烷烃及其衍生物对C(sp3)能力的构效关系H键的H原子转移反应

IF 1.9 4区 化学 Q2 CHEMISTRY, ORGANIC
Yan-Hua Fu, Liguo Yang, Zhongyuan Zhou, Fang Wang, Guang-Bin Shen, Xiao-Qing Zhu
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引用次数: 0

摘要

烷烃的供氢原子能力是一个研究热点,目前已经得到了广泛的研究。本文研究了脂肪族、苯基、烯丙基烷烃及其烷烃衍生物与CumO•在298k乙腈中发生的20次氢原子转移反应的二阶速率常数。测定了热动力学参数ΔG≠0 (XH)、键解离自由能ΔGo(XH)和动力学固有阻力能ΔG≠XH/X,并用于评价这些底物在热力学、动力学和HAT反应中的供氢能力。详细讨论了构效关系,包括电子、立体电子和空间效应,烷烃中引入了- CH3、- Ph、- Cl,环烷烃中引入了N原子。结果表明:给h能力的顺序为:烯丙链烷烃→环烷烃→链烷烃→苄链烷烃→卤代烷烃。甲基的引入,Ph值,或者Cl烷烃和N原子的碳环的引入减少Δ去(XH),但增加ΔG≠XH / X,和ΔG≠o (XH)是合成这两个参数的结果。验证了ΔG≠0 (XH)的可靠性,证明了参数的准确性和可靠性。通过本文的研究,不仅可以定量评价这些烷烃及其衍生物在HAT反应中的ΔGo(XH)、ΔG≠XH/X和ΔG≠o(XH),还可以清楚地研究烷烃的构效关系。
本文章由计算机程序翻译,如有差异,请以英文原文为准。

Structure–activity relationship of alkanes and alkane derivatives for the abilities of C(sp3)H bonds toward their H-atom transfer reactions

Structure–activity relationship of alkanes and alkane derivatives for the abilities of C(sp3)H bonds toward their H-atom transfer reactions

Hydrogen atom-donating ability of alkane is a research hotspot and has been extensively studied. In this article, the second-order rate constants of 20 hydrogen atom transfer (HAT) reactions between aliphatic, benzylic, and allylic alkanes and alkane derivatives with CumO in acetonitrile at 298 K were studied. The thermo-kinetic parameter ΔG≠o(XH), bond dissociation free energy ΔGo(XH), and kinetic intrinsic resistance energy ΔGXH/X were determined and used to evaluate the H-donating abilities of these substrates in thermodynamics, kinetics, and HAT reactions. Structure–activity relationships including the factors (electronic, stereoelectronic, and steric effects), introduction of CH3, Ph, or Cl in alkanes, and introduction of N atom in cycloalkane were discussed carefully. The results show that the order of H-donating abilities is allylic alkanes > cycloalkanes > chain alkanes ≈ benzylic alkanes > haloalkanes. The introduction of CH3, Ph, or Cl in alkanes and the introduction of N atom to the carbon ring reduce ΔGo(XH) but increase ΔGXH/X, and ΔG≠o(XH) is the synthesis result of these two parameters. The reliability of ΔG≠o(XH) was verified, and the accuracy and reliability of the parameters were proved. Through the study of this paper, not only the ΔGo(XH), ΔGXH/X, and ΔG≠o(XH) of these alkanes and derivatives in HAT reaction can be quantitatively evaluated but also the structure–activity relationship of alkane is clearly researched.

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来源期刊
CiteScore
3.60
自引率
11.10%
发文量
161
审稿时长
2.3 months
期刊介绍: The Journal of Physical Organic Chemistry is the foremost international journal devoted to the relationship between molecular structure and chemical reactivity in organic systems. It publishes Research Articles, Reviews and Mini Reviews based on research striving to understand the principles governing chemical structures in relation to activity and transformation with physical and mathematical rigor, using results derived from experimental and computational methods. Physical Organic Chemistry is a central and fundamental field with multiple applications in fields such as molecular recognition, supramolecular chemistry, catalysis, photochemistry, biological and material sciences, nanotechnology and surface science.
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