共查询到20条相似文献，搜索用时 15 毫秒
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Weichao Zhang 《Molecular physics》2013,111(23):2901-2917
The mechanism and products of the reaction of 2-methyl-3-buten-2-ol (MBO232) with Cl atoms in the presence of O2 have been elucidated by performing high-level quantum chemistry calculations. The geometries of the reactants, intermediates, transition states, and products are optimized at the MP2(full)/6-311G(d,?p) level, and their single-point energies are refined at the CCSD(T)/6-311?+?G(d,?p) level. The potential energy surface profiles have been constructed at the CCSD(T)/6-311?+?G(d,?p)//MP2(full)/6-311G(d,?p)?+?0.95?×?ZPE level of theory, and the possible channels involved in the reaction are also discussed. The calculations indicate that the reaction predominantly proceeds via the addition of Cl atoms to the double bond rather than the direct abstraction of the H atoms in MBO232. The nascent adducts (CH3)2C(OH)CHCH2Cl (IM1) and (CH3)2C(OH)CHClCH2 (IM2) do not undergo subsequent isomerization and dissociation reactions, but rather react with O2. The theoretical results show that the major products are CH2ClCHO and CH3C(O)CH3 for the reaction of MBO232?+?Cl in the presence of O2, which is in good agreement with the experimental finding. 相似文献
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Carlos Alberto Huerta Aguilar Jayanthi Narayanan Narinder Singh Pandiyan Thangarasu 《Journal of Physical Organic Chemistry》2014,27(5):440-449
The oxidation of para‐substituted anilines (X–C6H4NH2, X = –CH3, –H, –Cl, –NO2) with chlorine dioxide was studied as a means of eliminating these pollutants. The oxidation rate decreases from that for 4‐methylaniline to that for 4‐nitroanilinem in agreement with the Hammett plot; the oxidation kinetics is second order in aniline and first order in ClO2, for which a possible mechanism is proposed. Liquid chromatography and gas chromatography mass spectrometry results show that benzoquinone is formed as the major intermediate in aniline/ClO2 oxidation, and the reaction is pH‐dependent as the rate constant increases with increasing pH. To further support our proposed mechanism, Density Functional Theory (DFT) computations at both B3LYP/6‐311 + G(d,p) level with the polarizable continuum model with an integral equation formalism solvation model (i.e., with water) were carried out, showing that activation energy barriers predict the same reactivity trend as shown by the kinetics experiments. Copyright © 2014 John Wiley & Sons, Ltd. 相似文献
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I. Iriepa B. Gil-Alberdi E. Galvez J. Sanz-Aparicio I. Fonseca A. Orjales A. Berisa C. Labeaga 《Journal of Physical Organic Chemistry》1998,11(2):125-132
A series of esters derived from 3-methyl-2,4-diphenyl-3-azabicyclo[3.3.1]nonan-9α-ol ( 1 ) was synthesized and studied by 1H and 13C NMR spectroscopy, and the crystal structure of 3-methyl-2,4-diphenyl-9α-(3,5-dimethylbenzoyloxy)-3-azabicyclo[3.3.1]nonane ( 2 ) was determined by x-ray diffraction. The compounds studied display in CDCl3 a preferred flattened chair–chair conformation. This bicycle conformation is similar to that found for 2 in the crystal state. Pharmacological assays on mice were performed to evaluate drug-induced behavioral alteration, peripheral or central acute toxicity and analgesic activity. © 1998 John Wiley & Sons, Ltd. 相似文献
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A. E. Mucientes F. J. Poblete M. A. Rodriguez F. Santiago 《Journal of Physical Organic Chemistry》1997,10(9):662-668
