DOI: https://doi.org/10.24959/ophcj.19.169808

The comparative quantum chemical study of the epoxidation reaction mechanism of eugenol and isoeugenol with peracetic and perbenzoic acids

O. M. Agafonov, S. I. Okovytyy, M. Ye. Blazheyevskiy

Abstract


Aim. To study the kinetics of the epoxidation reaction for eugenol and isoeugenol with perbenzoic acid, carry out the comparative quantum chemical study of the epoxidation reaction mechanism of eugenol and isoeugenol isomers (2-cis and 2-trans) with peracetic and perbenzoic acids.
Results and discussion. The kinetics of the epoxidation reaction of isomeric terpenoids eugenol and isoeugenol with perbenzoic acid in the medium of methylene chloride medium at 293 K was studied using the method of iodometric titration. It was shown that the rate constant of the epoxidation reaction for eugenol was in 5.5 times higher than for isoeugenol. According to the results of quantum chemical calculations using the UBH&HLYP/6-31G (d) approximation, the structures of transition states of eugenol and isoeugenol formed during the epoxidation reactions studied were proposed, and the activation energies for the corresponding reactions were calculated. Based on the results of the studies conducted it was found that the ratio of the activation energies during the interaction of eugenol and isoeugenol with peracetic and perbenzoic acids showed the higher reactivity of isoeugenol.
Experimental part. To study the kinetics of the epoxidation reaction the method of iodometric titration was used. The method of the functional density (software Gaussian 09, approximation UBH&HLYP/6-31G (d)) was applied for calculation.
Conclusions. The results of the quantum chemical study of the epoxidation reaction mechanism of eugenol and isoeugenol are consistent with the kinetic data experimentally obtained; it confirms the correctness of using the UBH&HLYP/6-31G (d) approximation for studying the features of epoxidation of isomeric terpenoids with organic peracids.

Keywords


terpenoids; quantum chemical research; reaction mechanism; reaction kinetics; epoxidation; peracetic acid; perbenzoic acid

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References


Koch, W., Holthausen, M. C. (2001). A chemist’s guide to density functional theory, 2nd ed. Weinheim: Wiley-VCH Verlag GmbH, 306. https://doi.org/10.1002/3527600043

Shi, H., Zhang, Z., Wang, Y. (2005). Mechanism on epoxidation of alkenes by peracids: A protonation-promoted pathway and its quantum chemical elucidation. Journal of Molecular Catalysis A: Chemical, 238(1-2), 13–25. https://doi.org/10.1016/j.molcata.2005.04.046

Filimonova, N. B., Vorob’ev, A. V., Bozhenko, K. V., Moiseeva, N. I., Dolin, S. P., Gekhman, A. E., Moiseev, I. I. (2010). A quantum-chemical study of the oxidation of ethylene by peroxyacetic acid derivatives. Russian Journal of Physical Chemistry B, 4(2), 235–241. https://doi.org/10.1134/s1990793110020089

Becke, A. D. (1988). Density-functional exchange-energy approximation with correct asymptotic behavior. Physical Review A, 38(6), 3098–3100. https://doi.org/10.1103/physreva.38.3098

Andersson, M. P., Uvdal, P. (2005). New Scale Factors for Harmonic Vibrational Frequencies Using the B3LYP Density Functional Method with the Triple-ζ Basis Set 6-311+G(d,p). The Journal of Physical Chemistry A, 109(12), 2937–2941. https://doi.org/10.1021/jp045733a

Kumara, A., Sahoob, D. (2013). Eugenol and its derivatives as Antimicrobial Agents. Journal of Antimicrobials Photon, 128, 133–140.

