Address: 17 Naberezhnaya Severnoy Dviny, Arkhangelsk 163002 Russian Federation. Northern (Arctic) Federal University named after M.V.Lomonosov. Office 1425

Phone / Fax: (818-2) 21-61-18
E-mail: forest@narfu.ru
http://lesnoizhurnal.ru/en/

RussianEnglish



Archive

Identification of the Crystalline Product of Liquid-Phase Oxidation of α-Pinene with Atmospheric Oxygen in the Presence of Cobalt (II) Stearate

Версия для печати
Creative Commons License
These works are licensed under a Creative Commons Attribution 4.0 International License.

A.A. Sosnovskaya, V.L. Fleisher

Complete text of the article:

Download article (pdf, 1.4MB )

UDС

547.596.092.1

DOI:

10.37482/0536-1036-2021-4-173-180

Abstract

One of the possible directions of liquid-phase oxidation of α-pinene by atmospheric oxygen leads to the formation of a mixture of terpene oxygen-containing compounds (epoxides, alcohols, ketones, etc.). The problem of this direction is the formation of a large amount of 2,3-epoxypinane which over time turns into trans-sobrerol, campholene aldehyde, trans-pinocarveol, trans-carveol, and trans-3-pinen-2-ol as a result of hydrolysis. One of the abovementioned substances with a solid crystalline structure is trans-sobrerol. Sobrerol is widely used in perfumery for synthesis of synthetically fragrant substances and pharmaceutical industry, in particular, it is a part of medicines with mucolytic action, as well as in the treatment of headaches and diseases such as rhinorrhea and chronic bronchitis. The aim of this work is to identify a crystalline product produced by liquid-phase oxidation of α-pinene with atmospheric oxygen in the presence of cobalt (II) stearate. The process of liquid-phase oxidation was carried out in the following conditions: temperature – 70 °С, air consumption – 16.67 cm3/s, duration – 5 h, amount of catalyst – 0.2–0.5 wt.%. Then the mixture was exposed to steam distillation in order to separate monomers (they contain terpene oxygen-containing compounds and hydrocarbons) from polymers. As a result of settling and storage of the mixture, crystals were found and isolated from the mother liquor solution. Their identification was carried out using IR and 13C NMR spectroscopy as well as scanning electron microscopy. It was found that the spatial organization of the isolated crystals and the standard sample (Sigma Aldrich) is represented by multilayer rectangular plates. Analysis of the IR spectra of the crystals showed that the absorption band at a wave number of 3318 cm–1 corresponds to intramolecular and intermolecular hydrogen bonds in hydroxyl groups, at wave numbers of 2887, 2935,2975 cm–1 it corresponds to methyl groups. The results obtained are comparable with the results of the IR-spectrum of the standard sample. Given the results of previous studies of 1H NMR spectrum [15] and 13C NMR spectrum, it was determined that the resulting crystalline product of liquid-phase oxidation of α-pinene is trans-sobrerol.

Authors

Alexandra A. Sosnovskaya, Postgraduate Student; ResearcherID: AAK-1321-2021, ORCIDhttps://orcid.org/0000-0001-7556-2284
Viachaslau L. Fleisher, Candidate of Engineering, Assoc. Prof.; ResearcherID: AAM-6580-2021, ORCID: https://orcid.org/0000-0003-2997-7707
e-mail: a.sosnovskaya94@gmail.comv_fleisher@list.ru

Affiliation

Belarusian State Technological University, Sverdlova str., 13a, Minsk, 220006, Republic of Belarus

Keywords

α-pinene, trans-sobrerol, verbenol, verbenone, liquid-phase oxidation, cobalt (II) stearate, α-pinene epoxide

For citation

Sosnovskaya A.A., Fleisher V.L. Identification of the Crystalline Product of Liquid-Phase Oxidation of α-Pinene with Atmospheric Oxygen in the Presence of Cobalt (II) Stearate. Lesnoy Zhurnal [Russian Forestry Journal], 2021, no. 4, pp. 173–180. DOI: 10.37482/0536-1036-2021-4-173-180

References

1. Alekseev I.N., Ipatova E.U., Frolova L.L. Monoterpenoids NMR and IR Spectra Atlas. Moldova, LAP LAMBERT Academic Publishing, 2017. 380 p.

