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Oxyfunctionalization of natural terpenes catalyzed by La1−xSrxMnO3 in water as solvent: an experimental and theoretical study

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Abstract

The catalytic behavior of La0.4Sr0.6MnO3 (PM3), La0.8Sr0.2MnO3 (PM2), and LaMnO3 (PM1) has been studied in the oxidation of natural terpenes (α-pinene, β-pinene, limonene, and valencene) in water. To find the best catalytic performance, several parameters were investigated such as the catalyst amount, the nature of the oxidant agent, the oxidant ratio, the temperature, the reaction time, and the nature of the solvent with the α-pinene as the model substrate. PM3 catalyst exhibited the best activity in the oxidation reaction using hydrogen peroxide as an oxidant agent giving a good yield towards verbenone with 50%. The recyclability of the catalyst performances showed remarkable stability after four cycles. Moreover, the photocatalytic mechanism of α-pinene using La1−xSrxMnO3 catalyst was performed through the density functional theory method, and the possible attack site for the photocatalytic reaction between α-pinene and the hydroperoxyl radical (⋅OOH) was predicted using the condensed Fukui function and obtained findings are in good agreement with the experimental results.

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References

  1. Denicourt-Nowicki A, Rauchdi M, Ali MA, Roucoux A (2019) Catalytic oxidation processes for the upgrading of terpenes: state-of-the-art and future trends. Catalysts 9:893. https://doi.org/10.3390/catal9110893

    Article  CAS  Google Scholar 

  2. Sheldon RA, Van Bekkum H (2007) Fine chemicals through heterogeneous catalysis

  3. Zhang W, Jiang P, Wang Y et al (2014) Selective oxidation over a metalloporphyrinic metal–organic framework catalyst and insights into the mechanism of bicarbonate ion as co-catalyst. Chem Eng J 257:28–35. https://doi.org/10.1016/j.cej.2014.07.045

    Article  CAS  Google Scholar 

  4. Chen J, Jiang Q-D, Chai Y-P et al (2016) Natural terpenes as penetration enhancers for transdermal drug delivery. Molecules 21:1709. https://doi.org/10.3390/molecules21121709

    Article  CAS  PubMed  PubMed Central  Google Scholar 

  5. Mander S, Kim DH, Thi Nguyen H et al (2019) SP-8356, a (1S)-(–)-verbenone derivative, exerts in vitro and in vivo anti-breast cancer effects by inhibiting NF-κB signaling. Sci Rep 9:6595. https://doi.org/10.1038/s41598-019-41224-y

    Article  CAS  PubMed  PubMed Central  Google Scholar 

  6. Selvaraj M, Kandaswamy M, Park DW, Ha CS (2010) Highly efficient and clean synthesis of verbenone over well ordered two-dimensional mesoporous chromium silicate catalysts. Catal Today 158:286–295. https://doi.org/10.1016/j.cattod.2010.03.061

    Article  CAS  Google Scholar 

  7. Wang H, Cheng H, Lai F, **ong D (2022) CuAPO-5 as a multiphase catalyst for synthesis of verbenone from α-pinene. Materials 15:8097. https://doi.org/10.3390/ma15228097

    Article  CAS  PubMed  PubMed Central  Google Scholar 

  8. Desai NC, Chudasama JA, Patel BY et al (2017) Catalysis by the entangled complexes in matrix structure of zeolite-Y over α-pinene. Microporous Mesoporous Mater 242:245–255. https://doi.org/10.1016/j.micromeso.2017.01.023

    Article  CAS  Google Scholar 

  9. Mdletshe LS, Makgwane PR, Ray SS (2019) Fabrication of bimetal CuFe2O4 oxide redox-active nanocatalyst for oxidation of pinene to renewable aroma oxygenates. Nanomaterials 9:1140. https://doi.org/10.3390/nano9081140

    Article  CAS  PubMed  PubMed Central  Google Scholar 

  10. Becerra JA, González LM, Villa AL (2016) Kinetic study of α-pinene allylic oxidation over FePcCl16–NH2–SiO2 catalyst. J Mol Catal A Chem 423:12–21. https://doi.org/10.1016/j.molcata.2016.05.029

    Article  CAS  Google Scholar 

  11. Aberkouks A, Mekkaoui AA, Ait Ali M et al (2020) Selective allylic oxidation of terpenic olefins using Co–Ag supported on SiO2 as a novel, efficient, and recyclable catalyst. J Chem 2020:1–11. https://doi.org/10.1155/2020/1241952

    Article  CAS  Google Scholar 

  12. Rauchdi M, Ait Ali M, Roucoux A et al (2017) Novel access to verbenone via ruthenium nanoparticles-catalyzed oxidation of A-pinene in neat water Novel access to verbenone via ruthenium nanoparticles-catalyzed oxidation of α-pinene in neat water. Appl Catal A Gen. https://doi.org/10.1016/j.apcata.2017.11.016ï

