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991.
Ivan Bernal Steven F. Watkins 《Acta Crystallographica. Section C, Structural Chemistry》2013,69(8):808-810
Intermolecular hydrogen bonding is an integral part of many crystal structures. Hydrogen bonding sometimes results in one‐, two‐ or three‐dimensional supramolecular assemblies, a common feature of which is positional disorder of H atoms related to space‐group symmetry. Yet some reported structures fail to include all possible donor–acceptor close contacts, or to seek H‐atom electron densities associated with apparent D—H...A trios, while some H‐atom positions violate principles of chemistry or crystal physics. Modern diffraction equipment and sophisticated computing systems provide high‐quality data; thus, failure to characterize and report fully an accurate, complete and physically correct hydrogen‐bonding model should not be acceptable. We illustrate the relevant issues with three published examples in the hope of slowing the proliferation of these problems, with the scientifically desirable goal of improving the accuracy of crystallographic models while also providing improved search keys for information retrieval. 相似文献
992.
Matthew Polson Mark M. Turnbull Jan L. Wikaira 《Acta Crystallographica. Section C, Structural Chemistry》2013,69(10):1152-1156
The hydrobromide and hydrochloride salts of 2‐amino‐5‐iodopyridine were prepared from aqueous solutions. The hydrobromide salt, C5H6IN2+·Br−·0.5H2O, crystallizes as a hemihydrate, and exhibits hydrogen bonding and π‐stacking which stabilize the crystal structure. The hydrochloride salt, C5H6IN2+·Cl−·H2O·0.375HCl, crystallized as the hydrate and exhibits similar hydrogen bonding and π‐stacking in the lattice. The most interesting feature of the hydrochloride salt is the presence of an additional fractional HCl molecule which introduces disorder in the location of the water molecule. The additional proton from the fractional HCl molecule is accounted for by the presence of a partial hydronium ion on one of the water sites. 相似文献
993.
Lipeng Zhou Beibei Dong Si Tang Hong Ma Chen Chen Xiaomei Yang Jie Xu 《Journal of Energy Chemistry》2013,22(4):659-664
Sulfonated carbon as a strong and stable solid acid catalyst exhibited excellent catalytic performance in various acid-catalyzed reactions. Here, sulfonated carbon, as catalyst for oxidation reaction, was prepared via the carbonization of starch followed by sulfonation with concentrated sulfuric acid. N2 physisorption, X-ray diffraction, Fourier transform infrared spectroscopy, X-ray fluorescence and acid-base titration were used to characterize the obtained materials. The catalytic activity of sulfonated carbon was studied in the oxidation of aldehydes to carboxylic acids using 30 wt% H2O2 as oxidant. This oxidation protocol works well for various aldehydes including aromatic and aliphatic aldehydes. The sulfonated carbon can be recycled for three times without obvious loss of activity. 相似文献
994.
Reaction of 2-benzoyl-6-hydroxy-3-methyl-5-(2′-substituted-2′,3′-dihydro-1,5-benzothiazein-4′-yl) benzofurans (4a-f) with a mixture of acetic anhydride and pyridine afforded 6-acetoxy-2-benzoyl-3-methyl-5-(3′-acetyl-2′-substitutedstyryl-2′,3′-dihydrobenzothiazole-2′-yl) benzofurans (5a-f) as sole products in good yields. A reaction mechanism for the ring contraction is proposed. All the compounds (5a-f) were screened for their antifeedant activity by the “Non-Choice test method” using 6 h prestarved fourth instar larvae of Spodoptera litura F. Compounds 5a, 5c and 5d exhibited highest antifeedant activity. 相似文献
995.
Stefan Baj 《合成通讯》2013,43(14):2385-2391
Cyclic ketones have been efficiently oxidized with hydrogen peroxide using acidic ionic liquids (ILs) as solvents. This is a new method for the synthesis of lactones with high yields that does not utilize any additional catalysts and enables ILs to be recycled. 相似文献
996.
A clean, mild, and efficient catalytic deoximation procedure compatible with several common functional groups has been developed using 30% hydrogen peroxide activated by iodine catalyst in aqueous acetonitrile under essentially neutral conditions. The mechanistic features of an iodonium ion–driven nucleophilic cleavage of oximic C[dbnd]N have been revealed. 相似文献
997.