Guimarães, A. C., Meireles, L. M., Lemos, M. F., Guimarães, M. C. C., Endringer, D. C., Fronza, M., Scherer, R. (2019). Antibacterial Activity of Terpenes and Terpenoids Present in Essential Oils. Molecules, 24(13), 2471. https://doi.org/10.3390/molecules24132471

De Almeida, A. L., Caleffi-Ferracioli, K. R., de L Scodro, R. B., Baldin, V. P., Montaholi, D. C., Spricigo, L. F., Nakamura-Vasconcelos, S. S., Hegeto, L. A., Sampiron, E. G., Costacurta, G. F., Dos, S., Yamazaki, D. A., Gauze, F. G., Siqueira, V. L., Cardoso, R. F. (2019). Eugenol and derivatives activity against Mycobacterium tuberculosis, nontuberculous mycobacteria and other bacteria. Future Microbiology, 14, 331–344. https://doi.org/10.2217/fmb-2018-0333

Hu, Q., Zhou, M., Wei, S. (2018). Progress on the Antimicrobial Activity Research of Clove Oil and Eugenol in the Food Antisepsis Field. Journal of Food Science, 83(6), 1476–1483. https://doi.org/10.1111/1750-3841.14180

Marchese, A., Barbieri, R., Coppo, E., Orhan, I. E., Daglia, M., Nabavi, S. F., Izadi, M., Abdollahi, M., Nabavi, S. M., Ajami, M. (2017). Antimicrobial activity of eugenol and essential oils containing eugenol: A mechanistic viewpoint. Critical Reviews in Microbiology, 43(6), 668–689. https://doi.org/10.1080/1040841x.2017.1295225

Ferreira, S. B., Dantas,T. B., de Figuerêdo Silva, D., Ferreira, P. B., de Melo, T. R., de Oliveira Lima E. (2018). In Silico and In Vitro Investigation of the Antifungal Activity of Isoeugenol against Penicillium citrinum. Current Topics in Medicinal Chemistry, 18(25), 2186–2196. https://doi.org/10.2174/1568026619666181130141818

Mateen, S., Rehman, M. T., Shahzad, S., Naeem, S. S., Faizy, A. F., Khan, A. Q., Khan, M. S., Husain, F. M., Moin, S. (2019). Anti-oxidant and antiinflammatory effects of Cinnamaldehyde and Eugenol on mononuclear cells of rheumatoid arthritis patients. European Journal of Pharmacology, 852, 14–24. https://doi.org/10.1016/j.ejphar.2019.02.031

Maurya, A. K., Agarwal, K., Gupta, A. C., Saxena, A., Nooreen, Z., Tandon, S., Ahmad, A., Bawankule, D. U. (2018). Synthesis of eugenol derivatives and its anti-inflammatory activity against skin inflammation. Natural Product Research, 1–10. https://doi.org/10.1080/14786419.2018.1528585

Barboza, J. N., da Silva Maia Bezerra Filho, C., Silva, R. O., Medeiros, J. V. R., de Sousa, D. P. (2018). An Overview on the Anti-inflammatory Potential and Antioxidant Profile of Eugenol. Oxidative Medicine and Cellular Longevity, 2018, 1–9. https://doi.org/10.1155/2018/3957262

Tsuchiya, H. (2017). Anesthetic Agents of Plant Origin: A Review of Phytochemicals with Anesthetic Activity. Molecules, 22(8), 1369. https://doi.org/10.3390/molecules22081369

Harassi, Y., Tilaoui, M., Idir, A., Frédéric, J., Baudino, S., Ajouaoi, S., Mouse, H. A., Zyad, A. (2019). Phytochemical analysis, cytotoxic and antioxidant activities of Myrtus communis essential oil from Morocco. Journal of Complementary and Integrative Medicine. https://doi.org/10.1515/jcim-2018-0100

Abdullah, M. L., Hafez, M. M., Al-Hoshani, A., Al-Shabanah, O. (2018). Anti-metastatic and anti-proliferative activity of eugenol against triple negative and HER2 positive breast cancer cells. BMC Complementary and Alternative Medicine, 18(1), 321. https://doi.org/10.1186/s12906-018-2392-5

Federation of American Societies for Experimental Biology. (1973). Evaluation of health aspects of oil of cloves as a food ingredient. Life Sciences Research Office. Report no SCOGS-19; U.S. Food and Drug Administration. Available at: http://www.faseb.org/Portals/2/PDFs/LSRO_Legacy_Reports/1973_SCOGS-19%20Oil%20of%20Cloves.pdf

