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The investigation of long-range 1H-15N heteronuclear shift correlation NMR experiments has gone from its inception in 1995 to a robust area of research with numerous studies now reported annually. The area has been reviewed twice, covering the literature through about mid-2000. The present report covers the period from where this author’s previous review stopped in late-1999 through the present. New long-range heteronuclear shift correlation methods that are applicable to long-range 1H-15N 2D heteronuclear shift correlation are discussed followed by a discussion of the impact of long-range 1H-15N data on Computer-Assisted Structure Elucidation methods and then a review of the applications of these techniques reported in the literature.

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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 method to measure the rate constant for the formation of symmetrical proton-bound dimers at ambient pressure was proposed. The sample is continuously delivered to the drift region of an ion mobility spectrometer where it reacts with a swarm of monomer ions injected by the shutter grid. Dimer ions are formed in the drift tube and a tail appears in the ion mobility spectrum. The rate constant is derived from the mobility spectra. The proposed approach was typically examined for methyl isobutyl ketone (MIBK), 2,4-dimethyl pyridine (DMP), and dimethyl methyl phosphonate (DMMP). The rate constants measured in this study were: 0.25 × 10-9, 0.86 × 10-10, and 0.47 × 10-10 cm3 s-1 for MIBK, DMP and DMMP, respectively. The logarithm of the measured rate constants were found to be almost independent of reciprocal temperature within 303 to 343 K, indicating that no activation energy is involved in the formation of proton-bound dimers.

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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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Lignocellulosic biomass is considered an abundant and renewable source to produce bio-oils with an objective of its value addition for fuels and chemicals. Upgrading strategies have immensely evolved as a result of ever progressing research in this field. Development of complete analytical protocol for bio-oil characterization at different stages of its production, storage, upgrading and during its use is essential for the purpose of its quality assurance and understanding. This report is aimed at developing a sample preparation procedure for bio-oils involving an extensive liquid-liquid extraction approach. Bio-oil obtained after slow pyrolysis of Jatropha Curcas seed cake was phase separated and subjected to solvent extraction. Various solvents were screened for their extraction capabilities towards available organic compounds of all functional group in the bio-oil. Ethyl acetate, dichloromethane, carbon tetrachloride, diethyl ether, benzene, cyclohexane and hexane were employed for extraction of aqueous phase under similar conditions. Recoveries of compounds containing varying functional groups indicated ethyl acetate and dichloromethane as optimum among all other solvents. During the extraction, partitioning of compounds between bio-oil phase and solvent occurred largely on the basis of polarity. Acidic and basic organic compounds present in the aqueous phase were determined after adjusting the pH of samples followed by dichloromethane extraction. A comprehensive detail of the extracted chemicals and their classification has been provided. The identification was carried out qualitatively with GC-MS and derivatization of polar chemicals was also carried out before analysis. These experiments compare the efficacy of various organic solvents for extracting diverse bio-oil pyrolytic products. The findings are important in ascertaining usefulness of organic solvents towards enrichment of available bio-oil chemical groups. The information may be either utilized for characterization purposes or their monitoring during upgrading process.

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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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This work demonstrated the potential of using a secondary drift gas of differing polarizability from the primary drift gas for confirmation of a positive response for drugs or explosives by ion mobility spectrometry (IMS). The gas phase mobilities of response ions for selected drugs and explosives were measured in four drift gases. The drift gases chosen for this study were air, nitrogen, carbon dioxide and nitrous oxide providing a range of polarizability and molecular weights. Four other drift gases (helium, neon, argon and sulfur hexafluoride) were also investigated but design limitations of the commercial instrument prevented their use for this application. When ion mobility was plotted against drift gas polarizability, the resulting slopes were often unique for individual ions, indicating that selectivity factors between any two analytes varied with the choice of drift gas. In some cases, drugs like THC and heroin, which are unresolved in air or nitrogen, were well resolved in carbon dioxide or nitrous oxide.

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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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Reactions catalyzed within inorganic and organic materials and at electrochemical interfaces commonly occur at high coverage and in condensed media,name: 2,4-Dimethylpyridine, Name is 2,4-Dimethylpyridine, belongs to chiral-nitrogen-ligands compound, is a common compound. name: 2,4-Dimethylpyridine, In an article, authors is Wang, Tielin, once mentioned the new application about name: 2,4-Dimethylpyridine.

Aqueous blends of 2-amino-2-methyl-1-propanol (AMP) and piperazine (PZ) appear to be commercially attractive solvents for post-combustion CO2 capture by absorption/stripping. An experimental study on the oxidative degradation of aqueous PZ solutions and AMP/PZ blends was carried out. The oxidative degradation experiments were performed in a 200mL glass batch reactor with an oxygen partial pressure of 250kPa, and at the temperatures of 80-120C. The amine loss was determined by cation ion chromatography (IC) while the degradation compounds were identified and quantified by gas chromatography-mass spectrometry (GC-MS), cation IC and anion IC. Possible chemical pathways of PZ oxidative degradation are proposed to account for the observed degradation products. As compared to oxidative degradation of single AMP and PZ solvents, no new product was observed in partially degraded AMP/PZ blends. However, PZ degraded faster in the blends than it degraded individually at identical degradation conditions.

