pyrethroids from chrysanthemum to modern industrial insecticide

314 Topics in Current Chemistry Editorial Board: K.N. Houk l C.A. Hunter l M.J. Krische l J M. Lehn S.V. Ley l M. Olivucci l J. Thiem l M. Venturi l P. Vogel C H. Wong l H. Wong l H. Yamamoto Topics in Current Chemistry Recently Published and Forthcoming Volumes Pyrethroids: From Chrysanthemum to Modern Industrial Insecticide Volume Editors: Noritada Matsuo, Tatsuya Mori Vol. 314, 2012 Unimolecular and Supramolecular Electronics II Volume Editor: Robert M. Metzger Vol. 313, 2012 Unimolecular and Supramolecular Electronics I Volume Editor: Robert M. Metzger Vol. 312, 2012 Bismuth-Mediated Organic Reactions Volume Editor: Thierry Ollevier Vol. 311, 2012 Peptide-Based Materials Volume Editor: Timothy Deming Vol. 310, 2012 Alkaloid Synthesis Volume Editor: Hans-Joachim Kno ¨ lker Vol. 309, 2012 Fluorous Chemistry Volume Editor: Istva ´ n T. 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Research & Development Laboratory 1-11, 1-chome, Daikoku-cho Toyonaka-shi Osaka, 561-0827 Japan n.matsuo@kincho.co.jp Dr. Tatsuya Mori Health & Crop Sciences Research Laboratory Sumitomo Chemical Co., Ltd 4-2-1 Takatsukasa Takarazuka, Hyogo 665-8555 Japan morit7@sc.sumitomo-chem.co.jp ISSN 0340-1022 e-ISSN 1436-5049 ISBN 978-3-642-27345-2 e-ISBN 978-3-642-27346-9 DOI 10.1007/978-3-642-27346-9 Springer Heidelberg Dordrecht London New York Library of Congress Control Number: 2011944823 # Springer-Verlag Berlin Heidelberg 2012 This work is subject to copyright. All rights are 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. 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Houk University of California Department of Chemistry and Biochemistry 405 Hilgard Avenue Los Angeles, CA 90024-1589, USA houk@chem.ucla.edu Prof. Dr. Christopher A. Hunter Department of Chemistry University of Sheffield Sheffield S3 7HF, United Kingdom c.hunter@sheffield.ac.uk Prof. Michael J. Krische University of Texas at Austin Chemistry & Biochemistry Department 1 University Station A5300 Austin TX, 78712-0165, USA mkrische@mail.utexas.edu Prof. Dr. Jean-Marie Lehn ISIS 8, alle ´ e Gaspard Monge BP 70028 67083 Strasbourg Cedex, France lehn@isis.u-strasbg.fr Prof. Dr. Steven V. Ley University Chemical Laboratory Lensfield Road Cambridge CB2 1EW Great Britain Svl1000@cus.cam.ac.uk Prof. Dr. Massimo Olivucci Universita ` di Siena Dipartimento di Chimica Via A De Gasperi 2 53100 Siena, Italy olivucci@unisi.it Prof. Dr. Joachim Thiem Institut fu ¨ r Organische Chemie Universita ¨ t Hamburg Martin-Luther-King-Platz 6 20146 Hamburg, Germany thiem@chemie.uni-hamburg.de Prof. Dr. Margherita Venturi Dipartimento di Chimica Universita ` di Bologna via Selmi 2 40126 Bologna, Italy margherita.venturi@unibo.it Dr. Tatsuya Mori Health & Crop Sciences Research Laboratory Sumitomo Chemical Co., Ltd 4-2-1 Takatsukasa Takarazuka Hyogo 665-8555 Japan morit7@sc.sumitomo-chem.co.jp Prof. Dr. Pierre Vogel Laboratory of Glycochemistry and Asymmetric Synthesis EPFL – Ecole polytechnique fe ´ derale de Lausanne EPFL SB ISIC LGSA BCH 5307 (Bat.BCH) 1015 Lausanne, Switzerland pierre.vogel@epfl.ch Prof. Dr. Chi-Huey Wong Professor of Chemistry, Scripps Research Institute President of Academia Sinica Academia Sinica 128 Academia Road Section 2, Nankang Taipei 115 Taiwan chwong@gate.sinica.edu.tw Prof. Dr. Henry Wong The Chinese University of Hong Kong University Science Centre Department of Chemistry Shatin, New Territories hncwong@cuhk.edu.hk Prof. Dr. Hisashi Yamamoto Arthur Holly Compton Distinguished Professor Department of Chemistry The University of Chicago 5735 South Ellis Avenue Chicago, IL 60637 773-702-5059 USA yamamoto@uchicago.edu vi Editorial Board Topics in Current Chemistry Also Available Electronically Topics in Current Chemistry is included in Springer’s eBook package Chemistry and Materials Science. 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Aims and Scope The series Topics in Current Chemistry presents critical reviews of the present and future trends in modern chemical research. The scope includes all areas of chemical science, including the interfaces with related disciplines such as biology, medicine, and materials science. The objective of each thematic volume is to give the non-specialist reader, whether at the university or in industry, a comprehensive overview of an area where new insights of interest to a larger scientific audience are emerging. vii Thus each review within the volume critically surveys one aspect of that topic and places it within the context of the volume as a whole. The most significant developments of the last 5–10 years are presented, using selected examples to illus- trate the principles discussed. A description of the laboratory procedures involved is often useful to the reader. The coverage is not exhaustive in data, but rather conceptual, concentrating on the methodological thinking that will allow the non- specialist reader to understand the