DFT研究C-H活化及Huisgen环加成反应机理
发布时间：2019-06-13 12:44
【摘要】：本论文主要根据密度泛函理论(DFT)研究芳基C-H氰基化的反应机理和2-(对甲苯基)氨基乙酸乙酯中Csp3-H活化的反应机理以及N-甲基吲哚与对甲苯磺酰叠氮Huisgen环加成的反应机理。第一部分使用了DFT的方法,在B3LYP/6-31+G(d,p)的理论水平下研究了2-苯基吡啶在CuBr作为催化剂的情况下C-H的氰基化反应的机理,同时使用了IEFPCM模型去模拟溶剂二甲基甲酰胺的作用。计算结果显示苯乙腈在氧气的作用下通过两种反应路径(a和b)生成苯甲酰氰;此外苯乙腈也可以与氧气负离子反应生成2-羟基-2-苯基乙腈;紧接着,生成的2-羟基-2-苯基乙腈发生氧化脱氢反应生成苯甲酰氰,这里有四种可能的反应方式(c,d,e和f)。其次介绍的是反应物2-苯基吡啶在催化剂CuBr的作用下通过三种可能的反应方式(g,h和i)生成终产物2-(2-吡啶基)苯甲腈,在反应过程中2-苯基吡啶中的N原子和铜催化剂起着定位基团的作用,有助于CN-负离子的引入;进而发生加成反应和氧化脱氢反应生成终产物2-(2-吡啶基)苯甲腈。另外我们也考虑了没有催化剂参与的路径j。计算结果可以为类似反应中的相互作用和反应机理提供有价值的参考和指导。第二部分使用DFT方法研究了2-(对甲苯基)氨基乙酸乙酯在取代基为氢和甲基的时候,在自由基引发剂TBPA的作用下和氧气发生反应生成吲哚衍生物和喹啉衍生物的反应机理,并且使用SMD模型模拟了溶剂的影响。通过计算福井函数和二元描述符来预测反应位点的活性。对于本部分中的两个反应,其Csp3-H的活化都有四条可能的反应路径。计算结果显示,第一个反应经过Csp3-H活化后会继续和氧气发生反应,而后通过两条可能的反应路径生成产物1,5-二甲基-2,3-二酮吲哚,并且先脱去乙醛分子,而后失去水分子的路径是最优路径。第二个反应经过Csp3-H活化后会继续发生脱氢反应生成双键,随后和反应物苯乙烯发生加成反应生成六元环,最后经过一系列的氧化脱氢反应生成产物2-乙酸乙酯基-4-苯基-6-甲基喹啉。计算的结果不仅符合实验现象,还可以为优化反应提供理论支持。第三部分使用DFT研究了N-甲基吲哚与对甲苯磺酰叠氮通过Huisgen环加成生成吲哚衍生物的反应机理,并且使用PCM模型模拟了溶剂的影响。采用福井函数和二元描述符来预测反应位点的原子活性。对于本部分中的三个反应,每个反应都有两条可能的反应路径(I和II),计算结果显示,单线态氧气在2-亚胺吲哚与对甲苯磺酰叠氮的第一个反应的氧化脱氢过程中起着重要作用;当反应没有氧气的参与,而是在氮气作为保护气的情况下,通过两种开环反应路径而断开两个共价键,随后发生1,2-氢迁和脱去氮气(或者脱去氮气和1,2-氢迁)反应。而水分子在第三个甲基取代的N-甲基吲哚与对甲苯磺酰叠氮的反应中的氢迁过程中起着重要作用。我们的计算结果表明这些反应在特定的条件下可以发生,与实验结果吻合。对N-甲基吲哚与对甲苯磺酰叠氮Huisgen环加成反应中竞争路径的理解可以为相关反应提供有价值的指导作用。
[Abstract]:The reaction mechanism of aryl-C-H-cyanoethylation and the reaction mechanism of 2-(p-tolyl) aminoethyl acetate (Csp3-H) and the reaction mechanism of N-methyl-1-(p-tolyl) azido-Huisgen ring were studied by density functional theory (DFT). In the first part, the method of DFT was used to study the mechanism of the cyanoethylation of C-H under the condition of B3LYP/6-31 + G (d, p), and the effect of the solution of the solvent dimethylmethylamine was simulated by using the IEFPCM model. The calculation result shows that the phenylacetonitrile is produced by the two reaction paths (a and b) under the action of oxygen, and also the benzyl cyanide can react with the oxygen anion to generate 2-hydroxy-2-phenylacetonitrile; and then, The resulting 2-hydroxy-2-phenylacetonitrile has an oxidative dehydrogenation reaction to produce a benzonitrile, where there are four possible ways of reaction (c, d, e, and f). The 2-(2-fluorophenyl) benzonitrile is produced by three possible reaction modes (g, h and i) under the action of the catalyst CuBr, and the N atom and the copper catalyst in the 2-phenyl-phenyl-benzenetil are used as a positioning group in the reaction process, And then the addition reaction and the oxidative dehydrogenation reaction are carried out to generate the end product 2-(2-fluorophenyl) benzonitrile. In addition, we consider the path j where no catalyst is involved. The calculation results can provide valuable reference and guidance for the interaction and reaction mechanism in the similar reaction. The second part uses the DFT method to study the reaction mechanism of 2-(p-tolyl) aminoethyl acetate when the substituent is hydrogen and methyl, under the action of the free-radical initiator TBPA and the reaction of the oxygen-generating reaction to produce the derivatives and the derivatives. And the effect of the solvent was simulated using the smd model. The activity of the reaction site is predicted by calculating the well function and the binary descriptor. For both reactions in this part, the activation of Csp3-H has four possible reaction paths. The results show that the first reaction will continue to react with the oxygen after the activation of the Csp3-H, and then the product 1,5-dimethyl-2,3-dione is generated by two possible reaction paths, and the acetaldehyde molecule is removed, and then the path of the water molecule is lost is the optimal path. After the second reaction is activated by the Csp3-H, the dehydrogenation reaction is continued to generate a double bond, and then a six-membered ring is generated by the addition reaction with the reactant styrene, and finally, the product 2-ethyl acetate-4-phenyl-6-methylphenyl ether is generated through a series of oxidative dehydrogenation reactions. The calculated results not only meet the experimental phenomena, but also provide theoretical support for the optimization of the reaction. The third part uses the DFT to study the reaction mechanism of N-methyl and p-tolyl-azido through the Huisgen ring, and the effect of the solvent is simulated by using the PCM model. The function of well and the binary descriptor are used to predict the atomic activity of the reaction site. For the three reactions in this part, each reaction has two possible reaction paths (I and II), and the calculated results show that the singlet oxygen plays an important role in the oxidative dehydrogenation of the first reaction of 2-imino-1 and p-tolyl azido. When the reaction does not involve oxygen, the two covalent bonds are turned off by two open-loop reaction paths in the case of nitrogen as a protective gas, followed by the reaction of 1,2-hydrogen removal and de-removal of nitrogen (or the removal of nitrogen and 1,2-hydrogen). And the water molecule plays an important role in the process of the hydrogen removal in the reaction of the third methyl-substituted N-methyl diazo compound and the p-tolyl-azido. Our results show that these reactions can occur under specific conditions and are in good agreement with the experimental results. The understanding of the competitive path in the addition reaction of N-methyl and p-tolyl-azido-Huisgen can provide valuable guidance for the related reactions.
