Properties and Exciting Facts About 2,4-Dimethylpyridine

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Reactions catalyzed within inorganic and organic materials and at electrochemical interfaces commonly occur at high coverage and in condensed media,Computed Properties of C7H9N, Name is 2,4-Dimethylpyridine, belongs to chiral-nitrogen-ligands compound, is a common compound. Computed Properties of C7H9N, In an article, authors is Tan, Lay Choo, once mentioned the new application about Computed Properties of C7H9N.

The purpose of the present work was to investigate a liquid chromatographic method for the measurement of relative hydrogen bond basicities of dilute species. This type of determination cannot be done with conventional reversed-phase liquid chromatography due to the silanophilic interactions of basic solutes with the silica packing material. The studies were done on a polymeric stationary phase with pendant phenol groups that act as powerful hydrogen bond donors. Solute retention was evaluated in terms of two hydrogen bond basicity scales, beta2H and beta2C, and a steric hindrance parameter, Es. beta2H and beta2C are basicity scales based on the free energy of forming 1:1 hydrogen bond complexes and the retention on a strong hydrogen bond donor gas chromatographic phase, respectively. The Es parameter characterizes the steric effect experienced by the solute acceptor site. It is shown that retention correlates very strongly with beta2H and less strongly with beta2C. The log k? values need only two descriptive parameters, i.e., beta2H and Es, to give a good fit. As a whole, retention on the phenolic polymeric phase provides an efficient method for the measurement of relative hydrogen bond basicities.

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

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2,4-, 2,5- and 2,6-Dimethylpyridines react with anils of aromatic aldehydes in the presence of dimethylformamide and potassium hydroxide to yield the corresponding distyrylpyridines (‘anil synthesis’).Under the same reaction conditions (4-methylstyryl)pyridines are converted to (stilbenylvinyl)pyridines.Similarly, the Schiff’s base derived from pyridine-3-carbaldehyde and chloranile on treatment with methyl- and p-tolyl-substituted aromatic hetericycles gives the corresponding (heteroaryl-styryl)pyridines, whereas with the Schiff’s bases derived from pyridine-2= and -4-carbaldehyde side reactions, such as dimerization followed by disproportionation predominate.

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

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For iodine or methanol complexes with meta- and para-substituted pyridines, the blue shift Deltaeta(I2) of the visible iodine transition can be correlated with the shift of the hydroxyl stretching vibration of methanol.The deviation of ortho-substituted pyridines is proportional to the steric parameter S0.The generality of Deltaeta(I2) as a spectroscopic indicator of basicity is analyzed and it is shown that multiparametric equations predicting the reactivity of electron donor-acceptor systems are limited due to steric effects.

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

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The reaction of cyclopentadiene with various bidentate dienophiles in the presence of 4-10 mol% of copper(II)-bis(oxazoline) complexes afforded excellent endo/exo selectivity as well as endo enantioselectivity (95-99% ee) and isolated yields. On the other hand, Diels-Alder reaction with Mg(II)- complexes afforded a modest (61% ee) reversal in enantioselectivity.

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

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The Host compound 2,2? bis(1-hydroxy-4,5-dihydro-2,3:6,7-dibenzocycloheptatrien-1-yl)-biphenyl, H1, has been employed to discriminate between all the pairs of lutidine isomers. The preference for guest enclathration follows the sequence 3,4-LUT>2,4-LUT?3,5-LUT>2,5-LUT>2,3-LUT>2,6-LUT. This has been confirmed by guest-release endotherms measured by DSC. Four other diol host compounds, H2?H5, were tested on pairs of lutidine isomers which were poorly separated by H1.

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Reference:
Chiral nitrogen ligands in late transition metal-catalysed asymmetric synthesis—I. 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 displacement of coordinated nitrogen donor bases (L)by chloride from complexes of the type [Pt(NSN)(L)](2+) [NSN=bis(2-pyri dylmethyl)sulphide; L=a series of pyridines, isoquinoline and NH3] as well as chloride substitution from the substrate [Pt(NSN)Cl](+) by Br(-) and I(-) have been studied in methanol at 25°C and constant ionic strength and compared with those of the corresponding platinum(II) complexes containing the 2,6-bis(methylsulphanyl)pyridine tridentate ligand. The two-term rate law usually found in substitutions at square-planar platinum(II) complexes is obeyed. Both the first and second-order rate constants for the displacement of L decrease as the basicity of the leavinggroup increases. pi interactions between coordinated pyridines and th e metal centre are suggested by comparison of their lability with that of ammonia as well as with that of para-substituted pyridines with enhanced pi system. Steric hindrance on the leaving base also significantly decreases the reactivity.

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

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Enantiomerically pure phosphinamides containing a pendant hydroxyl group catalyse the Al(III)-promoted ring opening of the meso epoxide in cyclohexene oxide with thiophenol in up to 80% enantiomeric excess.

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

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Investigations into the mechanistic aspects of the stereospecific interaction of the four optical isomers of aminoindanol on a silica based crown ether column were performed. The nature and concentration of the mobile phase’s counteranion affected the hydrophobic interaction but had little effect on the inclusion interaction. Minimal changes in the separation factor of the enantiomers were observed in the pH range of 1-5.2, but a minimum in the capacity factor was observed at pH 3.75. Van’t Hoff plots indicated a high entropy and a positive enthalpy at pH 5.2, while a lower entropy and a negative enthalpy were observed at and below pH 3.75. Hill plots indicated that there were more active binding sites at pH 3.0 as compared to pH 1.0 and that the binding ratio of aminoindanol to active sites was also greater. Apparently at higher pH values, as the silica becomes deprotonated, there is an additional electrostatic interaction between the protonated aminoindanol and the deprotonated silica sites.

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

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Ultrasound-assisted extraction (UAE) of polysaccharide from Maryland tobacco leaves was studied by response surface methodology. Furthermore, the crude polysaccharide was purified and two components (Fr-I and Fr-II) were obtained. FT-IR spectral analysis of the purified polysaccharide revealed prominent characteristic groups. The monosaccharide composition analysis by gas chromatography-mass spectrometry (GC/MS) indicated the main composition between Fr-I and Fr-II was different. Furthermore, thermo gravimetric analysis (TGA) indicated the degradation temperature (Td) of the Fr-I (241C) was higher than those of Fr-II (216o C). Detected by the pyrolysis gas chromatography-mass spectrometry (py-GC/MS), it was found that the main kinds of pyrolysis products from both Fr-I and Fr-II were similar. Finally, On the basis of hydroxyl and DPPH radical scavenging assay, Fr-II has stronger antioxidant activities than Fr-I. The thermal behavior and antioxidant activity might be attributed to the configuration of the chemical compositions.

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

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Self-assembly of a stereodynamic phosphine ligand, Pd(II), and a chiral amine, amino alcohol, or amino acid generates characteristic UV and CD signals that can be used for quantitative stereochemical analysis of the bound substrate. A robust mix-and-measure chiroptical sensing protocol has been developed and used to determine the absolute configuration, ee, and yield of an amine produced by Ir-catalyzed asymmetric hydrogenation of an iminium salt. The analysis requires only 1 mg of the crude reaction mixture and minimizes cost, labor, time, and waste.

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