A theoretical investigation to understand the difference in reactivities of secondary and tertiary propargylic alcohols with 1,3,5-trimethoxybenzene in presence of Brnøsted acid
Palash Jyoti Boruah, Moumita Debnath, Ankita Agarwal, Gitumoni Kalita, Paresh Nath Chatterjee, Amit Kumar Paul
{"title":"A theoretical investigation to understand the difference in reactivities of secondary and tertiary propargylic alcohols with 1,3,5-trimethoxybenzene in presence of Brnøsted acid","authors":"Palash Jyoti Boruah, Moumita Debnath, Ankita Agarwal, Gitumoni Kalita, Paresh Nath Chatterjee, Amit Kumar Paul","doi":"10.1002/kin.21714","DOIUrl":null,"url":null,"abstract":"<p>The work presented here establishes the experimental findings of the reaction between secondary/tertiary propargylic alcohol (PA) and 1,3,5-trimethoxybenzene (TMB) in the presence of acetonitrile solvent (MeCN) based on theoretical calculations. When secondary PA reacts, the reaction goes via S<sub>N</sub>2 pathway, where the reaction barrier is about 14.32 kcal/mol. On the other hand, tertiary PA reacts with TMB via S<sub>N</sub>2′ and S<sub>N</sub>1′ pathway, and the corresponding reaction barriers are 17.59 and 17.86 kcal/mol. Other possible pathways, namely, S<sub>N</sub>1, S<sub>N</sub>1′, etc. for secondary PA, and S<sub>N</sub>2, S<sub>N</sub>1 pathways for tertiary PA are also investigated and the associated barrier heights are found higher. Rates of those reactions are also calculated considering the rate-determining steps only. Reaction of secondary PA with TMB is found to be much faster than the reaction of tertiary PA and the results are in accordance with the experimental findings.</p>","PeriodicalId":13894,"journal":{"name":"International Journal of Chemical Kinetics","volume":null,"pages":null},"PeriodicalIF":1.5000,"publicationDate":"2024-03-06","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":"0","resultStr":null,"platform":"Semanticscholar","paperid":null,"PeriodicalName":"International Journal of Chemical Kinetics","FirstCategoryId":"92","ListUrlMain":"https://onlinelibrary.wiley.com/doi/10.1002/kin.21714","RegionNum":4,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":null,"EPubDate":"","PubModel":"","JCR":"Q4","JCRName":"CHEMISTRY, PHYSICAL","Score":null,"Total":0}
引用次数: 0
Abstract
The work presented here establishes the experimental findings of the reaction between secondary/tertiary propargylic alcohol (PA) and 1,3,5-trimethoxybenzene (TMB) in the presence of acetonitrile solvent (MeCN) based on theoretical calculations. When secondary PA reacts, the reaction goes via SN2 pathway, where the reaction barrier is about 14.32 kcal/mol. On the other hand, tertiary PA reacts with TMB via SN2′ and SN1′ pathway, and the corresponding reaction barriers are 17.59 and 17.86 kcal/mol. Other possible pathways, namely, SN1, SN1′, etc. for secondary PA, and SN2, SN1 pathways for tertiary PA are also investigated and the associated barrier heights are found higher. Rates of those reactions are also calculated considering the rate-determining steps only. Reaction of secondary PA with TMB is found to be much faster than the reaction of tertiary PA and the results are in accordance with the experimental findings.
本文介绍的工作以理论计算为基础,确定了仲/叔丙炔醇(PA)与 1,3,5- 三甲氧基苯(TMB)在乙腈溶剂(MeCN)存在下反应的实验结果。当二级 PA 发生反应时,反应通过 SN2 途径进行,反应势垒约为 14.32 kcal/mol。另一方面,三级 PA 通过 SN2′和 SN1′途径与 TMB 反应,相应的反应势垒分别为 17.59 和 17.86 kcal/mol。此外,还研究了其他可能的途径,即二级 PA 的 SN1、SN1′等途径,以及三级 PA 的 SN2、SN1 途径,发现相关的势垒更高。计算这些反应的速率时也只考虑了决定速率的步骤。发现仲 PA 与 TMB 的反应比仲 PA 与叔 PA 的反应快得多,结果与实验结果一致。
期刊介绍:
As the leading archival journal devoted exclusively to chemical kinetics, the International Journal of Chemical Kinetics publishes original research in gas phase, condensed phase, and polymer reaction kinetics, as well as biochemical and surface kinetics. The Journal seeks to be the primary archive for careful experimental measurements of reaction kinetics, in both simple and complex systems. The Journal also presents new developments in applied theoretical kinetics and publishes large kinetic models, and the algorithms and estimates used in these models. These include methods for handling the large reaction networks important in biochemistry, catalysis, and free radical chemistry. In addition, the Journal explores such topics as the quantitative relationships between molecular structure and chemical reactivity, organic/inorganic chemistry and reaction mechanisms, and the reactive chemistry at interfaces.