Synthesis and Chemistry of Agrochemicals VI PDF
Preview Synthesis and Chemistry of Agrochemicals VI
ACS SYMPOSIUM SERIES 800 Synthesis and Chemistry of Agrochemicals VI s.acs.org 00.fw001 b8 u0 p://p002- Don R. Baker, Editor 5, 2012 | htt0.1021/bk-2 Joseph GC.o nFsuelntaynet s, Editor 11 42 on June 2001 | doi: BucGkmeoanr gLeab Por.a Ltoarihesm In,t Eerdniattoiorn al, Inc. 163.35.uly 29, DuPont Agricultural Products ded by 89.on Date: J Thomas P. Selby, Editor oaati DuPont Agricultural Products wnlblic ou DP Thomas M. Stevenson, Editor DuPont Agricultural Products American Chemical Society, Washington, DC In Synthesis and Chemistry of Agrochemicals VI; Baker, D., et al.; ACS Symposium Series; American Chemical Society: Washington, DC, 2001. ACS Symposium Series 800 ISBN 0-8412-3783-2 The paper used in this publication meets the minimum requirements of American National Standard for Information Sciences—Permanence of Paper for Printed Library Materials, ANSI Z39.48-1984. Copyright © 2002 American Chemical Society s.acs.org 00.fw001 Distributed by Oxford University Press b8 u0 p://p002- 5, 2012 | htt0.1021/bk-2 11 2 on June 001 | doi: 42 163.35.uly 29, ded by 89.on Date: J oaati wnlblic All Rights Reserved. Reprographic copying beyond that permitted by Sections 107 or ou DP 108 of the U.S. Copyright Act is allowed for internal use only, provided that a per -chapter fee of $20.50 plus $0.75 per page is paid to the Copyright Clearance Center, Inc., 222 Rosewood Drive, Danvers, MA 01923, USA. Republication or reproduction for sale of pages in this book is permitted only under license from ACS. Direct these and other permission requests to ACS Copyright Office, Publications Division, 1155 16th St., N.W., Washington, DC 20036. The citation of trade names and/or names of manufacturers in this publication is not to be construed as an endorsement or as approval by ACS of the commercial products or services referenced herein; nor should the mere reference herein to any drawing, specification, chemical process, or other data be regarded as a license or as a conveyance of any right or permission to the holder, reader, or any other person or corporation, to manufacture, reproduce, use, or sell any patented invention or copyrighted work that may in any way be related thereto. Registered names, trademarks, etc., used in this publication, even without specific indication thereof, are not to be considered unprotected by law. PRINTED IN THE UNITED STATES OF AMERICA In Synthesis and Chemistry of Agrochemicals VI; Baker, D., et al.; ACS Symposium Series; American Chemical Society: Washington, DC, 2001. Foreword The ACS Symposium Series was first published in 1974 to provide a mechanism for publishing symposia quickly in book form. The purpose of the series is to publish timely, comprehensive books developed from ACS sponsored symposia based on current scientific research. Occasion s.acs.org 00.fw001 tailolynB,s e bwfoohoreekn sa tgharreee et oidnpegivc e tiolso ppoeuf dbk leifesrnho mian tbseyoremosktp ,to otsh iteah eps prcoohpneosmoserisedtd rt yab baylu edo itoehfne ccr oeo.n rtgenantsi zias b8 p://pu002-0 trheev ieawudeide nfocer .a pSpormoper ipaatpe earsn dm caoym pbree heexncsluivdee dc otvoe rbaegtete ra nfdo cfuosr itnhtee rbesoto tko; 5, 2012 | htt0.1021/bk-2 rooetvhveeirervswi eemwda oypr r biioen rt raotdodd uefcditn otaorly p acrchocavepiptdetears nc coaerm e poarrde dhreeejdne.sc iDtvioerannfe,t ss aso.n fdW c hmhaepannt euarsspc prariropept srp ieaaetrere-, 11 2 on June 001 | doi: pinrecApluasd reeadd r uiinnle tc,h aoemn vleyor alou-rrmiegaeidsn.ya Vl freoerrsbmeaaatritcm. h rpeappreordsu acntido nosr iogfi nparle vreiovuieswly ppaupbelriss haerde 163.35.4uly 29, 2 pAaCpeSr sB oaroek sn oDt eapcacretmpteendt. ded by 89.on Date: J oaati wnlblic ou DP In Synthesis and Chemistry of Agrochemicals