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首页> 外文期刊>The Journal of Organic Chemistry >Evidence for Different Types of Water Participation in the Solvolysis of 1-Adamantyl,tert-Butyl,and Methyl Chlorides from Density Functional Theory Computations
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Evidence for Different Types of Water Participation in the Solvolysis of 1-Adamantyl,tert-Butyl,and Methyl Chlorides from Density Functional Theory Computations

机译：密度泛函理论计算得出的不同类型的水参与1-金刚烷基，叔丁基和甲基氯的溶剂分解的证据

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摘要

The activation energy in the gas phase (DELTAE) and the free energy of activation (DELTAG) in water solution for the hydrolysis of the monohydrates of methyl chloride (MeCl),tert-butyl chloride (t-BuCl),and 1-adamantyl chloride (AdCl) have been computed with the B3LYP/631-G(d) method and the polarizable continuum (PCM) solvation model.There is a fair agreement between the DELTAG values computed by us and the experimental data.The mechanistic implications of our computations are in severe contradiction with conventional representations.Thus,the computed nucleophilic solvent assistance (NSA) for the backside attack of a water molecule in the hydrolysis of MeCl is slightly lower than the corresponding NSA for t-BuCl.Hence,the hydrolysis of both MeCl and t-BuCl takes place mainly according to the classical S_N2 mechanism.The most relevant difference is that DELTAG for the frontside attack of water to t-BuCl is disfavored only by ca.2 kcal/mol with regard to the backside attack but by ca.23 kcal/mol in the case of MeCl.The higher solvolysis rate in water of t-BuCl in relation to AdCl is not due to steric factors affecting the specific solvation of the corresponding transition states,but to differential bulk solvent effects,which are accounted for by the PCM model.
机译：气相中的活化能（DELTAE）和水溶液中的活化自由能（DELTAG）用于水解氯甲烷（MeCl），叔丁基氯（t-BuCl）和1-金刚烷基氯的一水合物（AdCl）是使用B3LYP / 631-G（d）方法和可极化连续介质（PCM）溶剂化模型计算的，我们计算出的DELTAG值与实验数据之间有一个合理的共识。因此，对于水分子在MeCl水解中的背面攻击的计算亲核溶剂辅助（NSA）略低于t-BuCl的相应NSA。因此，这两种MeCl的水解t-BuCl主要根据经典的S_N2机理发生。最相关的区别是，水对t-BuCl的正面攻击的DELTAG相对于背面攻击仅受约2 kcal / mol的不利影响.23相对于AdCl，t-BuCl在水中的更高溶剂分解速率不是由于位阻因素影响了相应过渡态的特定溶剂化，而是由于不同的本体溶剂效应所致。通过PCM模型。

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  • 来源
    《The Journal of Organic Chemistry》 |2005年第25期|p.10238-10246|共9页
  • 作者

    Antonio Garcia Martinez; Enrique Teso Vilar; Jose Osio Barcina; Santiago de la Moya Cerero;

  • 作者单位

    Departamento de Quimica Organica I,Facultad de Ciencias Quimicas,Universidad Complutense de Madrid,Ciudad Universitaria,28040 Madrid,Spain,and Departamento de Quimica Organica y Biologia,Facultad de Ciencias,Universidad Nacional de Education a Distan;

    Departamento de Quimica Organica I,Facultad de Ciencias Quimicas,Universidad Complutense de Madrid,Ciudad Universitaria,28040 Madrid,Spain,and Departamento de Quimica Organica y Biologia,Facultad de Ciencias,Universidad Nacional de Education a Distan;

    Departamento de Quimica Organica I,Facultad de Ciencias Quimicas,Universidad Complutense de Madrid,Ciudad Universitaria,28040 Madrid,Spain,and Departamento de Quimica Organica y Biologia,Facultad de Ciencias,Universidad Nacional de Education a Distan;

    Departamento de Quimica Organica I,Facultad de Ciencias Quimicas,Universidad Complutense de Madrid,Ciudad Universitaria,28040 Madrid,Spain,and Departamento de Quimica Organica y Biologia,Facultad de Ciencias,Universidad Nacional de Education a Distan;

  • 收录信息 美国《科学引文索引》(SCI);美国《工程索引》(EI);美国《生物学医学文摘》(MEDLINE);美国《化学文摘》(CA);
  • 原文格式 PDF
  • 正文语种 eng
  • 中图分类 有机化学;
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