Polyfunctionalized pyrrolidines by Ugi multicomponent reaction followed by palladium-mediated SN2' cyclizations

A 4-component Ugi reaction with a suitable isocyanide, followed by a novel secondary transformation involving a Pd(II)-mediated (R5 = H) or a Pd(0)-mediated (R5 = CO2Me) SN2' cyclization to give highly functionalized N-acyl-2-vinylpyrrolidines, is reported. The overall yields are usually good and in most cases the Pd(0)-catalyzed reaction gave the final product in almost quantitative yield.     

Visible-Light-Induced Insertion of Sulfur Dioxide Mediated by Electron Donor–Acceptor Complex: Synthesis and Photophysical Properties of 3-Sulfonyl Indolizines

This work investigates a light-driven 3-component sulfonylation reaction of indolizines without needing any external photocatalyst. The mechanistic investigations support the formation of an electron donor–acceptor (EDA) complex in situ. This transformation offers a mild and sustainable approach with high functional group tolerance for the synthesis of 3-sulfonylated indolizines. This compound class has valuable photophysical properties and represents promising candidates in various applications related to fluorescence.     

Multicomponent self-modelling curve resolution in high-performance liquid chromatography by iterative target transformation analysis

Iterative target transformation factor analysis can provide a method for resolving elution profiles consisting of any number of compounds. The results obtained for 3-component resolution are consistent with the results obtained with conventional methods of curve resolution. The same restrictions with regard to overlap and relative signal heights of the compounds seem to apply to the conventional method of curve resolution and the proposed method. The method is tested on data from high-performance liquid chromatography with a diode-array detector obtained for polynuclear aromatic hydrocarbons and for proteins.     

Picture change and calculations of expectation values in approximate relativistic theories

The effect of the so-called picture change on expectation values of one-electron operators in approximate two(one)-component relativistic theories is discussed. This effect is expected to be particularly large for operators which assume large values in the vicinity of heavy nuclei. The numerical results illustrating the picture change effect on electric field gradients at nuclei have been obtained in the spin-free Pauli and Douglas–Kroll approximations. It has been found that the picture change effect lowers the electric field gradient at I in HI by about 1 a.u. Very large picture change effect (−8 a.u.) has been calculated for HAt. It is concluded that in accurate calculations of expectation values of operators involving high inverse powers of the electron–nucleus distance the picture change, which accompanies the transformation of the Dirac (Dirac–Coulomb) equation to approximate two(one)-component relativistic Hamiltonians, must be taken into account. © 1998 John Wiley & Sons, Inc. Int J Quant Chem 68: 159–174, 1998     

Perimetric scale-shape coordinates for triatomic molecules

Perimetric nuclear coordinates of a triatomic molecule treat all three nuclei equivalently and are not subject to the triangle conditions. Through an appropriate orthogonal transformation they can be separated into one scale coordinate, viz., the circumference, and two shape coordinates, which are determined by the angles. The parameter space of the shape coordinates is an equilateral triangle. The basic formulas are given and the relationship between points in coordinate space and molecular shapes are elucidated. Received: 10 January 1996 / Accepted: 2 January 1997     

Reactive Uptake of N(2)O(5) on Aqueous H(2)SO(4) Solutions Coated with 1-Component and 2-Component Monolayers

Reactive uptake of N(2)O(5) on aqueous sulfuric acid solutions was studied in the presence of 1-component (octadecanol) and 2-component (octadecanol + phytanic acid) monolayers. In the 1-component monolayer experiments, the reactive uptake coefficient depended strongly on the molecular surface area of the surfactant. Also, the 1-component monolayer showed significant resistance to mass transfer even when the fractional surface coverage of the surfactant was less than 1. For example, a monolayer of 1-octadecanol with a fractional surface coverage of 0.75 decreased the reactive uptake coefficient by a factor of 10. This is consistent with previous studies. In the 2-component monolayer experiments, the reactive uptake coefficient depended strongly on the composition of the monolayer. When the monolayer contained only straight-chain molecules (1-octadecanol), the reactive uptake coefficient decreased by a factor of 42 due to the presence of the monolayer. However, when the monolayer contained 0.20 mole fraction of a branched surfactant (phytanic acid) the reactive uptake coefficient only decreased by a factor of 2. Hence, a small amount of branched surfactant drastically changes the overall resistance to reactive uptake. Also, our results show that the overall resistance to reactive uptake of 2-component monolayers can be predicted reasonably accurately by a model that assumes the resistances to mass transfer can be combined in parallel.     

