首页> 外文期刊>The Journal of Organic Chemistry >Kinetic study on michael-type reactions of β-nitrostyrenes with cyclic secondary amines in acetonitrile: Transition-state structures and reaction mechanism deduced from negative enthalpy of activation and analyses of LFERs
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Kinetic study on michael-type reactions of β-nitrostyrenes with cyclic secondary amines in acetonitrile: Transition-state structures and reaction mechanism deduced from negative enthalpy of activation and analyses of LFERs

机译:β-硝基苯乙烯与环状仲胺在乙腈中迈克尔型反应的动力学研究:活化负焓和LFERs分析推导的过渡态结构和反应机理

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A kinetic study is reported for the Michael-type reactions of X-substituted β-nitrostyrenes (1a-j) with a series of cyclic secondary amines in MeCN. The plots of pseudo-first-order rate constant kobsd vs [amine] curve upward, indicating that the reactions proceed through catalyzed and uncatalyzed routes. The dissection of k_(obsd) into Kk_2 and Kk _3 (i.e., the rate constants for the uncatalyzed and catalyzed routes, respectively) revealed that Kk_3 is much larger than Kk_2, implying that the reactions proceed mainly through the catalyzed route when [amine] > 0.01 M. Strikingly, the reactivity of β-nitrostyrene (1g) toward piperidine decreases as the reaction temperature increases. Consequently, a negative enthalpy of activation is obtained, indicating that the reaction proceeds through a relatively stable intermediate. The Br?nsted-type plots for the reactions of 1g are linear with β_(nuc) = 0.51 and 0.61, and the Hammett plots for the reactions of 1a-j are also linear with ρX = 0.84 and 2.10 for the uncatalyzed and catalyzed routes, respectively. The reactions are concluded to proceed through six-membered cyclic transition states for both the catalyzed and uncatalyzed routes. The effects of the substituent X on reactivity and factors influencing β_(nuc) and ρ_X obtained in this study are discussed.
机译:动力学研究报道了MeCN中X取代的β-硝基苯乙烯(1a-j)与一系列环状仲胺的迈克尔型反应。拟一级反应速率常数kobsd对[胺]的曲线向上弯曲,表明反应通过催化和未催化途径进行。将k_(obsd)分解为Kk_2和Kk _3(即分别为未催化和催化途径的速率常数)表明Kk_3比Kk_2大得多,这意味着当[胺]时反应主要通过催化途径进行> 0.01M。令人惊讶的是,随着反应温度的升高,β-硝基苯乙烯(1g)对哌啶的反应性降低。因此,获得了负的活化焓,表明反应通过相对稳定的中间体进行。 1g反应的Br?nsted型图与β_(nuc)= 0.51和0.61呈线性关系,而1a-j反应的Hammett图与ρX= 0.84和2.10呈线性关系,对于未催化和催化路线, 分别。结论是,对于催化的和未催化的路线,反应均通过六元环状过渡态进行。讨论了取代基X对反应性的影响以及影响本研究中获得的β_(nuc)和ρ_X的因素。

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