Efficient synthesis of novel functionalized pyrazolo-pyranoquinoline and tetrahydrodibenzo-[1,8]naphthyridinone derivatives

The facile and efficient synthesis of 1,4-dihydropyrazolo-pyrano-[2,3-b]quinoline derivatives from the reaction of 2-chloroquinoline-3-carbaldehydes and pyrazolones is described. Moreover, a one-pot method for the development of functionalized tetrahydrodibenzo[b,g][1,8]naphthyridinone derivatives is reported by using a three-component reaction of 2-chloroquinoline 3-carbaldehydes, pyrazolone, and enaminones catalyzed by l-proline in EtOH.     

Hydroarylation of cinnamic acid with phenols catalyzed by acidic ionic liquid [H-NMP]HSO<Subscript>4</Subscript>: computational assessment on substituent effect

Hydroarylation of cinnamic acid with different substituted phenols, in the presence of acidic ionic liquid, N-methyl-2-pyrrolidonum hydrosulfate ([H-NMP]HSO₄) gave the corresponding dihydrocoumarins in high yields and excellent selectivity. Among these substituted phenols, while methyl phenol afforded the corresponding dihydrocoumarin, nitrophenol under the same reaction conditions diverted the course of reaction, affording 3-(4-nitrophenyl)-3-phenylpropanoic acids. We investigated this behavior from the energetic and electronic points of view, using quantum chemistry computational methods. In this respect, the electronic energy change values for the conversion reaction of substituted phenyl cinnamate esters to dihydrocoumarin compounds have been obtained via density functional theory calculations. We demonstrated that the conversion reaction in the presence of CH₃ substituent is more favorable energetically than NO₂ substituent. Moreover, we have concentrated on topological analysis of electron density on some key bond and ring critical points and their associated bond paths to assess the conversion of substituted phenyl cinnamate esters to dihydrocoumarins. Our calculated results showed that para-methyl phenyl cinnamate has more of electronic tendency to undergo the intramolecular cyclization step and, consequently, generate the corresponding dihydrocoumarin.     

Novel electrosynthesis of a condensed thioheterocyclic system containing a 1,2,4-triazole ring

An efficient and convenient electrosynthesis of thioheterocyclic compounds 6a-d is described via a one-pot, two-component condensation of triazoles (1a,b) or triazine (1c) with acetylenedicarboxylic acid esters (2a,b).     

Allocation of advertising budget between multiple channels to support sales in multiple markets

We consider the allocation of a limited marketing budget between multiple channels in order to promote sales at multiple markets. The channels differ in their type, level of targetability (or reach), and costliness. We incorporate the “threshold effect” from each market in our resource allocation which requires some positive advertising investment in each market before much sales impact can be observed from it. The increased number of channels in recent years with the advent of digital advertising, along with the added complexity created by the threshold effect, necessitates the development of new allocation approaches. In this paper, we formulate the firm’s resource allocation decision as a nonlinear and nonseparable knapsack problem. We develop a branch and cut solution method which is enhanced by a heuristic approach. A set of numerical experiments illustrate the performance of our methods and evaluate the usefulness of two rule-of-thumb strategies commonly used in practice.     

Current applications of organocatalysts in asymmetric aldol reactions: An update

The aldol reaction is one of the most important carbon–carbon bond formations in synthetic organic chemistry. An enantioselective aldol reaction should provide an enantioenriched product. The organocatalytic asymmetric aldol reaction via an in situ generated enamine intermediate is one of the most powerful synthetic tools to achieve enantiomerically pure products. This approach is often used to obtain chiral β-hydroxycarbonyl compounds with excellent enantioselectivity. In this report, we update our previous review regarding the applications of organocatalysts in asymmetric aldol reactions leading to chiral β-hydroxycarbonyl compounds as versatile synthetic motifs frequently found in pharmaceutically desired intermediates and biologically active naturally occurring compounds.     

Strong Microheterogeneity in Novel Deep Eutectic Solvents

With the increasing application of template assisted syntheses in deep eutectic solvents and successful application of hydrophobic deep eutectic solvents in extraction processes, where microheterogeneity plays a major role, suggestions for novel deep eutectic solvents which exhibit strong microheterogeneity are desirable. Therefore, classical molecular dynamics simulations were carried out on deep eutectic solvent systems constructed of choline chloride and some of its derivatives mixed with ethylene glycol in a molar composition of 1 : 2 since this is the optimal parent composition. The derivatives consisted of a series of elongated alkyl side chains and elongated alcohol side chains. Of these series only choline chloride ethylene glycol has been investigated experimentally, the other systems are suggested and theoretically investigated as possible target for synthesis. Our domain analysis supported by the clear distinction of polar and nonpolar parts from the electrostatic potentials reveals that strong microheterogeneity within these novel hypothetical deep eutectic solvents exists. Rather stretched than crumbled side chains maximize possible interaction sites for both polar and nonpolar parts which make the suggested compounds valuable objectives for experiments in order to exploit the microheterogeneity in deep eutectic solvents.     

A Sharp Jump in Photocatalytic Activity of Elemental Sulfur for Dye Degradation in Alkaline Solution

Elemental sulfur is a low-cost and abundant substance as one of the largest by-products of the oil industry which was widely used in many industrial activities. Cyclo-octasulfur (S₈) is one of the sulfur allotropes that is a very stable substance in standard conditions. In this study, we report a low-cost and fast method for the degradation of methyl violet in water under visible light and also sunlight by using elemental sulfur (S₈). The results show that sulfur is a good photocatalyst which operates under visible light and can be utilized for degradation of methyl violet. The photocatalytic degradation of methyl violet in acidic, neutral, and alkaline media was investigated, and it was found that the photocatalytic efficiency increases dramatically in alkaline solution. The effects of the initial concentration of the dye, photocatalyst dosage, solution pH, and photocatalyst reusability were investigated. The kinetics of the reaction were studied in detail, and the photocatalytic rate equation was presented.     

Characterization of intermolecular interactions in crystalline aspirin: A computational NQR study

A computational study at the level of density functional theory was carried out to characterize the ¹⁷O and ²H nuclear quadrupole resonance (NQR) spectroscopy parameters in crystalline aspirin. To include O? H···O and C? H···O hydrogen bonding effects in the calculations, the most probable interacting molecules with the target molecule in the crystalline phase were considered through a pentamer cluster. The NQR calculations were performed with BLYP, B3LYP, and M06 functionals employing 6‐311++G** and Jensen's polarization‐consistent pcJ‐1 basis sets. Linear correlations are observed between the calculated ¹⁷O and ²H NQR parameters and the hydrogen bond strengths, suggesting the possibility of estimating hydrogen bonding information from calculated NQR data. Different contributions of various nuclei to hydrogen bonding interactions and observed trends of calculated NQR parameters are well justified by atoms in molecules analyses at the BCPs of these interactions. © 2011 Wiley Periodicals, Inc. Int J Quantum Chem, 2012