Hydrocarbons and Ethers of Extractive Substances of Siberian Larch Needles

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UDС

634.0.813.2

DOI:

https://doi.org/10.37482/0536-1036-2021-3-170-185

Abstract

Siberian larch (Larix sibirica L.) is the main commercial species in Russia. Currently, larch woody greens are underutilized. They are considered a waste product from logging. This is due to the lack of knowledge on the composition of compounds and the variability of the raw material source itself as a result of the fall of the needles. The research purpose is to study the composition of hydrocarbons and esters from Siberian larch needles in summer and autumn collection from the Tomsk region. The shredded needles were extracted with propan- 2-ol; then, after distillation of the solvent, substances soluble in petroleum ether (PE, 40–70 °С) were isolated. The latter were divided into free acids (31.5 % for green needles and 28.0 % for yellow needles) and neutral substances (59.8 and 48.1 %, respectively). Then, neutral substances were chromatographed on silica gel: hydrocarbons (2.43 and 3.02 %, hereinafter from neutral substances of green and yellow needles, respectively), esters (31.30 and 33.80 %) and triglycerides (11.70 % and 6.44 %). The ester and triglyceride fractions were exposed to alkaline hydrolysis and the acidic components of esters (9.12 and 24.80 %) and triacylglycerols (17.43 and 26.15 %) were produced. Fractions of unsaponifiable compounds, in addition to alcohols, contained unsaponifiables with unchanged Rf values on thin-layer chromatography (TLC). Fractions of unsaponifiables were chromatographed on silica gel, and then the isolated fractions were additionally chromatographed on silica gel with silver nitrate. The isolated compounds were identified by nuclear magnetic resonance (NMR) spectroscopy. In the acidic component of esters, the main components are linoleic and linolenic acids. Hydrocarbons are represented by sesquiterpenes in both collections of needles. A new aromatic hydrocarbon for coniferous plants, geranyl-p-cymene, has been identified. For the first time, polyprenols were isolated from Siberian larch greens, the structure of which differs from spruce and pine polyprenols by chain length according to NMR spectroscopy and mass spectrometry data. They contain from 14 to 20 isoprene links in the chain of molecules with predominance of prenol-17. The yield of polyprenols was 12.8–14.9 % of neutral substances of yellow and green needles, respectively. Tetracyclic triterpene alcohols and sterols were isolated from green needles. Triterpene alcohols were not found in yellow needles.

Authors

Darya S. Mikson, Assistant; ResearcherID: AAK-1624-2020, ORCID: https://orcid.org/0000-0001-7828-2966
Viktor I. Roshchin, Doctor of Chemistry, Prof.; ResearcherID: AAK-4435-2020, ORCID: https://orcid.org/0000-0002-5410-9496

Affiliation

Saint Petersburg State Forest Technical University, Institutskiy per., 5, Saint Petersburg, 194021, Russian Federation; e-mail: ms.mikson@mail.ru, kaf.chemdrev@mail.ru

Keywords

Larix sibirica, woody greens, needles, hydrocarbons, esters, fatty acids, geranylpcymen, polyprenols

For citation

Mikson D.S., Roshchin V.I. Hydrocarbons and Ethers of Extractive Substances of Siberian Larch Needles. Lesnoy Zhurnal [Russian Forestry Journal], 2021, no. 3, pp. 170–185. DOI: 10.37482/0536-1036-2021-3-170-185

