Table Of ContentSiegfried Huneck and Isao Yoshimura
Identification of Lichen Substances
Springer
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Siegfried Huneck Isao Yoshimura
Identification
of Lichen Substances
With 67 Figures
Springer
Dr. SIEGFRIED HUNECK
Fliederweg 34a
06179 Langenbogen/Saalkreis
Germany
Professor Dr. ISAo YOSHIMURA
Kochi Gakuen College
292 Asahitenjincho
Kochi 780
Japan
Cover photo by courtesy of Roman Turk. Photo showing various Lecidea and
Porpidia species on gneiss.
Formula: (+ )-Rhizocarpic acid
ISBN-13:978-3-642-8S24S-9
Library of Congress Cataloging-in-Publication Data
Huneck, S. (Siegfried), 1928-
Identification of lichen substances / S. Huneck, I. Yoshimura.
P. cm.
Includes bibliographical references (p. ) and index.
ISBN-13:978-3-642-85245-9 e-ISBN-13:978-3-642-85243-5
DOl: 10.1007/978-3-642-85243-5
1. Lichen products-Handbooks, manuals, etc. 2. Lichens
Analysis-Handbooks, manuals, etc. I. Yoshimura, l. (Isao)
II. Title.
QK581.H86 1996
S89.1-dc20
96-3927
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© Springer-Verlag Berlin Heidelberg ~996
Softcover reprint of the hardcover 1st edition 1996
Product Liability: The publisher can give no guarantee for information about drug dosage and application
thereof contained in this book. In every individual case the respective user must check its accuracy by consulting
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SPIN 1006312331/3137 - 5432 1 0 - Printed on acid-free paper
Dedicated
to our friends John A. Elix,
Benno Feige, Wolfgang Steglich
and Raffaele Tabacchi
Acknowledgments
We are grateful to Prof. Dr. J.A. Elix (Canberra), Prof. Dr. C. Leuckert
(Berlin), Prof. Dr. R. Tabacchi (Neuchatel) and Dr. P.A. Cohen
(Vancouver) for providing reprints and unpublished data, and to Dr.
H.T. Lumbsch (Essen) for checking the names of the lichens. S. Huneck
thanks his wife Ruth for manifold help in preparing the manuscript and
the Fonds der Chemischen Industrie (Frankfurt/Main) for financial
support.
S. HUNECK
1. YOSHIMURA
Contents
1 Introduction. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 1
1.1 Short History of the Study of Lichen Substances. . . . . . . . 1
1.2 General Meaning of Lichen Substances
and Their Use in Past and Present Time. . . . . . . . . . . . . . 3
1.2.1 Biological Activities of Lichen Substances. . . . . . . . . . . . 3
1.2.2 Use of Lichens in Folk Medicine. . . . . . . . . . . . . . . . . . . 4
1.2.3 Lichens as Raw Material for Dyes . . . . . . . . . . . . . . . . . . 5
1.2.4 Lichens as Basic Material for Perfume. . . . . . . . . . . . . . . 5
1.2.5 The Biological Meaning of Lichen Substances. . . . . . . . . 5
1.2.6 Lichens as Biomonitors . . . . . . . . . . . . . . . . . . . . . . . . . 6
1.2.7 Lichens as Biodeterioration . . . . . . . . . . . . . . . . . . . . . . 6
1.2.8 Chemotaxonomy of Lichens ..................... 6
1.3 Cultur~ of Lichens and Their Symbionts . . . . . . . . . . . . . . 9
2 Identification of Lichen Substances. . . . . . . . . . . . . . . . . . 11
2.1 Extraction and Purification of Lichen Substances. . . . . . . 11
2.2 Melting Point. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 13
2.3 Colour Reactions and Other Reactions
for the Identification of Lichen Substances. . . . . . . . . . . . 13
2.4 UV Spectroscopy. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 15
2.4.1 Depsides......................................... 17
2.4.2 Depsidones....................................... 17
2.4.3 y-Lactones....................................... 17
2.4.4 Chromones and Xanthones . . . . . . . . . . . . . . . . . . . . . . . . . 17
2.4.5 Dibenzofuranes .................................. . 18
2.4.6 Pulvinic Acid Derivatives .......................... . 18
2.4.7 Quinones ....................................... . 18
2.5 IR Spectroscopy .................................. . 18
2.6 NMR Spectroscopy ... " ........................... . 19
2.6.1 lH-NMR Spectroscopy ............................ . 19
2.6.2 13C-NMR Spectroscopy ............................ . 20
2.7 Mass Spectrometry ............................... . 22
2.8 Optical Rotation .......................... 28
<' •••••••
X Contents
2.9 Optical Rotatory Dispersion (ORD) and
Circular Dichroism (CD) .......................... . 28
2.10 Microcrystallization .............................. . 47
2.11 Thin Layer Chromatography ....................... . 47
2.12 High Performance Liquid Chromatography (HPLC) .... . 51
2.13 Gas Liquid Chromatography (GLC) ................. . 107
2.14 X-Ray Analysis .................................. . 109
2.15 Laser Microprobe Mass Spectrometry (LAMMA) ...... . 109
2.16 Derivatization ................................... . 109
2.17 Cleavage of Depsides ............................. . 112
3 Data of Lichen Substances ......................... . 125
