Advertisement

Journal of Wood Science

, Volume 63, Issue 4, pp 360–368 | Cite as

Natural autoxidation of longifolene and anti-termite activities of the products

  • Akisato Mukai
  • Koetsu Takahashi
  • Tatsuya Ashitani
Original article

Abstract

Here, we investigated the reaction mechanism of longifolene autoxidation and the bioactivities of its products. A longifolene sample was autoxidized at 120 °C or room temperature, and the products were analyzed by gas chromatography. Longicamphenylone, norlongilactone, isolongifolic acid, longifolic acid, and longifolene–hydroxy ketone were detected as the products in the autoxidation at 120 °C. During the reaction, longifolene was converted into the other autoxidation products via the formation of longifolene oxide as an intermediate. Anti-termite activities of the longifolene and its autoxidation products were examined against a Japanese subterranean termite (Reticulitermes speratus Kolbe) by paper disk methods in Petri dishes. Longifolene and the autoxidation products exhibited anti-R. speratus activities, and all the autoxidation products had stronger termiticidal and antifeedant activities than longifolene.

Keywords

Bioactivity Longifolene Natural autoxidation Sesquiterpene Termite 

Notes

Acknowledgements

We thank Dr. Shizuo Nagahama, Professor Emeritus of Sojo University, for supplying authentic samples. This research was supported by JSPS KAKENHI (Grant No. JP15K07503).

References

  1. 1.
    Torssell K (1997) Natural product chemistry. Swedish Pharmaceutical Press, Stockholm, pp 42–79Google Scholar
  2. 2.
    Ashitani T, Nagahama S (1999) Direct episulfidation of caryophyllene and humulene. Nat Prod Lett 13:163–167CrossRefGoogle Scholar
  3. 3.
    Ashitani T, Borg-Karlson AK, Fujita K, Nagahama S (2008) Reaction mechanism of direct episulfidation of caryophyllene and humulene. Nat Prod Res 22:495–498CrossRefPubMedGoogle Scholar
  4. 4.
    Ashitani T, Kusumoto N, Borg-Karlson AK, Fujita K, Takahashi K (2013) Antitermite activity of β-caryophyllene epoxide and episulfide. Zeit Naturforsch 68C:302–306CrossRefGoogle Scholar
  5. 5.
    Ashitani T, Garboui SS, Schubert F, Vongsombath C, Liblikas I, Pålsson K, Borg-Karlson AK (2015) Activity studies of sesquiterpene oxides and sulfides from the plant Hyptis suaveolens (Lamiaceae) and its repellency on Ixodes ricinus (Acari: Ixodidae). Exp Appl Acarol 67:595–606CrossRefPubMedGoogle Scholar
  6. 6.
    Nagahama S, Tazaki M (1987) Terpenoides X. natural autoxidation of thujopsene. Bull Chem Soc Jpn 60:4453–4454CrossRefGoogle Scholar
  7. 7.
    Ashitani T (2013) Bioactivity of tree extracts—autoxidation and antitermitic activity of unutilized sesquiterpene (in Japanese). Green Spirits 8:3–7 Google Scholar
  8. 8.
    Ashitani T (2016) Anti-fungal and anti-insect properties of terpenoids (in Japanese). In: Ohira T, Miyazawa M (eds) Advanced technologies for terpenoids. CMC publishing, Tokyo, pp 74–81Google Scholar
  9. 9.
    Hirao N (1937) Pinene source in Japan (III) (in Japanese). Nippon Kagaku Kaishi 58:229–233CrossRefGoogle Scholar
  10. 10.
    Nishida K, Uota H (1937) Ueber den unterschied des gehalts an α-, und β-pinen im terpentinöl durch verschiedenheit des produktionsorts (in Japanese). J Jpn For Soc 19:298–306Google Scholar
  11. 11.
    Tsuruta K, Yoshida Y, Kusumoto N, Sekine N, Ashitani T, Takahashi K (2011) Inhibition activity of essential oils obtained from Japanese trees against Skeletonema costatum. J Wood Sci 57:520–525CrossRefGoogle Scholar
  12. 12.
    Yatagai M (2016) What are terpenoids? (in Japanese) In: Ohira T, Miyazawa M (eds) Advanced technologies for terpenoids. CMC Publishing, Tokyo, pp 1–10Google Scholar
  13. 13.
    Kasano M, Matsubara Y (1978) Oxidation of longifolene with lead tetraacetate (in Japanese). J Oleo Sci 27:309–311Google Scholar
  14. 14.
    Dimitrov V, Rentsch GH, Linden A, Hesse M (2003) The ozonolysis of longifolene: a tool for the preparation of useful chiral compounds. Configuration determination of new stereogenic centers by NMR spectroscopy and X-ray crystallography. Helv Chem 86:106–121CrossRefGoogle Scholar
  15. 15.
    Nayak UR, Dev S (1963) Studies in sesquiterpenes-XIX: action of perbenzoic acid on longifolene. Tetrahedron 19:2269–2280CrossRefGoogle Scholar
  16. 16.
    Nayak UR, Dalavoy VS, Deodhar VB (1989) Benzyltriethylammonium chloride-catalyzed permanganate oxidation of longifolene. Ind J Chem 28B:1055–1056Google Scholar
  17. 17.
    Bowman RM, Chambers A, Jackson WR (1966) The epoxidation of p-menth-1-and-3-ene. J Chem Soc C 612–615. doi: 10.1039/J39660000612
  18. 18.
    Nomura M, Fujihara Y (1988) Decomposition reaction of longifolene oxide, isolongifolene oxide and β-caryophyllene oxide with acids in the presence of synthetic zeolites. J Oleo Sci 37:97–101Google Scholar
  19. 19.
    Kusumoto N, Ashitani T, Hayasaka Y, Murayama T, Ogiyama K, Takahashi K (2009) Antitermitic activities of abietane-type diterpenes from Taxodium distichum cones. J Chem Ecol 35:635–642CrossRefPubMedGoogle Scholar
  20. 20.
    Morikawa T, Ashitani T, Kofujita H, Takahashi K (2014) Antitermitic activity of extracts from Chamaecyparis obtusa branch heartwood. Eur J Wood Wood Prod 72:651–657CrossRefGoogle Scholar
  21. 21.
    Lhomme J, Ourisson G (1964) Longifolene (VIII)—mechanism of oxidation of longifolene by peracids (in French). Bull Soc Chem Fr 5:1888–1889Google Scholar
  22. 22.
    Joshi AP, Nayak UR, Dev S (1976) Studies in sesquiterpenes-l 3-hydroxylongifolaldehyde, the elusive intermediate in the abnormal perbenzoic acid oxidation of longifolene. Tetrahedron 32:1423–1425CrossRefGoogle Scholar
  23. 23.
    Tanaka J, Takabe K, Kawakita M, Ito M (1978) Katagiri T (1978), Abnormal ozonolysis of methylenebicyclo [m. n. 1] alkanes (in Japanese). Nippon Kagaku Kaishi 2:284–287. doi: 10.1246/nikkashi.1978.284 CrossRefGoogle Scholar

Copyright information

© The Japan Wood Research Society 2017

Authors and Affiliations

  1. 1.The United Graduate School of Agricultural ScienceIwate UniversityMoriokaJapan
  2. 2.Faculty of AgricultureYamagata UniversityTsuruokaJapan

Personalised recommendations