【学位授予单位】：兰州大学
【学位级别】：博士
【学位授予年份】：2017
【分类号】：O621.25
本文编号：2498538
[Abstract]:The reaction mechanism of aryl-C-H-cyanoethylation and the reaction mechanism of 2-(p-tolyl) aminoethyl acetate (Csp3-H) and the reaction mechanism of N-methyl-1-(p-tolyl) azido-Huisgen ring were studied by density functional theory (DFT). In the first part, the method of DFT was used to study the mechanism of the cyanoethylation of C-H under the condition of B3LYP/6-31 + G (d, p), and the effect of the solution of the solvent dimethylmethylamine was simulated by using the IEFPCM model. The calculation result shows that the phenylacetonitrile is produced by the two reaction paths (a and b) under the action of oxygen, and also the benzyl cyanide can react with the oxygen anion to generate 2-hydroxy-2-phenylacetonitrile; and then, The resulting 2-hydroxy-2-phenylacetonitrile has an oxidative dehydrogenation reaction to produce a benzonitrile, where there are four possible ways of reaction (c, d, e, and f). The 2-(2-fluorophenyl) benzonitrile is produced by three possible reaction modes (g, h and i) under the action of the catalyst CuBr, and the N atom and the copper catalyst in the 2-phenyl-phenyl-benzenetil are used as a positioning group in the reaction process, And then the addition reaction and the oxidative dehydrogenation reaction are carried out to generate the end product 2-(2-fluorophenyl) benzonitrile. In addition, we consider the path j where no catalyst is involved. The calculation results can provide valuable reference and guidance for the interaction and reaction mechanism in the similar reaction. The second part uses the DFT method to study the reaction mechanism of 2-(p-tolyl) aminoethyl acetate when the substituent is hydrogen and methyl, under the action of the free-radical initiator TBPA and the reaction of the oxygen-generating reaction to produce the derivatives and the derivatives. And the effect of the solvent was simulated using the smd model. The activity of the reaction site is predicted by calculating the well function and the binary descriptor. For both reactions in this part, the activation of Csp3-H has four possible reaction paths. The results show that the first reaction will continue to react with the oxygen after the activation of the Csp3-H, and then the product 1,5-dimethyl-2,3-dione is generated by two possible reaction paths, and the acetaldehyde molecule is removed, and then the path of the water molecule is lost is the optimal path. After the second reaction is activated by the Csp3-H, the dehydrogenation reaction is continued to generate a double bond, and then a six-membered ring is generated by the addition reaction with the reactant styrene, and finally, the product 2-ethyl acetate-4-phenyl-6-methylphenyl ether is generated through a series of oxidative dehydrogenation reactions. The calculated results not only meet the experimental phenomena, but also provide theoretical support for the optimization of the reaction. The third part uses the DFT to study the reaction mechanism of N-methyl and p-tolyl-azido through the Huisgen ring, and the effect of the solvent is simulated by using the PCM model. The function of well and the binary descriptor are used to predict the atomic activity of the reaction site. For the three reactions in this part, each reaction has two possible reaction paths (I and II), and the calculated results show that the singlet oxygen plays an important role in the oxidative dehydrogenation of the first reaction of 2-imino-1 and p-tolyl azido. When the reaction does not involve oxygen, the two covalent bonds are turned off by two open-loop reaction paths in the case of nitrogen as a protective gas, followed by the reaction of 1,2-hydrogen removal and de-removal of nitrogen (or the removal of nitrogen and 1,2-hydrogen). And the water molecule plays an important role in the process of the hydrogen removal in the reaction of the third methyl-substituted N-methyl diazo compound and the p-tolyl-azido. Our results show that these reactions can occur under specific conditions and are in good agreement with the experimental results. The understanding of the competitive path in the addition reaction of N-methyl and p-tolyl-azido-Huisgen can provide valuable guidance for the related reactions.
【学位授予单位】：兰州大学
【学位级别】：博士
【学位授予年份】：2017
【分类号】：O621.25
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