共查询到20条相似文献,搜索用时 31 毫秒
1.
用密度泛函理论(DFT)方法在B3LYP/6-31G*水平上研究了苯甲醛肟与炔丙醇加成反应的微观机制和热力学、动力学行为. 结果表明, 在苯甲醛肟与炔丙醇加成反应过程中, 8个可能反应通道的过渡态中均形成非平面五元环结构, 其中苯甲醛肟的Z、E构型特征得到了部分保留, 但主要部分的键长、键角均发生了变化, 电荷也进行了重新分布. 苯甲醛肟以羟基型参与反应的4个反应通道均为吸热反应和热力学非自发过程, 它们均具有较高的反应势垒、较慢的反应速率和较小的平衡常数; 而以离子型参与反应的四个反应通道均为放热反应和热力学自发过程, 它们的反应势垒较低, 反应速度较快, 平衡常数也较大, 故苯甲醛肟应主要以离子型参与反应. 炔丙醇的两种取向对应着加成反应的两种产物, 反应达到平衡后, 3-羟甲基二氢异噁唑为主要产物. 相似文献
2.
The thermodynamics and mechanism of the reaction of elemental mercury with ozone has been studied computationally. The effect of water and water dimer molecules on the reaction has also been investigated. For dry reaction, we obtained two pathways and geometry optimization, atoms in molecules analysis and vibrational frequencies of all component of reaction have been used for confirming of reaction mechanism. Thermodynamic variable of reaction has been calculated. For the reaction in the presence of the water, our studies focus on ozone‐mercury complex reaction with water and water dimer and obtained the mechanism of reactions. Comparison of wet and dry reaction shows the energy profile of reaction decreases with water molecule correspond to experimental prediction. Calculated thermodynamic variable of all reaction shows the Gibbs free energy of reaction decreases with the number of water molecule. 相似文献
3.
4.
本文提出了反应类等键反应方法,将通常用于热力学性质计算的等键反应方法推广用于类反应中反应势垒和反应焓变的计算. 对碳氢燃料低温燃烧反应机理中的一类重要反应类:?烷基自由基过氧化氢裂解生成烯烃和HO2自由基的反应势垒和反应焓变进行了计算. 通过对该类16个反应中的5个代表反应分别在不同计算水平HF、DFT、MP2、CCSD(T)的比较计算发现,采用等键反应方法可在较低从头算级别计算得到类反应较高精度的反应势垒,提高了计算的效率和精度. 本文采用反应类等键反应方法在B3LYP/6-311G(d,p)计算水平对该类16个反应进行了反应势垒和反应焓变的计算,并建立了反应势垒和反应能的线性自由能关系:delta V=71.02+0.41?delta E. 相似文献
5.
脯氨酸催化的不对称有机反应 总被引:1,自引:0,他引:1
脯氨酸作为一种结构简单、商品化的、廉价小分子手性催化剂,在多种不对称催化反应中表现出非常好的催化性能,本文综述了近年来脯氨酸直接催化的不对称有机反应涉及Aldol反应,Mannich反应,Michael反应,Diels-Alder反应,直接α-胺化反应,α-氧胺化反应,Baylis-Hillman反应,还原反应和氧化反应的进展并展望了其应用前景。 相似文献
6.
7.
Direct dynamics within the framework of DFT was used to study the long-time puzzling mechanism of the reaction between F2 and ethylene. Three types of reactions are widely accepted : F atom elimination reaction, HF elimination reaction and the addition reaction. Several reaction mechanisms have been proposed, but only the radical mechanism can reasonably explain the initial reaction at low temperature. In this article, our calculations support the radical mechanism and the reaction mechanisms of the three reactions, and they are described in detail by trajectory simulation. The reactions in a cryogenic matrix with the reaction mechanism were also discussed. 相似文献
8.
9.
There are two different views on the definition of reaction molecularity in physical chemistry textbooks and related literatures so far. We give a deep discussion about this conception herein. Starting with the development of chemical kinetics and the definition of elementary reaction and state-state reaction, we clarify that elementary reaction and state-state reaction are the conceptions belonging to macro-and micro-systems, respectively, and reaction molecularity is also belonging to micro-conception. Based on this conclusion, we think that the more reasonable definition of reaction molecularity should be "the number of chemical particles that take part in a state-state reaction (or an elementary chemi-physical reaction) as a reactant". 相似文献
10.