Kegley, S., Conlisk, E., Moses, M. (2010). Marin Municipal Water District. Herbicide Risk Assessment. Chapter 6. Clove Oil (Eugenol). Berkeley: Pesticide Research Institute, 25. Available at: https://www.marinwater.org/DocumentCenter/View/259/Herbicide-Risk-Assessment-Chapter-1-Summary-January-10-2010

Elgendy, E. M., Khayyat, S. A. (2008). Oxidation reactions of some natural volatile aromatic compounds: anethole and eugenol. Russian Journal of Organic Chemistry, 44(6), 823–829. https://doi.org/10.1134/s1070428008060079

Naboka, V. M., Agafonov, O. M. (2015). Quantum-chemical investigation of the mechanism of euvgenol and isoeugenol epoxidation by peracetic acid. Topical issues of new drugs development, Kharkiv, 2015, 90–91.

Frisch, M. J., Trucks, G. W., Schlegel, H. B., Scuseria, G. E., Robb, M. A., Chesseman, J. R. (2009). Gaussian 09, Revision A.02. Gaussian, Inc., Wallingford CT.

Guben-Vejl’. (1967). Metody organicheskoj himii: Vol. 1-2. Moscow: Himija, 2, 1032.


GOST Style Citations


1. Koch, W. A chemist’s guide to density functional theory / W. Koch, M. C. Holthausen. – 2nd ed. – Weinheim : Wiley-VCH Verlag GmbH, 2001. – 306 p. https://doi.org/10.1002/3527600043


2. Shi, H. Mechanism on epoxidation of alkenes by peracids: A protonation-promoted pathway and its quantum chemical elucidation / H. Shi, Z. Zhang, Y. Wang // J. Mol. Catal. A: Chem. – 2005. – Vol. 238, Issue 1–2. – P. 13–25. https://doi.org/10.1016/j.molcata.2005.04.046


3. A quantum-chemical study of the oxidation of ethylene by peroxyacetic acid derivatives / N. B. Filimonova, A. V. Vorob’ev, K. V. Bozhenko et al. // Russ. J. Phys. Chem. B. – 2010. – Vol. 4, Issue 2. – P. 235–241. https://doi.org/10.1134/s1990793110020089


4. Becke, A. D. Density-functional exchange-energy approximation with correct asymptotic behavior / A. D. Becke // Phys. Rev. A. – 1988. – Vol. 38, Issue 6. – P. 3098–3100. https://doi.org/10.1103/physreva.38.3098


5. Andersson, M. P. New scale factors for harmonic vibrational frequencies using the B3LYP density functional method with the triple-ζ basis set 6-311+G(d,p) / M. P. Andersson, P. Uvdal // J. Phys. Chem. A. – 2005. – Vol. 109, Issue 12. – P. 2937–2941. https://doi.org/10.1021/jp045733a


6. Kumara, A. Eugenol and its derivatives as antimicrobial agents / A. Kumara, D. Sahoob // J. Antimicrob. Photon. – 2013. – Vol. 128. – P. 133–140.


7. Antibacterial activity of terpenes and terpenoids present in essential oils / A. C. Guimarães, L. M. Meireles, M. F. Lemos et al. // Molecules. – 2019. – Vol. 24, Issue 13. – P. 2471. https://doi.org/10.3390/molecules24132471


8. Eugenol and derivatives activity against Mycobacterium tuberculosis, nontuberculous mycobacteria and other bacteria / A. L. De Almeida, K. R. Caleffi-Ferracioli, R. B. de L Scodro et al. // Future Microbiol. – 2019. – Vol. 14. – P. 331–344. https://doi.org/10.2217/fmb-2018-0333


9. Hu, Q. Progress on the antimicrobial activity research of clove oil and eugenol in the food antisepsis field / Q. Hu, M. Zhou, S. Wei // J. Food Sci. – 2018. – Vol. 83, Issue 6. – P. 1476–1483. https://doi.org/10.1111/1750-3841.14180


10. Antimicrobial activity of eugenol and essential oils containing eugenol : A mechanistic viewpoint / A. Marchese, R. Barbieri, E. Coppo et al. // Crit. Rev. Microbiol. – 2017. – Vol. 43, Issue 6. – P. 668–689. https://doi.org/10.1080/1040841x.2017.1295225


