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Dr. Antonio M. Rodríguez Dr. Pilar Prieto Prof. Antonio de la Hoz Prof. Ángel Díaz-Ortiz D. Raúl Martín Prof. José I. García 《ChemistryOpen》2015,4(3):308-317
The aim of this work was to determine the parameters that have decisive roles in microwave-assisted reactions and to develop a model, using computational chemistry, to predict a priori the type of reactions that can be improved under microwaves. For this purpose, a computational study was carried out on a variety of reactions, which have been reported to be improved under microwave irradiation. This comprises six types of reactions. The outcomes obtained in this study indicate that the most influential parameters are activation energy, enthalpy, and the polarity of all the species that participate. In addition to this, in most cases, slower reacting systems observe a much greater improvement under microwave irradiation. Furthermore, for these reactions, the presence of a polar component in the reaction (solvent, reagent, susceptor, etc.) is necessary for strong coupling with the electromagnetic radiation. We also quantified that an activation energy of 20–30 kcal mol−1 and a polarity (μ) between 7–20 D of the species involved in the process is required to obtain significant improvements under microwave irradiation. 相似文献
3.
Experimental and Theoretical Studies on the Rearrangement of 2‐Oxoazepane α,α‐Amino Acids into 2′‐Oxopiperidine β2,3,3‐Amino Acids: An Example of Intramolecular Catalysis 下载免费PDF全文
Dr. Diego Núñez‐Villanueva Dr. M. Ángeles Bonache Laura Lozano Dr. Lourdes Infantes Prof. José Elguero Prof. Ibon Alkorta Prof. M. Teresa García‐López Dr. Rosario González‐Muñiz Dr. Mercedes Martín‐Martínez 《Chemistry (Weinheim an der Bergstrasse, Germany)》2015,21(6):2489-2500
Enantiopure β‐amino acids represent interesting scaffolds for peptidomimetics, foldamers and bioactive compounds. However, the synthesis of highly substituted analogues is still a major challenge. Herein, we describe the spontaneous rearrangement of 4‐carboxy‐2‐oxoazepane α,α‐amino acids to lead to 2′‐oxopiperidine‐containing β2,3,3‐amino acids, upon basic or acid hydrolysis of the 2‐oxoazepane α,α‐amino acid ester. Under acidic conditions, a totally stereoselective synthetic route has been developed. The reordering process involved the spontaneous breakdown of an amide bond, which typically requires strong conditions, and the formation of a new bond leading to the six‐membered heterocycle. A quantum mechanical study was carried out to obtain insight into the remarkable ease of this rearrangement, which occurs at room temperature, either in solution or upon storage of the 4‐carboxylic acid substituted 2‐oxoazepane derivatives. This theoretical study suggests that the rearrangement process occurs through a concerted mechanism, in which the energy of the transition states can be lowered by the participation of a catalytic water molecule. Interestingly, it also suggested a role for the carboxylic acid at position 4 of the 2‐oxoazepane ring, which facilitates this rearrangement, participating directly in the intramolecular catalysis. 相似文献
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András Gy. Németh Renáta Szabó Dr. Attila Domján Prof. György M. Keserű Dr. Péter Ábrányi-Balogh 《ChemistryOpen》2021,10(1):16-27
The development of a new three-component chromatography-free reaction of isocyanides, amines and elemental sulfur allowed us the straightforward synthesis of thioureas in water. Considering a large pool of organic and inorganic bases, we first optimized the preparation of aqueous polysulfide solution from elemental sulfur. Using polysulfide solution, we were able to omit the otherwise mandatory chromatography, and to isolate the crystalline products directly from the reaction mixture by a simple filtration, retaining the sulfur in the solution phase. A wide range of thioureas synthesized in this way confirmed the reasonable substrate and functional group tolerance of our protocol. 相似文献
6.