The oxidation kinetics of propan-1-ol by alkaline hexacyanoferrate(III) catalyzed by ruthenium trichloride were studied spectrophotometrically. The initial rate method was used for kinetic analysis. The reaction rate shows a fractional order in [oxidant] and [substrate] and a first-order dependence on [RuCl3]. The dependence on [OH−] is complicated. A reaction mechanism involving two active catalytic species is proposed. Each one of these species forms an intermediate complex with the substrate. The attack of these complexes by hexacyanoferrate(III) in rate-determining step produces a radical species which is further oxidized in the subsequent step. © 1997 John Wiley & Sons, Ltd. 相似文献
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Mahelet Aweke Tadesse Carlo Galli Patrizia Gentili 《Journal of Physical Organic Chemistry》2011,24(7):529-538
The aminoxyl radical 6‐trifluoromethyl‐benzotriazol‐N‐oxyl (TFNO) has been generated from the parent hydroxylamine 6‐CF3‐1‐hydroxy‐benzotriazole (TFBT) by one‐electron oxidation with a CeIV salt and characterized by spectrophotometry and cyclic voltammetry (CV). Rate constants of H‐abstraction (kH) by TFNO from a number of H‐donor benzylic substrates have been determined spectrophotometrically in MeCN solution at 25 °C. A radical H‐atom transfer (HAT) route of oxidation is substantiated for TFNO by several pieces of evidence. The kinetic data also testify the relevance of stereoelectronic effects upon the HAT reactivity of TFNO. Copyright © 2010 John Wiley & Sons, Ltd. 相似文献
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我们合成了一类多苯基取代的烯丙基锗烷类化合物,并测量了这三种化合物的拉曼光谱和红外光谱。经光谱分析,指认了主要波数所对应的分子振动。在这三种化合物的拉曼光谱中,Ge-Ph均在1000cm-1附近出现非常强的振动峰;烯丙基中的C=C键在1615 cm-1和1595 cm-1附近出现强的振动峰;在1585 cm-1附近出现芳香环的多重振动峰;在3050 cm-1(m)1、025 cm-1(m)、615 cm-1(m)附近出现芳香环的C-H伸缩振动,C-H面内弯曲振动和C-H面外弯曲振动峰;与饱和碳原子相连接的Ge-C振动峰分别出现在595 cm-1、592 cm-1和597 cm-1。在红外光谱中,这类化合物的Ge-C振动和饱和Ge-C振动较为明显,分别出现在1090 cm-1(s)附近和625 cm-1~577 cm-1(w)之间。 相似文献
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A kinetic study of the reactions of N-chlorosuccinimide (NCS) with glycine (Gly), sarcosine (Sar), 2-methylalanine (2MA), proline (Pro) and pyrrolidine (Pyr) was carried out. The reactions were found to be first order with respect to both NCS and the amine or amino acid and order −1 in proton concentration. In order to calculate the experimental activation parameters, the effect of temperature on the reaction rates was studied. The ionic strength and buffer concentration were found to have no effect on the rate constant. A reaction mechanism involving Cl+ transfer from NCS to the amine or amino acid to form an N-chloro compound is proposed © 1997 John Wiley & Sons, Ltd. 相似文献
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3-三苯基锗基-1,1-二苯基-1-丁醇类化合物的拉曼光谱和红外光谱研究 总被引：2，自引：0，他引：2
我们合成３－三苯基锗基－１,１－二苯基－１－丙醇及同系物３－三苯基锗基－１,１－二苯基－１－丁醇;３－三苯基锗基－２－甲基－１,１－二苯基－１－丙醇,这些化合物都是有机锗类化合物,是具有抗肿瘤活性的化合物３－三苯基锗基－１－二苯基－１－丙醇的类似物,它们可能具有生物活性。我们测量了它们的拉曼光谱及红外光谱。经光谱分析,指认了主要波数所对应的分子振动。在这三种化合物中,Ｇｅ－Ｐｈ的伸缩振动出现在１０ 相似文献
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采用密度泛函理论(DFT)研究了2-甲基-1,3-顺丁二烯在Ni(I)催化下与苯甲醛反应生成高烯丙基醇的反应机理.在B3LYP/6-31+G*水平上对反应过程中所有反应物、过渡态、中间体以及产物的几何构型进行了优化,通过能量和振动分析确认了过渡态的真实性;并且在相同基组水平上应用自然键轨道(NBO)和分子中的原子(AIM)理论分析了这些化合物的成键特征和轨道间的相互作用.研究发现了两条可能的反应通道IA与IB,其控制步骤活化能分别为64.20 kJ·mol-1、51.63 kJ·mol-1,由以上比较结果可以看出,反应通道IA与IB在整个反应过程可能同时发生,但IB通道具有较低的活化能,即IB通道为整个反应的最优反应通道,与实验结果一致. 相似文献
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利用改进型通用交叉分子束装置和脉冲直流放电产生脉冲氟原子束实验方法 ,研究了氟原子和 1,3 丁二烯分子的反应散射 .只有一个脱氢原子反应通道被观测到 ,没有观测到碳碳单键、碳碳双键断裂以及氟化氢分子的生成 .直接测量到反应产物的角度分布和飞行时间质谱 .通过把实验数据从实验室坐标系转化到质心坐标系 ,得到反应产物在不同质心角度下的平动能分布和角度分布 .从反应产物的三维速度分布 角度分布 通量图中 ,得出氟原子和 1,3 丁二烯反应生成氢原子的过程是通过形成了一个长寿命的中间体 相似文献
