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1.
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
2.
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
3.
4.
Palladium-containing zeolites catalyze the cycloisomerization of diethyl diallylmalonate to dimethylcyclopentenes. When the reaction is carried out in toluene, the performance of the palladium catalyst depends on the pore size of the zeolites. At 60 °C, palladium adsorbed on large pore size Beta zeolite (pore size ∼7.4 Å) is more active than medium pore size ZSM-5 (pore size ∼5.4 Å). This lower activity of ZSM-5 compared to Beta is attributable to the restricted diffusion of reagent and products through the ZSM-5 channels as compared to Beta zeolite. However, due to the gas-like diffusion characteristic of the supercritical state, the activity of ZSM-5 increases and becomes identical to that of Beta zeolite using supercritical CO2 as medium. 相似文献
5.
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
6.
Despite the large cost of bodily injury (BI) claims in motor insurance, relatively little research has been done in this area. Many companies estimate (and therefore reserve) bodily injury compensation directly from initial medical reports. This practice may underestimate the final cost, because the severity is often assessed during the recovery period. Since the evaluation of this severity is often only qualitative, in this paper we apply an ordered multiple choice model at different moments in the life of a claim reported to an insurance company. We assume that the information available to the insurer does not flow continuously, because it is obtained at different stages. Using a real data set, we show that the application of sequential ordered logit models leads to a significant improvement in the prediction of the BI severity level, compared to the subjective classification that is used in practice. We also show that these results could improve the insurer’s reserves notably. 相似文献
7.
Pedro lvarez‐Boo Jos Sergio Casas Alfonso Castieiras María Delfina Couce Eduardo Freijanes Eva Novoa Jos Sordo 《应用有机金属化学》2003,17(9):725-729
Reaction of dichloro‐ and dibromodimethyltin(IV) with 2‐(pyrazol‐1‐ylmethyl)pyridine (PMP) afforded [SnMe2Cl2(PMP)] and [SnMe2Br2(PMP)] respectively. The new complexes were characterized by elemental analysis and mass spectrometry and by IR, Raman and NMR (1H, 13C) spectroscopies. Structural studies by X‐ray diffraction techniques show that the compounds consist of discrete units with the tin atom octahedrally coordinated to the carbon atoms of the two methyl groups in a trans disposition (Sn? C = 2.097(5), 2.120(5) Å and 2.110(6), 2.121(6) Å in the chloro and in the bromo compounds respectively), two cis halogen atoms (Sn? Cl = 2.4908(16), 2.5447(17) Å; Sn? Br = 2.6875(11), 2.7464(9) Å) and the two donor atoms of the ligand (Sn? N = 2.407(4), 2.471(4) Å and 2.360(5), 2.455(5) Å). In both cases, the Sn? N(pyridine) bond length is markedly longer than the Sn? N(pyrazole) distance. Copyright © 2003 John Wiley & Sons, Ltd. 相似文献
8.
José A. Anquela Teresa Cortés Miguel Gómez-Lozano Mercedes Siles-Molina 《Acta Mathematica Hungarica》2004,103(3):177-196
We investigate the basic properties of the different socles that can be considered in not necessarily semiprime associative
systems. Among other things, we show that the socle defined as the sum of minimal (or minimal and trivial) inner ideals is
always an ideal. When trivial inner ideals are included, this inner socle contains the socles defined in terms of minimal
left or right ideals.
This revised version was published online in June 2006 with corrections to the Cover Date. 相似文献
9.
Joaquin Barbera Anne-Marie Levelut Mercedes Marcos Pilar Romero Jose Luis Serrano 《Liquid crystals》1991,10(1):119-126
We present a comparative study of various metallomesogenic complexes, using X-ray diffraction methods. For a given ligand linked to different metal atoms (Cu, Ni, VO), the nature of this central atom influences mainly the magnetic susceptibilities of the mesophases. With different ligands, which keep the close neighbourhood of the metal atom unchanged, the apparent length of the mesogenic unit is longer for short ligands than for longer ones. This unexpected behaviour is qualitatively well explained by taking into account the global shape of the different complexes. 相似文献
10.
We analyse some identifiers which can univocally identify hyperbolic components and Misiurewicz points of one-dimensional quadratic maps. After seeing the equivalence among the different identifiers and how to go from one to another, we show which are the best for some specific tasks. Likewise, we present the analytic expressions, some of them shown for the first time in this paper, to calculate these identifiers. Some experimental considerations are taken into account. 相似文献