    Article  Google Scholar 

  13. Hasnaoui A, Fkhar L, Nayad A et al (2020) Synthesis and characterization of magnetic perovskites La1–xSrxMnO3: green catalyst for oxidation of olefins in aqueous medium. Inorg Chem Commun 116:107892. https://doi.org/10.1016/j.inoche.2020.107892

    Article  CAS  Google Scholar 

  14. Frisch MJ, Trucks GW, Schlegel HB et al (2009) Fox, Gaussian 09, Revision D.01. Gaussian Inc, Wallingford

    Google Scholar 

  15. Becke AD (1993) Density-functional thermochemistry. III. The role of exact exchange. J Chem Phys 98:5648–5652. https://doi.org/10.1063/1.464913

    Article  CAS  Google Scholar 

  16. Roy LE, Hay PJ, Martin RL (2008) Revised basis sets for the LANL effective core potentials. J Chem Theory Comput 4:1029–1031. https://doi.org/10.1021/ct8000409

    Article  CAS  PubMed  Google Scholar 

  17. Lee C, Yang W, Parr RG (1988) Development of the Colle-Salvetti correlation-energy formula into a functional of the electron density. Phys Rev B 37:785–789. https://doi.org/10.1103/PhysRevB.37.785

    Article  CAS  Google Scholar 

  18. Reed AE, Curtiss LA, Weinhold F (1988) Intermolecular interactions from a natural bond orbital, donor-acceptor viewpoint. Chem Rev 88:899–926. https://doi.org/10.1021/cr00088a005

    Article  CAS  Google Scholar 

  19. Geerlings P, De Proft F, Langenaeker W (2003) Conceptual density functional theory. Chem Rev 103:1793–1874. https://doi.org/10.1021/cr990029p

    Article  CAS  PubMed  Google Scholar 

  20. Yunphuttha C, Porntheeraphat S, Midpanon S et al (2018) Improving the catalytic activity of lanthanum manganese oxide with strontium do** for hydrogen peroxide reduction reaction in micro direct alcohol-hydrogen peroxide fuel cell. J Power Sources 392:251–259. https://doi.org/10.1016/j.jpowsour.2018.04.072

    Article  CAS  Google Scholar 

  21. Lee YN, Lago RM, Fierro JLG, González J (2001) Hydrogen peroxide decomposition over Ln1−xAxMnO3 (Ln = La or Nd and A = K or Sr) perovskites. Appl Catal A Gen 215:245–256. https://doi.org/10.1016/S0926-860X(01)00536-1

    Article  CAS  Google Scholar 

  22. Li** S, Lihua H, Hui Z et al (2008) La substituted Sr2MnO4 as a possible cathode material in SOFC. J Power Sources 179:96–100. https://doi.org/10.1016/j.jpowsour.2007.12.090

    Article  CAS  Google Scholar 

  23. Librando V, Tringali G (2005) Atmospheric fate of OH initiated oxidation of terpenes. Reaction mechanism of α-pinene degradation and secondary organic aerosol formation. J Environ Manag 75:275–282. https://doi.org/10.1016/j.jenvman.2005.01.001

    Article  CAS  Google Scholar 

  24. Ancel JE, Maksimchuk NV, Simakova IL, Semikolenov VA (2004) Kinetic peculiarities of α-pinene oxidation by molecular oxygen. Appl Catal A Gen 272:109–114. https://doi.org/10.1016/j.apcata.2004.05.020

    Article  CAS  Google Scholar 

  25. Grzeszczak J, Wróblewska A, Bosacka M et al (2023) Studies on the catalytic activities of ZSM-5 zeolites with different aluminum contents in the green oxidation of α-pinene to high value-added products. Chem Eng Res Des 192:338–349. https://doi.org/10.1016/j.cherd.2023.02.031

    Article  CAS  Google Scholar 

  26. Neuenschwander U, Guignard F, Hermans I (2010) Chemsuschem 3:75–84

    Article  CAS  PubMed  Google Scholar 

  27. Liu P, Liu X, Saburi T et al (2021) Thermal stability and oxidation characteristics of α-pinene, β-pinene and α-pinene/β-pinene mixture. RSC Adv 11:20529–20540. https://doi.org/10.1039/D1RA02235K

    Article  CAS  PubMed  PubMed Central  Google Scholar 

  28. Dong H, Xu S, Wang J et al (2019) Selective aerobic allylic oxidation of α-pinene catalyzed by metalloporphyrins in the absence of solvents and additives. J Chem Res 43:419–425. https://doi.org/10.1177/1747519819869558

    Article  CAS  Google Scholar 

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Acknowledgements

The authors thank the Center of Analysis and Characterization (CAC) of Cadi Ayyad University for the GC-MS and XRD analyses.

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Correspondence to Ali Hasnaoui.

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Hasnaoui, A., Nayad, A., Fkhar, L. et al. Oxyfunctionalization of natural terpenes catalyzed by La1−xSrxMnO3 in water as solvent: an experimental and theoretical study. Reac Kinet Mech Cat 136, 1467–1482 (2023). https://doi.org/10.1007/s11144-023-02428-6

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