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Due to the water-insoluble nature of Hg0, its oxidization to Hg2+, which is water-soluble, is a viable approach for its effective removal at coal-fired plants using existing flue gas desulfurization (FGD) unit. In this study, the adsorption and oxidation of elemental mercury on an Mn-doped g-C3N4 material were investigated. The spin-polarized density functional theory method was adapted to optimize the geometry structures and then to determine the corresponding electronic structures, while the CI-NEB method was adopted to search for the stable intermediates during the reaction(s). The analysis of energy and project density of states shows that the Mn-g-C3N4 exhibits an excellent affinity to Hg atoms. It is found that it is feasible for Hg atoms to oxidize on the Mn-g-C3N4 surface via two possible E-R paths, but with relatively high energy barriers. This research provides insights into a viable way for mercury removal using O2 as the oxidizing agent. 相似文献
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The oxidations of pentan‐1‐ol with 12 dichromates, fluorochromates, chlorochromates and bromochromate of heterocyclic bases in acidic medium exhibit identical kinetic behavior; first order each with respect to the chromium(VI) reagents and alcohol, and are acid catalyzed. The Arrhenius plots show two common points of intersection, one by the three quinolinium complexes and the other by the rest, suggesting the involvement of the quinolinium moiety in the transition state to be different from that of the other heterocyclic bases. Copyright © 2003 John Wiley & Sons, Ltd. 相似文献
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V.E. Markushin 《Hyperfine Interactions》1999,119(1-4):11-21
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Anna Wypych-Stasiewicz Adam Szejgis Agnieszka Chmielewska Adam Bald 《Journal of Molecular Liquids》2007,130(1-3):34-37
The electrical conductivities of NaBPh4, NBu4I, NaI, NaCl, NaBr and NaClO4 have been studied in the mixtures of propan-1-ol with water. The obtained results were analysed using the Fuoss–Justice equation. The individual limiting ionic conductivities of Na+, NBu4+, BPh4−, I−, Cl−, Br−, ClO4− ions have been determined using the Fuoss–Hirsch assumption. The dependencies of the limiting molar conductances Λo and Walden products Λoη versus mixed solvent composition have been discussed. 相似文献
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A. E. BELIKOV 《Molecular physics》2013,111(6):343-347
The electron beam fluorescence technique was applied to measure the rotational energy relaxation cross-sections in carbon monoxide free jets. The data were obtained in the low temperature region from 20 to 200 K and compared with the results of ultrasound, thermal conductivity, free jet and line broadening experiments. The overall scatter of the experimental data runs to one order of magnitude, and their temperature dependence differs. This fact calls for further theoretical and experimental investigations of rotational relaxation rates in carbon monoxide. 相似文献
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利用多孔碳实现SO2脱除和高值资源化具有耗水少、吸附剂可循环等优点,是当前重要技术方向,探究SO2在碳材料纳米空间中的吸附转化机制是该技术的理论基础。前期研究表明O2存在的条件下,碳材料中SO2会被催化氧化形成SO3,但具体的吸附催化位点和氧化路径有待进一步研究。本文采用密度泛函理论计算了SO2碳材料锯齿形不饱和碳原子处的吸附和催化氧化路径,发现:SO2和O2在不饱和碳原子处发生化学吸附。当O2在不饱和碳原子处优先吸附时,SO2会与活化的O2反应生成SO3和化学吸附态的O;当SO2在不饱和碳原子处优先吸附时,O2会在S原子附近活化,活化后的O2会与SO2反应生成气相SO3、化学吸附态SO3。本文计算结果为用于硫资源化的高性能碳材料合成提供了理论指导。 相似文献