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Kinetic study on electrochemical oxidation of catechols in the presence of cycloheptylamine and aniline: Experiments and digital simulation

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Abstract

Oxidative coupling reaction of some catechols has been studied by cyclic voltammetry at the glassy carbon electrode in different experimental conditions. The electrogenerated o-banzoquinone participates in a coupling reaction with anionic and dianionic forms of catechol. Based on EC mechanism, the observed homogenous rate constants of the coupling reaction of catechols were estimated by analyzing the cyclic voltammetric responses using the simulation software DIGIELCH. This paper deals with reaction of o-benzoquinones derived by the oxidation of catechol (CAT), 3-methylcatechol (3-MC), 3-methoxycatechol (3-MOC) and 3,4-dihydroxybenzoic acid (3,4-DHBA) with cycloheptylamine (a primary aliphatic amine) and aniline (a primary aromatic amine) as nucleophiles to gain mechanistic insight. The outcome indicates participation of o-benzoquinone in the Michael addition reaction with the studied primary amines. The best fit of the experimental and simulated results was obtained for ECE mechanism. The calculated/estimated homogeneous rate constants (k obs) for Michael addition reaction were found to vary in the order CAT >3-MC >3-MOC >3,4-DHBA and CAT >3,4-DHBA >3-MC >3-MOC for cycloheptylamine and aniline, respectively. These data are in agreement with the trend of electronic properties (electron-donating/-withdrawing) of the substitutions on the catechol ring.

Oxidative coupling reaction of some catechols has been studied in the presence of cycloheptylamine and aniline as nucleophiles to gain mechanistic insight.

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Acknowledgments

Authors acknowledge Bu-Ali Sina University Research Council and Center of Excellence in Development of Environmentally Friendly Methods for Chemical Synthesis (CEDEFMCS) for their support of this work.

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Authors and Affiliations

  1. Faculty of Chemistry, Bu-Ali Sina University, 65178-38683, Hamedan, Iran

    DAVOOD NEMATOLLAHI, FATEMEH GHASEMI & SADEGH KHAZALPOUR

  2. Department of Chemistry, Institute for Advanced Studies in Basic Sciences (IASBS), Zanjan, Iran

    FAHIMEH VARMAGHANI

  3. Center for Research in Basic Sciences and Contemporary Technologies, IASBS, Zanjan, Iran

    FAHIMEH VARMAGHANI

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  1. DAVOOD NEMATOLLAHI
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  2. FATEMEH GHASEMI
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Correspondence to DAVOOD NEMATOLLAHI.

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NEMATOLLAHI, D., GHASEMI, F., KHAZALPOUR, S. et al. Kinetic study on electrochemical oxidation of catechols in the presence of cycloheptylamine and aniline: Experiments and digital simulation. J Chem Sci 128, 1887–1894 (2016). https://doi.org/10.1007/s12039-016-1193-y

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