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An Improved Liquid-Phase Synthesis of Simle Alkylpyridines

The synthesis of pyridines from mixtures of aldehydes or ketones and NH3 in the liquid phase has been reinvestigated, using continuous dosage of the carbonyl components to the reaction mixture.The main product from the reaction of acetaldehyde and formaldehyde is 3-methylpyridine (6), which is also the main product from the reaction of acrolein or a mixture of crotonaldehyde and formaldehyde under the same conditions.The reaction of other aldehydes with formaldehyde give 3,5-dialkylpyridines, e.g. 10, 16.Acetone reacts with either formaldehyde or acetaldehyde to give polysubstituted alkylpyridines.A mechanistic pathway is proposed which accounts for the formation of the observed products.

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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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Geometries and tautomerism of OHN hydrogen bonds in aprotic solution probed by H/D isotope effects on 13C NMR chemical shifts

The 1H and 13C NMR spectra of 17 OHN hydrogen-bonded complexes formed by CH313COOH(D) with 14 substituted pyridines, 2 amines, and N-methylimidazole have been measured in the temperature region between 110 and 150 K using CDF3/CDF2Cl mixture as solvent. The slow proton and hydrogen bond exchange regime was reached, and the H/D isotope effects on the 13C chemical shifts of the carboxyl group were measured. In combination with the analysis of the corresponding 1H chemical shifts, it was possible to distinguish between OHN hydrogen bonds exhibiting a single proton position and those exhibiting a fast proton tautomerism between molecular and zwitterionic forms. Using H-bond correlations, we relate the H/D isotope effects on the 13C chemical shifts of the carboxyl group with the OHN hydrogen bond geometries.

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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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Prediction of the chromatographic retention of acid-base compounds in pH buffered methanol-water mobile phases in gradient mode by a simplified model

Retention of ionizable analytes under gradient elution depends on the pH of the mobile phase, the pKa of the analyte and their evolution along the programmed gradient. In previous work, a model depending on two fitting parameters was recommended because of its very favorable relationship between accuracy and required experimental work. It was developed using acetonitrile as the organic modifier and involves pKa modeling by means of equations that take into account the acidic functional group of the compound (carboxylic acid, protonated amine, etc.). In this work, the two-parameter predicting model is tested and validated using methanol as the organic modifier of the mobile phase and several compounds of higher pharmaceutical relevance and structural complexity as testing analytes. The results have been quite good overall, showing that the predicting model is applicable to a wide variety of acid-base compounds using mobile phases prepared with acetonitrile or methanol.

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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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Differences in proton-proton coupling constants of N+-CH2-CH2 protons of some betaines, N+-(CH2)2-3-COO-, and their complexes in aqueous solution

Synthesis and 1H NMR spectra in D2O of 4 betaines and 19 betaine complexes with mineral acids containing 2 or 3 CH2 groups in the tether, N+-(CH2)n-COO-, n=2,3, and diverse volume of the positively charged groups are reported. In compounds containing three CH2 groups in the tether and three substituents at the nitrogen atom or alpha, alpha?-disubstituted pyridine ring, a characteristic multiplet for an AA?MM?X2 spin system is observed. This is consistent with preference for trans conformation (68-85%). In the spectra of compounds with two CH2 groups in the tether or three CH2 groups and unsubstituted pyridine ring, the multiplet changes to a triplet and gives apparent A2X2 and A2M2X2 spectra, respectively, consistent with no significant conformational preference. Both the number of CH2 groups in tether and the bulkiness of the charged groups are responsible for the observed differences of N+CH2 multiplicity and reflect changes in conformational preferences. According to the PM3 calculations, in the gas phase a gauche-like conformer is more stable than the trans, but in aqueous solution it is reverse.

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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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Iridium-catalyzed C-H borylation of pyridines

The iridium-catalysed C-H borylation is a valuable and attractive method for the preparation of aryl and heteroaryl boronates. However, application of this methodology for the preparation of pyridyl and related azinyl boronates can be challenged by low reactivity and propensity for rapid protodeborylation, particularly for a boronate ester ortho to the azinyl nitrogen. Competition experiments have revealed that the low reactivity is due to inhibition of the active catalyst through coordination of the azinyl nitrogen lone pair at the vacant site on the iridium. This effect can be overcome through the incorporation of a substituent at C-2. Moreover, when this is sufficiently electron-withdrawing protodeborylation is sufficiently slowed to permit isolation and purification of the C-6 boronate ester. Following functionalization, reduction of the directing C-2 substituent provides the product arising from formal ortho borylation of an unhindered pyridine ring. This journal is the Partner Organisations 2014.