2.  Bukharkina T.V., Verzhichinskaya S.V., Grechishkina O.S., Karadzhev M.A. Preparation of Ethylbenzene for Reproducible Experiment on Its Liquid-Phase Oxidation by Molecular Oxygen in Presence of Cobalt Stearate. Uspekhi v khimii i khimicheskoy tekhnologii [Advances in Chemistry and Chemical Technology], 2016, vol. 30, no. 11, pp. 41–43.

3. Verzhichinskaya S.V., Malinkin D.A., Scharipov D.A. Scheme of Transformations in Induction Period of Liquid Phase Oxidation of Ethylbenzene by Atmospheric Oxygen in the Presence of Cobalt Stearate. Uspekhi v khimii i khimicheskoy tekhnologii [Advances in Chemistry and Chemical Technology], 2014, vol. 28, no. 10, pp. 35–38.

4. Il’ina I.I., Maksimchuk N.V., Semikolenov V.A. Catalytic Synthesis of Aromatic Substances from Plant Monoterpenes. Rossijskij himicheskij zhurnal [Russian Journal of General Chemistry], 2004, vol. XLVIII, no. 3, pp. 38–53.

5. Kislitsin A.N., Klabukova I.N., Kosyukova L.V., Trofimov A.N. Investigation of the Process of Liquid-Phase Initiated Oxidation of α-Pinene by Atmospheric Oxygen. Message 1. Khimija Rastitel’nogo Syr’ja [Chemistry of plant raw material], 2003, no. 1, pp. 53–59.

6. Kislitsin A.N., Klabukova I.N., Trofimov A.N. Investigation of the Process of Liquid-Phase Initiated Oxidation of α-Pinene by Atmospheric Oxygen. Message 2. Khimija Rastitel’nogo Syr’ja [Chemistry of plant raw material], 2003, no. 4, pp. 31–36.

7. Kislitsin A.N., Klabukova I.N., Trofimov A.N. On the Chemistry of Liquid-Phase Oxidation of α-Pinene by Atmospheric Oxygen. Khimija Rastitel’nogo Syr’ja [Chemistry of plant raw material], 2004, no. 3, pp. 109–116.

8. Men’shikov S.Yu., Mishina Yu.V., Mikushina Yu.V., Ostroushko A.A. A Comparative Study of Aerobic Oxidation of Turpentine. Zhurnal prikladnoy khimii [Russian Journal of Applied Chemistry], 2008, vol. 81, iss. 1, pp. 56–58. DOI: https://doi.org/10.1134/S1070427208010126

9.  Patlasov V.P., Savinykh, V.I. Kushnir S.R. Lukoyanov V.P. Investigation of the Continuous Process of Oxidation of α-Pinene. Lesnoy Zhurnal [Russian Forestry Journal], 1999, no. 5, pp. 75–81.

10. Perkel’ A.L., Voronina S.G., Buneyeva V.V., Nepomnyashchikh I.M., Nosacheva I.M. Peroxide Precursors of Carbon Chain Degradation in the Processes of Liquid-Phase Oxidation of Saturated Compounds at the Stages Following the Formation of Alcohol and Ketone. Vestnik Kuzbasskogo gosudarstvennogo tekhnicheskogo universiteta [Bulletin of the Kuzbass State Technical University], 2003, no. 5, pp. 92–103.

11. Rakhimov A.I. Chemistry and Technology of Organic Peroxide Compounds. Moscow, Khimiya Publ., 1979. 392 p.

12. Sosnovskaya A.A., Fleisher V.L. The Co2+/H2O2 System as a Catalyst for the Liquid-Phase Oxidation of α-Pinene. Technology of Organic Substances: Proceedings of the 83rd Scientific and Technical Conference. Minsk, BSTU Publ., 2019, p. 18.

