Rosa M. Claramunt, Dionisia Sanz, Ibon Alkorta, José Elguero
{"title":"Addition reaction of azoles to acetone-d6: NMR and computational studies","authors":"Rosa M. Claramunt, Dionisia Sanz, Ibon Alkorta, José Elguero","doi":"10.1002/poc.4612","DOIUrl":null,"url":null,"abstract":"<p>The reactivity of imidazole, pyrazole, 1,2,4-triazole, 1,2,3-triazole, and tetrazole with acetone (propan-2-one) has been studied by <sup>1</sup>H and <sup>13</sup>C NMR using acetone-<i>d</i><sub><i>6</i></sub> as solvent at temperatures ranging from 173 to 300 K at 10 K intervals. Simultaneously, the reaction has been theoretically calculated at the B3LYP/6-311++G(d,p) level, and experimental and theoretical results have been compared. The equilibrium constants between azoles and adducts α,α-dimethyl-azole-methanol were analyzed, assuming that the straight part of the plots –R ln <i>K</i><sub>e</sub> vs. 1/T can be used to determine Δ<i>H</i> and Δ<i>S</i>. Calculated and experimental data are related, but the theoretical values are proportionally higher. The tautomerism of triazoles and tetrazole has been considered in order to discuss the reactions.</p>","PeriodicalId":16829,"journal":{"name":"Journal of Physical Organic Chemistry","volume":null,"pages":null},"PeriodicalIF":1.9000,"publicationDate":"2024-05-22","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"https://onlinelibrary.wiley.com/doi/epdf/10.1002/poc.4612","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.4612","RegionNum":4,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":null,"EPubDate":"","PubModel":"","JCR":"Q2","JCRName":"CHEMISTRY, ORGANIC","Score":null,"Total":0}
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Abstract
The reactivity of imidazole, pyrazole, 1,2,4-triazole, 1,2,3-triazole, and tetrazole with acetone (propan-2-one) has been studied by 1H and 13C NMR using acetone-d6 as solvent at temperatures ranging from 173 to 300 K at 10 K intervals. Simultaneously, the reaction has been theoretically calculated at the B3LYP/6-311++G(d,p) level, and experimental and theoretical results have been compared. The equilibrium constants between azoles and adducts α,α-dimethyl-azole-methanol were analyzed, assuming that the straight part of the plots –R ln Ke vs. 1/T can be used to determine ΔH and ΔS. Calculated and experimental data are related, but the theoretical values are proportionally higher. The tautomerism of triazoles and tetrazole has been considered in order to discuss the reactions.
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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