2-芳基恶唑啉和氮杂双环衍生物合成机理的理论研究

发布时间：2018-06-30 08:33

本文选题：2-芳基恶唑啉衍生物 + 氮杂双环衍生物　；参考：《济南大学》2016年硕士论文

【摘要】：本文归纳总结了2-芳基恶唑啉衍生物和氮杂双环衍生物的合成意义和国内外研究现状,选取了腈类化合物与氨基醇合成2-芳基恶唑啉衍生物和二烯醛化合物与乙氮烯合成氮杂双环化合物两类合成反应为研究对象,我对它们各自的四个合成反应体系的反应机理分别进行了理论研究,目的在于探讨2-芳基恶唑啉和氮杂双环类化合物的合成反应规律。本文采用的研究方法是密度泛函理论B3LYP法,采用基组6-311++G**进行计算,利用高斯程序Gaussian 09,全面优化了反应势能面上各个能量最低点(即我们通常所说的“驻点”)的构型,我们全部通过振动分析进一步确认各平衡结构构型、过渡态构型的真假性(虚频有且只有一个)和各物种的热力学函数,并考虑了甲醇的溶剂化效应。为了确认过渡态的属性,我们进一步计算了内禀反应坐标(IRC)。我们通过对腈类化合物与氨基醇合成2-芳基恶唑啉衍生物的四个反应体系合成机理的理论探究,证实它们的反应原理是大致相同的,反应的历程包含了三个化学反应,三个化学反应由五个基元反应而构成。腈类化合物首先与溶剂甲醇发生了一加成反应,生成了一中间产物。然后,它依次通过一置换反应,异构化反应,环化反应,脱NH3反应生成了最终产物2-芳基恶唑啉衍生物。三个化学反应的摩尔吉布斯自由能变(?rGm)均小于零,并且三个化学反应都是放热反应。我们通过对二烯醛化合物与乙氮烯合成氮杂双环衍生物的四个反应体系合成反应理的理论探究,证实它们的反应原理是大致相同的,反应过程包括三个步骤。二烯醛化合物与乙氮烯首先通过一氢迁移反应生成了一中间体。然后,它依次通过一异构化反应,环化反应生成了最终产物氮杂双环化合物。所研究反应的摩尔吉布斯自由能变(?rGm)均小于零,都是放热反应。
[Abstract]:In this paper, the significance of synthesis of 2-aryl oxazoline derivatives and aza-heterocyclic derivatives and the current research situation at home and abroad are summarized and summarized. The synthesis of 2-aryl oxazoline derivatives from nitriles and amino alcohols and the synthesis of azobicyclic compounds from dienal compounds and ethylenes were studied. In this paper, we have studied the reaction mechanism of their four synthetic reaction systems respectively. The aim of this study is to study the synthesis of 2-aryl oxazoline and azobicyclic compounds. The research method used in this paper is the density functional theory (DFT) B3LYP method, the basis set 6-311 GW * is used to calculate, and the Gao Si program Gaussian 09 is used to optimize the configuration of the lowest point of energy on the surface of the reaction potential (that is, the "stationary point"). Through vibration analysis, we further confirm the true and false (virtual frequency and only one) and thermodynamic functions of each equilibrium structure, transition state configuration, and consider the solvation effect of methanol. In order to confirm the properties of the transition state, we further calculate the intrinsic reaction coordinates (IRC). The mechanism of synthesis of 2-aryl oxazoline derivatives from nitrile compounds and amino alcohols has been investigated theoretically. It has been proved that the reaction mechanism is approximately the same, and the reaction process includes three chemical reactions. Three chemical reactions consist of five elementary reactions. Nitriles first reacted with solvent methanol to form an intermediate product. Then, the final product 2-aryl oxazoline derivative was obtained by a displacement reaction, an isomerization reaction, a cyclization reaction and a deNH3 reaction. The molar Gibbs free energy variation (RGm) of the three chemical reactions is less than zero, and the three chemical reactions are exothermic reactions. Through the theoretical study on the synthesis of azobicyclic derivatives from dienal compounds and ethylenes, it is proved that their reaction mechanism is approximately the same, and the reaction process consists of three steps. Dienal compounds first reacted with ethylenes to form an intermediate through a hydrogen migration reaction. Then, the final product nitrogen heterobicyclic compounds were obtained by one isomerization reaction and the cyclization reaction. The molar Gibbs free energy variations (RGm) of the reactions studied are all less than zero and they are all exothermic reactions.
【学位授予单位】：济南大学
【学位级别】：硕士
【学位授予年份】：2016
【分类号】：O626

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