Pyrolytic behavior of substituted N‐aminoheteroaromatics: Synthesis of pyrazolo[1,5‐a]pyridine and 3‐substituted 3‐oxopropionitrile derivatives

Flash vacuum pyrolysis (FVP) of 1,7‐bis‐(3‐aroylideneamino)‐4,6,10,12‐tetramethyl‐2,8‐dioxo‐1,7‐diazacyclododeca‐3,5,9,11‐tetraene‐3,9‐dicarbonitriles 11a‐c at 650°C and 0.02 Torr yielded 5,7‐dimethyl‐3‐(4‐methylbenzoyl)‐pyrazolo[1,5‐a]pyridine‐4‐carbonitrile 14 , 4,6‐dimethyl‐2‐oxo‐1,2‐dihydropyridine‐3‐carbonitrile 16 and 3‐aryl‐3‐oxo‐propionitriles 17a,b . A plausible mechanism is suggested to account for the formation of the products.     

Synthesis of 1-alkyl and 1,3-dialkyl-2-benzimidazolones from 1-alkenyl-2-benzimidazolones using phase-transfer catalysis technique

A general synthetic route to 1-alkyl and 1,3-dialkyl-2-benzimidazolones from 1-alkenyl-2-benzimidazolones using phase-transfer catalysis conditions is described.     

Decarboxylative homocoupling of (hetero)aromatic carboxylic acids

A variety of hetero(aromatic) carboxylic acids are shown to undergo decarboxylative homocoupling, mediated by a Pd/Ag system. This novel methodology for the synthesis of symmetrical biaryls avoids the use of haloarenes and organometallic compounds as starting materials.     

Synthesis of a tetracyclic G∧C scaffold for the assembly of rosette nanotubes with 1.7 nm inner diameter

The synthesis of a tetracyclic self-complementary molecule 4 for self-assembly into rosette nanotubes is presented. This new heterocycle has a core structure containing two pyrido[2,3-d]pyrimidine molecules fused together and features the Watson-Crick hydrogen bond donor-acceptor arrays of both guanine (G) and cytosine (C). Current methods to synthesize pyrido[2,3-d]pyrimidines require harsh conditions and long reaction times and result usually in low product yields. This is particularly problematic for the direct incorporation of functional groups that cannot withstand these conditions. Here, we present an efficient approach to access the multifunctional pyrido[2,3-d]pyrimidine intermediate 2 under relatively mild conditions using three regioselective S(N)Ar reactions at C2, C4, and C7 on the trichloro compound 1. The electron-withdrawing group and amino functionalities on 2 are then used as a handle to install the third and fourth rings of 4 using a Friedla?nder-type condensation followed by mixed urea synthesis and cyclization.     

Effects of conventional heating on the stability of major olive oil phenolic compounds by tandem mass spectrometry and isotope dilution assay

The quality of olive oils is sensorially tested by accurate and well established methods. It enables the classification of the pressed oils into the classes of extra virgin oil, virgin oil and lampant oil. Nonetheless, it would be convenient to have analytical methods for screening oils or supporting sensorial analysis using a reliable independent approach based on exploitation of mass spectrometric methodologies. A number of methods have been proposed to evaluate deficiencies of extra virgin olive oils resulting from inappropriate technological treatments, such as high or low temperature deodoration, and home cooking processes. The quality and nutraceutical value of extra virgin olive oil (EVOO) can be related to the antioxidant property of its phenolic compounds. Olive oil is a source of at least 30 phenolic compounds, such as oleuropein, oleocanthal, hydroxytyrosol, and tyrosol, all acting as strong antioxidants, radical scavengers and NSAI-like drugs. We now report the efficacy of MRM tandem mass spectrometry, assisted by the isotope dilution assay, in the evaluation of the thermal stability of selected active principles of extra virgin olive oil.     

