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Rafael Dias do Espírito Santo Rosineide Costa Simas Alviclér Magalhães Vanessa Gonçalves dos Santos Thais Regiani Ana Cristina Isler Natiza Graziele Martins Marcos Nogueira Eberlin Eduardo René Pérez González 《Journal of Physical Organic Chemistry》2013,26(4):315-321
Molecules containing the guanidinic nuclei possess several pharmacological applications, and knowing the preferred isomers of a potential drug is important to understand the way it operates pharmacologically. Benzoylguanidines were synthesized in satisfactory to good yields and characterized by NMR, Electrospray Ionization Mass Spectrometry (ESI‐MS) and Fourrier Transform InfraRed Spectroscopy techniques (FTIR). E/Z isomerism of the guanidines was studied and confirmed by NMR analysis in solution (1H‐13C Heteronuclear Single Quantum Coherence (HSQC) and Heteronuclear Multiple‐Bond Correlation (HMBC), 1H‐15N HMBC, 1H‐1H Correlation Spectroscopy (COSY) and Nuclear Overhauser Effect Spectroscopy (NOESY) experiments) at low temperatures. Compounds with p‐Cl and p‐Br aniline moiety exist mainly as Z isomer with a small proportion of E isomer, whereas compounds with p‐NO2 moiety showed a decrease in proportion of isomer Z. The results are important for the application of these molecules as enzymatic inhibitors. Copyright © 2013 John Wiley & Sons, Ltd. 相似文献
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Gutmann's Donor Numbers Correctly Assess the Effect of the Solvent on the Kinetics of SNAr Reactions in Ionic Liquids 下载免费PDF全文
Jazmín Alarcón‐Espósito Prof. Dr. Renato Contreras Prof. Dr. Ricardo A. Tapia Dr. Paola R. Campodónico 《Chemistry (Weinheim an der Bergstrasse, Germany)》2016,22(37):13347-13351
We report an experimental study on the effect of solvents on the model SNAr reaction between 1‐chloro‐2,4‐dinitrobenzene and morpholine in a series of pure ionic liquids (IL). A significant catalytic effect is observed with reference to the same reaction run in water, acetonitrile, and other conventional solvents. The series of IL considered include the anions, NTf2?, DCN?, SCN?, CF3SO3?, PF6?, and FAP? with the series of cations 1‐butyl‐3‐methyl‐imidazolium ([BMIM]+), 1‐ethyl‐3‐methyl‐imidazolium ([EMIM]+), 1‐butyl‐2,3‐dimethyl‐imidazolium ([BM2IM]+), and 1‐butyl‐1‐methyl‐pyrrolidinium ([BMPyr]+). The observed solvent effects can be attributed to an “anion effect”. The anion effect appears related to the anion size (polarizability) and their hydrogen‐bonding (HB) abilities to the substrate. These results have been confirmed by performing a comparison of the rate constants with Gutmann's donicity numbers (DNs). The good correlation between rate constants and DN emphasizes the major role of charge transfer from the anion to the substrate. 相似文献
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Pontes F. M. L. Oliveira S. F. Espínola J. G. P. Arakaki L. N. H. Fonseca M. G. Airoldi C. 《Journal of Thermal Analysis and Calorimetry》2004,75(3):975-988
Solid adducts SbX3·L-pic (X=Cl, I and L=α-, β- and γ-picolines) were synthesized and characterized by elemental analysis, 1H and 13C NMR, IR spectroscopy and thermal analysis. The infrared spectroscopy and the magnetic resonance for 1H and 13C nuclei of these compounds suggest that the ligands coordinate through nitrogen atom. Kinetic studies were accomplished by
means of thermogravimetric data, through isothermal and non-isothermal techniques. The best adjusting models for adducts thermal
decomposition were R1 for isothermal and R1 and R2 for the non-isothermal methods. The energy of activation values obtained by isothermal method indicate the following orders
of thermal stability for adducts: i) SbCl3·α-pic>SbCl3·β-pic>SbCl3·γ-pic and ii) SbI3·β-pic>SbI3·γ-pic>SbI3·α-pic. The activation energy values obtained by non-isothermal were higher than those from isothermal methods, showing the
order of stability:iii) SbCl3·α-pic<SbCl3·β-pic<SbCl3·γ-pic and iv) SbI3·β-pic>SbI3·α-pic=SbI3··γ-pic. These obtained data through R1 model presented the kinetic compensation effect for trichloride adducts, which could be associated to both isothermal and
non-isothermal processes.
This revised version was published online in August 2006 with corrections to the Cover Date. 相似文献
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Luiza N. H. Arakaki Josiane S. Diniz A. L. P. Silva Vera Lucia S. Augusto Filha Maria G. Fonseca J. G. P. Espínola T. Arakaki 《Journal of Thermal Analysis and Calorimetry》2009,97(2):377-382
The divalent copper, nickel, cobalt and trivalent chromium, molybdenium and iron chelate compounds derived from bis(acetylacetone)
ethylenediimine were grafted on activated silica gel using a batch process in methanolic solution. The sequence of the maximum
retention capacity was Cr(III)>Mo(III)>Fe(III)>Co(II)>Ni(II)>Cu(II). Calorimetric titration was employed to study the interaction
of activated silica gel with these series of metal chelate compounds. Exothermic enthalpic results were obtained throughout
all interactions process. The spontaneity of these systems was reflected in negative and positive free Gibbs energy from entropic
values. 相似文献
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N.?do Espírito-SantoEmail author S.?Fornari K.?Frensel J.?Ripoll 《manuscripta mathematica》2003,111(4):459-470
Given an orientable hypersurface M of a Lie group with a bi-invariant metric we consider the map N : M n that translates the normal vector field of M to the identity, which is a natural extension of the usual Gauss map of hypersurfaces in Euclidean spaces; it is proved that the Laplacian of N satisfies a formula similar to that satisfied by the usual Gauss map. One may then conclude that M has constant mean curvature (cmc) if and only if N is harmonic; some other aplications to cmc hypersurfaces of are also obtained. 相似文献