld refinement indicate formation of a single phase conforming to R\( \overset{-}{3} \)m space group in all the three cases, LiCo_1?x Fe _x O₂ with x = 0.01, 0.02, and 0.08. The electrical resistivity in all the compounds decreases by four orders of magnitude with increasing temperature from 300 to 1000 K, a semiconducting behavior. The Seebeck coefficient is found to be very high, >700 μV K^?1 in all the cases, and increases with increasing temperature and Fe⁺³ substitution. The thermal conductivity, on the other hand, has been found to decrease with temperature in all the compounds from 3.5 W m^?1 K^?1 at room temperature to 1 W m^?1 K^?1 at 973 K, a consequence of phonon-phonon scattering. High resistivity of the compounds limits power factor indicating that carrier concentration and mobility need to be increased to realize a high figure-of-merit.     

Substituent Effect on Absorption and Fluorescence Properties of Thieno[3, 2-<Emphasis Type="Italic">c</Emphasis>]Pyridine Derivatives

New substituted thieno[3,2-c]pyridine derivatives 5 were synthesized by the reaction of 3-bromo-4-chlorothieno[3,2-c]pyridine 1 with cyclic amine 2, which further on Suzuki reaction with boronic acids 4 converted to corresponding 3-arylthieno[3,2-c]pyridine 5. Substituent R³ has predominant effect on fluorescence properties of thienopyridines. However, the electron donor amine at C₄ has no effect on fluorescence properties of thienopyridines.

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Graphical Abstract New thieno[3,2-c]pyridine derivatives were synthesized from 3-bromo-4-chlorothieno[3,2-c]pyridine and cyclic amines, which by on Suzuki reaction with boronic acids converted to corresponding 3-arylthieno[3,2-c]pyridine. Substituent R3 has predominant effect on fluorescence properties of thienopyridines. However, the electron donor amine at C4 has no effect on fluorescence properties of thienopyridines