International Journal of New Chemistry
ISC, DOAJ, CAS, Google Scholar......

Unraveling the Ozonolysis Mechanism of Terpinolene: Insights from DFT Studies

Document Type : Research Paper

Authors

Ali Azimi 1
Marjan Jebeli Javan 2
Shahin Ahmadi 3
Morteza Rouhani 1
Zohreh Mirjafary 1

1 Department of Chemistry, Science and Research Branch, Islamic Azad University, P.O. Box: 14515-775, Tehran, Iran

2 Department of Organic Chemistry, Faculty of Pharmaceutical Chemistry, Tehran medical sciences, Islamic Azad University, Tehran, Iran

3 Department of Pharmaceutical Chemistry, Faculty of Pharmaceutical Chemistry, Tehran medical sciences, Islamic Azad University, Tehran, Iran

https://doi.org/10.22034/ijnc.2024.713327
Abstract
A computational investigation of the ozonolysis of terpinolene has been fulfilled by using density functional (DFT) method. To specify primary intermediates’ formation from the ozonolysis of terpinolene, quantum chemical calculations were done. Using B3LYP method with 6-311++G(d,p) basis set, the structures were optimized for all suggested reaction mechanisms. The primary reaction steps of terpinolene ozonolysis were studied focusing on the primary ozonide formation and its fragmentation into Criegee intermediates and carbonyl compounds. Two distinct mechanistic pathways were delved into for the ozonolysis of terpinolene that results in ketone compounds. The activation energy formation of the primary ozonide intermediate in pathways 1 and 2 are 37.88 & 46.29 kcal mol-1, respectively. The results would increase the conception of the reaction mechanism of alkene ozonolysis and supply a vision into the realization the mechanism of transformation of this pollutant into non-toxic structures.

