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A study of the kinetics and mechanism of chromic acid oxidation of isosorbide, a chiral biomass-derived substrate, in aqueous perchlorate solution

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Abstract

The oxidation of isosorbide (S) by chromic acid (CrVI) has been studied in aqueous perchlorate solution at a constant ionic strength of 3.0 mol dm−3 and temperature of 25 °C. The course of the reaction was followed spectrophotometrically. The reaction exhibited first-order dependence on [CrVI], less than unit order with respect to [S], and fractional-second-order dependence with respect to [H+]. Variation of the ionic strength or dielectric constant of the medium had no significant effects on the oxidation rate. Addition of MnII inhibited the oxidation rate. The oxidation product of isosorbide was identified as the corresponding monoketone derivative, namely (1S,4S,5R)-4-hydroxy-2,6-dioxabicyclo[3.3.0] octan-8-one. A mechanism for the oxidation is proposed, and the corresponding rate-law expression has been deduced. The activation parameters associated with the second-order rate constant are presented and discussed.

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Acknowledgements

We thank the department of Chemistry, Umm Al-Qura University for the use of all instrumentation facilities and Prof. M. Majdoub for discussions.

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Authors and Affiliations

  1. Chemistry Department, Faculty of Applied Sciences, Umm Al-Qura University, 21955, Mecca, Saudi Arabia

    Ahmed Fawzy, Nizar El Guesmi, Ismail I. Althagafi & Basim H. Asghar

  2. Chemistry Department, Faculty of Science, Assiut University, 71516, Assiut, Egypt

    Ahmed Fawzy

  3. Département de Chimie, Faculté des Sciences de Monastir, University of Monastir, Avenue de l’Environnement, 5019, Monastir, Tunisia

    Nizar El Guesmi

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  1. Ahmed Fawzy
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  2. Nizar El Guesmi
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  4. Basim H. Asghar
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Correspondence to Ahmed Fawzy or Nizar El Guesmi.

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Fawzy, A., Guesmi, N.E., Althagafi, I.I. et al. A study of the kinetics and mechanism of chromic acid oxidation of isosorbide, a chiral biomass-derived substrate, in aqueous perchlorate solution. Transit Met Chem 42, 229–236 (2017). https://doi.org/10.1007/s11243-017-0126-z

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