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Carbon-Hydrogen Bond Dissociation Energies in Alkylbenzenes. Proton Affinities of the Radicals and the Absolute Proton Affinity Scale

Rate constants (k) were measured for proton-transfer reactions from alkylbenzene ions RH+ to a series of reference bases B, i.e., RH+ + B -> BH+ + R*.For exothermic reactions (DeltaH BH+ + C6H5CH2* is fast (reaction efficiency = k/kcol >/= 0.5) when B = MeO-t-Bu or stronger bases, but k/kcol is significantly smaller when B is n-Pr2O or weaker bases.From the falloff curve of reaction efficiency vs.PA(B), we find PA(n-Pr2O) = PA(C6H5CH2*) + 0.8 kcal mol-1 = 200.0 kcal mol-1.Since PA(C6H5CH2*) is obtained from known thermochemical data, this relation defines the absolute PA of n-Pr2O.Through a ladder of known PA, we then obtain PA(i-C4H8) = 186.8 kcal mol-1; we also obtain the absolute PAs of other oxygen bases.Falloff curves of reaction efficiencies of 3-FC6H4CH3+, C6H5C2H5+, C6H5-n-C3H7+, and C6H5-i-C3H7+ with these reference bases give then the following PAs of R* and R-H bond dissociation energies (Do) (all in kcal mol-1) as R*, PA(R*), Do(R-H): 3-FC6H4CH2*, 197.2, 89.4; , 197.9, 86.2; , 199.1, 86.1; , 199.6, 86.1.In similar manner, rate constants for H+ transfer from C6H5NH2+ to reference pyridines and amines yield PA(C6H5NH*) = 221.5 and Do(C6H5NH-H) = 85.1 kcal mol-1 (1 kcal mol-1 = 4.18 kJ mol-1).

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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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In heterogeneous catalysis, the catalyst is in a different phase from the reactants. Safety of (1S,2R)-1-Amino-2,3-dihydro-1H-inden-2-ol, At least one of the reactants interacts with the solid surface in a physical process called adsorption in such a way. 126456-43-7, name is (1S,2R)-1-Amino-2,3-dihydro-1H-inden-2-ol. In an article£¬Which mentioned a new discovery about 126456-43-7

Micro-structured reactors as a tool for chiral modifier screening in gas-liquid-solid asymmetric hydrogenations

A continuous micro-structured reactor equipped with a perforated (5 mum) membrane is used for the investigation of the gas-liquid-solid asymmetric hydrogenation of ethylpyruvate on a Pt/gamma-Al2O3 catalyst modified with chiral inductors under high hydrogen pressure (45 bar). Up to eight chiral inductors have been evaluated, the best enantioselectivity (63%) being obtained with cinchonidine. The very low reaction volume (100 mul) offers short operating time. Solvent effect, deactivation studies and the effect of modifier leaching are also reported.

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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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Liquid Chromatographic Study of Solute Hydrogen Bond Basicity

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£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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Solvent Effect on CuCl2-Pyridine Derivative Complexes: UV-VIS ans E.S.R. Study of the CuCl2-2,4-Dimethylpyridine-Solvent Systems

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£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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In heterogeneous catalysis, the catalyst is in a different phase from the reactants. Application In Synthesis of (1S,2R)-1-Amino-2,3-dihydro-1H-inden-2-ol, At least one of the reactants interacts with the solid surface in a physical process called adsorption in such a way. 126456-43-7, name is (1S,2R)-1-Amino-2,3-dihydro-1H-inden-2-ol. In an article£¬Which mentioned a new discovery about 126456-43-7

Diversification of ortho-Fused Cycloocta-2,5-dien-1-one Cores and Eight- to Six-Ring Conversion by sigma Bond C?C Cleavage

Sequential treatment of 2-C6H4Br(CHO) with LiC?CR1(R1=SiMe3, tBu), nBuLi, CuBr?SMe2and HC?CCHClR2[R2=Ph, 4-CF3Ph, 3-CNPh, 4-(MeO2C)Ph] at ?50 C leads to formation of an intermediate carbanion (Z)-1,2-C6H4{CA(=O)C?CBR1}{CH=CH(CH?)R2} (4). Low temperatures (?50 C) favour attack at CBleading to kinetic formation of 6,8-bicycles containing non-classical C-carbanion enolates (5). Higher temperatures (?10 C to ambient) and electron-deficient R2favour retro sigma-bond C?C cleavage regenerating 4, which subsequently closes on CAproviding 6,6-bicyclic alkoxides (6). Computational modelling (CBS-QB3) indicated that both pathways are viable and of similar energies. Reaction of 6 with H+gave 1,2-dihydronaphthalen-1-ols, or under dehydrating conditions, 2-aryl-1-alkynylnaphthlenes. Enolates 5 react in situ with: H2O, D2O, I2, allylbromide, S2Me2, CO2and lead to the expected C-E derivatives (E=H, D, I, allyl, SMe, CO2H) in 49?64 % yield directly from intermediate 5. The parents (E=H; R1=SiMe3, tBu; R2=Ph) are versatile starting materials for NaBH4and Grignard C=O additions, desilylation (when R1=SiMe) and oxime formation. The latter allows formation of 6,9-bicyclics via Beckmann rearrangement. The 6,8-ring iodides are suitable Suzuki precursors for Pd-catalysed C?C coupling (81?87 %), whereas the carboxylic acids readily form amides under T3P conditions (71?95 %).

