Synthesis and determination of pKa values of some new 3,4-disubstituted-4,5-dihydro-1H-1,2,4-triazol-5-one derivatives in non-aqueous solvents

3-Alkyl(Aryl)-4-amino-4,5-dihydro-1H-1,2,4-triazol-5-ones (2) reacted with 2-furoyl chloride and thiophene-2-carbonyl chloride to afford the corresponding 3- alkyl(aryl)-4-(2-furoylamino)-4,5-dihydro-1H-1,2,4-triazol-5-ones (3) and 3-alkyl(aryl)- 4-(2-thienylcarbonylamino)-4,5-dihydro-1H-1,2,4-triazol-5-ones (4), respectively. The new compounds synthesized were characterized by using IR, 1H-NMR, 13C-NMR and UV spectral data together with elemental analysis. In addition, to investigate the effects of solvents and molecular structure upon acidity, compounds 3 and 4 were titrated potentiometrically with tetrabutylammonium hydroxide in four non-aqueous solvents (isopropyl alcohol, tert-butyl alcohol, N,N-dimethylformamide and acetonitrile). The half-neutralization potential values and the corresponding pKa values were determined for all cases.     

Effect of Polycondensation Reaction Conditions on the Properties of Thermotropic Liquid‐Crystalline Copolyester

In this study a range of wholly aromatic copolyesters based on kink m‐acetoxybenzoic acid (m‐ABA) monomer (33 mol%) and equimolar‐linear p‐acetoxybenzoic acid (p‐ABA), hydroquinone diacetate (HQDA) and terephthalic acid (TPA) monomers (67 mol%) have been synthesized by melt polycondensation reaction process at 280°C and 260°C for different time intervals. Characterization of copolyesters were performed by solution viscosity measurement, wide–angle X‐ray diffraction (WAXD), differential scanning calorimetry (DSC), hot‐stage polarized light microscopy, proton‐nuclear magnetic resonance analysis (¹H‐NMR). According to the results obtained, copolyesters showed thermotropic liquid crystalline behavior in an appropriate temperature range. The copolyesters were prepared in high yields. It was observed that the intrinsic viscosities of the copolyesters are increased regularly with increasing polymerization time and temperature. All the copolyesters were soluble in a trifluoroacetic acid/dichloromethane (30:70 v/v) except the copolyesters which were synthesized at 280°C in 5 h. According to the WAXD results; the degree of crystallinity of copolyesters were found to be between 5–15%. DSC and hot stage polarized light microscopy results showed that all the copolyesters are melt processable and a significant molecular interaction exist in a very broad temperature range (160°C and 165°C) in the nematic mesophase. The T_g values are increased with an increasing polycondensation reaction time and temperature and they were observed between 93–126°C. Fibers prepared by a hand‐spinning technique from the polymer melt exhibit well‐developed fibrillar structure parallel to the fiber axis.     

Wave propagation in stereo-lithographical (STL) bone replicas at oblique incidence

Comparisons between predictions of a Biot-Allard model allowing for angle-dependent elasticity and angle-and-porosity dependent tortuosity and transmission data obtained at normal incidence on water-saturated replica bones are extended to oblique incidence. The model includes two parameters which are adjusted for best fit at normal incidence. Using the same parameter values, it is found that predictions of the variation of transmitted waveforms with angle through two types of bone replica are in reasonable agreement with data despite the fact that scattering is not included in the theory.     

Photoluminescence and thermoluminescence properties of SnO2 nanoparticles embedded in Li20-K20-B203 with Cu-doping

Cu-doped borate glass co-doped with SnO2 nanoparticles is fabricated by melt quenching. The structure and morphology of the samples are examined by X-ray diffraction and field emission scanning electron microscopy. Up-conversion enhancement is observed in the photoluminescence （PL） and thermolumines- cence （TL） intensities of the glass. PL emission spectra are identified in the blue and green regions, and a fourfold increase in emission intensity may be observed in the presence of embedded SnO2 nanoparticles. The glow curve is recorded at 215℃, and fourfold increases in TL intensity are obtained by addition of 0.1 mol% SnO2 nanoparticles to the glass. Higher TL responses of the samples are observed in the energy range of 15-100 KeV. At energy levels greater than -0.1 MeV, however, flat responses are obtained. The activation energy and frequency factor of the second-order kinetic reaction are calculated by the peak shape method.     

Selling to the “Newsvendor” with a forecast update: Analysis of a dual purchase contract

We consider a supply chain in which a manufacturer sells to a procure-to-stock retailer facing a newsvendor problem with a forecast update. Under a wholesale price contract, the retailer waits as long as she can and optimally places her order after observing the forecast update. We show that the retailer’s wait-and-decide strategy, induced by the wholesale price contract, hinders the manufacturer’s ability to (1) set the wholesale price and maximize his profit, (2) hedge against excess inventory risk, and (3) reduce his profit uncertainty. To mitigate the adverse effect of wholesale price contract, we propose the dual purchase contract, through which the manufacturer provides a discount for orders placed before the forecast update. We characterize how and when a dual purchase contract creates strict Pareto improvement over a wholesale price contract. To do so, we establish the retailer’s optimal ordering policy and the manufacturer’s optimal pricing and production policies. We show how the dual purchase contract reduces profit variability and how it can be used as a risk hedging tool for a risk averse manufacturer. Through a numerical study, we provide additional managerial insights and show, for example, that market uncertainty is a key factor that defines when the dual purchase contract provides strict Pareto improvement over the wholesale price contract.     

Synthesis of N‐Alkylated Indolines and Indoles from Indoline and Aliphatic Ketones

A survey of redox aminations of indoline with aliphatic ketones using bismuth nitrate as catalyst is described. A reaction of an equivalent amount of indoline and aliphatic cyclic and acyclic ketones provides a mixture of excessive alkylated indole derivatives over typically redox isomerization and reductive alkylation pathways while using of the five equivalent of indoline provides N‐alkylated indolines as a reductive alkylation product. The desired N‐alkyl indoles from the oxidation of N‐alkyl indolines were obtained in excellent yields.     

Redox Amination Scope of Benzylic Ketones with Indoline: Synthetic and Mechanistic Insights

Bi(NO₃)₃·5H₂O‐Catalyzed redox amination scope and mechanistic insights of benzylic ketones with indoline are discussed. The experimental results demonstrate that the formation of N‐alkyl‐substituted indole/indoline derivatives over typically competitive redox and reductive amination processes is depending upon the reaction condition for the benzylic ketones.     

Structural properties of Dirichlet series with harmonic coefficients

An infinite family of functional equations in the complex plane is obtained for Dirichlet series involving harmonic numbers. Trigonometric series whose coefficients are linear forms with rational coefficients in hyperharmonic numbers up to any order are evaluated via Bernoulli polynomials, Gauss sums, and special values of L-functions subject to the parity obstruction. This in turn leads to new representations of Catalan’s constant, odd values of the Riemann zeta function, and polylogarithmic quantities. Consequently, a dichotomy result is deduced on the transcendentality of Catalan’s constant and a series with hyperharmonic terms. Moreover, making use of integrals of smooth functions, we establish Diophantine-type approximations of real numbers by values of an infinite family of Dirichlet series built from representations of harmonic numbers.     

Palladium‐catalyzed regioselective C2‐arylation of 5‐aminoindole

Pd(II)‐catalyzed C‐H arylations of 5‐aminoindole using iodobenzenes as aryl source was studied. Despite pivalamide directing group at 5‐position of the indole, the direct C2‐arylation of the indole observed in high yields and with high regioselectivity.