DFT研究C-H活化及Huisgen環(huán)加成反應(yīng)機(jī)理
發(fā)布時間：2019-06-13 12:44
【摘要】：本論文主要根據(jù)密度泛函理論(DFT)研究芳基C-H氰基化的反應(yīng)機(jī)理和2-(對甲苯基)氨基乙酸乙酯中Csp3-H活化的反應(yīng)機(jī)理以及N-甲基吲哚與對甲苯磺酰疊氮Huisgen環(huán)加成的反應(yīng)機(jī)理。第一部分使用了DFT的方法,在B3LYP/6-31+G(d,p)的理論水平下研究了2-苯基吡啶在CuBr作為催化劑的情況下C-H的氰基化反應(yīng)的機(jī)理,同時使用了IEFPCM模型去模擬溶劑二甲基甲酰胺的作用。計算結(jié)果顯示苯乙腈在氧氣的作用下通過兩種反應(yīng)路徑(a和b)生成苯甲酰氰;此外苯乙腈也可以與氧氣負(fù)離子反應(yīng)生成2-羥基-2-苯基乙腈;緊接著,生成的2-羥基-2-苯基乙腈發(fā)生氧化脫氫反應(yīng)生成苯甲酰氰,這里有四種可能的反應(yīng)方式(c,d,e和f)。其次介紹的是反應(yīng)物2-苯基吡啶在催化劑CuBr的作用下通過三種可能的反應(yīng)方式(g,h和i)生成終產(chǎn)物2-(2-吡啶基)苯甲腈,在反應(yīng)過程中2-苯基吡啶中的N原子和銅催化劑起著定位基團(tuán)的作用,有助于CN-負(fù)離子的引入;進(jìn)而發(fā)生加成反應(yīng)和氧化脫氫反應(yīng)生成終產(chǎn)物2-(2-吡啶基)苯甲腈。另外我們也考慮了沒有催化劑參與的路徑j(luò)。計算結(jié)果可以為類似反應(yīng)中的相互作用和反應(yīng)機(jī)理提供有價值的參考和指導(dǎo)。第二部分使用DFT方法研究了2-(對甲苯基)氨基乙酸乙酯在取代基為氫和甲基的時候,在自由基引發(fā)劑TBPA的作用下和氧氣發(fā)生反應(yīng)生成吲哚衍生物和喹啉衍生物的反應(yīng)機(jī)理,并且使用SMD模型模擬了溶劑的影響。通過計算福井函數(shù)和二元描述符來預(yù)測反應(yīng)位點的活性。對于本部分中的兩個反應(yīng),其Csp3-H的活化都有四條可能的反應(yīng)路徑。計算結(jié)果顯示,第一個反應(yīng)經(jīng)過Csp3-H活化后會繼續(xù)和氧氣發(fā)生反應(yīng),而后通過兩條可能的反應(yīng)路徑生成產(chǎn)物1,5-二甲基-2,3-二酮吲哚,并且先脫去乙醛分子,而后失去水分子的路徑是最優(yōu)路徑。第二個反應(yīng)經(jīng)過Csp3-H活化后會繼續(xù)發(fā)生脫氫反應(yīng)生成雙鍵,隨后和反應(yīng)物苯乙烯發(fā)生加成反應(yīng)生成六元環(huán),最后經(jīng)過一系列的氧化脫氫反應(yīng)生成產(chǎn)物2-乙酸乙酯基-4-苯基-6-甲基喹啉。計算的結(jié)果不僅符合實驗現(xiàn)象,還可以為優(yōu)化反應(yīng)提供理論支持。第三部分使用DFT研究了N-甲基吲哚與對甲苯磺酰疊氮通過Huisgen環(huán)加成生成吲哚衍生物的反應(yīng)機(jī)理,并且使用PCM模型模擬了溶劑的影響。采用福井函數(shù)和二元描述符來預(yù)測反應(yīng)位點的原子活性。對于本部分中的三個反應(yīng),每個反應(yīng)都有兩條可能的反應(yīng)路徑(I和II),計算結(jié)果顯示,單線態(tài)氧氣在2-亞胺吲哚與對甲苯磺酰疊氮的第一個反應(yīng)的氧化脫氫過程中起著重要作用;當(dāng)反應(yīng)沒有氧氣的參與,而是在氮氣作為保護(hù)氣的情況下,通過兩種開環(huán)反應(yīng)路徑而斷開兩個共價鍵,隨后發(fā)生1,2-氫遷和脫去氮氣(或者脫去氮氣和1,2-氫遷)反應(yīng)。而水分子在第三個甲基取代的N-甲基吲哚與對甲苯磺酰疊氮的反應(yīng)中的氫遷過程中起著重要作用。我們的計算結(jié)果表明這些反應(yīng)在特定的條件下可以發(fā)生,與實驗結(jié)果吻合。對N-甲基吲哚與對甲苯磺酰疊氮Huisgen環(huán)加成反應(yīng)中競爭路徑的理解可以為相關(guān)反應(yīng)提供有價值的指導(dǎo)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.
【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
本文編號：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.
【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
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