{"title":"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","authors":"Yan-Hua Fu, Liguo Yang, Zhongyuan Zhou, Fang Wang, Guang-Bin Shen, Xiao-Qing Zhu","doi":"10.1002/poc.4550","DOIUrl":null,"url":null,"abstract":"<p>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<sup>•</sup> in acetonitrile at 298 K were studied. The thermo-kinetic parameter Δ<i>G</i><sup>≠o</sup>(XH), bond dissociation free energy Δ<i>G</i><sup>o</sup>(XH), and kinetic intrinsic resistance energy Δ<i>G</i><sup>≠</sup><sub>XH/X</sub> 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 <span></span>CH<sub>3</sub>, <span></span>Ph, or <span></span>Cl in alkanes, and introduction of <i>N</i> 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 <span></span>CH<sub>3</sub>, <span></span>Ph, or <span></span>Cl in alkanes and the introduction of <i>N</i> atom to the carbon ring reduce Δ<i>G</i><sup>o</sup>(XH) but increase Δ<i>G</i><sup>≠</sup><sub>XH/X</sub>, and Δ<i>G</i><sup>≠o</sup>(XH) is the synthesis result of these two parameters. The reliability of Δ<i>G</i><sup>≠o</sup>(XH) was verified, and the accuracy and reliability of the parameters were proved. Through the study of this paper, not only the Δ<i>G</i><sup>o</sup>(XH), Δ<i>G</i><sup>≠</sup><sub>XH/X</sub>, and Δ<i>G</i><sup>≠o</sup>(XH) of these alkanes and derivatives in HAT reaction can be quantitatively evaluated but also the structure–activity relationship of alkane is clearly researched.</p>","PeriodicalId":16829,"journal":{"name":"Journal of Physical Organic Chemistry","volume":null,"pages":null},"PeriodicalIF":1.9000,"publicationDate":"2023-06-07","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":"0","resultStr":"{\"title\":\"Structure–activity relationship of alkanes and alkane derivatives for the abilities of C(sp3)H bonds toward their H-atom transfer reactions\",\"authors\":\"Yan-Hua Fu, Liguo Yang, Zhongyuan Zhou, Fang Wang, Guang-Bin Shen, Xiao-Qing Zhu\",\"doi\":\"10.1002/poc.4550\",\"DOIUrl\":null,\"url\":null,\"abstract\":\"<p>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<sup>•</sup> in acetonitrile at 298 K were studied. The thermo-kinetic parameter Δ<i>G</i><sup>≠o</sup>(XH), bond dissociation free energy Δ<i>G</i><sup>o</sup>(XH), and kinetic intrinsic resistance energy Δ<i>G</i><sup>≠</sup><sub>XH/X</sub> 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 <span></span>CH<sub>3</sub>, <span></span>Ph, or <span></span>Cl in alkanes, and introduction of <i>N</i> 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 <span></span>CH<sub>3</sub>, <span></span>Ph, or <span></span>Cl in alkanes and the introduction of <i>N</i> atom to the carbon ring reduce Δ<i>G</i><sup>o</sup>(XH) but increase Δ<i>G</i><sup>≠</sup><sub>XH/X</sub>, and Δ<i>G</i><sup>≠o</sup>(XH) is the synthesis result of these two parameters. The reliability of Δ<i>G</i><sup>≠o</sup>(XH) was verified, and the accuracy and reliability of the parameters were proved. Through the study of this paper, not only the Δ<i>G</i><sup>o</sup>(XH), Δ<i>G</i><sup>≠</sup><sub>XH/X</sub>, and Δ<i>G</i><sup>≠o</sup>(XH) of these alkanes and derivatives in HAT reaction can be quantitatively evaluated but also the structure–activity relationship of alkane is clearly researched.</p>\",\"PeriodicalId\":16829,\"journal\":{\"name\":\"Journal of Physical Organic Chemistry\",\"volume\":null,\"pages\":null},\"PeriodicalIF\":1.9000,\"publicationDate\":\"2023-06-07\",\"publicationTypes\":\"Journal Article\",\"fieldsOfStudy\":null,\"isOpenAccess\":false,\"openAccessPdf\":\"\",\"citationCount\":\"0\",\"resultStr\":null,\"platform\":\"Semanticscholar\",\"paperid\":null,\"PeriodicalName\":\"Journal of Physical Organic Chemistry\",\"FirstCategoryId\":\"92\",\"ListUrlMain\":\"https://onlinelibrary.wiley.com/doi/10.1002/poc.4550\",\"RegionNum\":4,\"RegionCategory\":\"化学\",\"ArticlePicture\":[],\"TitleCN\":null,\"AbstractTextCN\":null,\"PMCID\":null,\"EPubDate\":\"\",\"PubModel\":\"\",\"JCR\":\"Q2\",\"JCRName\":\"CHEMISTRY, ORGANIC\",\"Score\":null,\"Total\":0}","platform":"Semanticscholar","paperid":null,"PeriodicalName":"Journal of Physical Organic Chemistry","FirstCategoryId":"92","ListUrlMain":"https://onlinelibrary.wiley.com/doi/10.1002/poc.4550","RegionNum":4,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":null,"EPubDate":"","PubModel":"","JCR":"Q2","JCRName":"CHEMISTRY, ORGANIC","Score":null,"Total":0}
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 ΔG≠XH/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 ΔG≠XH/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), ΔG≠XH/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.
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.