Recent progress in measurements of oscillatory forces and liquid properties under confinement

The present review paper focuses on direct measurements of oscillatory forces. Beside the surface forces apparatus (SFA), atomic force microscopy (AFM) has emerged as the most commonly used technique to measure surface forces. Recent instrumental advances of both methods are highlighted in the review. Different systems, showing oscillatory forces are classified. Principle distinction is made between 1-component liquids (water, organic liquids and liquid crystals), pseudo 1-component liquids (ionic liquids and microemulsions) and 2-component liquids (dispersions containing polyelectrolytes, micelles or nanoparticles). In the last few years, the oscillatory force studies address particle characterisation, synergistic effects in multicomponent systems, the introduction of ‘switchable’ forces, and resolving liquid properties under confinement. Last but not least, the ability of AFM and SFA to measure oscillatory forces is discussed.     

Titanium catalyzed one-pot multicomponent coupling reactions for direct access to substituted pyrimidines

A titanium-catalyzed 3-component coupling reaction can be used to generate tautomers of 1,3-diimines. These diimines produced in situ undergo condensation with amidines in a one-pot procedure to provide substituted pyrimidines. Seventeen examples of pyrimidines are provided using this one-pot, 4-component procedure from simple starting materials. In some cases, catalyst architecture can be tuned to control the regioselectivity of the alkyne addition. Finally, the regioselectivity of amidine addition to unsymmetrical 1,3-diimines is discussed.     

Morphology of large ZSM-5 crystals unraveled by fluorescence microscopy

Understanding the internal structure of ZSM-5 crystallites is essential for improving catalyst performance. In this work, a combination of fluorescence microscopy, AFM, SEM, and optical observations is employed to study intergrowth phenomena and pore accessibility in a set of five ZSM-5 samples with different crystal morphologies. An amine-functionalized perylene dye is used to probe acid sites on the external crystal surface, while DAMPI (4-(4-diethylaminostyryl)- N-methylpyridinium iodide) is used to map access to the straight channels in MFI from the outer surface. The use of these dyes is validated by studying the well-understood rounded-boat type ZSM-5 crystals. Next coffin-shaped ZSM-5 crystals are considered; we critically evaluate the seemingly conflicting 2-component and 3-component models that have been proposed to account for the hourglass structure in these crystals. The data prove that observation of an hourglass structure is essentially unrelated to a 90 degree rotation of the pyramidal crystal components under the (010) face. Hence, in perfectly formed coffin-shaped crystals, the straight channels can be accessed from (010). However, in other crystal batches, sections with a 90 degrees rotation can be found; they are indeed located inside the crystal sections under (010) but often only partially occupy these pyramidal components. In such a case, both straight and sinusoidal pores surface at the hexagonal face. The results largely support the 3-component model, but with the added notion that 90 degree rotated sections (as proposed in the 2-component model) are most likely to be formed inside the defect-rich, pyramidal crystal sections under the (010) faces.     