Shu‐Xian Hu Jian‐Guo Yu Eddy Y. Zeng 《International journal of quantum chemistry》2013,113(8):1128-1136
Calculations using density functional theory were performed to explore the mechanisms for atmospheric degradation of isopropyl methyl methylphosphonate (IMMP). The potential energy surface profiles for OH‐initiated reaction of IMMP were constructed, and all possible degradation channels were considered. Rate constants were further calculated using transition state theory. It was established from these calculations that H‐abstractions from alkyl groups have much lower energy barriers than substitutions of alkoxyl groups, and four possible H‐abstraction channels are competitive. Investigations into the secondary reactions under the presence of O2/NO were also performed. It is shown that O2 addition, reaction of peroxide radicals with NO to form RO radicals, and removal of ·RO are the major degradation pathways for alkyl radicals. Four selected products, CH3OP(O)(CH3)OC(O)CH3, CH3OP(O)(O)CH3, (CH3)2CHOP(O)(CH3)OH, and (CH3)2CHOP(O)(CH3)OCH?O, are predicted to be the major products in this study. © 2013 Wiley Periodicals, Inc. 相似文献
998.
Qian‐Lin Tang 《International journal of quantum chemistry》2013,113(16):1992-2001
Practical copper (Cu)‐based catalysts for the water–gas shift (WGS) reaction was long believed to expose a large proportion of Cu(110) planes. In this work, as an important first step toward addressing sulfur poisoning of these catalysts, the detailed mechanism for the splitting of hydrogen sulfide (H2S) on the open Cu(110) facet has been investigated in the framework of periodic, self‐consistent density functional theory (DFT‐GGA). The microkinetic model based on the first‐principles calculations has also been developed to quantitatively evaluate the two considered decomposition routes for yielding surface atomic sulfur (S*): (1) H2S → H2S* → SH* → S* and (2) 2H2S → 2H2S* → 2SH* → S* + H2S* → S* + H2S. The first pathway proceeding through unimolecular SH* dissociation was identified to be feasible, whereas the second pathway involving bimolecular SH* disproportionation made no contribution to S* formation. The molecular adsorption of H2S is the slowest elementary step of its full decomposition, being related with the large entropy term of the gas‐phase reactant under realistic reaction conditions. A comparison of thermodynamic and kinetic reactivity between the substrate and the close‐packed Cu(111) surface further shows that a loosely packed facet can promote the S* formation from H2S on Cu, thus revealing that the reaction process is structure sensitive. The present DFT and microkinetic modeling results provide a reasonably complete picture for the chemistry of H2S on the Cu(110) surface, which is a necessary basis for the design of new sulfur‐tolerant WGS catalysts. © 2013 Wiley Periodicals, Inc. 相似文献
999.
M. Merced Montero‐Campillo M. Natália D. S. Cordeiro 《International journal of quantum chemistry》2013,113(16):2002-2011
Experimental studies show that copper complexes can be effectively anchored onto the pores of mesoporous solids, having a good catalytic performance in several reactions, among them the aziridination of olefins and in particular, styrene. In this work, the mechanism of the aziridination of styrene catalyzed by a bis(oxazoline) copper(I) complex was studied in detail by means of density functional theory (DFT) calculations. For such reactions in the homogeneous phase, our calculations revealed a wide diversity of reaction‐pathways, which have not been considered in previous studies, and should be taken into account due to the small energy differences between them. What is more, our results show that there is a strong dependence on the chosen DFT functional. This has profound implications on the way the heterogeneous reaction is studied. © 2013 Wiley Periodicals, Inc. 相似文献
1000.
Qiaoxia Guo Wennian Wang Weiling Teng Liwei Chen Yanqing Wang Baojian Shen 《合成通讯》2013,43(17):2574-2584
A convenient one-pot method for the synthesis of substituted quinolines via the reaction of aniline and aldehyde in the presence of a Lewis acid (AlCl3) and an oxidant (H2O2) has been developed. Hydrogen peroxide was found to promote the reaction by its function as a hydrogen hunter, hindering the formation of by-product N-alkylaniline. The effect of the oxidant on the yield and selectivity was studied. When the molar ratio of aniline, n-butyraldehyde, and H2O2 was 1:3:0.5 at 25 °C, the yield of 3-ethyl-2-propylquinoline was improved from 64% (reaction without H2O2) to 84% (with H2O2), and the quinoline selectivity was improved to almost 100%. Moreover, the reaction time was obviously reduced. The substituent effect was also investigated in this work. 相似文献