Biochemistry of Plant Phenolics

recent advances in phytochemistry Biochemistry of Plant Phenolics volume 12

RECENT ADVANCES IN PHYTOCHEMISTRY Recent Volumes in the Series Volume 9 Volume 10 Volume 11 Volume 12 Phytochemistry in Disease and Medicine Proceedings of the Fourteenth Annual Meeting, Western Carolina University, Cullowhee, North Carolina, August, 1974 Biochemical Interaction Between Plants and Insects Proceedings of the Fifteenth Annual Meeting, Tampa, Florida, August, 1975 The Structure, Biosynthesis, and Degradation of Wood Proceedings of the Sixteenth Annual Meeting, Vancouver, Canada, August, 1976 Biochemistry of Plant Phenolics Proceedings of the Joint Symposium of the Phytochemical Society of Europe and the Phytochemical Society of North America, Ghent, Belgium, August, 1977 A Continuation Order Plan is available for this series. A continuation order will bring delivery of each new volume immediately upon publication. Volumes are billed only upon actual shipment. For further information please contact the publisher.

recent advances in phytochemistry Biochemistry of Plant Phenolics volume 12 Edited by Tony Swain Boston University Boston, Massachusetts Jeffrey B. Harborne University of Reading Reading, England and Chris F. Van Sumere University of Ghent Ghent, Belgium PLENUM PRESS. NEW YORK AND LONDON

Main entry under title: Library of Congress Cataloging in Publication Data Biochemistry of plant phenolics. (Recent advances in phytochemistry; v. 12) "Proceedings of the first joint symposium of the Phytochemical Society of Europe and the Phytochemical Society of North America, held at the Rijksuniversiteit, Ghent, Belgium." Includes index. 1. Phenols-Congresses. 2. Botanical chemistry-congresses. I. Swain, T. II. Harborne, Jeffrey B. III. Sumere, C. F. van. IV. Phytochemical Society of Europe. V. Phytochemical Society of North America. VI. Series. [DNLM: 1. Phenols Congresses. 2. Plants-Congresses. W1 RE105Y v. 12/0K898.P57 B615 1977] OK861.R38 vol. 12 [OK898.P57] 581.1 '9'208s ISBN-13: 978-1-4684-3374-6 e-isbn-13: 978-1-4684-3372-2 DOl: 10.1007/978-1-4684-3372-2 Proceedings of the First Joint Symposium of the Phytochemical Society of Europe and the Phytochemical Society of North America, held at the Rijksuniversiteit, Ghent, Belgium, August 29-September 2, 1977 1979 Plenum Press, New York Softcover reprint of the hardcover 1 st edition 1979 A Division of Plenum Publishing Corporation 227 West 17th Street, New York, N.Y. 10011 All rights reserved No part of this book may be reproduced, stored in a retrieval system, or transmitted, in any form or by any means, electronic, mechanical, photocopying, microfilming, recording, or otherwise, without written permission from the Publisher

PREFACE Phenolic compounds have attracted the attention of those interested in plant constituents for over 200 years. First as dyestuffs, meaicinals and tannins and, much later, because of their potential use in examining the systematic and evolutionary relationships of plants, and their implication in defence against both herbivores and phytopathogens. It is not surprising, therefore, that the first formally organised Society of Phytochemists, the Plant Phenolics group which was established in England in 1958, should have devoted themselves to an intensive study of these compounds. They were quickly followed by a like group in North America. But, by the mid-1960's, it was obvious to the members of both societies that their net was spread wider than just phenolic compounds and in 1965 both adopted a more appropriate name, The Phytochemical Society (now Phytochemical Society of Europe (PSE), and The Phytochemical Society of North America (PSNA) respectively). In spite of this broadening of interest, both societies have continued to devote a major portion of their deliberations to phenolic compounds and it is entirely appropriate, therefore, that their first joint Symposium, held in the late summer of 1977 at the Rijksuniversiteit te Gent, Belgium, should be concerned with "The Biochemistry of Plant Phenolics." First occasions are often difficult, but the chief organiser of this Symposium, Professsor Ch~is van Sumere, Head of the Laboratorium voor Plantenbiochemie of the Rijksuniversiteit te Gent with his charming wife and enthusiastic staff overcame all obstacles. Because of their careful planning, new friends quickly became old friends and the Symposium was a resounding success. On behalf of the members of both the PSE and PSNA, the Groupe Polyphenole and all others who participated, I would like to thank them all. v

PREFACE No international meeting can succeed these days without financial support. Many think that such help is a matter of form. I know that those of us in the PSE, PSNA and other organisations do not. We are, therefore, grateful to the following Belgian based firms, Analis N.V., B.A.T. Benelux Ets, Conforma N.V., Hewlett Packard (Benelux) N.V., Jeol (Europe) B.V., Kredietbank Gent, LKB, Merck N.V., Vander Elst N.V., Vel N.V., Artois and Philips Duphar B.V. (Nederlands), Sandoz S.A., and Zyma S.A. (Switzerland), and T. J. Lipton Inc. (U.S.A.): in addition members of the PSNA are grateful for a travel grant from the National Science Foundation which enabled them to participate. Finally, I would like to thank my co-editors, Jeffrey Harborne and Chris Van Sumere for their help; and more especially, all the authors who have borne the brunt of my peccadillos, and, I hope, survived. Variations in presentation are unavoidable in a volume as large as this, so readers should just lean back, take the extra rich fare and enjoy it. The creme de la creme of world phenolic experts are represented here. It is doubtful whether any future volume will be so rich a representaion of talent. T. Swain P.s. Those responsible in Plenum Press do their super job if thanked or not. I hope you all appreciate them as I do. T.S. March 1978

CONTENTS 1. 2. 3. 4. Recent Advances in the Separation of Plant Phenolics.. C.F. Van Sumere, W. Van Brussel, K. Vante Casteele, and L. Van Rompaey Advances in the Spectroscopy of Plant Phenolics... V. M. Chari and H. Wagner The Shikimate Pathway. H. G. Floss An Introduction to the Enzymology of Phenylpropanoid Biosynthesis K. R. Hanson and E. A. Havir 1 29 59 91 5. Recent Work on Cinnamoyl CoA Derivatives 139 6. 7. M. H. Zenk Recent Advances in the Chemistry and Biochemistry of Lignin..... G. G. Gross Selected Topics in Flavonoid Biosynthesis. H. Grisebach 177 221 vii

viii CONTENTS 8. Biochemistry of the Coumarins 249 S. A. Brown 9. Recent Advances in the Chemistry and Biochemistry of Quinone Pigments 287 R. H. Thompson 10. Biosynthesis of Gossypol 313 P. Heinstein, R. Widmaier, P. Wegner, and J. Howe 11. Metabolism and Degradation of Phenolic Compounds in Plants 339 W. Barz and W. Hoesel 12. Metabolism of the Aromatic Amino Acids by Fungi 371 C.-K. Wat and G. H. N. Towers 13. Oxidases in Aromatic Metabolism 433 V. S. Butt 14. Variation in and Functional Significance of Phenolic Conjugation in Plants 457 J. B. Harborne 15. Vegetable Tannins 475 E. Haslam 16. The Physiology of Phenolic Compounds in Plants 525 J. W. McClure

CONTENTS 17. Phenolic Substances and Plant Disease ix 557 J. Friend 18. Phenolic Compounds in Plants of Pharmaceutical Interest.... 589 H. Wagner 19. Phenolics in the Environment 617 T. Swain Index 641