Properties and Exciting Facts About 2,4-Dimethylpyridine

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A Rh(I)-catalyzed direct arylation of pyridine and quinoline heterocycles has been developed. The method provides rapid entry into an important class of substituted heterocycles employing inexpensive and readily available starting materials. Copyright

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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 mobilities of a set of common alpha-amino acids, four tetraalkylammonium ions, 2,4-dimethyl pyridine (2,4-lutidine), 2,6-di-tert-butyl pyridine (DTBP), and valinol were determined using electrospray ionization-ion mobility spectrometry-quadrupole mass spectrometry (ESI-IMS-QMS) while introducing 2-butanol into the buffer gas. The mobilities of the test compounds decreased by varying extents with 2-butanol concentration in the mobility spectrometer. When the concentration of 2-butanol increased from 0.0 to 6.8mmolm-3 (2.5×102ppmv), percentage reductions in mobilities were: 13.6% (serine), 12.2% (threonine), 10.4% (methionine), 10.3% (tyrosine), 9.8% (valinol), 9.2% (phenylalanine), 7.8% (tryptophan), 5.6% (2,4-lutidine), 2.2% (DTBP), 1.0% (tetramethylammonium ion, TMA, and tetraethylammonium ion, TEA), 0.0% (tetrapropylammonium ion, TPA), and 0.3% (tetrabutylammonium ion, TBA). These variations in mobility depended on the size and steric hindrance on the charge of the ions, and were due to the formation of large ion-2-butanol clusters. This selective variation in mobilities was applied to the resolution of a mixture of compounds with similar reduced mobilities such as serine and valinol, which overlapped in N2-only buffer gas in the IMS spectrum. The relative insensitivity of tetraalkylammonium ions and DTBP to the introduction of 2-butanol into the buffer gas was explained by steric hindrance of the four alkyl substituents in tetraalkylammonium ions and the two tert-butyl groups in DTBP, which shielded the positive charge of the ion from the attachment of 2-butanol molecules. Low buffer gas temperatures (100C) produced the largest reductions in mobilities by increasing ion-2-butanol interactions and formation of clusters; high temperatures (250C) prevented the formation of clusters, and no reduction in ion mobility was obtained with the introduction of 2-butanol into the buffer gas. Low temperatures and high concentrations of 2-butanol produced a series of ion clusters with one to three 2-butanol molecules in compounds without steric hindrance. Clusters of two and three molecules of 2-butanol were also visible. Ligand-saturation on the positive ions with 2-butanol molecules occurred at high concentrations of modifier (6.8mmolm-3 at 150C); when saturated, no further reduction in mobility occurred when 2-butanol was introduced into the buffer gas.

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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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Ion mobility spectrometry (IMS) separates gas-phase ions drifting under an electric field according to their size to charge ratio. We used electrospray ionization-drift tube IMS coupled to quadrupole mass spectrometry to obtain the mobilities of common amino acids, amines, valinol, atenolol, and the chemical standards tetramethylammonium ion (TMA), tetraethylammonium ion (TEA), tetrapropylammonium ion (TPA), and tetrabutylammonium (TBA) ions, 2,4-lutidine and 2,6-di-tert-butyl pyridine (DTBP). The mobilities were obtained in pure nitrogen or when shift reagents (SR) such as ammonia, 2-butanol, ethyl lactate, methanol, methyl 2-chloropropionate, nitrobenzene, 1-phenyl ethanol, trifluoromethyl benzyl alcohol, and water were introduced in the buffer gas. We found important differences in the buffer gas temperature between different regions of the drift tube and differences between the buffer gas and drift tube temperatures, which is normally used instead of the buffer gas temperature in reduced mobility calculations. Therefore, we used the buffer gas temperature instead of the drift tube temperature and a calibration method with two types of chemical standards, finding excellent precision, reproducibilities from 0.3 to 0.6% for reduced mobilities (K0) of the chemical standards during nine months. Repeatability during this period was 0.17% for the drift times of all the analytes. We also show that the changes in instrumental parameters such as temperature, pressure and voltage that produce important variations in drift times are small; for this, we recommend to calculate K0 from calibration with chemical standards instead of replacing instrumental parameters in the IMS fundamental equations.

