DFT研究C-H活化及Huisgen环加成反应机理
[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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