Vladimir A. Borovikov Francisco Javier Mendoza 《Journal of Fourier Analysis and Applications》2002,8(4):399-406
We study the pointwise convergence problem for the inverse Fourier transform of piecewise smooth functions, i.e., whether SrD f (\bx) ? f (\bx)S_{\rho D} f (\bx) \to f (\bx) as r? ¥\rho \to \infty . r? ¥\rho \to \infty . Here for \bx,\bxi ? \Rn\bx,\bxi \in \Rn SrDf(\bmx)=\dsf1(2p)n/2\intlirD [^(f)](\bxi) e\dst iá\bmx,\bxi? d\bxi . S_{\rho D}f(\bm{x})=\dsf1{(2\pi)^{n/2}}\intli_{\rho D} \widehat{f}(\bxi) e^{\dst i\langle\bm{x},\bxi\rangle} d\bxi~. is the partial sum operator using a convex and open set DD containing the origin, and rD={ r\bxi:\bxi ? D }\rho D=\left\{ \rho \bxi:\bxi\in D \right\}. 相似文献
7.
JOSEF MÁLEK JINDŘICH NEČAS K. R. RAJAGOPAL 《Archive for Rational Mechanics and Analysis》2002,165(3):243-269
To describe the flows of fluids over a wide range of pressures, it is necessary to take into account the fact that the viscosity
of the fluid depends on the pressure. That the viscosity depends on the pressure has been verified by numerous careful experiments.
While the existence of solutions local-in-time to the equations governing the flows of such fluids are available for small,
special data and rather unrealistic dependence of the viscosity on the pressure, no global existence results are in place.
Our interest here is to establish the existence of weak solutions for spatially periodic three-dimensional flows that are
global in time, for a large class of physically meaningful viscosity-pressure relationships.
(Accepted May 1, 2002) Published online November 15, 2002
Communicated by S. S. ANTMAN 相似文献
8.
Pierre Degond Stéphane Génieys Ansgar Jüngel 《Journal de Mathématiques Pures et Appliquées》1997,76(10):991-1015
The time-dependent equations for a charged gas or fluid consisting of several components, exposed to an electric field, are considered. These equations form a system of strongly coupled, quasilinear parabolic equations which in some situations can be derived from the Boltzmann equation. The model uses the duality between the thermodynamic fluxes and the thermodynamic forces. Physically motivated mixed Dirichlet-Neumann boundary conditions and initial conditions are prescribed.The existence of weak solutions is proven. The key of the proof is (i) a transformation of the problem by using the entropic variables, or electro-chemical potentials, which symmetrizes the equations, and (ii) a priori estimates obtained by using the entropy function. Finally, the entropy inequality is employed to show the convergence of the solutions to the thermal equilibrium state as the time tends to infinity. 相似文献
9.
Howard Jacobowitz Gerardo Mendoza 《Transactions of the American Mathematical Society》2003,355(10):4201-4222
We study embeddings of complex vector bundles, especially line bundles, in the complexification of the tangent bundle of a manifold. The aim is to understand implications of properties of interest in partial differential equations.
10.
Ansgar Jüngel 《Mathematische Nachrichten》1997,185(1):85-110
A multi-dimensional transient drift-diffusion model for (at most) three charged particles, consisting of the continuity equations for the concentrations of the species and the Poisson equation for the electric potential, is considered. The diffusion terms depend on the concentrations. Such a system arises in electrophoretic modeling of three species (neutrally, positively and negatively charged) and in semiconductor theory for two species (positively charged holes and negatively charged electrons). Diffusion terms of degenerate type are also possible in semiconductor modeling. For the initial boundary value problem with mixed Dirichlet - Neumann boundary conditions and general reaction rates, a global existence result is proved. Uniqueness of solutions follows in the Dirichlet boundary case if the diffusion terms are uniformly parabolic or if the initial and boundary densities are strictly positive. Finally, we prove that solutions exist which are positive uniformly in time and globally bounded if the reaction rates satisfy appropriate growth conditions. 相似文献