13. Sosnovskaya A.A., Fleisher V.L. Investigation of the Structure of Crystalline Product of Liquid-Phase Oxidation of α-Pinene by Atmospheric Oxygen in the Presence of Cobalt (II) Stearate X-Ray Diffraction Analysis, IR- and NMR-Spectroscopy. Technology of Organic Substances: Proceedings of the 84rd Scientific and Technical Conference. Minsk, BSTU Publ., 2020, pp. 30–32.

14. Sosnovskaya A.A., Fleisher V.L., Borkina Y.V. Optimization of Liquid-Phase α-Pinene Oxidation with Oxygen in Presence of Cobalt (II) Stearate. Vestsi Natsyyanal’nai akademii navuk Belarusi. Seryya khimichnykh navuk [Proceedings of the National Academy of Sciences of Belarus. Chemical series], 2019, vol. 55, no. 2, pp. 233–239. DOI: https://doi.org/10.29235/1561-8331-2019-55-2-233-239

15. Hawkins E.G.E. Organic Peroxides: Their Formation and Reactions. Trans. from English. Moscow, Khimiya Publ., 1964. 536 p.

16. Emanuel’ N.M., Denisov E.T., Mayzus Z.K. Chain Reactions of Oxidation of Hydrocarbons in the Liquid Phase. Moscow, Nauka Publ., 1965. 375 p.

17. Emanuel’ N.M., Zaikov G.E., Mayzus Z.K. The Role of the Medium in Radical Chain Reactions of Oxidation of Organic Compounds. Moscow, Nauka Publ., 1973. 278 p.

18. Allal B.A., Firdoussi L.E., Allaoud S., Katim A., Castanet Y., Mortreux A. Catalytic Oxidation of α-Pinene by Transition Metal Using t-Butyl Hydroperoxide and Hydrogen Peroxide. Journal of Molecular Catalysis A: Chemical, 2003, vol. 200, iss. 1-2, pp. 177–184. DOI: https://doi.org/10.1016/S1381-1169(03)00038-4

19. Becerra J.-A., Villa A.-L. Thermodynamic Analysis of α-Pinene and Limonene Allylic Oxidation over a FePcCl16-NH2-SiО2 Catalyst. Chemical Engineering & Technology, 2018, vol. 41, iss. 1, pp. 124–133. DOI: https://doi.org/10.1002/ceat.201700118

20. Durbetaki A.J., Linder S.M. Preparation of Sobrerol. Patent US, no. 2949489, 1960.

21. Lajumen M.K., Maunula T., Koskinen A.M.P. Co(II) Catalysed Oxidation of α-Pinene by Molecular Oxygen. Part 2. Tetrahedron, 2000, vol. 56, iss. 41, pp. 8167–8171. DOI: https://doi.org/10.1016/S0040-4020(00)00742-0

22. Naróg D., Szczepani A., Sobkowiak A. Iron(II, III)-Catalyzed Oxidation of Limonene by Dioxygen. Catalysis Letters, 2008, vol. 120, iss. 3-4, pp. 320–325. DOI: https://doi.org/10.1007/s10562-007-9290-7

23. Oliveira P., Rojas-Cervantes M.L., Ramos A.M., Fonseca I.M., Botelho do Rego A.M., Vital J. Limonene Oxidation over V2O5/TiO2 Catalysts. Catalysis Today, 2006, vol. 118, iss. 3-4, pp. 307–314. DOI: https://doi.org/10.1016/j.cattod.2006.07.032

24. Sun Kw.K., Jeongi Ch., Sup P.S., Gun Ch.S., Soo Kw.S., Kwang-Pyo L., Min L.S. Composition for Preventing or Treating Muscle Weakness Related Diseases Comprising Sobrerol. Patent WO, no. WO 2017043935 A1, 2017.


Identification of the Crystalline Product of Liquid-Phase Oxidation of α-Pinene with Atmospheric Oxygen in the Presence of Cobalt (II) Stearate

 

Make a Submission


ADP_cert_2024.png

Lesnoy Zhurnal (Russian Forestry Journal) was awarded the "Seal of Recognition for Active Data Provider of the Year 2024"

INDEXED IN: 

scopus.jpg

DOAJ_logo-colour.png

logotype.png

Логотип.png