Herbicide Classes in Development: Mode of Action, Targets, Genetic Engineering, Chemistry PDF
Preview Herbicide Classes in Development: Mode of Action, Targets, Genetic Engineering, Chemistry
Peter Boger· Ko Wakabayashi· Kenji Hirai {Eds.} Herbicide Classes in Development Springer Berlin Heidelberg New York Barcelona Hong Kong London Milan Paris Tokyo Peter Boger· Ko Wakabayashi· Kenji Hirai {Eds.} Herbicide Classes in Development Mode of Action, Targets, Genetic Engineering, Chemistry With 96 Figures, 2 in Color, and 53 Tables Springer Professor Dr. PETER BOGER University of Konstanz Department of Plant Physiology and Biochemistry D-78457 Konstanz Germany Professor Dr. Ko WAKABAYASHI Tamagawa University Department of Physiology and Biochemistry Machida-shi, Tokyo 194-8610 Japan Dr. KENJI HIRAI Sagami Chemical Research Center Hayakawa 2743-1, Ayase Kanagawa 252-1193 Japan ISBN-13:978-3-642-63972-2 Springer-Verlag Berlin Heidelberg New York Library of Congress Cataloging-in-Publication Data Herbicide classes in development : mode of action, targets, genetic engineering, chemistry I Peter Boger, Ko Wakabayashi, Kenji Hirai (eds.). p. cm. Includes bibliographical references. ISBN-13: 978-3-642-63972-2 e-ISBN-13:978-3-642-59416-8 DOl: 10.1007/978-3-642-59416-8 1. Herbicides. 2. Herbicide-resistant crops. L Boger, Peter. II. Wakabayashi, K. (Ko), 1938- III. Hirai, Kenji, 1953- SB951.4 .H425 2002 632'.954 - dc21 2002070471 This work is subject to copyright. All rights reserved, whether the whole or part of the material is concerned, specifically the rights of translation, reprinting, reuse of illustrations, recitation, broadcasting, reproduction on microfilm or in any other way, and storage in data banks. Duplication of this publication or parts thereof is permitted only under the provisions of the German Copyright Law of September 9, 1965, in its current version, and permission for use must always be obtained from Springer-Verlag. Violations are liable for prosecution under the German Copyright Law. Springer-Verlag Berlin Heidelberg New York a member of BertelsmannSpringer Science + Business Media GmbH http://www.springer.de © Springer-Verlag Berlin Heidelberg 2002 Softcover reprint of the hardcover 1st edition 2002 The use of general descriptive names, registered names, trademarks, etc. in this publication does not imply, even in the absence of a specific statement, that such names are exempt from the relevant protective laws and regulations and therefore free for general use. Cover design: D&P, Heidelberg Typesetting: SNP Best-set Typesetter Ltd., Hong Kong SPIN 10774148 3113130 - 5 4 3 2 1 0 - Printed on acid-free paper Preface Chemical pest control is in use in practically every country in the world since agrochemicals play a decisive role in ensuring food supply and protection against damage by pests, insects and pathogenic fungi. Particularly in the half century since World War II, food production has risen dramatically in most parts of the world. In the last 20 years, the yield of major crops has roughly doubled in Western agriculture and there is still the potential for further achievements, particularly in the developing countries. The world's cereal and rice production, now more than 2 billion tons/year, has to increase by 2.4% annually to cope with the rising food demand caused mainly by the growing population and improvement of living standards in most of the developing countries. Such a demand for food has to be achieved by higher yields from the restricted arable land already in use. Global farm land resources are about 1.4 billion ha, of which 1.2 billion ha is cultivated with major crops. Experts agree that a future substantial addition of new produc tive areas is unlikely. Those with a high yield potential are already in use; new fields with a lower output may possibly be obtained by cultivation of arid or cold areas. More recently, new areas of large-scale farmland have been devel oped in tropical regions of Latin America, primarily in Argentina and Brazil, at the cost of the destruction of tropical rain forest. The 1980s were an exciting period for the development of modern herbi cides, for both industry and academia. Acetolactate synthase (ALS) inhibitors, represented by the sulfonylurea (SU) and imidazolinone (lMI) classes, were introduced into chemical weed control. The start of the widespread use of new acetyl-CoA carboxylase (ACCase) inhibitors such as the phenoxypro pionate and cyclohexanedione classes brought about a major turning point in the subsequent evolution of agrochemicals. The discovery of fiuoro modified tetrahydrophthalimides as PPO (= protoporphyrinogen oxidase, Protox) inhibitors, such as fiumiclorac-pentyl, is another breakthrough in the explosive development of the next-generation of cyclic imide classes. These new herbicide chemistries, which combine excellent activity with unparalleled lower dosage, crop safety, specific mechanism of action and/or structural high novelty, have been rapidly adopted worldwide and have had an amazing impact on agriculture. Today, the use rate of modern herbicides is in the range of 100-300ga.i.lha, with a declining tendency. In particular, the very low use rates of original SU and cyclic imide herbicides have prompted agrochemical researchers to find VI Preface more highly active compounds, which has led to successive discoveries of as many as 39 kinds of new ALS-inhibiting herbicides, including the triazolopy rimidines and pyrimidyloxybenzoates, and no less than 18 new cyclic imide classes of PPO inhibitors in the 1990s. The chemistry of these ALS and PPO herbicides has been the most dynamic area of research in the past 20 years. The latest phenoxypropionate ACCase inhibitors are applied in the range of 100-150ga.i.!ha and SU and cyclic imide herbicides require an even lower amount, down to 5ga.i.!ha for some commercially active ingredients. Obvi ously, soil overloading with chemicals or leaching problems is not an issue with such low application doses. To date, more than 400 herbicides have been registered, or are in the regis tration process, and these form the active ingredients of thousands of com mercial products. Among the registered herbicides whose modes of action are currently understood, 269 kinds of herbicides are used around the world and these are categorized according to their target sites, modes of action, similar ity of induced symptoms or chemical classes by the Herbicide Resistance Action Committee (HRAC) in cooperation with the Weed Science Society of America (WSSA). About ten enzymatic herbicide targets have been characterized in detail, some more may be determined by mode of action studies in the future. Accord ingly, the mainstream of herbicide investigation is the search for and synthe sis of new structures acting upon these known targets. Therefore, this book should update the state of target-oriented research by dealing with the follow ing topical herbicide classes: (1) ALS inhibitors, (2) carotenogenesis inhibitors (bleaching herbicides), (3) inhibitors of aromatic amino acid biosynthesis (glyphosate), (4) inhibitors of glutamine synthetase (glufosinate), (5) ACCase inhibitors, (6) inhibitors of very long-chain fatty acid biosynthesis, (7) cellu lose biosynthesis inhibitors, and (8) PPO (or Protox) inhibitors. This book presents timely physiological and biochemical information on those inhibitors and herbicide classes which are the focus of today's research and development. For example, auxin-type compounds and photosynthesis inhibitors are not dealt with. Each of the first eight chapters covers, at least in part, the relevant aspects relating to symptoms of herbicidal activity, mode of action to provide a ratio nal approach for weed resistance management, biochemical characteristics of the target enzyme, model assays and cell-free biochemical tests to obtain quan titative phytotoxic inhibition data for larger compound series, and molecular genetics of the herbicide target(s) with special reference to transformed inhibitor-resistant plants. Development of transgenic herbicide-resistant crops is a strong issue today and will grow in importance. Therefore, Chapter 9, in particular, outlines the methods of how a plant is transformed and a resistant crop is developed, describing the cloning of gene(s), complementation, vector constructs, PCR mediated gene mutation, selection, and crossings. An extended Chapter 10 provides agrochemical characteristics and major synthetic routes of the typical Preface VII herbicides cited in Chapters 1-8. Structural evolutions of the inhibitor/herbi cide classes belonging to these chapters are chronologically reviewed from the viewpoint of molecular design by illustrating representative compounds for the last decade. However, only some new synthetic pathways for Protox inhibitors will be documented since detailed information up to 1997 has been reviewed in Peroxidizing Herbicides, published by Springer in 1999. Many herbicides and synthetic compounds interfering with plant metabo lism exist as optical isomers exhibiting specific phytotoxic or regulatory activities. The R-form of phenoxypropionate ACCase inhibitors is far more active than the S-isomer. In contrast, the S-forms of dimethenamid or meto lachlor are active, but