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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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alpha-Trifluoromethyl benzyl alcohol (F) was introduced as a “shift reagent” in the buffer gas of an electrospray ionization ion mobility spectrometer coupled to a quadrupole mass spectrometer to explain the mobility shifts of selected compounds; ion mobilities depended on ion sizes and F-ion adducts binding energies calculated using Gaussian 09 at the X3LYP/6-311++G(d,p) level. The mobility shifts with the introduction of F in the buffer gas were: – 13% (ethanolamine), – 10.6% (serine), – 8.6% (threonine), – 7.3% (phenylalanine), – 7.0% (tyrosine), – 6.2 (tributylamine), – 5.1% (valinol), – 4.7% (methionine), – 3.9% (tryptophan), – 3.1% (tribenzylamine), – 1.3% (2,6-di-tert-butyl pyridine, DTBP), – 1.2% (2,4-lutidine, 2,4-dimethyl pyridine), and – 0.1% (atenolol). These mobility shifts showed a decreasing trend with the increase in molecular weight from ethanolamine to tribenzylamine excluding some ions due to steric hindrance (2,4-lutidine, DTBP and tetraalkylammonium ions), formation of intramolecular bridges (atenolol and methionine) or low binding energy with F (valinol). Ethanolamine (61.1 g/mol) showed the largest mobility shift (- 13%) due to its low molecular weight and tribenzylamine showed the smallest one due to its large size. We found a similar trend in mobility shifts when methyl chloro propionate, trifluoromethyl benzyl alcohol, ethyl lactate, nitrobenzene or 2-butanol were used as SRs. We also found that penicillamine adducts with F were not seen in the mass or mobility spectra probably because of the formation of an intramolecular bridge in this compound; F produced the average lowest mobility shifts of all SRs tried before, even of smaller size (methyl chloro propionate, phenylethanol, ethyl lactate, nitrobenzene, and 2-butanol) because of the inductive effects exerted by the three fluorine atoms that decreased F proton affinity and hindered its adduction to analyte ions. In summary, intramolecular bridges, size, inductive effects, steric hindrance and adduct binding energy were used to explain mobility shifts when trifluoromethyl benzyl alcohol was used as a “shift reagent” in ion mobility spectrometry.

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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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A facile synthesis of a new bisoxazoline ligand is described. This ligand contains a urea bridging unit and is capable of stabilizing bimetallic complexes. An X-ray crystal structure of a bis-copper complex is reported.

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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 electronic (400 – 800 nm; 298.2 K) and E.S.R. spectra (298 K; 77K) have been measured for CuCl2-2,4-dimethylpyridine(2,4-Me2py)-solvent systems (solvents: aliphatic and aromatic hydrocarbons, carbon tetrachloride, chloroform, 1,1,2,2-tetrachloroethane).In all the media CuCl2 forms electrically neutral strongly distorted six-coordinated complexes, the extent of tetragonality being greater than for analogous complexes with non-alpha-substituted pyridines.In contrast to aliphatic and aromatic hydrocarbons protic solvents and, unexpectedly, aprotic carbon tetrachloride solvate the CuCl2-Me2py complex comparatively strongly, most probably through interactions with the chlorine ligand.The results for 2,4-Me2py were compared with those for pyridine, 4-ethylpyridine and isoquinoline and discussed in terms of steric effects on solvation.In particular, alpha-substitution seems to hinder the solvation of the complex by the amine. – Keywords: Solvent effect; Copper(II) chloride complexes; Pyridine derivative complexes

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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

Properties and Exciting Facts About 2,4-Dimethylpyridine

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Metalation of 2,4-dimethylpyridine and -quinolines by strong basic reagents in ethyl ether in the absence of HMPA affords 2-lithiomethyl derivatives regardless of the reaction length.The use of THF in such metalations promotes the formation of the 2-lithiomethyl reagents which isomerize to the more thermodynamically stable 4-lithiomethyl derivatives after relatively long reaction periods or in the presence of amines or an excess of the parent heterocycle.The latter derivatives appear to be formed directly from the heterocycles in ammonia or in the presence of HMPA.The results are discussed in terms of “coordination-only” versus “acid-base” limiting mechanisms for metalations as a function of ion pairing.NMR spectra for certain of the carbanions in ethyl ether and THF are described which support the above concepts.Related metalations of 2,4-dimethylquinoline-N-oxide give only the 2-lithiomethyl derivative.Similar reactions of 7-hydroxy-2,4-dimethyl-1,8-naphthyridine lead in synthetically useful yields to derivatization of the 2- and 4-methyl groups via dianions by using n-butyllithium in ethyl ether and sodium amide in liquid ammonia, respectively, followed by the addition of appropriate electrophiles.

