多元缩合生成新型巴比妥酸盐衍生物反应机理的理论研究

Theoretical Studies of Multicomponent Condensation Synthesis of Novel Barbiturate Derivatives

作者: 专业:物理化学 导师:唐明生 年度:2010 学位:硕士  院校: 郑州大学

Keywords

density functional theory (DFT), mechanism, multicomponent reaction, prop-2-en-1-amine, ethyl propiolate, alloxan, barbiturate, pyridine, methyl but-2-ynoate, 1,3-dimethylallxan, spiro-oxazinobarbiturate

        本论文采用密度泛函理论研究了两个多元缩合反应的反应机理:论文第一部分对伯胺、丙炔酸酯和四氧嘧啶衍生物缩合反应生成巴比妥酸盐衍生物的反应机理进行了探求;论文的第二部分从理论上研究了由吖嗪、活泼炔和1,3-二甲基四氧嘧啶缩合生成新型螺旋状-噁嗪类巴比妥酸盐化合物的反应机理。第一个课题是“伯胺、丙炔酸酯和四氧嘧啶衍生物缩合生成巴比妥酸盐的反应机理研究”,这个课题运用密度泛函的方法在B3LYP/6-311++G(d,p)水平下对伯胺、丙炔乙酯和四氧嘧啶的反应机理进行了研究。这个反应机理包含两个部分:第一部分是伯胺和丙炔乙酯经过两条相互竞争的反应路径(路径a和路径b)反应生成富电子的烯胺;第二部分是烯胺亲核进攻四氧嘧啶,经由四条不同的反应路径生成最终的产物巴比妥酸盐衍生物(路径b1、路径b2、路径b3和路径b4)。计算结果表明路径b4是最优的反应通道,并且水分子在反应过程中起到的质子转移媒介的作用。另外我们的计算结果也表明反应可以在常温下顺利进行,这与实验事实符合。第二个课题是“吖嗪、炔和1,3-二甲基四氧嘧啶缩合生成螺旋状-噁嗪类巴比妥酸盐的理论研究”。在这个课题中,我们运用密度泛函的方法对吡啶、丁炔甲酯和1,3-二甲基四氧嘧啶缩合生成螺旋状-噁嗪类巴比妥酸盐的反应机理分别在B3LYP/6-31G(d,p)(气相)和B3LYP/6-311++G(d,p)(液相)条件下进行了研究。具体的反应分为三个步骤:首先,吡啶亲核进攻丁炔甲酯得到中间体M1;然后M1和1,3-二甲基四氧嘧啶发生亲核反应生成另一个中间体M2;最后伴随着一个C2-O7键的生成得到了最终的产物螺旋状-噁嗪类巴比妥酸盐。计算结果表明所设计的反应路径在常温下即可顺利进行。考虑了无水CH2C12溶剂效应的液相反应路径决速步能垒是18.02 kcal/mol,这样低的能垒和实验事实符合的非常好。
    Density functional theory (DFT) calculations have been carried out to study the mechanisms of two muticomponent condensation reactions in the paper. The first is a research on the multicomponent reaction mechanism of prop-2-en-1-amine and alkyl propiolate with alloxan derivative. And the second is the theoretical investigation about mechanism of the synthesis of spiro-oxazinobarbiturate from azine, activated acetylene and 1,3-dimethylalloxan.The multicomponent reaction mechanisms of prop-2-en-l-amine and ethyl propiolate with alloxan were studied using density functional theory (DFT). The reaction mechanisms were found to consist of two stages. First, the prop-2-en-l-amine reacts with ethyl propiolate to form an electron-richβ-aminoacrylate through two competitive channels (channels a and b). Second, a nucleophilic addition ofβ-aminoacrylate to alloxan occurs via four possible channels (channels b1, b2, b3 and b4). The calculated results revealed that the most energetically favorable path is channel b4 and suggested that the water molecule plays as a proton transfer intermediate in the reaction. Our calculations demonstrated that the reaction occurs easily at room temperature, which agrees well with the experiment.The second topic is "A theoretical investigation of the synthesis of spiro-oxazinobarbiturate from azine, acetylene and 1,3-dimethylalloxan". The multicomponent reaction mechanisms of pyridine and methyl but-2-ynoate with 1,3-dimethylalloxan were studied using density functional theory at the B3LYP/6-31G(d,p) (gas-phase) and B3LYP/6-311++G(d,p) (liquid-phase) level of theory, respectively. The reaction mechanisms were found to consist of three steps. First, a nucleophilic addition of pyridine to methyl but-2-ynoate occurs, resulting in a zwitterionic intermediate M1. Second, M1 reacts with 1,3-dimethylallxan to yield the other intermediate M2. Last, the product of spiro-oxazinobarbiturate generates with a new bond form. The calculated results revealed that the suggested reaction channel is an energetically favorable path. The rate-limiting energy barrier for the reaction channel, in which the solvation effects were considered using PCM as implemented with the dry CH2Cl2, is 18.02 kcal/mol. Our calculations demonstrated that the reaction occurs easily at room temperature, which agrees well with the experiment.
        

多元缩合生成新型巴比妥酸盐衍生物反应机理的理论研究

摘要4-5
Abstract5-6
目录7-9
第一章 前言9-13
    1.1 巴比妥酸盐类化合物简述9-12
        1.1.1 巴比妥酸盐类化合物的应用9
        1.1.2 巴比妥酸盐类化合物的合成9-10
        1.1.3 课题一的研究内容10-11
        1.1.4 课题二的研究内容11-12
    1.2. 本论文的研究意义12-13
第二章 量子化学简介13-29
    2.1 量子化学发展简史13-15
    2.2 量子化学的计算类别15-21
        2.2.1 分子轨道法15-20
        2.2.2 密度泛函理论20-21
    2.3 常用基组21-29
        2.3.1 极小基组22-23
        2.3.2 劈裂价壳层(SV)基组23-24
        2.3.3 极化和弥散基组24-25
        2.3.4 机组的选择25-27
        2.3.5 势能面27-29
第三章 伯胺、丙炔酸酯和四氧嘧啶衍生物缩合生成巴比妥酸盐反应机理的理论研究29-44
    3.1 引言29-30
    3.2 实验环境30
    3.3 计算细节30
    3.4 结果与讨论30-44
        3.4.1 R1和R2的反应31-34
        3.4.2 P1和R3的反应34-43
        3.4.3 结论43-44
第四章 吖嗪、炔和1,3-二甲基四氧嘧啶缩合生成螺旋状-噁嗪类巴比妥酸盐的理论研究44-54
    4.1 引言44-46
    4.2 实验环境46
    4.3 计算细节46
    4.4 结果和讨论46-54
        4.4.1 气相条件下的反应路径47-50
        4.4.2 液相条件下的反应路径50-53
        4.4.3 结论53-54
参考文献54-63
个人简介及研究生期间发表的论文63-64
致谢64
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