Keywords

Ozonolysis mechanism
Terpinolene
Quantum chemical calculations
DFT
Subjects
[1]        J. Hammes, A. Lutz, T. Mentel, C. Faxon, M. Hallquist, Atmospheric Chemistry and Physics., 19, 13037 (2019).
[2]        M. Glasius, AH. Goldstein, ACS Publications., 2016.
[3]        M. Hallquist, JC.Wenger, U. Baltensperger, Y. Rudich, D. Simpson, M. Claeys, J. Dommen, N. Donahue, C. George, A. Goldstein., Atmospheric Chemistry and Physics., 9, 5155 (2009).
[4]        PJ. Ziemann, R. Atkinson, Chemical Society Reviews., 41, 6582 (2012).
[5]        M. Ehn, JA. Thornton, E. Kleist, M. Sipilä, H. Junninen, I. Pullinen, M. Springer, F. Rubach, R. Tillmann, B. Lee, Nature., 506, 476 (2014).
[6]        G. McFiggans, TF. Mentel, J. Wildt, I. Pullinen, S. Kang, E. Kleist, S. Schmitt, M. Springer, R. Tillmann, C. Wu, Nature., 565, 587 (2019).
[7]        R. Mauldin Iii, T. Berndt, M. Sipilä, P. Paasonen, T. Petäjä, S. Kim, T. Kurtén, F. Stratmann,  V-M. Kerminen, M. Kulmala, Nature., 488, 193 (2012).
[8]        BC. Singer, BK. Coleman, H. Destaillats, AT. Hodgson, MM. Lunden, CJ. Weschler, WW. Nazaroff, Atmospheric Environment., 40, 6696 (2006).
[9]        G. Sarwar, R. Corsi, Atmospheric Environment., 41, 959 (2007).
[10]      S. Rossignol, C. Rio, A. Ustache, S. Fable, J. Nicolle, A. Même, B. D'anna, M. Nicolas, E. Leoz, L. Chiappini, Atmospheric Environment., 75, 196 (2013).
[11]      D. Shallcross, C. Taatjes, C. Percival, Indoor Air., 24, 495 (2014).
[12]      R. Atkinson, J. Arey, Atmospheric Environment., 37, 197 (2003).
[13]      A. Guenther, CN. Hewitt, D. Erickson, R. Fall, C. Geron, T. Graedel, P. Harley, L. Klinger, M. Lerdau, W. McKay, Journal of Geophysical Research: Atmospheres., 100, 8873 (1995).
[14]      L. Baptista, R. Pfeifer, EC. da Silva, G. Arbilla, The Journal of Physical Chemistry A., 115, 10911 (2011).
[15]      S-s. Li, X-y. Yang, Y-s. Xu, L. Jiang, RSC advances., 9, 20100, (2019).
[16]      M. Almatarneh, E. Al-Shamaileh, Z. Ahmad, A. Abu-Saleh, I. Elayan, Acta Physica Polonica A., 132, 1149 (2017).
[17]      MJ. Newland, AR. Rickard, T. Sherwen, MJ. Evans, L. Vereecken, A. Muñoz, M. Ródenas, WJ. Bloss, Atmospheric Chemistry and Physics., 18, 6095 (2018).
[18]      M.J. Frisch, G.W. Trucks, H.B. Schlegel, G.E. Scuseria, M. a. Robb, J.R. Cheeseman, G. Scalmani, V. Barone, G. a. Petersson, H. Nakatsuji, X. Li, M. Caricato, V. Marenicha., J. Bloino, B.G. Janesko, R. Gomperts, B. Mennucci, H.P. Hratchian, J. V. Ortiz, F. Izmaylova, J.L. Sonnenberg, Williams, F. Ding, F. Lipparini, F. Egidi, J. Goings, B. Peng, A. Petrone, T. Henderson, D. Ranasinghe, V.G. Zakrzewski, J. Gao, N. Rega, G. Zheng, W. Liang, M. Hada, M. Ehara, K. Toyota, R. Fukuda, J. Hasegawa, M. Ishida, T. Nakajima, Y. Honda, O. Kitao, H. Nakai, T. Vreven, K. Throssell, J.r. J. a. Montgomery, J.E. Peralta, F. Ogliaro, M.J. Bearpark, J.J. Heyd, E.N. Brothers, K.N. Kudin, V.N. Staroverov, T. a. Keith, R. Kobayashi, J. Normand, K. Raghavachari, P. Rendella., JC. Burant, S.S. Iyengar, J. Tomasi, M. Cossi, J.M. Millam, M. Klene, C. Adamo, R. Cammi, J.W. Ochterski, R.L. Martin, K. Morokuma, O. Farkas, J.B. Foresman, Fox D.J. G16_C01. 2016. p. Gaussian 16, Revision C.01, Gaussian, Inc., Wallin.
[20]      Frisch, M. J., Trucks, G. W., Schlegel, H. B., Scuseria, G. E., Robb, M. A., Cheeseman, J. R., ... & Fox, D. J. (2009). Gaussian 2009. Revision A, 2.
[19]      T. Leonardo, EC. da Silva, G. Arbilla, The Journal of Physical Chemistry A., 112, 6636 (2008).
[20]      AD. Becke, The Journal of Chemical Physics., 109, 2092 (1998).
[21]      C. Lee, W. Yang, RG. Parr, Physical Review B., 37, 785 (1988).
[22]      E. Cances, B. Mennucci, J. Tomasi, The Journal of Chemical Physics., 107, 3032 (1997).
[23]      H. Hratchian, H. Schlegel, Journal of Chemical Theory and Computation., 1, 61 (2005).
[24]      HP. Hratchian, HB. Schlegel, The Journal of Chemical Physics., 120, 9918 (2004).
[25]      K. Fukui, Accounts of Chemical Research., 14, 363 (1981).
[26]      D. Zhang, R. Zhang, Journal of the American Chemical Society., 124, 2692 (2002).
[27]      TL. Nguyen, R. Winterhalter, G. Moortgat, B. Kanawati, J. Peeters, L. Vereecken, Physical Chemistry Chemical Physics., 11, 4173 (2009).
[28]      TL. Nguyen, J. Peeters, L. Vereecken, Physical Chemistry Chemical Physics., 11, 5643 (2009).
[29]      QS. Li, J. Yang, S. Zhang, The Journal of Physical Chemistry A., 109, 9284 (2005).
[30]      http://cccbdbnistgov/
International Journal of New Chemistry
Volume 11, Issue 4
Winter 2024
Pages 443-456

Home

Reviewers