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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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New adducts with the composition [Co2Gd(NO3)(Piv)6L2] (L=2,4-lutidine (lut) (1), 2-phenylpyridine (PhPy) (4), 2-ethynylpyridine (EtPy) (5)) and [Co2Eu(NO3)(Piv)6(EtPy)2] (6) were synthesized. According to X-ray diffraction data, the molecular complexes comprise two atoms of cobalt(II) and one central atom of gadolinium(III) bridged by carboxylate ligands. The donor base molecules are coordinated to cobalt atoms. Magnetic measurements of the new and previously synthesized complexes with quinoline (2) and pyridine (3) ligands showed the ferromagnetic nature of the coupling between the metal centers in the CoII 2GdIII core with JCo-Gd parameters in the range of 0.15?0.18 cm?1. DFT calculations supported the ferromagnetic type of coupling for these complexes. Simultaneous thermal analysis of 1 and 2 showed the thermal stability of the complexes up to 180 C and the stepwise nature of thermolysis, which includes the stages of elimination of the donor base molecules and the thermal decomposition of the pivalate moieties in the complex.

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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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Dimedone enamines were applied for the first time as new dienophiles in hetero-Diels-Alder reactions with inverse electron demand. Cycloadditions of barbituric acid 5-ylidene alditols with dimedone enamines were performed in dichloromethane at room temperature for 3 days and fused uracils-chromeno[2,3-d]pyrimidine-2,4-diones were obtained in good 73-87% yields. Only one enantiomerically pure stereoisomer was obtained in each studied cycloaddition. Analysis of 1H NMR and 2D NMR spectra allowed for the determination that cycloadducts exist in solution as mixture of the neutral form and dipolar ion. The prepared fused uracils contain both amine and enol functional groups, so share amphiprotic properties and they are zwitterions in solid state. The new class of compounds-amino enols was synthesized, which similarly to amino acids exists as zwitterions. In obtained cycloadducts amino groups and sugar moieties are close each other and they both are in cis configuration and in axial position. It was also shown that different alkenes can be used as dienophiles towards barbituric acid 5-ylidene alditols, for example, styrene or 1-amino-2-thiocarbamoyl-cyclopent-1-ene.

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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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Chemical research careers are more diverse than they might first appear, as there are many different reasons to conduct research and many possible environments. COA of Formula: C7H9N, Name is 2,4-Dimethylpyridine, belongs to chiral-nitrogen-ligands compound, is a common compound. COA of Formula: C7H9NCatalysts allow a reaction to proceed via a pathway that has a lower activation energy than the uncatalyzed reaction. In an article, authors is Hauck, Brian C., once mentioned the new application about COA of Formula: C7H9N.

Ion mobility spectrometry (IMS) is a well established technique for the detection of many compounds of interest based on the reduced mobility (K0) values of their ions. While having the advantage of small size, weight, and power, IMS has been subject to low specificity and is subject to interferences that can cause false alarms in detectors used for security applications. The rate of false positive alarms is directly related to the detection window width required to maintain a high rate of true positive detections. These window widths are in turn a result of the historically available accuracy of reference measurements and the range of responses by multiple detectors. The windows cannot be arbitrarily reduced without risking an increase in the rate of false negative responses. Ongoing work has focused on high accuracy calibration as a means of decreasing the false alarm rates by reducing the variability between detectors which would allow for narrower detection windows. Central to the calibration procedure is the selection of an appropriate calibrant (or reference standard) that can be easily characterized and known with a high degree of certainty across a range of instrumental conditions. This review evaluates a number of previously proposed and potential calibrants against seven recommended criteria of suitability. We examine the sources of false positive alarms in IMS-based detectors and propose a calibration procedure based on high accuracy reference measurements. Initial results of applying this procedure in a post-processing manner are promising towards reducing detector variability and detection window width.

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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