VI; Baker, D., et al.; ACS Symposium Series; American Chemical Society: Washington, DC, 2001. Preface Major changes in the synthesis and development of new agrochemicals has occurred in the past few years of the 20th century. Mergers and acquisitions within the industry have also changed the research environment. As we enter the 21st century, various agricultural biotechnological efforts are supplementing and replacing standard agrochemicals. However, the rise of biotechnology has not been without some controversy due to unresolved health concerns and political org 001 issues. Therefore, it is widely believed that traditional crop protection agents acs.0.pr will play a major role in agriculture for some time to come. ubs.080 The editors of these volumes have organized synthesis symposia at each p://p002- American Chemical Society (ACS) national meeting since 1984. These 5, 2012 | htt0.1021/bk-2 casiyhmme mpoiosfst irayp rhooafvv iend eibwneg e ancg hsreopmcohnisestomsr iecwda ilbt hay g teahn et fsoA. rCuSmT Dhefio vrci suiprorrnee nsote fn bAtoingogrko chthhaees m csihycaanpltsthe ewrssii stht a akthneedn 11 from the symposia presented at the Las Vegas ACS National Meeting held in the une doi: summer of 1997 through the Washington, DC ACS National Meeting held in the 2 on J001 | summer of 2000. Each of the chapter authors was requested to present the 42 current status of the work at the time of preparation of the manuscript. In many 163.35.uly 29, tchaes ems eceotninsgid. eTrahbelsye mchoarep teerfsf oprtr ehseans t bae eunn idqounee l osoinkc ien ttoh et hwe odriks cwovase rpyr persoecnetesds oaft y 89.ate: J our current and future agrochemical products. Not all of the chapters represent bD wnloaded blication wmfoira llt oearthilaseolrss p tihrnoatvte riwdesielt le ade v leienan rttnhuiean lgbly ieo bxloep gecirocieamln mceefef rebccoitasth lio zffeo odr. r gthaIonts ieics mwhoooplrekecdinu tglhe asin.t tthheiss ef icehlda patnerds DoPu As with the previous volumes, our goal is to inform the reader of the current trends in research for safe, efficient, biologically active agrochemicals. The organization of this book is similar to that of the preceding volumes. After the overview chapter, a section describes efforts in the discovery of new herbicides. The next section describes the discovery of new insecticides and highlights the discovery of and development of the new DuPont insecticide Indoxacarb. The final section deals with the control of plant fungal diseases. Acknowledgments We express our thanks to the authors and their employers who have shared with us the details of their interesting research results—first at the xi In Synthesis and Chemistry of Agrochemicals VI; Baker, D., et al.; ACS Symposium Series; American Chemical Society: Washington, DC, 2001. symposia and then in going that extra mile to prepare the chapters for publication. We hope that you our readers—whether you are our fellow synthesis chemists, or microbiologists, entomologists, plant physiologists, biotechnologists, as well as medicinal and pharmaceutical chemists—will find the chapters interesting, useful, and above all stimulating! Last, but not least, we also wish to thank DuPont and Buckman Laboratories International, without their generous support of these symposia, this volume could not have been published. Don R. Baker Consultant bs.acs.org 800.pr001 1Od5rrb iMnakdueatr,h @C DAhr oi9mv4ee5 .6c3o m u0 p://p002- Joseph G. Fenyes 5, 2012 | htt0.1021/bk-2 BM12ue5cm6k pmNhaoinsr, t LhT aMNb oc3rL8ae1toa0nr8i Be so Iunlteevranradti onal, Inc. ne 1oi: 1 [email protected] ud 2 on J001 | George P. Lahm 89.163.35.4e: July 29, 2 BDStuuiniPledo-inHntg aA s3kg0er0illc, uRPl.etOusre. aaBlr coPhxr o 3Cd0eu ncttesr y at Newark, DE 19714-0030 bD wnloaded blication gTehoorgme.ap.sla Phm. @Seulbsay.d upont.com Do Pu