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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 C,N double bond of pyridine, quinoline and isoquinoline as heterodipolarophile react with diarylnitrilimines 2, generated in situ by dehydrohalogenation of N-phenylbenzhydrazonoyl chlorides 1, in a cycloaddition with complete regioselectivity.A facile route to hitherto unreported 1,3-diaryl-1,8a-dihydro<1,2,4>triazolo<4,3-a>pyridines 3, 1,3-diaryl-3,3a-dihydro<1,2,4>triazolo<4,3-a>quinolines 4, and 1,3-diaryl-1,10b-dihydro<1,2,4>triazolo<3,4-a>isoquinolines 5 has been developed.In a similar way, cycloadditions are carried out with C-ethoxycarbonyl- and C-acetyl-N-phenylnitrilimines.The ring cleavage of 3 in acidic medium yields the corresponding <(arylhydrazono)methyl>pyridinium chlorides 7.The conversion of the open-chain products back to 3 has been carried out in pyridine containing triethylamine.Anodic oxidation of 3 – 5 in aprotic medium affords the <1,2,4>triazolohetarenium perchlorates 9 – 11.The yields in such reactions are either similar or better than with chemical oxidants.The thermally initiated cycloreversion of 3 and 5 is discussed, judging from the facts that the thermolysis afford 2:1 cycloadducts.Key Words: Nitrilimines / <1,2,4>Triazolopyridines / 1,3-Dipolar cycloadditions

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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 scope and mechanism of the isomerization of arylamines to methyl-substituted aromatic heterocycles have been studied.Aniline, toluidines, naphthylamines and m-phenylenediamine all reacted to the corresponding ortho-methyl-substituted aza-aromatiics when exposed to high NH3 pressure and elevated temperature in the presence of acid catalysts.Zeolites with a three-dimensional pore structure, especially H-ZSM-5, showed the best performance.Optimum reaction conditions are around 600 K and 10 MPa.Two mechanisms which had been proposed earlier for this apparent N-ortho C exchange reaction proved untenable.Neither incorporation of the N atom into the aromatic ring nor a mechanism based on an intramolecular Ritter reaction could explain the required high NH3 pressure or the product distribution.Two new mechanisms are proposed which can explain all observations.In both mechanisms, reaction starts with addition of NH3 to the arylamine, followed by ring opening.In one mechanism an alkyno-imine intermediate is formed; in the other mechanism an enamino-imine intermediate is formed through a reverse aldol reaction.In both cases ring closure and NH3 elimination lead to the required aromatic heterocycles.The high NH3 pressure is explained by the need to add NH3 to the aromatic ring, and the high temperature by the need to desorb NH3 from the acid 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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Syntheses are reported for tripyridine macrocycles 2 and 3 and some of their alkyl derivatives. The macrocycles are designed to stabilize to various extents coordinated d8 metal precursors and d6 alkane oxidative addition products (ptIV), therefore allowing favorable kinetics and thermodynamics of (e.g., PtII) the cleavage of substrate H-C(sp3) bonds. Both the Chichibabin protocol and oxidative coupling of carbanions by copper(I) iodide were used for the macrocyclization step. Crystal structures of singly and doubly protonated 2 establish atom connectivity in the macrocycle, and reveal structural features which are obscured in solution NMR by rapid proton migration.

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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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Transformation and intramolecular alkyl ligand activation in beta-diketiminato nickel(II) complexes were studied using the PBE density functional.

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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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Reactions of pyridines and imidazoles with substituted phenyl acetates and trifluoroacetates have been studied in acetonitrile and in water-acetonitrile containing 0.56 mol/dm3 of water.The water isotope effects, steric effects, the effect of water in the reaction medium, and the derived Broensted beta and Hammett rho values have been used as mechanistic criteria.Pyridines and imidazoles catalyse the hydrolysis of phenyl trifluoroacetates by general base catalysis while imidazole acts as nucleophile toward 4-nitrophenyl and 2,4-dinitrophenyl acetates.As indicated by the second-order dependence on amine concentration beside the first-order term in amine, the reaction of imidazole exhibits general base catalysis in the case of both phenyl acetates and phenyl trifluoroacetates.This reaction obviously is general base-catalysed nucleophilic reaction of imidazole.The activation parameters DeltaH* and DeltaS* derived for the reactions of pyridine and imidazole with 4-nitrophenyl trifluoroacetate and for the reaction of imidazole with 4-nitrophenyl acetate are consistent with the proposed reaction mechanisms.

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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