3.1 General Remarks and Abbreviations of the Data ....... . 125
3.2 N-Containing Compounds ......................... . 126
3.3 P-Containing Compounds ......................... . 130
3.4 S-Containing Compounds ......................... . 131
3.5 Polyols, Monosaccharides, Carbohydrates ............ . 131
3.6 Aliphatic and Cycloaliphatic Compounds ............ . 136
3.6.1 Neutral Compounds .............................. . 136
3.6.2 Acids ........................................... . 141
3.7 Aromatic Compounds ............................ . 155
3.7.1 Monocyclic Aromatic Compounds .................. . 155
3.8 Quinones ....................................... . 164
3.8.1 Benzoquinones .................................. . 164
3.8.2 Naphthaquinones and bis-Naphthaquinones .......... . 164
3.8.3 Anthraquinones, Anthrones, bis-Anthraquinones
and bis-Anthrones ............................... . 168
3.8.4 Biphenylquinones ................................ . 183
3.8.5 Terphenylquinones ............................... . 184
3.8.6 Phenanthrenequinones ............................ . 184
3.8.7 Perylenequinones ................................ . 185
3.9 Chromanes and Chromones ....................... . 185
3.10 Xanthones and bis-Xanthones ...................... . 190
3.11 Dibenzofuranes . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 218
3.12 Diphenylether.... . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 229
3.13 Biphenyls.. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 236
3.14 Diphenylmethanes . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 236
3.15 Nostoclides.. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 236
3.16 Depsides. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 237
3.16.1 Didepsides ............................... '. . . . . . . . 237
3.16.2 Tri- and Tetra-Depsides . . . . . . . . . . . . . . . . . . . . . . . . . . . . 302
3.16.3 Benzyldepsides....... . . . . . . . . . . . . . . . . . . . . . . . . . . .. 311
3.17 Depsidones... . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 313
Contents X
3.18 Depsones. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 353
3.19 Naphthopyranes... . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 356
3.20 Terpenoids . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 356
3.20.1 Monoterpenoids.................................. 356
3.20.2 Sesquiterpenoids. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .. 359
3.20.3 Diterpenoids..................................... 360
3.20.4 Sesterterpenoids. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 361
3.20.5 Triterpenoids..................................... 362
3.20.6 Steroids. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .. 388
3.20.7 Carotenoids...... . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 396
3.21 Pulvinic Acid Derivatives. . . . . . . . . . . . . . . . . . . . . . . . . .. 399
3.22 Cleavage Products of Depsides and Depsidones . . . . . . . . 403
Literature. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 447
Addenda .............................................. 475
Subject Index.. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 479
·1 Introduction
1.1 Saxony, Germany, died 1917 at Feuerbach near
Short History of the Study Stuttgart), who published 18 papers on lichen
substances in the period between 1861 and 1905
of Lichen Substances
and wrote an article on Flechtenstoffe in the
Lichens - symbiotic organisms of fungi and 1912 edition of Abderhalden's Biochemisches
algae - contain a great number of organic Handlexikon.
compounds, the so-called lichen substances The lichen substances first known in their
which are more or less typical of this group structure were vulpinic acid (Spiegel 1883) and
of cryptogames. The lichen substances com
prise quite different classes of compounds
like amino acid derivatives, sugar alcohols,
aliphatic acids, 'Y-, 0- and macrocyclic lactones,
mono cyclic aromatic compounds, quinones,
chromones, xanthones, dibenzofuranes, de
psides, depsidones, depsones, terpenoids, ste
roids and carotenoids. This multitude of
compounds made the study of their chemistry
attractive from the early times of organic chem
istry. Bebert (1831) isolated vulpinic acid in
1831, Alms (1832) picrolichenic acid in 1832,
and Knop (1844) usnic acid in 1844. Gmelin
(1858) published a review on lichen substances
already in 1858.
The classical period of lichen chemistry is
connected with two names: W. Zopf and O.
Hesse. W. Zopf (Fig. 1) was a botanist (born
1846 at Ro:Bleben, Thuringia, Germany, died
1909 at Miinster/Westfalen) and published
a series of papers on lichen substances which
he summarized in the well-known book Die
Flechtenstoffe in chemischer, botanischer,
pharmakologischer und technischer Beziehung,
published in 1907. Zopf's contrahent was the
chemist O. Hesse (born 1835 at Obereula, Fig. 1. W. Zopf
