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Scientific opinion on flavouring group evaluation 77, revision 3 (FGE.77Rev3): consideration of pyridine, pyrrole and quinoline derivatives evaluated by JECFA (63rd meeting) structurally related to pyridine, pyrrole, indole and quinoline derivatives evaluated by EFSA in FGE.24Rev2

The Panel?on Food Contact Materials, Enzymes, Flavourings and Processing Aids of the EFSA was requested to consider evaluations of flavouring substances assessed since 2000 by the Joint FAO/WHO Expert Committee on Food Additives (JECFA) and to decide whether further evaluation is necessary, as laid down in Commission Regulation (EC) No 1565/2000. The present consideration concerns a group of 22 pyridine, pyrrole and quinoline derivatives evaluated by JECFA (63rd meeting). The revision of this consideration is made since additional genotoxicity data have become available for 6-methylquinoline [FL-no: 14.042]. The genotoxicity data available rule out the concern with respect to genotoxicity and accordingly the substance is evaluated through the Procedure. For all 22 substances [FL-no: 13.134, 14.001, 14.004, 14.007, 14.030, 14.038, 14.039, 14.041, 14.042, 14.045, 14.046, 14.047, 14.058, 14.059, 14.060, 14.061, 14.065, 14.066, 14.068, 14.071, 14.072 and 14.164] considered in this Flavouring Group Evaluation (FGE), the Panel?agrees with the JECFA conclusion, ?No safety concern at estimated levels of intake as flavouring substances? based on the Maximised Survey-derived Daily Intake (MSDI) approach. Besides the safety assessment of these flavouring substances, the specifications for the materials of commerce have also been evaluated, and the information is considered adequate for all the substances. For the following substances [FL-no: 13.134, 14.001, 14.030, 14.041, 14.042, 14.058, 14.072], the Industry has submitted use levels for normal and maximum use. For the remaining 15 substances, use levels are needed to calculate the modified Theoretical Added Maximum Daily Intakes (mTAMDIs) in order to identify those flavouring substances that need more refined exposure assessment and to finalise the evaluation.

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Reference£º
Chiral nitrogen ligands in late transition metal-catalysed asymmetric synthesis¡ªI. Addressing the problem of ligand lability in rhodium-catalysed hydrosilations,
Nitrogen-Containing Ligands for Asymmetric Homogeneous and Heterogeneous Catalysis

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The kinetics of the decompositions of the proton bound dimers of 1,4-dimethylpyridine and dimethyl methylphosphonate from atmospheric pressure ion mobility spectra

The rate constants for the dissociations, A2H+ ? AH+ + A, of the symmetrical proton bound dimers of 2,4-dimethylpyridine and dimethyl methylphosphonate have been determined using an ion mobility spectrometer operating with air as drift gas at ambient pressure. Reaction time was varied by varying the drift electric field. The rate constants were derived from the mobility spectra by determining the rate at which ions decomposed in the drift region. Arrhenius plots with a drift gas containing water vapor at 5 ppmv gave the following activation energies and pre-exponential factors: 2,4-dimethylpyridine, 94 ¡À 2 kJ mol-1, log A (s-1) = 15.9 ¡À 0.4; dimethyl methylphosphonate, 127 ¡À 3 kJ mol-1, log A (s-1) = 15.6 ¡À 0.3. The enthalpy changes for the decompositions calculated from the activation energies are in accord with literature values for symmetrical proton bound dimers of oxygen and nitrogen bases. The results for dimethyl methylphosphonate were obtained over the temperature range 478-497 K and are practically independent of water concentration (5-2000 ppmv). The activation energy for 2,4-dimethylpyridine, obtained over the temperature range 340-359 K, decreased to 31 kJ mol-1 in the presence of 2.0 ¡Á 103 ppmv of water. At the low temperature, a displacement reaction involving water may account for the decrease. The reduced mobilities of the protonated molecules and the proton bound dimers have been determined over a wide temperature range. While the values for the dimers are essentially independent of the water concentration in the drift gas, those of the protonated molecules show a strong dependence.

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Reference£º
Chiral nitrogen ligands in late transition metal-catalysed asymmetric synthesis¡ªI. Addressing the problem of ligand lability in rhodium-catalysed hydrosilations,
Nitrogen-Containing Ligands for Asymmetric Homogeneous and Heterogeneous Catalysis

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Qualitative analysis of trace constituents by ion mobility increment spectrometer

