DFT研究C-H活化及Huisgen環(huán)加成反應(yīng)機(jī)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.
【學(xué)位授予單位】:蘭州大學(xué)
【學(xué)位級別】:博士
【學(xué)位授予年份】:2017
【分類號】:O621.25
【參考文獻(xiàn)】
相關(guān)期刊論文 前10條
1 周夏禹;榮春英;盧天;劉述斌;;用Hirshfeld電荷定量標(biāo)度親電性和親核性:含氮體系(英文)[J];物理化學(xué)學(xué)報;2014年11期
2 姚飛;曾榮今;王慧;沈鵬飛;;1,3-偶極環(huán)加成反應(yīng)合成新型的吡喃-嘧啶并噻唑類化合物[J];湖南科技大學(xué)學(xué)報(自然科學(xué)版);2011年02期
3 池俊杰;夏宇;張曉勤;曲貴晨;常偉林;王建偉;;1,3-偶極環(huán)加成反應(yīng)在含能材料中的應(yīng)用[J];化學(xué)推進(jìn)劑與高分子材料;2011年03期
4 令玉林;劉彬;李筱芳;于賢勇;易平貴;;1,3-偶極環(huán)加成反應(yīng)合成螺哌啶-六氫吡嗪類化合物[J];湖南科技大學(xué)學(xué)報(自然科學(xué)版);2010年04期
5 李筱芳;于賢勇;馮亞青;;1,3-偶極環(huán)加成反應(yīng)合成螺噻唑并[3,2-a]嘧啶類化合物[J];有機(jī)化學(xué);2010年05期
6 劉述斌;;概念密度泛函理論及近來的一些進(jìn)展(英文)[J];物理化學(xué)學(xué)報;2009年03期
7 杜鼎;方建新;;具有生物活性的喹啉類化合物的最新進(jìn)展[J];有機(jī)化學(xué);2007年11期
8 王炳祥;徐助雄;吳婧;;吡啶葉立德與查爾酮1,3-偶極環(huán)加成反應(yīng)制備2-苯基-3-乙;械醄J];有機(jī)化學(xué);2006年11期
9 胡曉芬,馮亞青,李筱芳;手性Lewis酸催化硝酮與烯烴的1,3-偶極環(huán)加成反應(yīng)[J];有機(jī)化學(xué);2005年01期
10 扈艷紅,劉世領(lǐng),仝欽宇,黃發(fā)榮,沈永嘉,齊會民,杜磊;1,3-偶極環(huán)加成反應(yīng)合成1-(取代芐基)-1,2,3-三唑類化合物[J];有機(jī)化學(xué);2004年10期
,本文編號:2498538
本文鏈接:http://sikaile.net/shoufeilunwen/gckjbs/2498538.html