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Chemistry of the Condensed Tannin B-ring

  • Peter E. Laks

Abstract

The chemistry of the condensed tannin B-ring is closely related to that of the parent phenols — phenol, catechol, and pyrogallol. Many of the same reactions observed for the simple phenols can be reproduced on the tannin B-ring. These include esterification, etherification, and elec­trophilic addition for all the types, and metal chelation, oxidation, free-radical scavenging and ketal formation for the catechol and/or pyro­gallol related B-rings. The latter four characteristics are particularly important, contributing to the biological activity and potential utiliza­tion of the more common types of condensed tannins. The B-ring also has an important effect on the C-2 in the pyran ring. The reactivity of this position is discussed. There is a considerable amount of litera­ture available on the reactions of monomeric flavonoids. Inferences are drawn from this information about comparable reactions being possible for the condensed tannins.

Keywords

Electron Spin Resonance Condensed Tannin Oxidative Coupling Western Hemlock Coniferyl Alcohol 
These keywords were added by machine and not by the authors. This process is experimental and the keywords may be updated as the learning algorithm improves.

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References

  1. 1.
    Forrester, A.R.; Wardell, J.L. Nuclear hydroxy derivatives of benzene and its homologues. In: Coffey, S. (ed.) Rodd’s Chemistry of Carbon Compounds. IIIA:289 (1971).Google Scholar
  2. 2.
    Erdtman, H. Formation of complex oxidation and condensation products of phenols - origin and nature of humic acid. I. Reactivity of simple monocycle quinones. Proc. Roy. Soc. 143A: 196 (1933).Google Scholar
  3. 3.
    Hathway, D.E.; Seakins, J.W.T. Autoxidation of catechin. Nature 176: 218 (1955).CrossRefGoogle Scholar
  4. 4.
    Weinges, K.; Bahr, W.; Ebert, W.; Goritz, K.; Marx, H.-D. Konstitution, enstsehung, and bedeutung der flavonoid gerbstoffe. Fortschr. Chem. Org . Naturst. 17: 158 (1969).Google Scholar
  5. 5.
    Scott, G. Atmospheric Oxidation and Antioxidants. Elsevier, Amsterdam (1965).Google Scholar
  6. 6.
    Musso, H. Phenol oxidation reactions. Angew. Chem. Internat. Edit. 2: 723 (1963).CrossRefGoogle Scholar
  7. 7.
    McNelis, E. Oxidative coupling reactions of 2,6 xylenol with activated manganese dioxide. J. Org . Chem. 31: 1255 (1966).Google Scholar
  8. 8.
    Pedersen, J.A. Electron spin resonance studies of oxidative processes of quinones and hydroquinones in alkaline solution; formation of primary and secondary semiquinone radicals. J. Chem. Soc., Perkin Trans. 2: 424 (1973).Google Scholar
  9. 9.
    Stone, T.J.; Waters, W.A. Aryloxy-radicals. Part IV. Electron spin resonance spectra of some ortho-monobenzosemiquinones and secondary radicals derived therefrom. J. Chem. Soc.: 1488 (1965).Google Scholar
  10. 10.
    Jensen, O.H.; Pedersen, J.A. The oxidative transformations of (+)-catechin and (-)-epicatechin as studied by ESR. Tetrahedron 39: 1609 (1983).CrossRefGoogle Scholar
  11. 11.