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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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Benzo[f]azino[2,1-a]phthalazinium Cations: Novel DNA Intercalating Chromophores with Antiproliferative Activity

New azaquinolizinium-type cations have been obtained from isochromane. The synthesis was completed over seven steps and included as the key feature an intramolecular Westphal condensation. This first example of the intramolecular process allowed the preparation of benzo[f]pyrido[2,1-a]phthalazinium and benzo[f]quino[2,1-a]phthalazinium salts, which were evaluated as DNA intercalators, DNA topoisomerase I inhibitors, and antiproliferative compounds. Both cationic systems behave as DNA intercalators and exhibit antiproliferative activity. The pentacyclic benzo[f]quino[2,1-a]phthalazinium cations also have an inhibitory effect on the catalytic activity of DNA topoisomerase I, without trapping of cleavage complexes. Structural characterization using density functional theory indicates that the fused ring systems are slightly nonplanar, and additional molecular modeling studies suggest a preferred orientation for the intercalating chromophores within a typical CpG or TpG intercalation site.

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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 catalyzed pathway has a lower Ea, but the net change in energy that results from the reaction is not affected by the presence of a catalyst. Computed Properties of C7H9N, If a proposed mechanism predicts the wrong experimental rate law, however, the mechanism must be incorrect.Welcome to check out more blogs about 108-47-4, in my other articles.

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Process Modelling and Simulation of Degradation of 2-amino-2-methyl-1-propanol (AMP) Capture Plant

The presence of contaminants in the flue gas stream such as O2, CO2, SOX, and NOX can cause solvent degradation in solvent-based CO2 capture processes. In this study, the major degradation products reactions of the AMP-based CO2 capture process has been included in the Aspen Plus V8.4 simulation software using equilibrium reactions. Assessing the solvent degradation, solvent concentration and flowrate were varied. The results showed that the AMP losses reduced by decreasing solvent flowrate and concentration. Largest energy savings are observed when increasing concentration up to 34 wt. %.

The catalyzed pathway has a lower Ea, but the net change in energy that results from the reaction is not affected by the presence of a catalyst. Computed Properties of C7H9N, If a proposed mechanism predicts the wrong experimental rate law, however, the mechanism must be incorrect.Welcome to check out more blogs about 108-47-4, in my other articles.

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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Dopants and gas modifiers in ion mobility spectrometry

The ion mobility techniques, including the most commonly used drift-tube ion mobility spectrometry (IMS) and differential mobility spectrometry (DMS), are used successfully for the detection of a wide range of organic compounds in the gas phase. In order to improve detection quality, admixtures are added to gas streams flowing through the detector. Dopants mostly prevent the ionization of interfering chemicals however, better detection may be also achieved by shifting the peaks in the drift-time spectra, enabling ionization of analytes with low proton affinities and, thus, facilitating photoionization. Fundamental information about ion-molecule reactions including the role of dopants is presented. The term ‘gas modifiers’ refers to substances that influence the ion transport by changing the mobility of ions without changing the chemistry of the ionization. The mechanism of the gas modifier’s interaction with an analyte in ion separation in drift tube IMS and DMS is explained in this paper.

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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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LATERAL METALLATION OF METHYLATED NITROGENOUS HETEROCYCLES

Me groups on nitrogenous heterocycles can be conveniently metallated by a variety of strongly basic reagents to afford synthetically useful carbanions.The negative charge of such anions resides predominantly on the ring N atoms.The site of lithiation on pyridines and quinolines bearing Me groups in both the 2- and 4-positions depends upon the ability of the ring N atom to complex with the metallating agents.Carbanions derived from methylated pyridines, quinolines, naphthyridines, isoquinolines, pyrido<4,3-b>carbazoles, pteridines, pyrido<3,4-b>indoles and quinoxalines are discussed.References are provided describing condensations of these reagents with a variety of both common and uncommon 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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Lewis acid-catalyzed c-h functionalization for synthesis of isoindolinones and isoindolines

The Lewis acid-catalyzed C-H functionalization of 2-substituted azaarenes with N-sulfonylaldimines has been developed, which provides a rapid and efficient approach for synthesis of heterocycle-containing isoindolinones and isoindolines. 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