References

1. Bobrov E.G. Forest-Forming Conifers of the USSR. Leningrad, Nauka Publ., 1978. 189 p.
3. Dylis N.V. Siberian Larch: Materials on Systematics, Geography and History. Moscow, MOIP Publ., 1947. 137p.
4. Karaman Yu.K., Lobanova E.G. Endocannabinoids and Eicosamoids: Biosynthesis and Interactions with Immune Response. Meditsinskaya immunologiya [Medical Immunology], 2013, vol. 15, no. 2, pp. 119–130. DOI: https://doi.org/10.15789/1563-0625-2013-2-119-130
5. Mikson D.S., Roshchin V.I. Hydrocarbons of Neutral Substances of Siberian Larch Needles of Different Vegetation Periods. New Advances in Chemistry and Chemical Technology of Plant Raw Materials: Proceedings of the VII All-Russian Conference with International Participation. Barnaul, ASU Publ., 2017, pp. 223–224.
6. Mikson D.S., Roshchin V.I. The Siberian Larch Group Composition and Acid Needles at Different Vegetation Periods. Khimija Rastitel’nogo Syr’ja [Chemistry of plant raw material], 2019, no. 4, pp. 207–214. DOI: https://doi.org/10.14258/jcprm.2019045477
7. Pentegova V.A., Dubovenko Zh.V., Raldugin V.A., Shmidt E.N. Terpenoids of Coniferous Plants. Novosibirsk, Nauka Publ., 1987. 97p.
8. Plemenkov V.V. Introduction to the Chemistry of Natural Compounds. Kazan, 2001. 376 p.
9. Raldugin V.A., Korotkikh L.Ya., Yaroshenko N.I., Pentegova V.A. Regio- and Stereo- Selective Oxidation of Cementene with Selenium Dioxide. Khimiya Prirodnykh Soedinenii [Chemistry of Natural Compounds], 1978, no. 3, pp. 410–411.
10. Roshchin V.I., Baranova R.A., Beloozerskikh O.A., Solov’yev V.A. Composition of Extractive Substances of Needles and Shoots of Norway Spruce. Wood chemistry, 1983, no. 4, pp. 56–61.
11. Rysin L.P. Conifer Forests of Russia. Izvestiya Samarskogo nauchnogo tsentra Rossiyskoy akademii nauk [Izvestia of Samara Scientific Center of the Russian Academy of Sciences], 2012, vol. 14, no. 1(4), pp. 1106–1109.
12. Tkachev A.V. Study of Volatile Substances of Plants. Novosibirsk, Ofset Publ., 2008. 969 p.
13. Tomchuk R.I., Tomchuk G.N. Woody Greens and Their Use in the National Economy. Moscow, Lesnaya promyshlennost’ Publ., 1973. 360 p.
14. Troshina A.V., Roshchin V.I. Hydrocarbons of Neutral Substances from the Branch Bark of Siberian Larch. Izvestiya akademii nauk. Seriya khimicheskaya [Russian Chemical Bulletin], 2014, no. 9, pp. 2160–2168. DOI: https://doi.org/10.1007/s11172-014-0714-4
15. Alan S., Kürkçüoğlu M., Başer K.H.C. The Composition of the Essential Oils of Calamintha pamphylica Subspecies. Turkish Journal of Biology, 2011, vol. 35, no. 2, pp. 259–265. DOI: https://doi.org/10.3906/biy-0806-12
16. Calder P.C. Very Long-Chain n-3 Fatty Acids and Human Health: Fact, Fiction and the Future. Proceedings of the Nutrition Society, 2018, vol. 77, iss. 1, pp. 52–72. DOI: https://doi.org/10.1017/S0029665117003950
17. Flatt V.D., Campos C.R., Kraemer M.P., Bailey B.A., Satyal P., Setzer W.N. Compositional Variation and Bioactivity of the Leaf Essential Oil of Montanoa guatemalensis from Monteverde, Costa Rica: A Preliminary Investigation. Medicines, 2015, vol. 2(4), pp. 331–339. DOI: https://doi.org/10.3390/medicines2040331
18. Layé S., Nadjar A., Joffre C., Bazinet R.P. Anti-Inflammatory Effects of Omega-3 Fatty Acids in the Brain: Physiological Mechanisms and Relevance to Pharmacology. Pharmacological Reviews, 2018, vol. 70(1), pp. 12–38. DOI: https://doi.org/10.1124/pr.117.014092
19. Salem M., Zeidler A., Böhm M. GC/MS Analysis of Oil Extractives from Wood and Bark of Pinus sylvestris, Abies alba, Picea abies and Larix decidua. Bioresources, 2016, vol. 10, no. 4, pp. 7725–7737. DOI: https://doi.org/10.15376/biores.10.4.7725-7737
20. Silk P.J., Mayo P.D., LeClair G., Brophy M., Pawlowski S., MacKay K., Hillier N.K., Hughes C., Sweeney J.D. Semiochemical Attractants for the Beech Leaf-Mining Weevil, Orchestes fagi. Entomologia Experimentalis et Applicata, 2015, vol. 164, iss. 2, pp. 102–112. DOI: https://doi.org/10.1111/eea.12603