11. In silico and in vitro investigation of the antifungal activity of isoeugenol against Penicillium citrinum / S. B. Ferreira, T. B. Dantas, D. de Figuerêdo Silva et al. // Curr. Top. Med. Chem. – 2018. – Vol. 18, Issue 25. – P. 2186–2196. https://doi.org/10.2174/1568026619666181130141818


12. Anti-oxidant and anti-inflammatory effects of cinnamaldehyde and eugenol on mononuclear cells of rheumatoid arthritis patients / S. Mateen, M. T. Rehman, S. Shahzad et al. // Eur. J. Pharmacol. – 2019. – Vol. 852. – P. 14–24. https://doi.org/10.1016/j.ejphar.2019.02.031

 

13. Synthesis of eugenol derivatives and its anti-inflammatory activity against skin inflammation / A. K. Maurya, K. Agarwal, A. C. Gupta et al. // Nat. Prod. Res. – 2018. – P. 1–10. https://doi.org/10.1080/14786419.2018.1528585


14. An overview on the anti-inflammatory potential and antioxidant profile of eugenol / J. N. Barboza, C. da Silva Maia Bezerra Filho, R. O. Silva et al. // Oxid. Med. Cell. Longev. – 2018. – Vol. 2018. – P. 1–9. https://doi.org/10.1155/2018/3957262


15. Tsuchiya, H. Anesthetic agents of plant origin: a review of phytochemicals with anesthetic activity / H. Tsuchiya // Molecules. – 2017. – Vol. 22, Issue 8. – P. 1369. https://doi.org/10.3390/molecules22081369


16. Phytochemical analysis, cytotoxic and antioxidant activities of Myrtus communis essential oil from Morocco / Y. Harassi, M. Tilaoui, A. Idir, J. Frédéric, S. Baudino, S. Ajouaoi, H. A. Mouse, A. Zyad // J. Complement. Integr. Med. – 2019.

https://doi.org/10.1515/jcim-2018-0100


17. Anti-metastatic and anti-proliferative activity of eugenol against triple negative and HER2 positive breast cancer cells / M. L. Abdullah, M. M. Hafez, A. Al-Hoshani, O. Al-Shabanah // BMC Complement Altern. Med. – 2018. – Vol. 18, Issue 1. – P. 321. https://doi.org/10.1186/s12906-018-2392-5


18. Federation of American Societies for Experimental Biology. (1973). Evaluation of health aspects of oil of cloves as a food ingredient. Life Sciences Research Office. Report no SCOGS-19; U.S. Food and Drug Administration. [Електронний ресурс]. – Режим доступу : http://www.faseb.org/Portals/2/PDFs/LSRO_Legacy_Reports/1973_SCOGS-19%20Oil%20of%20Cloves.pdf


19. Kegley, S. Marin Municipal Water District. Herbicide Risk Assessment. Chapter 6. Clove Oil (Eugenol) / S. Kegley, E. Conlisk, M. Moses. – Berkeley: Pesticide Research Institute, 2010. – 25 p. [Електронний ресурс]. – Режим доступу : https://www.marinwater.org/DocumentCenter/View/259/Herbicide-Risk-Assessment-Chapter-1-Summary-January-10-2010


20. Elgendy, E. M. Oxidation reactions of some natural volatile aromatic compounds : anethole and eugenol / E. M. Elgendy, S. A. Khayyat // Russ. J. Organ. Chem. – 2008. – Vol. 44, Issue 6. – P. 823–829. https://doi.org/10.1134/s1070428008060079


21. Naboka, V. M. Quantum-chemical investigation of the mechanism of euvgenol and isoeugenol epoxidation by peracetic acid / V. M. Naboka, O. M. Agafonov // Topical issues of new drugs development: Abstracts оf International Scientific and Practical Conference of Young Scientists and Students (April 23, 2015, Kharkiv). – Kharkiv : NUPh, 2015. – P. 90–91.


22. Gaussian 09, Revision A.02 / M. J. Frisch, G. W. Trucks, H. B. Schlegel et al. – Gaussian, Inc., Wallingford CT, 2009.


23. Губен-Вейль. Методы органической химии: в 2 т. / Губен-Вейль. – М. : Химия, 1967. – Т. 2. – 1032 с.





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