Hydrogen–Deuterium Exchange in Basic Near-Critical and Supercritical Media: An Experimental and Theoretical Study,The Journal of Physical Chemistry A

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Hydrogen–Deuterium Exchange in Basic Near-Critical and Supercritical Media: An Experimental and Theoretical Study
The Journal of Physical Chemistry A ( IF 2.7 ) Pub Date : 2020-03-24 , DOI: 10.1021/acs.jpca.9b10892
Pia R. Alburquerque ₁ , B. Ramu Ramachandran ₂ , Thomas Junk ₃ , Tolga N. V. Karsili ₃

Affiliation

Treatment of homo- and heterocyclic aromatic substrates with basic deuterium oxide under near- or supercritical conditions results in rapid base-catalyzed hydrogen–deuterium exchange (HDE) in aromatic and benzylic positions. It has been postulated that HDE follows a simple deprotonation–reprotonation mechanism, but little evidence has been provided to date. This study correlates experimentally observed proton exchanges in n-butylbenzene with ab initio calculations of the acidities and potential energy (PE) profiles. In addition to providing further support for carbanion intermediacy in HDE, these results offer new insights into substrate acidities in near- and supercritical aqueous media and the optimal conditions required for their isotope exchange.

中文翻译：

基本近临界和超临界介质中氢-氘交换的实验和理论研究

在近临界或超临界条件下，用碱性氘化氢处理均相和杂环芳族底物可在芳族和苄基位置快速进行碱催化的氢-氘交换（HDE）。据推测，HDE遵循简单的去质子-质子化机制，但迄今为止几乎没有证据。这项研究将实验观察到的正丁基苯中的质子交换与酸度和势能（PE）曲线的从头计算相关联。除了为HDE中的碳负离子中间体提供进一步支持外，这些结果还为洞悉近临界和超临界水介质中的底物酸度及其同位素交换所需的最佳条件提供了新见解。

更新日期：2020-03-24

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