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61.
Gas‐phase elimination kinetics of selected aliphatic α,β‐unsaturated aldehydes catalyzed by hydrogen chloride 下载免费PDF全文
Libia L. Julio José R. Mora Alexis Maldonado Gabriel Chuchani 《Journal of Physical Organic Chemistry》2015,28(4):261-265
The gas‐phase elimination of 2‐methyl‐2‐propenal catalyzed by HCl yields propene and CO gas, while E‐2‐pentenal with the same catalyst gives butene and CO gas. The kinetics determinations were carried out in a static system with the reaction vessels deactivated with allyl bromide and the presence of the free radical inhibitor toluene. Temperature and pressure ranges were 350.0–410.0 °C and 34–76 Torr. The elimination reactions are homogeneous and unimolecular, and follow a first‐order rate law. The rate coefficients for the reactions are expressible by the following Arrhenius equations: Data from the kinetic and thermodynamic parameters of these catalyzed elimination reactions implies a mechanism of a concerted five‐membered cyclic transition state structure for the formation of the corresponding olefin and carbon monoxide. Copyright © 2015 John Wiley & Sons, Ltd. 相似文献
62.
Jéssica Venância Faria Maurício Silva dos Santos Percilene Fazolin Vegi Julio Cesar Borges Alice M.R. Bernardino 《Tetrahedron letters》2013
In this Letter, we described the synthesis of new 5-(5-amino-1-aryl-1H-pyrazole-4-yl)-1H-tetrazoles 2a–c from 5-amino-1-aryl-1H-pyrazole-4-carbonitriles 1a–c as well as the unexpected 1H-pyrazolo[3,4-d]pyrimidine derivatives 6a–c from 5-amino-1-aryl-3-methyl-1H-pyrazole-4-carbonitriles 4a–c, instead of 5-(5-amino-1-aryl-3-methyl-1H-pyrazole-4-yl)-1H-tetrazoles 5a–c as desired. In an attempt to obtain these tetrazole derivatives containing the methyl group at C3-position in the pyrazole ring, the amino group in 5-amino-1-(4-methoxyphenyl)-3-methyl-1H-pyrazole-4-carbonitrile 4c was protected by the reaction with sodium hydride and di-tert-butyl-dicarbonate (Boc). The tetrazole derivative 5c was synthesized from the protected compound 7c using analogue methodology to obtain 2a–c and 6a–c. 相似文献
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66.
Genivaldo Julio Perptuo Jan Janczak 《Acta Crystallographica. Section C, Structural Chemistry》2005,61(3):o165-o167
The crystal structure of the title compound, C4H12N+·C6H3N2O·H2O, is built up from tetramethylammonium cations, 2,5‐dinitrophenolate anions and water molecules. The nitro groups are almost coplanar with the aryl ring, which exhibits significant distortion from an ideal hexagonal form. The X‐ray geometry of the tetramethylammonium cation shows slight distortion from the tetrahedral symmetry predicted by molecular orbital calculations. The O—H⋯O hydrogen‐bonded water and 2,5‐dinitrophenolate units are related by an inversion center and form dimers. The 2,5‐dinitrophenolate anions, related by an inversion center and translation, are stacked to form a column along the [100] direction. 相似文献
67.
Julio González-Díaz Federica Briata Ignacio García-Jurado Fioravante Patrone 《International Journal of Game Theory》2012,41(3):517-552
The aim of this study is to identify and characterize the parts of an extensive form game that are ??relevant?? to determining whether the outcome of a certain strategy profile is an equilibrium outcome. We formally define what we mean by ??relevant?? and refer to the associated collection of information sets as essential. We apply this idea to a number of classic equilibrium concepts and discuss some implications of our approach. 相似文献
68.
M. Villegas A. C. Caballero M. Quintanilla J. A. Sanz-García E. Cantelar F. Cussó 《Applied physics. B, Lasers and optics》2011,102(3):651-658
The preparation of LiNbO3:Er3+/Yb3+ nanocrystals and their up-conversion properties have been studied. It is demonstrated that polyethyleneimine- (PEI) assisted dispersion procedures allow obtaining stable aqueous LiNbO3:Er3+/Yb3+ powder suspensions, with average size particles well below the micron range (100–200 nm) and the isoelectric point of the suspension reaching values well above pH 7. After excitation of Yb3+ ions at a wavelength of 980 nm, the suspensions exhibit efficient, and stable, IR-to-visible (green and red) up-conversion properties, easily observed by the naked eye, very similar to those of the starting crystalline bulk material. 相似文献
69.
María Virginia Mirífico José Alberto Caram Ana María Gennaro Carlos J. Cobos Enrique Julio Vasini 《Journal of Physical Organic Chemistry》2011,24(11):1039-1044
Radical anions from several 3,4‐aryl‐disubstituted derivatives of 1,2,5‐thiadiazole 1,1‐dioxide were accumulated through chemical reduction of the substrates in aprotic solvents. The radical anions were characterized by electron spin resonance and cyclic voltammetry. DFT theoretical calculations were also performed for the 3,4‐diphenyl derivative. The course of the reductions was followed using cyclic voltammetry. Uncommon reductants, such as amides, were found to be effective under certain conditions. Copyright © 2010 John Wiley & Sons, Ltd. 相似文献
70.
Miguel Alcaide Lidia Lpez Alessandro Tanferna Julio Blas Fabrizio Sergio Fernando Hiraldo 《Electrophoresis》2010,31(8):1353-1356
Major histocompatibility complex (MHC) genotyping still remains one of the most challenging issues for evolutionary ecologists. To date, none of the proposed methods have proven to be perfect, and all provide both important pros and cons. Although denaturing capillary electrophoresis has become a popular alternative, allele identification commonly relies upon conformational polymorphisms of two single‐stranded DNA molecules at the most. Using the MHC class II (β chain, exon 2) of the black kite (Aves: Accipitridae) as our model system, we show that the simultaneous analysis of overlapping PCR amplicons from the same target region substantially enhances allele discrimination. To cover this aim, we designed a multiplex PCR capable to generate four differentially sized and labeled amplicons from the same allele. Informative peaks to assist allele calling then fourfold those generated by the analysis of single PCR amplicons. Our approach proved successful to differentiate all the alleles (N=13) isolated from eight unrelated birds at a single optimal run temperature and electrophoretic conditions. In particular, we emphasize that this approach may constitute a straightforward and cost‐effective alternative for the genotyping of single or duplicated MHC genes displaying low to moderate sets of divergent alleles. 相似文献