not the R-form. In addition, glufosinate and bialaphos, produced by fermentation, are optically active compounds and their racemic isomers are less inhibitory. Accordingly, Chapter 11 outlines prominent exam ples, their enantioselective synthesis and general biological activity. Chapter 12 deals with new considerations on transcuticular penetration based on quantitative analysis of its kinetics by a logistic-kinetic model. The last chapter relates the findings presented in Chapter 6 on chloroacetamides and function ally equivalent novel structures focusing on structure-activity relationships. These are based on herbicidal greenhouse activity and quantitative inhibition of cell-free microsomal fatty-acid elongation. There is a continuous need for new active ingredients. Changes in agricul tural politics, occurrence of herbicide-resistant species and changing toxico logical and environmental fate requirements demand the development of more effective, more selective and environmentally benign herbicides. It is believed that members of the modern herbicide classes covered in this volume fulfill these requests. No volume presenting a combination of synthetic chemistry with herbicide physiology, biochemistry and engineered resistance, compa rable to the format outlined here, has yet been published. Treatises on the mode of action of herbicide classes included in the present chapters are almost 10 years old. A demand for this book by herbicide researchers can be safely assumed. We also believe that the contributions should be a valuable resource for established colleagues working on plant protection, and for advanced stu dents of organic and agricultural chemistry, as well as plant biochemistry. Finally, it is hoped that readers will be stimulated by the information and mes sages presented. They may help to further develop integrated weed manage ment practices that deliver a sustained food crop production. In writing this volume, the editors thank the authors for their outstanding contributions and for making their expertise available. They are also grateful for the help and advice of many colleagues, including graduate students, tech nicians and many other unnamed colleagues. P. BOGER, K. HIRAI, AND K. WAKABAYASHI Konstanz, Germany, Ayase, Kanagawa and Tokyo/Machida, Japan, April 2002 Contents 1 Acetolactate Synthase Inhibitors TSUTOMU SHIMIZU, ISHIZUE NAKAYAMA, Kozo NAGAYAMA, TAKESHIGE MIYAZAWA, and YUKIO NEZU 1.1 Introduction ................... ... ........... ....... 1 1.2 Acetolactate Synthase-Inhibiting Herbicides Actively Developed in the Late 1990s ........ ... .... ... .......... 2 1.3 Discovery of Pyrimidinyl Carboxy Herbicides (Pyrimidinylsalicylate Class Herbicides) ... ......... ...... 5 1.3.1 Discovery of the Lead Structures. . . . . . . . . . . . . . . . . . . . 5 1.3.2 Discovery and Optimizations of the Secondary Lead Structure. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 7 1.3.3 Further Optimizations of the Pyrimidinyl Carboxy Herbicides ........................ ...... 9 1.4 Herbicidal Activity of Pyrimidinyl Carboxy Herbicides ...... 10 1.4.1 Pyrithiobac-Sodium for Use in Cotton ...... ......... 10 1.4.2 Bispyribac-Sodium for Use in Rice .................. 10 1.4.3 Bispyribac-Sodium for Vegetation Management. . . . . . . . 11 1.4.4 Pyriminobac-Methyl for Use in Rice. . . . . . . . . . . . . . . . . 11 1.5 Physiological Plant Response to Pyrimidinyl Carboxy Herbicides .......................................... 12 1.6 Mode of Action and Selectivity of Pyrimidinyl Carboxy Herbicides . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 13 1.6.1 Primary Target . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 13 1.6.2 Inhibition of Bacterial Acetolactate Synthase .... ...... 14 1.6.3 Selectivity . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 15 1.7 Biological Characteristics of the Target Enzyme ............ 16 1.7.1 Kinetic Studies of Plant Acetolactate Synthase ......... 16 1.7.2 Subunit Compositions of Plant Acetolactate Synthase .. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 17 1.7.3 Recombinant Systems. . . . . . . . . . . . . . . . . . . . . . . . . . . . . 18 1.8 Inhibition Mechanism of the Target Enzyme by Pyrimidinyl Carboxy Herbicides. . . . . . . . . . . . . . . . . . . . . . . 19 1.8.1 Inhibition Kinetics with Plant Acetolactate Synthase . . . . 19 1.8.2 Inhibition Kinetics with Bacterial Acetolactate Synthase . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 22 X Contents 1.9 Molecular Genetics of Target Enzyme .................... 22 1.9.1 Acetolactate Synthase Genes of Plants. . . . . . . . . . . . . . . . 