information presented. Discussion of possible future research directions in the area is welcome. Review articles for the individual volumes are invited by the volume editors. In references Topics in Current Chemistry is abbreviated Top Curr Chem and is cited as a journal. Impact Factor 2010: 2.067; Section “Chemistry, Multidisciplinary”: Rank 44 of 144 viii Topics in Current Chemistry Also Available Electronically Preface Pyrethrum has been used as an insecticide for around 150 years, and there has been no other insecticide which has so successfully contributed to the control of sanitary pests. Numerous analogs have been developed by chemists worldwide since the elucidation of the chemical structure of pyrethrins, which are the insecticidal ingredients of pyrethrum. As a result, their application has expanded extensively to various fields. To date, many eminent books have been published by scientists in this field and have contributed to advancing pyrethroid science. Pyrethroids refer to the general name for pyrethrins, insecticidal ingredients of pyrethrum, and their synthetic analogs. They exhibit quick action on insects in a small amount. At the same time, they show selective toxicity to insects over mammals. These features of pyrethroids are therefore ideal for use as household insecticides. Since both humans and insects are organisms with a nervous system, compounds with high insecticidal potency may be highly toxic also to humans, as seen in many organophosphorous compounds and carbamates. In the previous century, the absolute configuration of 6 insecticidal ingredients consisting of natural pyrethrins were elucidated and, with the advancement from natural pyre- thrins to synthetic pyrethroids, their applications have developed from household insecticides for indoor use against sanitary pests to outdoor use in agriculture, forestry, construction and livestock. The development of photostable pyrethroids has led to their infinite use in various fields throughout the world. While many drugs and agricultural chemicals have been developed from natural products with biological activities, no other compounds have been studied for a longer time and in more countries than pyrethroids. Synthetic pyrethroids have advanced markedly by modifying the chemical structure of pyrethrins and now even compounds with structures far from natural pyrethrins are called pyrethroids. This is probably the result of pursuing higher insecticidal activities, although they belong to pyrethroids in terms of electrophysiological activities . Notabl y, * Please see the section entitled “Further Reading” for details about these books. ix household insecticides should be discriminated from photostable pyrethroids for outdoor use from development stages. For household insecticides, safety for humans and pets is extremely important, and residues of photostable synthetic pyrethroids and impurities, degraded products and secondary synthetic products contained in the compounds in rooms and their influence on the environment are to be evaluated strictly. In this century, the most awaited development is that of highly safe pyrethroids which are produced based on the original natural pyrethrins with excellent insecticidal activity, safety and less resistance. However, for pyrethrum, it takes about 2 years from seeding to flowering and therefore, investigations of the mechanism of biosynthesis to improve production efficiency and advancements in this field are also expected. Although “pyrethroids” have been developed without a concrete definition, it is quite difficult to define this group of compounds based on their chemical structures. As such, I would like to propose the following definition: “Pyrethroids” are a collective term for compounds that are obtained by modi- fying the structure of natural insecticidal ingredients, pyrethrins, contained in pyrethrum while maintaining safety, to improve efficacy and provide different characteristics from pyrethrins that show high selective toxicity comparable to pyrethrins. Since 1995 some new types of pyrethroids with high insecticidal potency have been developed for practical use. For this reason we decided to publish a volume written by experts in various fields to review the development of new pyrethroids and offer future perspectives. This volume includes chapters on the progress and the future of pyrethroids, the biosynthesis of natural pyrethrins, newly developed polyfluorobenzyl-type pyrethroids with potent insecticidal activity, the mode of action, mammal toxicology, biotransformation and enzymatic reactions, environ- mental behavior, and ecotoxicology of pyrethroids. We hope that this book will contribute greatly to the further development of pyrethroids. October 2011 Dr. Yoshio Katsuda Further Reading M. Jacobson and D.G. Crosby (1971). “Naturally Occurring Insecticides”, Marcel Dekker, INC., New York. J.E. Casida (1973). “Pyrethrum, The natural insecticide”, Academic Press, New York and London. R.H. Nelson (1975). “Pyrethrum Flowers, Third edition”, McLaughlin Gormley King Co., Minneapolis. M. Elliott (1977), “Synthetic Pyrethroids”, ACS Symposium Series, American Chemical Society, Washington, D.C. J.E. Casida and G.B. Quistad (1995). “Pyrethrum Flowers, Production, chemistry, toxicology, and uses”, Oxford University Press, New York and Oxford. x Preface [...]