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Chemistry of Natural Compounds

, Volume 44, Issue 6, pp 719–723 | Cite as

Synthesis of lomazarin and norlomazarin, pigments from Lomandra hastilis

  • D. N. PelageevEmail author
  • M. N. Panchenko
  • N. D. Pokhilo
  • V. A. Denisenko
  • V. F. Anufriev
Article

5,8-Dihydroxy-2,3,6-trimethoxy-7-ethyl-1,4-naphthoquinone (1) was used to synthesize in high yield 5,8-dihydroxy-7(1′-hydroxyethyl)-2,3,6-trimethoxy-1,4-naphthoquinone (lomazarin, 3), a pigment from Lomandra hastilis. Alkaline hydrolysis of lomazarin produced mainly 5,6,8-trihydroxy-2,3-dimethoxy-1,4-naphthoquinone (9) through a retro-aldol decomposition of the 6-keto-form of 5,6,8-trihydroxy-7(1′-hydroxyethyl)-2,3-dimethoxy-1,4-naphthoquinone (13b) formed during the reaction. 2,5,8-Trihydroxy-7(1′-hydroxyethyl)-3,6-dimethoxy-1,4-naphthoquinone (norlomazarin, 4a), a pigment of L. hastilis, and its 3,5,8-trihydroxy-7(1′-hydroxyethyl)-2,6-dimethoxy isomer 4b were formed as a difficultly separable mixture in addition to quinone 9.

Key words

echinochrome trimethyl ether lomazarin norlomazarin Lomandra hastilis retro-aldol reaction spinochrome D dimethyl ether Echinotrix calamaris tricrozarin B Tritonia crocosmaeflora 

Notes

Acknowledgment

The work was financially supported partially by a grant of the RAS Presidium (Molecular and Cellular Biology Program), the interdisciplinary integrated project of the Far-East and Siberian Branches of the RAS (No. 07-II-CO-05-020), a grant of the RFBR No. 06-04-96974, and State Contract No. 02.522.11.2013.

References

  1. 1.
    R. E. Moore, H. Singh, C. W. J. Chang, and P. J. Scheuer, Tetrahedron, 23, 3271 (1967).CrossRefGoogle Scholar
  2. 2.
    V. P. Anufriev and V. L. Novikov, Tetrahedron Lett., 36, 2515 (1995).CrossRefGoogle Scholar
  3. 3.
    R. H. Thomson, Naturally Occurring Quinones, 2nd Ed., Academic Press, London-New York (1971), p. 734.Google Scholar
  4. 4.
    R. H. Thomson, Naturally Occurring Quinones, 3rd Ed., Chapman & Hall, London-New York (1987).Google Scholar
  5. 5.
    R. H. Thomson, Naturally Occurring Quinones, 4th Ed., Blackie Academic and Professional, London-New York (1997), p. 746.Google Scholar
  6. 6.
    V. A. Anufriev, G. B. Elyakov, S. G. Polonik, N. D. Pokhilo, O. P. Shestak, A. Y. Yakubovskaya, S. A. Osadchii, G. A. Tolstikov, and E. E. Shul’ts, RF Pat. No. 2,277,083 (2006); Byull. Izobret., No. 15 (2006).Google Scholar
  7. 7.
    S. G. Polonik, N. D. Pokhilo, V. V. Makhan’kov, and V. F. Anufriev, Khim. Prir. Soedin., 73 (2008).Google Scholar
  8. 8.
    G. B. Elyakov, O. B. Maksimov, N. P. Mishchenko, E. A. Kol’tsova, S. A. Fedoreev, L. I. Glebko, N. P. Krasovskaya, and A. A. Artyukov, RF Pat. No. 2,137,472 (1999); Byull. Isobret., No. 26 (1999); RF Pat. No. 2,134,107 (1999); Byull. Izobret., No. 22 (1999).Google Scholar
  9. 9.
    R. G. Cooke and J. B. Robinson, Aust. J. Chem., 23, 1695 (1970).Google Scholar
  10. 10.
    J. R. Cannon, Y. Matsuki, V. A. Patrick, and A. H. White, Aust. J. Chem., 40, 1191 (1987).Google Scholar
  11. 11.
    N. D. Pokhilo, M. I. Kiseleva, V. V. Makhan’kov, and V. F. Anufriev, Khim. Prir. Soedin., 228 (2008).Google Scholar
  12. 12.
    K. Masuda, S. Funayama, K. Komiyama, and I. Umezava, J. Nat. Prod., 50, 958 (1987).PubMedCrossRefGoogle Scholar
  13. 13.
    G. V. Malinovskaya, A. Ya. Chizhova, and V. F. Anufriev, Izv. Akad. Nauk Ser. Khim., 1019 (1999).Google Scholar
  14. 14.
    V. Karnojitzki, Les Peroxides Organiques, Hermann, 6 Rue de la Sorbonne, Paris V (1958).Google Scholar
  15. 15.
    W. Bachmann and W. Struve, in: Organic Reactions, R. Adams, ed., J. Wiley and Sons, New York (1942).Google Scholar

Copyright information

© Springer Science+Business Media, Inc. 2008

Authors and Affiliations

  • D. N. Pelageev
    • 1
    Email author
  • M. N. Panchenko
    • 2
  • N. D. Pokhilo
    • 1
  • V. A. Denisenko
    • 1
  • V. F. Anufriev
    • 1
  1. 1.Pacific Institute of Bioorganic Chemistry, Far-East BranchRussian Academy of Sciences, Russian Federation100-Letiya VladivostokaRussia
  2. 2.Institute of Chemistry and Applied EcologyFar-East State University, Russian Federationul. Oktyabr’skayaRussia

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