Ion mobility increment spectrometry (IMIS) is a high sensitive selective ionization technology for detection and identification of ultra-trace constituents, including toxic compounds, CW-agents, drugs and explosives in ambient air or liquid sample. Like an ion mobility spectrometry (IMS), this technology rests on sampling air containing a mixture of trace constituents, its ionization, spatial separation of produced ions and separated ions detection. Unlike IMS, ions of different types in IMIS are separated by ion mobility increment, alpha. Value alpha, is a function of the parameters: electric field strength and form, atmospheric pressure. To exclude the influence of these parameters on an alpha, the method of explosives identification by a standard compound was suggested. As a standard compound iodine was used. The relationship among the mobility coefficient increments equal to the relationship among the compensation voltage alpha i/alphaiodine = Ui/Uiodine is determined, where i are ions of 1,3-dinitrobenzene, 1,3,5-trinitrobenzene, p-mononitrotoluene, 2,4-dinitrotoluene and 2,4,6-trinitrotoluene This relationship is practically independent of the above mentioned parameters in the range 25 < E/N < 90 Td. The limits of the relative error of this relationship are determined both from spectra of individual compounds and nitrocompound-iodine mixtures. We¡¯ll also look at important developments in the pharmaceutical industry because understanding organic chemistry is important in understanding health, medicine, the role of 108-47-4, and how the biochemistry of the body works.Synthetic Route of 108-47-4

Reference£º
Chiral nitrogen ligands in late transition metal-catalysed asymmetric synthesis¡ªI. Addressing the problem of ligand lability in rhodium-catalysed hydrosilations,
Nitrogen-Containing Ligands for Asymmetric Homogeneous and Heterogeneous Catalysis

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Inhibition of the histone demethylase JMJD2E by 3-substituted pyridine 2,4-dicarboxylates

Based on structural analysis of the human 2-oxoglutarate (2OG) dependent JMJD2 histone Nepsilon-methyl lysyl demethylase family, 3-substituted pyridine 2,4-dicarboxylic acids were identified as potential inhibitors with possible selectivity over other human 2OG oxygenases. Microwave-assisted palladium-catalysed cross coupling methodology was developed to install a diverse set of substituents on the sterically demanding C-3 position of a pyridine 2,4-dicarboxylate scaffold. The subsequently prepared di-acids were tested for in vitro inhibition of the histone demethylase JMJD2E and another human 2OG oxygenase, prolyl-hydroxylase domain isoform 2 (PHD2, EGLN1). A subset of substitution patterns yielded inhibitors with selectivity for JMJD2E over PHD2, demonstrating that structure-based inhibitor design can enable selective inhibition of histone demethylases over related human 2OG oxygenases.

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Reference£º
Chiral nitrogen ligands in late transition metal-catalysed asymmetric synthesis¡ªI. Addressing the problem of ligand lability in rhodium-catalysed hydrosilations,
Nitrogen-Containing Ligands for Asymmetric Homogeneous and Heterogeneous Catalysis

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Steric and electronic influences on the rate of addition of pyridines to the tricarbonyl(cycloheptadienyl) iron(II) cation

Kinetic studies of the reversible addition of pyridines to the cation + provide detailed information on the influence of steric and electronic factors on the nucleophilicity of amines towards coordinated organic substrates.Broensted plots of log k1 (forward rate constant) against the pKa’s of the amine conjugate acids demonstrate the dependence of rate on amine basicity and reveal that successive blocking of the 2- and 6-positions of pyridine by methyl (or formyl) groups leads to marked non-additive steric retardation.

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Reference£º
Chiral nitrogen ligands in late transition metal-catalysed asymmetric synthesis¡ªI. Addressing the problem of ligand lability in rhodium-catalysed hydrosilations,
Nitrogen-Containing Ligands for Asymmetric Homogeneous and Heterogeneous Catalysis

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A Simple and Efficient Method for the Preparation of Heterocyclic N-Oxide

Pyridine, 2-methylpyridine, 3-methylpyridine, 4-methylpyridine, 2,4-dimethylpyridine, 2,6-dimethylpyridine, quinoline, isoquinoline and 2-chloropyridine are readily oxidized to their N-oxides with a solution of trichloroisocyanuric acid, acetic acid, sodium acetate and water in acetonitrile and methylene dichloride in 78%-90% yields.

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Reference£º
Chiral nitrogen ligands in late transition metal-catalysed asymmetric synthesis¡ªI. Addressing the problem of ligand lability in rhodium-catalysed hydrosilations,
Nitrogen-Containing Ligands for Asymmetric Homogeneous and Heterogeneous Catalysis

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Substituted pyridine-2,4-dicarboxylic acid derivatives and medicaments based on these compounds

The invention relates to substituted pyridine-2,4-dicarboxylic acid derivatives of the formula I STR1 in which R1 and R2 have the meanings given. The invention also relates to a process for the preparation of the abovementioned compounds and to their use as medicaments, in particular as fibrosuppressants and immunosuppressants.