手性磷酸催化剂在不对称合成中的应用 总被引:2,自引:0,他引:2
手性磷酸是2004年报道的一类具有新型结构的强酸性Bronsted酸催化剂,近几年来的研究取得了很大的进展,已经成为有机小分子催化剂的一个重要分支。手性磷酸在催化一系列亚胺的加成和还原反应比如Mannich、亚胺的氢转移、亚胺的膦酰化、Pictet-Spengler、 Strecker、aza-Diels-Alder、 Friedel-Craft和α-重氮酯的烷基化等反应时都表现出了非常好的催化活性和立体选择性。本文主要综述了手性磷酸催化剂应用于亚胺相关反应的研究进展。 相似文献
11.
Ozone has been reacted with phenol in thin supported layers, and the dynamics of this reaction has been investigated. The stoichiometry of this reaction coincides with the stoichiometry of the same reaction in solution. Specific reaction rate (β) has been determined for various phenol conversions. The effective rate constant of the reaction, estimated by extrapolating β to zero reaction time, is significantly higher than the rate constant of the reaction in solution. The reaction between ozone and phenol is diffusion-controlled. The reaction products form a barrier layer, which protects the deeper phenol layers against ozone. The barrier layer is as thick as 8–15 phenol monolayers. 相似文献
12.
13.
对影响肉桂醇电极氧化的各种因素作了进一步的讨论.实验结果表明固体聚合物电解质内水的含量、pH 以及浸入离子交换膜中的二价锰离子的浓度均对该电极反应的电位以及后续化学反应的速度有很大的影响,在较高的温度下反应时,有利手提高生成肉桂醛的电流效率. 相似文献
14.
固体聚合物电解质在肉桂醇电解氧化中的应用(II)——后续化学反应在电催化反应中的地位及其影响因素 总被引:4,自引:0,他引:4
对影响肉桂醇电极氧化的各种因素作了进一步的讨论. 实验结果表明固体聚合物电解质内水的含量、pH 以及浸入离子交换膜中的二价锰离子的浓度均对该电极反应的电位以及后续化学反应的速度有很大的影响, 在较高的温度下反应时, 有利手提高生成肉桂醛的电流效率. 相似文献
15.
16.
17.
质谱因具有分辨率高、灵敏度好、响应快速以及结构鉴定能力强等特点,近年来在反应监测研究领域应用广泛.本文介绍了基于质谱的经典在线直接采样实时监测方案;综合评述了常压质谱离子化技术在反应监测领域的发展和应用,主要包括基于常压质谱的快反应监测、微滴加速在长时间反应研究中的应用,以及其它常压质谱在反应监测中的应用;并对质谱在反应监测研究领域面临的挑战和发展趋势进行了总结和展望. 相似文献
18.
We compare free energy calculations for the methyl transfer reaction catalyzed by catechol O-methyltransferase using the quantum mechanical/molecular mechanical free energy method with implicit and explicit solvents. An analogous methylation reaction in a solution is also studied. For the explicit solvent model, we use the three-point transferable intermolecular potential model, and for the implicit model, we use the generalized Born molecular volume model as implemented in CHARMM. We find that activation and reaction free energies calculated with the two models are very similar, despite some structural differences that exist. A significant change in the polarization of the environment occurs as the reaction proceeds. This is more pronounced for the reaction in a solution than for the enzymatic reaction. For the enzymatic reaction, most of the changes take place in the protein rather than in the solvent, and, hence, the benefit of having an instantaneous relaxation of the solvent degrees of freedom is less pronounced for the enzymatic reaction than for the reaction in a solution. This is a likely reason why energies of the enzyme reaction are less sensitive to the choice of atomic radii than are energies of the reaction in a solution. 相似文献
19.
尽管已有大量化学反应数据可供使用,但化学家仍常常感到很难便捷地从中得到所需的信息.这主要是由于反应数据库基于结构的检索方法与化学家解决问题的方法相去甚远.为解决这一问题而发展了一种通过对反应进行二级分类得到精细描述反应知识的层次模型的方法.第一次分类时不同的同类反应都在由一组普适性好的称作反应结构一级描述符构成的空间中进行.在第一次分类结果的基础上,得到每一类反应的公共结构特征作为第二次分类的结构描述符,利用它们进行更精细的分类,即可从原始反应数据中得到所需的基核反应.由特定反应、基核反应和基型反应就可将反应知识更合理地组织在同类反应知识库中,使它们得到更好的利用. 相似文献
20.
Reaction temperature is one of the key parameters in the synthesis of metal-organic frameworks (MOFs). Though there is no convergence with regard to the various experimental parameters, reaction temperature has been found to have remarkable influence on the formation and structure of MOFs, especially toward the control of topology and dimensionality of the MOF structures. Theoretically, the reaction temperature affects directly the reaction energy barrier in reaction thermodynamics and the reaction rate in the reaction kinetics. This review aims to show the influence of reaction temperature on crystal growth/assembly, structural modulation and transformation of MOFs, and to provide primary information and insights into the design and assernblv of desired MOFs. 相似文献