    Sears, K.D.; Casebier, R.L.; Hergert, H.L.; Stout, G.H.; McCandlish, L.E. The structure of catechinic acid. A base rearrangement product of catechin. J. Org . Chem. 39: 3244 (1974).CrossRefGoogle Scholar
  12. 12.
    Weinges, K.; Ebert, W. Isolierung eines kristallisierten dehydrierungsdimeren aus (+)catechin. Phytochemistry 7: 153 (1968).CrossRefGoogle Scholar
  13. 13.
    Duran, N.; Baeza, J.; Freer, J.; Rojas N. Biomass photochemistry: VI - Light-induced oxidation of phlobaphene from wood. Polym. Photochem. 6: 393 (1985).CrossRefGoogle Scholar
  14. 14.
    Brown, B.R.; Whiteoak, R.J. Polymerisation of flavans. Part VII. Oxidative polymerisation of catechin. J. Chem. Soc.: 6084 (1964).Google Scholar
  15. 15.
    Piretti, M.V.; Serrazanetti, G.P.; Paglione, G. The enzymatic oxidation of (+)-catechin in the presence of sodium benzenesulphinate. Ann. Chim. 67: 395 (1977).Google Scholar
  16. 16.
    Ahn, G.-Z; Gstirner, F. Enzymtische dimerisierung von (+)-catechin. Arch. Pharm. 303: 925 (1970).CrossRefGoogle Scholar
  17. 17.
    Weinges, K.; Huthwelker, D. Isolierung and konstitutionsbeweis eines 8,6’-verknupften dehydro-dicatechins (B4). Liebigs Ann. Chem. 731: 161 (1970).Google Scholar
  18. 18.
    Weinges, K.; Mattauch, H.; Wilkins, C.; Frost, D. Spektorskopiche und chemische konstitutionsaufklarung des dehydro-dicatechins A. Liebigs Ann. Chem. 754: 124 (1971).Google Scholar
  19. 19.
    Van Soest, T.C. Aufklarung der moleckularstruktur der dehydro-dicatechins A durch rontgenstrukturanalyse seines bromoheptamethylathers. Liebigs Ann. Chem. 754: 137 (1971).Google Scholar
  20. 20.
    Chen, K.; Pan, D.; Xu, G. Fluvances from Guijianyu (Euonymus alatus). Zhongcaoyao 17: 97 (1986).Google Scholar
  21. 21.
    Hathaway, D.E. Autoxidation of polyphenols. Part IV. Oxidative degradation of the catechin-autoxidation polymer. J. Chem. Soc.: 520 (1958).Google Scholar
  22. 22.
    Kodera, M.; Tanahashi, M.; Higuchi, T. Dehydrogenative co-polymerization of d-catechin and coniferyl alcohol. Wood Res. 65: 1 (1979).Google Scholar
  23. 23.
    Seshadri, T.R. Interconversions of flavonoid compounds. In: Geissman, T.A. (ed.) The Chemistry of Flavonoid Compounds. MacMillan Company, New York, p. 156 (1962).Google Scholar
  24. 24.
    Barton, G.M. Significance of western hemlock phenolic extractives in pulping and lumber. For. Prod. J. 18: 76 (1968).Google Scholar
  25. 25.
    Hrutfiord, B.J.; Luthi, R.; Hanover, K.F. Color formation in western hemlock. J. Wood Chem. Technol. 5: 451 (1985).CrossRefGoogle Scholar
  26. 26.
    Slater, T.F.; Scott, R. The free-radical scavenging action of (+)-Cyanidanol-3 in relation to the toxicity of carbon tetrachloride. In: Conn, H.O. (ed.). International Workshop on (+)Cyanidanol-3 in Diseases of the Liver. Royal Society of Medicine, International Congress and Symposium Series No. 47; Academic Press, London; pp. 33–39 (1981).Google Scholar
  27. 27.
    Hackett, A.M.; Shaw, I.C.; Griffiths, L.A. The prevention by (+)-Cyanidanol-3 of hepatitis-induced changes in the disposition of imipramine in the rat. Biochem. Pharm. 33: 2179 (1984).PubMedCrossRefGoogle Scholar
  28. 28.
