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The reactivity of cinnamic acid derivatives as lignin precursors

https://doi.org/10.32362/2410-6593-2020-15-4-7-13

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Abstract

Objectives. Cinnamic acid derivatives belong to a large class of phenolic compounds, which are widely distributed in plants and have high potential for use in the medical and industrial fields. They have various useful practical properties, e.g., antioxidant, anti-inflammatory, antiplatelet, and anti-melanogenic properties. Hydroxycinnamic acids are of particular interest as phenylpropanoids, which are the starting compounds of lignin. The aim of this work was to study the electronic structure and analyze the reactivity of the simplest representatives of phenylpropanoids formed during the biosynthesis of the coumaric (p-hydroxycinnamic), caffeic (3,4-dihydroxycinnamic), ferulic (3-methoxy-4-hydroxycinnamic), sinapic (3,5-dimethoxy-4- hydroxycinnamic), and 3,4-dimethoxycinnamic acids. These acids are the biogenetic precursors of most other phenolic compounds (coumarins, melanins, lignins, and flavonoids) and are found in almost all higher plants.

Methods. Calculations with full optimization of the geometric parameters were performed using the original Hartree–Fock theory and hybrid density functional method. All calculations were performed using the Firefly program.

Results. A comparative quantum chemical calculation of the geometric parameters of hydroxycinnamic acid molecules was conducted via two methods, and the values of the charges on atoms according to Mulliken were determined. It was found that with the addition of hydroxyl and methoxy substituents at the meta and para positions relative to the carboxyl fragment, the electron density shifts toward the benzene ring, and the symmetry of the molecule decreases. Additionally, in these structures, there is π,π-conjugation of the carboxyl fragment of the –СН=СНСООН molecule with the aromatic ring, which significantly affects the geometric configuration of the molecule. The maximum positive charge is concentrated on the C9 atom, while the maximum negative charge is on the oxygen atoms belonging to the methoxy substituents and the hydroxyl group, which confirms the role of oxygen atoms in the chemical transformations of acids.

Conclusions. Two different methods were used to calculate the geometric, electronic, and energy parameters and electrophilicity indices of the studied hydroxycinnamic acids in the gas phase. The obtained values were consistent (within the limits of error) with the experimental data as well as the results described in earlier works’ calculations by other methods.

About the Authors

O. K. Karimov
Department of General Chemical Technology Ufa State Petroleum Technological University
Russian Federation

Oleg K. Karimov, Cand. of Sci. (Engineering), Associate Professor

1, Kosmonavtov ul., Ufa, 450062 



G. Y. Kolchina
Department of Chemistry and Chemical Technology, Bashkir State University, Branch of the University in Sterlitamak
Russian Federation

Galina Y. Kolchina, Cand. of Sci. (Chemistry), Associate Professor

49, Lenina pr., Sterlitamak, 453103



G. A. Teptereva
Department of General, Analytical and Applied Chemistry, Ufa State Petroleum Technological University
Russian Federation

Galina A. Teptereva, Dr. of Sci. (Engineering), Associate Professor

1, Kosmonavtov ul., Ufa, 450062

 



I. A. Chetvertneva
Head of the SBM Service Center LLC of the Volga-Ural region
Russian Federation

Irina A. Chetvertneva, Cand. of Sci. (Engineering)

5, Vavilova ul., Moscow, 119330



E. K. Karimov
Department of General Chemical Technology,Ufa State Petroleum Technological University
Russian Federation

Eduard K. Karimov, Cand. of Sci. (Engineering), Associate Professor

1, Kosmonavtov ul., Ufa, 450062

 



A. R. Badretdinov
Department of General Chemical Technology, Ufa State Petroleum Technological University
Russian Federation

Almaz R. Badretdinov, Postgraduate Student

1, Kosmonavtov ul., Ufa, 450062



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Supplementary files

1. Structural formulas of hydroxycinnamic acids.
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Type Исследовательские инструменты
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Indexing metadata
  • A quantum chemical calculation of the geometric parameters of hydroxycinnamic acid molecules (coumaric, caffeic, ferulic, sinapic, and 3,4-dimethoxycinnamic acids) was performed using the limited Hartree–Fock and hybrid density functional methods.
  • It was shown that when hydroxyl and methoxy substituents are introduced into the meta and para positions relative to the carboxyl fragment, the electron density shifts toward the benzene ring, and, as a result, the molecular symmetry decreases.
  • For all compounds, the maximum positive charge is concentrated on the carbon atom of the carbonyl group, while the maximum negative charge is on the oxygen atoms belonging to the methoxy substituents and hydroxyl group, which confirms the role of oxygen atoms in the chemical transformations of acids.

For citation:


Karimov O.K., Kolchina G.Y., Teptereva G.A., Chetvertneva I.A., Karimov E.K., Badretdinov A.R. The reactivity of cinnamic acid derivatives as lignin precursors. Fine Chemical Technologies. 2020;15(4):7-13. (In Russ.) https://doi.org/10.32362/2410-6593-2020-15-4-7-13

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ISSN 2410-6593 (Print)
ISSN 2686-7575 (Online)