甲酸-乙酸-水-氯化钙体系汽液平衡盐效应的研究

本文采用Otsuki-Williams式汽液平衡釜测定了甲酸-乙酸-水体系及甲酸-乙酸-水-氯化钙体系在98658.28Pa下汽液平衡数据。氯化钙的加入量为0.5mol/(kg溶剂)。结合盐效应的作用情况,对相图进行了分析。研究结果表明:氯化钙的加入对体系起了物理化学作用,它与盐溶、盐析现象有关。     

Perturbation theory of relativistic corrections

Methods for perturbation theory of relativistic corrections for an electron in a Coulomb field are divided into three categories: (1) in terms of 4-component spinors; (2) in terms of the ‘large components’ of the Dirac spinor; (3) involving a Foldy-Wouthuysen type transformation, where one attempts to obtain a two-component spinor different from the ‘large component’. In methods of category 1 (the ‘direct perturbation theory’ of paper I of this series, the related approaches by Rutkowski as well as by Gesteszy, Grosse, and Thaller and a somewhat different one by Moore) the wave function, the energy and the Hamiltonian are analytic inc ^?2. No divergent terms arise. In methods of category 2 (that of the elemination of the small component as well as a similarity transformation in intermediate normalization) wave function and energy are still analytic inc ^?2, but the effective Hamiltonian no longer is. Regularized results can be obtained by controlled cancellation of divergent terms. In category 3 both the effective Hamiltonian and the wave function are highly singular and non-analytic inc ^?1. A controlled cancellation of divergent terms is at least very difficult. These pathologic feature survive in the non-relativistic limit and have hence little to do with relativistic effects. They are related to the fact that forr → 0 the sign of the quantum number κ rather than that of the energy determines which component of the Dirac spinor is large and which is small. In the limitr → 0 andc → ∞ the Foldy-Wouthuysen wave function of a 2p _1/2 state is a 1p wave function. Hierarchies of transformations of the Dirac equation and its non-relativistic limit are presented and discussed. Finally the problem of the regularization of effective Hamiltonians on 2-component level ‘for electrons only’ is addressed.     

A Scalable Metal-, Azide-, and Halogen-Free Method for the Preparation of Triazoles

A scalable metal-, azide-, and halogen-free method for the synthesis of substituted 1,2,3-triazoles has been developed. The reaction proceeds through a 3-component coupling of α-ketoacetals, tosyl hydrazide, and a primary amine. The reaction shows outstanding functional-group tolerance with respect to both the α-ketoacetal and amine coupling partners, providing access to 4-, 1,4-, 1,5-, and 1,4,5-substituted triazoles in excellent yield. This robust method results in densely functionalised 1,2,3-triazoles that remain challenging to prepare by azide–alkyne cycloaddition (AAC, CuAAC, RuAAC) methods and can be scaled in either batch or flow reactors. Methods for the chemoselective reaction of either aliphatic amines or anilines are also described, revealing some of the potential of this novel and highly versatile transformation.     

Strain-release 2-azaallyl anion addition/borylation of [1.1.1]propellane: synthesis and functionalization of benzylamine bicyclo[1.1.1]pentyl boronates

We report a 3-component reaction between N-benzyl ketimines, [1.1.1]propellane, and pinacol boronates to generate benzylamine bicyclo[1.1.1]pentane (BCP) pinacol boronates. These structures are analogous to highly sought diarylmethanamine cores, which are common motifs in bioactive molecules. We demonstrate the versatility of the boronate ester handle via downstream functionalization through a variety of reactions, including a challenging Pd-catalyzed (hetero)arylation that exhibits a broad substrate scope. Together, these methods enable the synthesis of high-value BCP benzylamines which are inaccessible by existing methods. Furthermore, we demonstrate the successful application of these newly developed (hetero)arylation conditions to a variety of challenging tertiary pinacol boronates, including nitrogen-containing heterocycles, 1,1-disubstituted cyclopropanes, and other BCP cores.

We report a 3-component reaction between N-benzyl ketimines, [1.1.1]propellane, and pinacol boronates to generate benzylamine bicyclo[1.1.1]pentane (BCP) pinacol boronates.     