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Reference£º
Chiral nitrogen ligands in late transition metal-catalysed asymmetric synthesis¡ªI. Addressing the problem of ligand lability in rhodium-catalysed hydrosilations,
Nitrogen-Containing Ligands for Asymmetric Homogeneous and Heterogeneous Catalysis

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Simultaneous abatement of diesel soot and NOX emissions by effective catalysts at low temperature: An overview

The diesel engine generally achieves the highest fuel, energy, and thermal efficiency due to its very high compression/expansion ratio (14:1 to 25:1). Diesel engines can have a thermal efficiency that exceeds 50%. The main problem is that they emit more pollution like fine black soot particulates (C8H to C10H) and nitrogen oxides (NOX). These pollutants have been causing serious problems for human health and the global environment and also impacts on the engine. There are many types of catalysts investigated for simultaneous control of these two pollutants, i.e., platinum group metals (PGM; Pt, Pd, Rh, and Ir) based, spinel-type oxides, hydrotalcite, rare earth metal oxides, mixed transient metal oxides, etc. The high raw material cost of PGM catalysts has become a significant issue, so developing non-PGM catalysts are one of the promising challenges. There are no extra reductants required because soot catalytically oxidizes itself in the presence of NOX at a faster rate than molecular oxygen and simultaneously NOX is reduced to nitrogen. The order of oxidation potential of NOX to oxidized soot in comparison to molecular oxygen is as follows: NO2?>?NO?>?O2. To meet the very strict EPA US 2010 and Euro VI regulations of particulate matter (PM) and NOX for heavy-duty and light-duty vehicular stringent emission, it is very important to apply the integrated catalytic systems to significantly remove PM and NOX simultaneously. Many papers related to simultaneous control of soot and NOX over different catalysts have been published but till now some of effective catalysts showing high conversion at low temperatures (possibly within the range typical of diesel exhaust: 150?450C) have not been reviewed. Thus, this article provides a summary of published information regarding the effective catalysts, their preparation methods, properties, and application for simultaneous control of diesel soot and NOX.

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Reference£º
Chiral nitrogen ligands in late transition metal-catalysed asymmetric synthesis¡ªI. Addressing the problem of ligand lability in rhodium-catalysed hydrosilations,
Nitrogen-Containing Ligands for Asymmetric Homogeneous and Heterogeneous Catalysis

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Reconciliation of calorimetrically and spectroscopically derived standard entropies for the six dimethylpyridines between the temperatures 250 K and 650 K: A stringent test of thermodynamic consistency

Reconciliation of standard entropies Delta0TSmo(cal) derived from calorimetric and thermophysical property studies with standard entropies Delta0TSmo(stat) derived with assigned vibrational spectra and the methods of statistical mechanics is used to demonstrate consistency between thermophysical properties for the six dimethylpyridines (Chemical Abstracts registry numbers: 2,3-dimethylpyridine, 583-61-9; 2,4-dimethylpyridine, 108-47-4; 2,5-dimethylpyridine, 589-93-5; 2,6-dimethylpyridine, 108-48-5; 3,4-dimethylpyridine, 583-58-4; 3,5-dimethylpyridine, 591-22-0). Properties considered include the critical temperature, critical pressure, vapor pressure, heat capacities of the solid and liquid, second and third virial coefficients, enthalpies of vaporization, vibrational assignment, and methyl group rotational barrier. The temperature-dependent properties are shown to be consistent over the entire temperature range from near T = 250 K to T = 650 K ( ? 0.95¡¤Tc, where Tc denotes the critical temperature). The analyses validate the methods and results reported previously, which provided the information required to derive the temperature-dependent properties to near Tc, i.e. into the temperature and pressure range typical of petroleum processing conditions. Sensitivities of Delta0TSmo(stat) to errors in the vibrational assignment and to the size of methyl group rotational barriers are discussed. Vibrational assignments for vapor-phase fundamentals at low wave number for 2,3-dimethylpyridine and 3,4-dimethylpyridine are shown to be in error and are corrected.

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Reference£º
Chiral nitrogen ligands in late transition metal-catalysed asymmetric synthesis¡ªI. Addressing the problem of ligand lability in rhodium-catalysed hydrosilations,
Nitrogen-Containing Ligands for Asymmetric Homogeneous and Heterogeneous Catalysis

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FREE-RADICAL ADDITION OF ALKYLPYRIDINES TO DIETHYL MALEATE

The homolytic addition of 2-, 3-, and 4-methylpyridines, 2,4- and 2,6-dimethylpyridines, 2,4,6-trimethylpyridine, 2-methyl-5-ethylpyridine, and 2-methylquinoline to diethyl maleate leads to the respective diethyl 3-pyridylpropane-1,2-dicarboxylates. Their unsaturated analogs diethyl 3-pyridyl-2-propene-1,2-dicarboxylates, formed as a result of rearrangement of the intermediate radicals with 1,3-H migration and subsequent disproportionation of the rearranged radicals, were also found.

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Reference£º
Chiral nitrogen ligands in late transition metal-catalysed asymmetric synthesis¡ªI. Addressing the problem of ligand lability in rhodium-catalysed hydrosilations,
Nitrogen-Containing Ligands for Asymmetric Homogeneous and Heterogeneous Catalysis