共查询到20条相似文献,搜索用时 93 毫秒
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利用Gaussian94从头计算程序在6-31G基组下对二十面体碳硼烷C2B10H12、CB11H12^-及其衍生物CB11H11Br^-进行了从头计算,结果表明,在亲电取代反应中,杂原子C具有对、空间定位效应,取代基-Br为邻,对位定位基因,与实验事实相符。 相似文献
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在芳烃亲电取代反应中,取代基的定位效应是有机化学工作者普遍关心的问题。从本世纪初就开始研究苯环上取代基对芳烃亲电取代反应定位效应的影响,根据反应中取代产物的 相似文献
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进行了系列的邻位取代苯基汞化合物亲电取代反应的等动力学相关分析研究,研究结果表明了用等动力学相关分析方法能够揭示有机化学反应中的主要影响因素.在邻位取代苯基氯化汞的SE 2机理中,当碘为亲电试剂时,反应的主要影响因素是取代基的立体位阻;而当亲电试剂由碘变为氯化氢时,影响反应的主要因素则变为取代基的静电诱导效应.在邻位取代苯基氯化汞的SE1机理中,相关分析结果证实了取代基的场效应是影响反应速率的主要因素.上述等动力学相关分析结果为邻位取代苯基氯化汞的亲电反应机理的研究提供了进一步的科学依据. 相似文献
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研究了一种基于Friedel-Crafts亲电取代的新型缩聚反应,反应基团是氮原子的苯对位氢原子和芴醇上的羟基,氮原子的富电子效应活化了苯对位氢原子的亲电取代能力,同时芴醇(似三苯甲醇结构)是高活性的烷基化试剂,使得小分子亲电取代反应可扩展为高分子缩聚反应.探索了两种缩合途径,"A-A,B-B"型共缩聚和"A-B"型自缩聚.4,4′-双(苯基-对甲苯基氨基)联苯(TPD)与芴醇共缩聚,得到数均分子量为1·5×104~2·0×104的共聚物,而芴醇的自缩聚,可得到单分散、立体环状结构的3聚体. 相似文献
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预测发生亲电取代反应的活性位点具有重要的理论和实际意义. 目前已提出了许多基于反应物自身电子结构的预测方法. 本文选择14 个单取代苯和8 个双取代苯作为测试集,对14 种预测方法的可靠性进行了详细的比较分析. 结果表明,福井函数、平均局部离子化能等体现局部电子软度的方法特别适合含有邻对位定位基的单取代苯和双取代苯体系,但对于含有单个间位定位基的体系,这类方法往往预测失败. 基于静电效应的预测方法整体表现明显不如体现局部软度的方法,但更适合含有单个间位定位基的体系. 对所有体系预测能力最稳健的是双描述符,因此可以作为普适性的预测方法. 相似文献
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亲电取代反应是一类基本的有机反应,其中以苯环上的亲电取代反应最常见。该反应的反应活性及反应的位点与苯环上已有的取代基有很大的关系。本文从波谱学的角度,利用核磁数据,阐述了已有的取代基如何影响苯环的电子云密度,进而影响苯环亲电取代反应的活性和取代的位置。本文视角新颖,将对学生的学习及科研产生启发。 相似文献
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利用电子效应解释一元取代苯环上亲电取代反应的定位规律,不但解释了各类定位基定位效应的不同,而且解释了同一类定位基邻位和对位产物比例的不同,而后者用被普遍使用的共振论则难以解释。 相似文献
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Origin of the Regioselectivity in the Gas‐Phase Aniline+CH3+ Electrophilic Aromatic Substitution 下载免费PDF全文
Dr. Daniel Kinzel Prof. Shmuel Zilberg Prof. Dr. Leticia González 《Chemphyschem》2015,16(11):2366-2374
Nonadiabatic ab initio molecular dynamics simulations are carried out to monitor the attack of CH3+ on aniline in the gas phase to form the corresponding σ complexes. The reaction is ultrafast and is governed by a single electron transfer within 30 fs, which involves two sequential conical intersections and finally produces a radical pair. Positive‐charge allocation in the aromatic compound is found to govern the substitution pattern in ortho, meta, or para position. Although the major products in the first step of the electrophilic aromatic substitution are the ortho and para σ complexes, initially 26 % of the simulated trajectories also form meta complexes, which then undergo H shifts, mainly to the para position. 相似文献
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The electrophilic substitution reaction occurring to the chelate ring of the complexes could be regarded as an indication of quasi-aromaticity of the ring systems, no catalyst was used and only triethylamine was employed, implying that the aroylating agents with different p-substituents are polarized enough to be effective electrophiles to attack the methine carbon of the electron-rich substrate 1. This property is probably the clue to polarization of the ligand electrons by the nickel( Ⅱ ) ion and to the participation of the nickel( Ⅱ ) in the π-bond systems of the two coordinated conjugated rings. The linearity relationship between vd-d maxima, E1/2OX(1) and σp are obtained, respectively. The electronic environment of central metal ion as well as the aromaticity of the ring system are affected by the electronic properties of the p-substituents. A comparison of the electrochemical results with each other showed .that when the electronegativity of the substituent was higher, the oxidation(Ni2+/Ni3+) 相似文献
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Electrophilic Aromatic Substitution with Silicon Electrophiles: Catalytic Friedel–Crafts C−H Silylation 下载免费PDF全文
《Angewandte Chemie (International ed. in English)》2017,56(1):52-59
Electrophilic aromatic substitution is a fundamental reaction in synthetic chemistry. It converts C−H bonds of sufficiently nucleophilic arenes into C−X and C−C bonds using either stoichiometrically added or catalytically generated electrophiles. These reactions proceed through Wheland complexes, cationic intermediates that rearomatize by proton release. Hence, these high‐energy intermediates are nothing but protonated arenes and as such strong Brønsted acids. The formation of protons is an issue in those rare cases where the electrophilic aromatic substitution is reversible. This situation arises in the electrophilic silylation of C−H bonds as the energy of the intermediate Wheland complex is lowered by the β‐silicon effect. As a consequence, protonation of the silylated arene is facile, and the reverse reaction usually occurs to afford the desilylated arene. Several new approaches to overcome this inherent challenge of C−H silylation by SEAr were recently disclosed, and this Minireview summarizes this progress. 相似文献