    Baumann, J.; Wurm, G.; Bruchhausen, F.v. Hemmu-tg der prostaglandinsynthetase durch flavonoide und phenolderivate im vergleich mit deren 02-radikalfangereigenschaften. Arch. Pharm. (Weinheim) 313: 330 (1980).CrossRefGoogle Scholar
  29. 29.
    Younes, M.; Siegers, C.-P. Inhibitory action of some flavonoids on enhanced spontaneous lipid peroxidation following glutathione depletion. Planta Med. 43: 240 (1981).PubMedCrossRefGoogle Scholar
  30. 30.
    Sorata, Y.; Takahama, U.; Kimura, M. Protective effect of quercetin and rutin on photosensitized lysis of human erythrocytes in the presence of hematoporphyrin. Biochim. et Biophys. Acta 799: 313 (1984).CrossRefGoogle Scholar
  31. 31.
    Husain, S.R.; Cillard, J.; Cillard, P. Hydroxy radical scavenging activity of flavonoids. Phytochemistry 26: 2489 (1987).CrossRefGoogle Scholar
  32. 32.
    Torel, J.; Cillard, J.; Cillard, P. Antioxidant activity of flavonoids and reactivity with peroxy radical. Phytochemistry 25: 383 (1986).CrossRefGoogle Scholar
  33. 33.
    Takechi, M.; Tanaka, Y.; Takehara, M.; Nonaka, G.-I.; Nishioka, I. Structure and antiherpetic activity among the tannins. Phytochemistry 24: 2245 (1985).CrossRefGoogle Scholar
  34. 34.
    Hemingway, R.W. Biflavonoids and proanthocyanidins. In:Rowe, J.W. (ed.) Natural Products Extraneous to the Lignocellulosic Cell Wall of Woody Plants. Springer-Verlag, New York, Chapter 6.6. (in press).Google Scholar
  35. 35.
    Ahn, B.-Z.; Gstirner, F. Uber catechin dimere der eichenrinde. Arch. Pharmaz. 304: 666 (1971).CrossRefGoogle Scholar
  36. 36.
    Ahn, B.-Z. Ein catehin trimer aus der eichenrinde. Arch. Pharmaz. 307: 186 (1974).CrossRefGoogle Scholar
  37. 37.
    Brandt, E.V.; Bezuidenhoudt B.C.B.; Roux, D.G. Direct synthesis of the first natural bi-isoflavonoid. J. Chem. Soc. Chem. Commun.: 1409 (1982).Google Scholar
  38. 38.
    Young, D.A.; Young, E.; Roux, D.G.; Brandt, E.V.; Ferreira, D. Synthesis of condensed tannins. Part 19. Phenol oxidative coupling of (+)-catediin and (+)-mesquitol. Conformation of bis-(+)-catechins. J. Chem. Soc. Perkin Trans. 1: 2354 (1987).Google Scholar
  39. 39.
    Muthy, S.S.N. Partial conversions in biflavonoids: Part 5. Confirmation of the structure of jeediflavonone, a biflavonone from Semecarpus anacardium. Phytochemistry 23: 925 (1984).Google Scholar
  40. 40.
    Collier, P.D.; Bryce, T.; Mallows, R.; Thomas, P.E.; Frost, D.J.; Korver, O.; Wilkins, C.K. The theaflavins of black tea. Tetrahedron 29: 125 (1973).CrossRefGoogle Scholar
  41. 41.
    Groenewoud, G.; Hundt, H.K.L. The microbial metabolism of (+)-catechin to two novel diarylpropan-2-ol metabolites in vitro. Xenobiotica 14 (9): 711 (1984).PubMedCrossRefGoogle Scholar
  42. 42.
    Das, N.P. Studies on flavonoid metabolism. Absorption and metabolism of (+)-catechin in man. Biochem. Pharm. 20: 3435 (1971).CrossRefGoogle Scholar
  43. 43.
    Katyal, M. Analytical reactions of hydroxyflavones. Talanta 24: 367 (1977).PubMedCrossRefGoogle Scholar
  44. 44.
    Dowd, L.E. Spectrophotometric determination of quercetin. Anal. Chem. 31(7):1184 (1959).Google Scholar
  45. 45.
    Sekhon, B.S.; Kaushal, G.P.; Bhatia, I.S. Use of zirconium(IV) and antimony(III) for structural investigation of flavonoids. Mikrochim. Acta (Wien) I1:421 (1983).Google Scholar