... 2 Pyrethroids are all classified into rank C, showing high fish toxicity, except for cycloprothrin (35) and etofenprox (36), which fall into rank B; therefore, the use of pyrethroids is limited in and around paddy fields, fishponds, and other water systems In contrast, silafluofen (37), with low fish toxicity, is the only compound classified into rank A among pyrethroids and has been used from 1995 as an insecticide. .. synthetic pyrethroids, but mosquito coils have been used worldwide for more than 110 years without changing in shape The different types of insecticide formulations used in the USA and Japan are considered to be attributed to the differences in climate and house construction style That is to say, mosquito coils are suitable to prevent mosquitoes from entering a house from outside in Japan where the... Meanwhile, the mosquito stick was improved and developed into a coil type with a burning time prolonged to 7–8 h, enough to cover human sleeping time Pyrethrum became the main source of household insecticides in sprays in the USA (1919) and mosquito coils (1895) as well as oil-based preparations (1924) in Japan Thereafter, the insecticidal ingredients shifted from pyrethrins to various synthetic pyrethroids, ... re-evaluated Thanispong et al [54] (2008) tested A aegypti colonies collected from nine areas in Thailand by exposure to insecticide- treated papers and reported strong development of resistance to DDT and permethrin According to a report by Kawada et al [55], the considerable development of resistance to photostable synthetic pyrethroids was observed with the involvement of a kdr mechanism in A aegypti... compounds) Progress and Future of Pyrethroids 15 poison as well as a contact poison and is stable for a long time in alkaline soils; therefore, it has taken root as a termiticide in Japan Moreover, while the use of pyrethroids has been greatly restricted in and around paddy fields and fishponds due to their high toxicity to fish, silafluofen, and etofenprox (see Table 2) show low fish toxicity and are commonly... 73 Kazuhiko Matsuda Mammal Toxicology of Synthetic Pyrethroids 83 Ryozo Tsuji, Tomoya Yamada, and Satoshi Kawamura Biotransformation and Enzymatic Reactions of Synthetic Pyrethroids in Mammals 113 Kazuki Mikata, Naohiko Isobe, and Hideo Kaneko Ecotoxicology of Synthetic Pyrethroids ... mosquitoes The issue of pyrethroid resistance in houseflies and mosquitoes and the countermeasures are described below 5.2.1 Houseflies It is said that the action site of pyrethroids in flies is on the neuroaxonal excitatory membrane, similarly to that of DDT Moreover, DDT-resistant M domestica is known to show high cross-resistance to synthetic pyrethroids and the kdr gene is involved in the onset of the resistance... chrysanthemic acid, and cinerin II analogs, i.e., esters of chrysanthemum acid have not been industrialized Although pyrethroids consist of natural pyrethrins and many photostable synthetic pyrethroids, they must be discriminated when discussing cross-resistance By topical application, Katsuda et al determined LD50 values of natural pyrethrins and several pyrethroids against the pyrethroid-susceptible CSMA... aegypti is active in blood-sucking in the daytime Moreover, an effective vaccine against dengue fever remains to be developed and there is no treatment available; therefore, it is essential to protect humans from mosquito bites and mosquito coils are considered to be the best method Using the topical application method, Katsuda et al [52] examined the allethrin susceptibility of A aegypti including two... household insecticides containing them in the perspectives of safety and low cross-resistance When developing novel pyrethroids, particularly for household insecticides for indoor use, attention should be paid not to place too much importance on insecticidal potency and ease of use while giving sufficient consideration to the indoor persistence of chemicals and safety Progress and Future of Pyrethroids . Volumes Pyrethroids: From Chrysanthemum to Modern Industrial Insecticide Volume Editors: Noritada Matsuo, Tatsuya Mori Vol. 314, 2012 Unimolecular and Supramolecular Electronics II Volume Editor:. Ame ´ lia P. Rauter, Pierre Vogel, Yves Queneau Vol. 295, 2010 Pyrethroids From Chrysanthemum to Modern Industrial Insecticide Volume Editors: Noritada Matsuo Á Tatsuya Mori With Contributions by P.J discriminated from photostable pyrethroids for outdoor use from development stages. For household insecticides, safety for humans and pets is extremely important, and residues of photostable synthetic pyrethroids