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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.
Zoltá n M. Balogh Marianna Csö rnyei 《Proceedings of the American Mathematical Society》2006,134(9):2667-2675
We give sufficient conditions for Sobolev and Lipschitz functions in terms of their lower scaled-oscillation. The sharpness of these conditions is shown by examples. Our examples also show that a Stepanov-type differentiability theorem does not hold under the boundedness assumption of the lower scaled-oscillation.
5.
Sauer, Shelah, Vapnik and Chervonenkis proved that if a set system on n vertices contains many sets, then the set system has full trace on a large set. Although the restriction on the size of the
groundset cannot be lifted, Frankl and Pach found a trace structure that is guaranteed to occur in uniform set systems even
if we do not bound the size of the groundset. In this note we shall give three sequences of structures such that every set
system consisting of sufficiently many sets contains at least one of these structures with many sets. 相似文献
6.
A. Ádám 《Acta Mathematica Hungarica》1989,54(3-4):291-296
7.
8.
D. Kaptás T. Kemény J. Balogh L. F. Kiss L. Gránásy I. Vincze 《Hyperfine Interactions》1994,94(1):1861-1865
The temperature dependence of the iron hyperfine field distribution is reported in melt-quenched amorphous Fe-Zr alloys. The most remarkable feature is the compositinal change in the shape of the average hyperfine field versus temperature curves. The unusual increase in the average hyperfine field below about 85 K is a characteristic feature of the RSG systems; however, no anomaly is observed in the width of the hyperfine field distribution as a function of temperature. The results cannot be properly explained in the framework of the existing spin glass models. 相似文献
9.
J. Balogh D. Kaptás L. F. Kiss T. Kemény L. Bujdosó I. Vincze 《Hyperfine Interactions》2006,169(1-3):1343-1347
Magnetic multilayers of 57Fe with nominal thickness, T
nom, between 0.4 and 1.0 nm separated by 3.0 nm Al spacer layers were prepared by alternate deposition of the constituents in
high vacuum. The samples were investigated at 4.2 K in external magnetic field. A fraction of Fe atoms corresponding to about
0.3 nm equivalent Fe-thickness was found to mix into the Al spacer. The extremely strong magnetic anisotropy observed for
T
nom < 0.8 nm is attributed to Fe layers of approximately two atomic planes thick. The anisotropy decreases considerably after
the building up of the third Fe atomic layer starts at T
nom = 0.8 nm, but full saturation was not achieved even for T
nom = 1 nm and 3 T magnetic field applied perpendicularly to the sample plane. 相似文献
10.
For ν≥0 let cνk be the k-th positive zero of the cylinder functionC v(t)=J v(t)cosα-Y v(t)sinα, 0≤α>π whereJ ν(t) andY ν(t) denote the Bessel functions of the first and the second kind, respectively. We prove thatC v,k 1+H(x) is convex as a function of ν, ifc νk≥x>0 and ν≥0, whereH(x) is specified in Theorem 1.1. 相似文献