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<p>Vinylcyclohexene (VCH) derivatives such as <i>β</i>-ionone and limonene as natural and industrial compounds are possibly present in aquatic environments, and their addition reaction with the disinfectant hypochlorous acid (HOCl) has raised concern due to the potential cytotoxicity of their products. However, little is known about the mechanism of the addition reaction of VCH in chlorination. In this study, reaction mechanisms, reactive sites, and substitution effects of VCH with HOCl were investigated using the quantum chemical computation method. The results indicate that the Cl<sup>+</sup> of HOCl preferentially attacks the endocyclic double C1=C2 bond to generate the carbocation and chloronium ion intermediates for 1-VCH and 3/4-VCH, respectively, and then hydroxylation occurs to yield chlorohydrins. Regarding the substituent effect, it was found that in most case, the double bond closer to/farther away from the site substituted by the –CH<sub>3</sub>/−CHO group becomes preferable to the other double bond, mainly due to the electron-donating/withdrawing property of the –CH<sub>3</sub>/–CHO group. Based on the above results, the reactive sites of some VCH derivatives were proposed. The findings of this work are helpful for a better understanding of the reaction mechanisms of complex olefins with HOCl and predicting their reactive sites.</p>

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Reaction mechanisms and reactive sites of vinylcyclohexene and its derivatives with hypochlorous acid: a computational study

  • 期刊论文

  • 发表日期：

    2025年7月4日

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  • Chunmei Han,
  • Yong Dong Liu,
  • Rugang Zhong

摘要

Vinylcyclohexene (VCH) derivatives such as β-ionone and limonene as natural and industrial compounds are possibly present in aquatic environments, and their addition reaction with the disinfectant hypochlorous acid (HOCl) has raised concern due to the potential cytotoxicity of their products. However, little is known about the mechanism of the addition reaction of VCH in chlorination. In this study, reaction mechanisms, reactive sites, and substitution effects of VCH with HOCl were investigated using the quantum chemical computation method. The results indicate that the Cl+ of HOCl preferentially attacks the endocyclic double C1=C2 bond to generate the carbocation and chloronium ion intermediates for 1-VCH and 3/4-VCH, respectively, and then hydroxylation occurs to yield chlorohydrins. Regarding the substituent effect, it was found that in most case, the double bond closer to/farther away from the site substituted by the –CH3/−CHO group becomes preferable to the other double bond, mainly due to the electron-donating/withdrawing property of the –CH3/–CHO group. Based on the above results, the reactive sites of some VCH derivatives were proposed. The findings of this work are helpful for a better understanding of the reaction mechanisms of complex olefins with HOCl and predicting their reactive sites.