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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

Extracurricular laboratory:new discovery of 2,4-Dimethylpyridine

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One-pot synthesis of indolizine via 1,3-dipolar cycloaddition using a sub-equivalent amount of K2Cr2O7 as an efficient oxidant under base free conditions

A one-pot method for synthesizing multi-substituted indolizines from alpha-halo-carbonyl compounds, pyridines and electron deficient alkenes was developed. A sub-equivalent amount of potassium dichromate was used as an oxidant under base free conditions. The transformation developed should be of economic efficiency.

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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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Regioselectivity in free radical bromination of unsymmetrical dimethylated pyridines

During a literature review some curious inconsistencies in the free radical bromination of picolines were noted. To achieve a better understanding of the mechanisms and regioselectivity we reran these reactions, extending our work to unsymmetrical lutidines using N-bromosuccinimide in limiting amount. Characterization of the products was done with GC/MS and H NMR. The regioselectivity of bromination in unsymmetrical dimethylpyridines shows that nitrogen in the ring is deactivating inductively. The competition between 2,3, 2,4, and 2,5 dimethyl pyridine toward bromination results with bromination in the methyl group farthest from the N in the ring. 3,4-Lutidine shows only the 4,4-dibrominated product.

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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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V1A RECEPTOR AGONISTS

Compounds of formula (I), salts thereof, and compositions and uses thereof are described. The compounds are useful as V1a vasopressin agonists, for the treatment of, e.g., complications of cirrhosis, including bacterial peritonitis, HRS2 and refractory ascites.

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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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Electric Literature of 108-47-4, Because a catalyst decreases the height of the energy barrier, its presence increases the reaction rates of both the forward and the reverse reactions by the same amount.108-47-4, Name is 2,4-Dimethylpyridine, molecular formula is C7H9N. In a article£¬once mentioned of 108-47-4

Difference in chemical composition of supercritical methanolysis products between two lignites

Dehydrated Xilinhaote lignite (XL) and Huolinguole lignite (HL) were depolymerized in supercritical methanol at 310 C and the resulting soluble reaction mixtures were analyzed with GC/MS. The results show that the GC/MS-detectable species can be classified into hydroxybenzenes (HBs), esters, ketones, alkanols, arenes, methoxybenzene, alkanes, alkenes, nitrogen-containing organic compounds, sulfur-containing organic compounds, aldehydes and other compounds. However, the difference in the product yield from different coals is significant. The most abundant products are HBs from XL and esters from HL.

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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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Fluorescent Copper(I) Complexes: an X-Ray Diffraction Study of Complexes of Copper(I) Iodide and Pyridine Derivatives of Rhombic, , and Polymeric Structure, <> and <>

Three previously unreported forms of complexes of CuI with a pyridine derivative have been isolated and examined by single-crystal X-ray techniques: (1) (3Me-py = 3-methylpyridine), stoicheiometry 1:1:2, monoclinic space group P21, a=7.912(2), b=19.390(6), c=8.774(2) Angstroem, beta=102.22(2)o, Z=2, R=0.047 for 2072 observed reflections, crystallizes with isolated rhombohedra of Cu2I2, each Cu being co-ordinated to two ligand molecules via nitrogen atoms; <> (2) and <> (3) (2,4Me2-py = 2,4-dimethylpyridine), stoicheiometries 1:1:1, (2), monoclinic space group P21/a, a=11.834(5), b=14,914(6), c=4.381(2) Angstroem, beta=93.80(4)o, Z=4, R=0.078 for 1082 reflections, (3), triclinic space group P1, a=11.648(8), b=4.328(3), c=10.198(4) Angstroem, alpha=77.64(5), beta=68.45(4), gamma=104.25(5)o, R=0.063 for 1731 reflections.Both (2) and (3) crystallize as edge-sharing Cu2I2 rhombs, with each copper atom bound to three iodide atoms and the nitrogen atom of a molecule of the Lewis base.

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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