22 1.9.2 Acetolactate Synthase-Inhibiting Herbicide-Resistant Crops (Including Arabidopsis thaliana) and Their Acetolactate Synthase Genes ....................... 24 1.9.3 Acetolactate Synthase-Inhibiting Herbicide-Resistant Weeds and Their Acetolactate Synthase Genes ......... 28 1.9.4 Genetic Engineering. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 31 References. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 32 2 Bleaching Herbicides: Action Mechanism in Carotenoid Biosynthesis, Structural Requirements and Engineering of Resistance GERHARD SANDMANN 2.1 Herbicidal Effect and Mode of Action .................... 43 2.2 Interaction of Inhibitors with Carotene Desaturation ........ 44 2.3 Structural Requirements for an Inhibitor of Phytoene Desaturase . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 47 2.4 Strategies for Genetic Engineering of Herbicide Resistance by Modification of the Carotenogenic Pathway ............. 50 2.4.1 Overexpression of a Susceptible Lycopene Cyclase in Synechococcus . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 50 2.4.2 Selection of Mutants with Resistant Phytoene Desaturase and Gene Transfer into Tobacco. . . . . . . . . . . 51 2.4.3 Naturally Resistant Phytoene Desaturase from Bacteria and Genetic Engineering of a Resistant Tobacco. . . . . . . . . . . . . . . . . . . . . . . . . . . . . 52 2.5 Conclusion and Perspectives . . . . . . . . . . . . . . . . . . . . . . . . . . . . 54 References. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 55 3 Inhibitors of Aromatic Amino Acid Biosynthesis (Glyphosate) DONALD R. GEIGER and MARK A. FUCHS 3.1 Introduction ........................................ 59 3.2 Symptoms of Herbicidal Activity ........................ 60 3.3 Mode of Action of Glyphosate .......................... 62 3.3.1 Overview of the Mode of Action. . . . . . . . . . . . . . . . . . . . 62 3.3.2 Primary Mode of Action .......................... 64 3.3.2.1 Biochemical Characteristics of the Target Enzyme................................. 64 3.3.2.2 Structural Characteristics of the Target Enzyme................................. 65 3.3.2.3 Interaction Between 5-Enolpyruvylshikimate 3-Phosphate Synthase and Glyphosate ......... 66 3.3.2.4 Molecular Requirements for Herbicidal Activity of Glyphosate . . . . . . . . . . . . . . . . . . . . . . 69 Contents XI 3.3.3 Secondary Physiological Consequences of Inhibition of 5-Enolpyruvylshikimate 3-Phosphate Synthase ...... 70 3.3.3.1 Inhibition of Chorismate Synthesis. . . . . . . . . . . . 70 3.3.3.2 Depletion of Photosynthetic Carbon Reduction Cycle Intermediate Metabolites ...... 71 3.3.3.3 Development of Secondary Damage Symptoms ............................... 72 3.3.3.4 Bases of Development of Lethal Symptoms Among Species ........................... 72 3.4 Mechanisms for Resistance and Tolerance to Glyphosate ....................................... 75 3.4.1 Development of Commercially Valuable Glyphosate- Resistant Plants ................................. 75 3.4.2 Tolerance to Field Doses of Glyphosate in Field-Grown Plants ............................ 77 3.5 Summary . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 79 References ............................................. 80 4 Inhibitors of Glutamine Synthetase GUENTER DONN and HELMUT KOCHER 4.1 Introduction ........................................ 87 4.2 Plant Glutamine Synthetase Isoforms and Their Function .... 87 4.3 Glutamine Synthetase Inhibitors ........................ 90 4.4 Discovery of the Herbicidal Activity of Phosphinothricin and Bialaphos ....................................... 91 4.5 Mode of Glutamine Synthetase Inhibition ................. 92 4.6 Effects of Glutamine Synthetase Inhibitors in Plants . . . . . . . . . 94 4.6.1 Visible Symptoms of Herbicidal Action .............. 94 4.6.2 Physiological Effects of Glutamine Synthetase Inhibition in Plants by Phosphinothricin ............. 94 4.7 Attempts to Generate Selectivity for Glufosinate ............ 96 4.7.1 Attempts to Select Glufosinate Tolerant Mutants ....... 97 4.7.2 Metabolic Inactivation of Glufosinate by Bar and Pat Enzymes ................................ 98 References ............................................. 99 5 Acetyl-CoA Carboxylase Inhibitors MALCOLM D. DEVINE 5.1 Introduction ........................................ 103 5.2 Symptoms of Herbicidal Activity ........................ 103 5.3 Biochemical Characteristics of the Target Enzyme .......... 104 5.4 Mode of Action of Cyclohexanedione and Aryloxyphenoxypropanoate Herbicides. . . . . . . . . . . . . . . . 105
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