  46. 46.
    Porter, L.J.; Markham, K.R. The aluminium(III) complexes of hydroxyflavones in absolute methanol. Part II. Ligands containing more than one chelating site. J. Chem. Soc. (C): 1309 (1970).Google Scholar
  47. 47.
    Jurd, L.; Geissman, T.A. Absorption spectra of metal complexes of flavonoid compounds. J. Org . Chem. 21: 1395 (1956).Google Scholar
  48. 48.
    Kennedy, J.A.; Powell, H.K.J. Polyphenol interactions with aluminium (III) and iron (III): Their possible involvement in the podzolization process. Aust. J. Chem. 38: 879 (1985).CrossRefGoogle Scholar
  49. 49.
    Kennedy, J.A.; Powell, H.K.J. Aluminium(III) and iron(III) 1,2-diphenolato complexes: a potentiometric study. Aust. J. Chem. 38: 659 (1985).CrossRefGoogle Scholar
  50. 50.
    Durkee, G.E. Micronutrient foliar sprays. Agrichem. West 1: 17 (1965).Google Scholar
  51. 51.
    Herrick, F.W. Chemistry and utilization of western hemlock bark extractives. J. Agric. Food Chem. 28: 228 (1980).CrossRefGoogle Scholar
  52. 52.
    Cecily, P.J.; Kunjappan, M.K. Preservation of cotton fish net twines by tanning: II. Fixation of tannin. Fish. Technol. 10: 24 (1973).Google Scholar
  53. 53.
    Furry, M.S.; Humfield, H. Mildew-resistant treastment on fabrics. Ind. Eng. Chem. 33: 538 (1941).CrossRefGoogle Scholar
  54. 54.
    Laks, P.E.; McKaig, P.A.; Hemingway, R.W. Flavonoid biocides: Wood preservatives based on condensed tannins. Holzforschung 42: 299 (1988).CrossRefGoogle Scholar
  55. 55.
    Laks, P.E. Wood preservation as trees do it. Proceedings of the American Wood Preservers ’ Association. p. 147 (1988).Google Scholar
  56. 56.
    Lotz, W.R.; Holloway, D.F. Wood Preservation. U.S. 4, 732, 817 (1988).Google Scholar
  57. 57.
    Schmidt, E.L.; Lotz, W.R. Tropical wood extracts as preservatives for southern pine. Proceedings of the American Wood Preservers ’ Association. p. 173 (1988).Google Scholar
  58. 58.
    Pizzi, A.; Conradie, W.E.; Jansen, A. Polyflavonoid tannins - A main cause of soft-rot failure in CCA-treated timber. Wood Sci. Technol. 20: 71 (1986).CrossRefGoogle Scholar
  59. 59.
    Randall, J.M.; Bermann, R.L.; Garrett, V.; Waiss, A.C.Jr. Use of bark to remove heavy metal ions from waste solutions. For. Prod. J. 24 (9): 80 (1974).Google Scholar
  60. 60.
    Randall, J.M.; Hautala, E.; Waiss, A.C.Jr. Removal and recycling of heavy metal ions from mining and industrial waste streams with agricultural byproducts. Proceedings of the Fourth Mineral Waste Utilization Symposium. Chicago, Illinois, May 7–8 (1974).Google Scholar
  61. 61.
    Randall, J.M.; Jautala, E.; Waiss, A.C.Jr.; Tschernitz, J.L. Modified barks as scavengers for heavy metal ions. For. Prod. J. 26 (8): 46 (1976).Google Scholar
  62. 62.
    Randall, J.M. Variations in effectiveness of barks as scavengers for heavy metal ions. For. Prod. J. 27 (11): 51 (1977).Google Scholar
  63. 63.
    Kramer, P.; Dara, S.S. Utilisation of agricultural wastes for decontaminating industrial/domestic wastewaters from toxic metals. Agric. Wastes 4: 213 (1982).CrossRefGoogle Scholar
  64. 64.