Particle growth of hybrid materials followed by dynamic light scattering

The hydrolysis of distannylated compounds in which the tin atoms are linked by an organic spacer has been studied under microemulsion conditions using dynamic light scattering and infrared spectroscopy. The experiments provided evidence that the growth of hybrid material particles occurs in the aqueous phase, outside the organic phase of the microemulsion. The growth rates of the particles were found to be strongly dependent on the nature of the spacers, a polymethylene chain inducing the fastest process. This different behavior was explained by a slower condensation process rather than a slower hydrolysis. The high surface areas measured for the hybrid materials could be explained by a possible coating of the hybrid particles by surfactant molecules, thus preventing either their growth or their aggregation.     

Combination of dynamic time warping and multivariate analysis for the comparison of comprehensive two-dimensional gas chromatograms: application to plant extracts

Comprehensive two-dimensional gas chromatography (GC x GC) is now recognized as the preferred technique for the detailed analysis and characterization of complex mixtures of volatile compounds. However, for comparison purposes, taking into account all the information contained in the chromatogram is far from trivial. In this paper, it is shown that the combination of peak alignment by dynamic time warping and multivariate analysis facilitated the comparison of complex chromatograms of tobacco extracts. The comparison is shown to be efficient enough to provide a clear discrimination among three types of tobacco. A tentative interpretation of loadings is presented in order to give access to the compounds which differ from one sample to another. Once located, mass spectrometry was used to identify markers of tobacco type.     

Hierarchical self-assembly of organic prolate nanospheroids from hydrophobic rosette nanotubes

Supramolecular synthesis emerged recently as a new formalism to devise complex architectures held through noncovalent forces. Much of the research endeavor has been devoted to the use of H-bonds as the alphabet for chemical information encoding, and the structures expressed have spanned the range of dimensions and shapes, from discrete to infinite networks. Here we describe the synthesis and characterization of a GwedgeC base bearing two C12 alkyl chains, which undergoes a solvent-controlled multistep hierarchical self-assembly process into lamellar prolate nanospheroids. These assemblies were characterized by AFM, SEM, TEM, XRD, and SAXS, and a mechanism for their formation is proposed.     

Existence of a Renormalised Solutions for a Class of Nonlinear Degenerated Parabolic Problems with L1 Data

We study the existence of renormalized solutions for a class of nonlinear degenerated parabolic problem. The Carathéodory function satisfying the coercivity condition, the growth condition and only the large monotonicity. The data belongs to L^1(Ω).     

Valorization of Moroccan Bentonite Deposits: “Purification and Treatment of Margin by the Adsorption Process”

The main objective of this work was to contribute to the reduction in the contamination of phenolic compounds contained in margin by an adsorption process on two types of raw bentonite. The margin used in the studies was collected from a semi-modern oil mill located in the Nador–Morocco region. The results of the physico-chemical analyses showed that the effluents of the oil mills showed that they are highly polluted, particularly in terms of the total suspended solids (TSS), chemical oxygen demand (COD), and iron content of around 154.82 (mg/L), and copper content of 31.72 (mg/L). The mineralogy of bentonites studied by X-ray diffraction (XRD) reveals the existence of two types of montmorillonite; theoretically, the diffraction peak (001) of the montmorillonite appears at 15 Å, with a basal spacing that corresponds to a calcium pole, and the diffraction peak (001) appears at 12Å, with a basal spacing that corresponds to a sodium pole. The specific surface area of the bentonite used is characterized by a large specific surface area, varying between 127.62 m²·g⁻¹ and 693.04 m²·g⁻¹, which is due to the presence of hydrated interleaved cations. This surface is likely to increase in aqueous solution depending on the solid/liquid ratio that modulates the degree of hydration. With a high cation exchange capacity (CEC) (146.54 meq/100 g), samples of margin mixed with raw bentonites at different percentages vary between 5% and 100%. The potential of Moroccan bentonite for the phenol adsorption of 9.17 (g/L) from aqueous solutions was investigated. Adsorption tests have confirmed the effectiveness of these natural minerals in reducing phenolic compounds ranging from 8.72% to 76.23% contained in the margin and the efficiency of heavy metal retention through microelements on raw bentonites. The very encouraging results obtained in this work could aid in the application of adsorption for the treatment of margin.