One-pot sequential multi-component reaction: Synthesis of 3-substituted indoles

Here, we have developed a 3-component one-pot sequential approach to 3-substituted indoles. The main advantages of this process are step economy, reduced waste, and operational simplicity. The method involves in situ generation of 3-indolylalcohols from the reaction of indoles and aldehydes in the presence of base. Further, nucleophilic substitution of 3-indolylalcohols with various nucleophiles affords 3-substituted indole derivatives. The reaction does not requires any hazardous and expensive metal catalyst. In addition, the reaction is carried out in (1:1) ethanol–water which is considered as environmentally benign solvent. On the other hand, nonsequential 3-component reaction results in the formation of unwanted bisindolylmethanes.     

Salt Effect of Vapor-Liquid Phase Equilibrium in the System Acetic Acid-Formic Acid-Water-Calcium Chloride

Vapor-liquid equilibrium data (VLE) were measured by usingotsudki-willlams still at 9.866×10 (Pa) for the 3-component systemAcOH-HCO2H-H2O and the 4-component system ACOH-HCO2H-H2O-CaCl2 in the VLE,CaCl used was 0.5 (mol/kg solv.).The results show that the favorable effect of CaCl is physical chemistry action,which relates to the phenomena of salting-out and salting-in.     

Studies on microemulsions

The microemulsions formed in the 4-component system water-potassium oleate-hexanol-dodecane have been investigated by time-average light scattering and small angle neutron scattering. A constant volume fraction ratio water: potassium oleate of 1.44 was used and at this constant composition, which gave a pseudo 3-component system, a wide region of the microemulsion domain was examined. In order to interpret the scattering data at finite volume fractions of the dispersed phase, water, allowance had to be made for interactions between the water-in-oil microemulsion droplets. This was carried out using a hard sphere model for the interaction. It is shown that using this model self-consistent results are obtained by light scattering and neutron scattering and an estimate can be made of the size of the particles in concentrated colloidal dispersions.     

Bimetallic catalytic synthesis of annelated benzazepines

A novel short synthetic route to annelated benzazepines, using additive enhanced palladium-indium catalytic 3-component cascade methodology is described.     

Insights into information contained in multiplicative scatter correction parameters and the potential for estimating particle size from these parameters

This paper investigates the nature of information contained in scatter correction parameters. The study had two objectives. The first objective was to examine the nature and extent of information contained in scatter correction parameters. The second objective is to examine whether this information can be effectively extracted by proposing a method to obtain particularly the mean particle diameter from the scatter correction parameters. By using a combination of experimental data and simulated data generated using fundamental light propagation theory, a deeper and more fundamental insight of what information is removed by the multiplicative scatter correction (MSC) method is obtained. It was found that the MSC parameters are strongly influenced not only by particle size but also by particle concentration as well as refractive index of the medium. The possibility of extracting particle size information in addition to particle concentration was considered by proposing a two-step method which was tested using a 2-component and 4-component data set. This method can in principle, be used in conjunction with any scatter correction technique provided that the scatter correction parameters exhibit a systematic dependence with respect to particle size and concentration. It was found that the approach which uses the MSC parameters gave a better estimate of the particle diameter compared to using partial least squares (PLS) regression for the 2-component data. For the 4 component data it was found that PLS regression gave better results but further examination indicated this was due to chance correlations of the particle diameter with the two of the absorbing species in the mixture.     

Implications of the phase rule for capillary systems containing surfaces and three-phase contact lines with surface and linear constraint relations

The phase rule is generalized to heterogeneous systems with moderately curved surfaces and linear or line-phase boundaries. It will be shown that the number of degrees of freedom or variancef of a capillary sysem is, in general, larger than that predicted by the classical Gibbs' phase rule. Restrictions on the value off for capillary systems is intimately connected with the imposition of mechanical constraints like the Laplace and Young equations of capillarity. As a direct consequence, it may be shown that the variance for anr-component, three-phase solid-liquid-vapour system (i.e., a liquid drop on a solid surface) is different from that of anr-component, liquid-liquid-vapour system. This conclusion has important implications for the existence or possible existence of equation-of-state type relations.