    Kumar, P.; Dara, S.S. Studies on binding of copper ions by some natural polymeric materials. Chemical Era December: 20 (1979).Google Scholar
  65. 65.
    Kumar, P.; Dara, S.S. Modified barks for scavenging toxic heavy metal ions. Indian J. Environ. Health. 22 (3): 196 (1980).Google Scholar
  66. 66.
    Kumar, V.; Sindhu, R.S. Removal of lead ions from its solution by the bark of Adina cordifolia. Proc. Nat. Acad. Sci. India 55(B), I: 94 (1985).Google Scholar
  67. 67.
    Fujii, M.; Shioya, S.-I. Nitric acid-formaldehyde treated coniferous barks as recoverying agents of uranium from sea water. /S WPC Posters: 97 (1987).Google Scholar
  68. 68.
    Rahman, M.D.; Richards, G.N. Interactions of starch and other polysaccharides with condensed tannins in hot water extracts of ponderosa pine bark. J. Wood Chem. Technol. 8: 111 (1988).CrossRefGoogle Scholar
  69. 69.
    Hara, M.; Asai, H.; Kitamikado, T.; Yamamoto, H.; Okushio, K.; Nakamura, K. Preparation of (-)-epigallocatechin gallate-aluminum hydroxide complex as antiulcer agent from tea extracts. Jpn. Kokai Tokkyo Koho JP 61,238, 728 (1986).Google Scholar
  70. 70.
    Bonati, A.; Mustich, G. Pharmacologically Active Polyphenolic Substances. U.S. 4, 166, 861 (1979).Google Scholar
  71. 71.
    Laks, P.E.; Pruner, M.S. Flavonoid biocides: Structure/activity relations of flavonoid phytoalexin analogues. Phytochemistry 28: 87 (1989).CrossRefGoogle Scholar
  72. 72.
    Laks, P.E. (unpublished results 1987 ).Google Scholar
  73. 73.
    Kennedy, J.A.; Munro, M.H.G.; Powell, H.K.J.; Porter, L.J.; Foo, L.Y. The protonation reactions of catechin, epicatechin and related compounds. Aust. J. Chem. 37: 885 (1984).CrossRefGoogle Scholar
  74. 74.
    Yazaki, Y.; Hillis, W.E. Molecular size distribution of radiata pine bark extracts and its effect on properties. Holzforschung 34: 125 (1980).CrossRefGoogle Scholar
  75. 75.
    Weinges, K.; Toribio, F.; Paulus, E. Die konformation als ursache sterioselektiver reaktionen. Ann. 688: 127 (1965).Google Scholar
  76. 76.
    Mayer, W.; Merger, F. Condensation of (+)-catechin with phloroglucinol: a model for the condensation of catechins and catechin tannins. Chem. and Indust. April: 485 (1959).Google Scholar
  77. 77.
    Laks, P.E.; Hemingway, R.W. Condensed tannins: base-catalyzed reactions of polymeric procyanidins with toluene-a-thiol. Lability of the interflavanoid bond and pyran ring. J. Chem. Soc. Perkin Trans. 1: 465 (1987).Google Scholar
  78. 78.
    Courbat, P.; Valenza, A. Medicaments containing epicatechin-2-sulfonic acids and salts thereof. U.S. 3, 888, 990 (1975).Google Scholar
  79. 79.
    Viviers, P.M.; Kolodziej, H.; Young, D.A.; Ferreira, D.; Roux, D.G. Synthesis of condensed tannins. Part 11. Intramolecular enantiomerism of the constituent units of tannins from the Anacardiaceae: stoichiometric control in direct synthesis: derivation of 1H nuclear magnetic resonance parameters applicable to higher oligomers. J. Chem. Soc. Perkin Trans. 1: 2555 (1983).Google Scholar

Copyright information

© Plenum Press, New York 1989

Authors and Affiliations

  • Peter E. Laks
    • 1
  1. 1.Institute of Wood ResearchMichigan Technological UniversityHoughtonUSA

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