Stine-Haskell Research Center DuPont Crop Protection Building 300, Room 126 P.O. Box 30 Newark, DE 19714-0030 [email protected] Thomas M. Stevenson Stine-Haskell Research Center DuPont Agricultural Products P.O. Box 30 Newark, DE 19714-0030 [email protected] xii In Synthesis and Chemistry of Agrochemicals VI; Baker, D., et al.; ACS Symposium Series; American Chemical Society: Washington, DC, 2001. Chapter 1 Synthesis of Agrochemicals and Agricultural Biotechnology in Modern Agriculture Don R. Baker1, Joseph G. Fenyes2, George P. Lahm3, Thomas P. Selby3, and Thomas M. Stevenson3 org 001 1Consultant, 15 Muth Drive, Orinda, CA 94563 bs.acs.800.ch 2Buckman Laboratories InteMrneamtiopnhaisl,, TInNc .3, 81120586 North McLean Boulevard, u0 3Stine-Haskell Research Center, DuPont Agricultural Products, P.O. Box p://p002- 30, Newark, DE 19714 5, 2012 | htt0.1021/bk-2 11 2 on June 001 | doi: 42 163.35.uly 29, pTrhoed upcrtosc eisss eovf oflivnidnign g ata nad draepviedl oppainceg. nTewhe creomp eprgreonteccet ioonf by 89.Date: J biniodutesctrhyn.o Alodgvya innc easg riinc uclotumrme ruenpirceasteionnts, ad antae wa cfqrounistiietiro fno, rd oautar ownloaded ublication rwsetooshrraladgpwein iadgne d trhaaenp di din hedoxuwcsh traytnh.g eey oTfr ehinleaf toerc mhtaoalt lieomnngo vedsiea r tnoh fe sicnaitgeernrincceeut l tuaarrreee DP explored in various aspects of this book. An update on the global crop protection market, evolving research models, the influence of biotechnology and the future for crop protection chemicals are topics in this chapter. © 2002 American Chemical Society 1 In Synthesis and Chemistry of Agrochemicals VI; Baker, D., et al.; ACS Symposium Series; American Chemical Society: Washington, DC, 2001. 2 Introduction The demand for agricultural products continues to grow in the face of one of the toughest agricultural economies in decades. World population passed 6 billion in October 1999 and continues to increase at an annual rate of 1.3 percent, or yearly at 78 million people. Further, four fifths of the world population is in underdeveloped countries, where 98% of the population growth has taken place (1). The increase in demand for the world food supply sits in stark contrast to the depressed agrochemical industry and the plight of the farmer facing reduced export demands and record low crop prices. The agricultural industry is thus faced with the challenge of maintaining the quality of a global food supply in sufficient quantity to meet growth demands. This org 001 takes place in a difficult economy where ever-increasing demands are rightly acs.0.ch placed on crop protection products to insure high margins of safety to people bs.80 and the environment. u0 p://p002- 15, 2012 | htt10.1021/bk-2 pcsporoendctiiTunfchiucetse i tdyit ontf doomu rs eutternhytce o thhvtaaeesrsr g ees ptedr eoepndme usaactn ntsda nse.dw v ohalSiruceihtg i onraanifpc itiic nda lanyttth desle cogiwqeruaneadtri lefidutiyc s eibn or fre taahctkeert osh,per n osvuphigrroohowtsne mchhteiiaongvnthe. 2 on June 001 | doi: rIfoenrsc irnseteaawsnec dpe r oaddnedum cttahsne. d esv oblyv inrge gnualtautroer yof tahgee inncdieuss,t ryt hwei ll ocnognotiinngu e dtoe vfeuleolp tmhee nnt eeodf 42 163.35.uly 29, But, today perhaps we sit at the threshold of what could be the most by 89.Date: J ismigpnaifcitc aonf tb tiroatnescfhonromloagtiyo.n tHhee ribnidcuisdter yre hsaisst asnete nc rosipnsc esu ictsh iansc eRpotuionnd, -tUhapt R ies atdhye oaded ation beans and insect resistant crops such as Bollgard cotton have emerged to take wnlblic their place in the farmers arsenal of crop protection. In the future we imagine ou farmers will grow customized crops which will be tracked from seed to field to DP consumer. The impact of biotechnology is perhaps more than we can envision at present. There has also been significant global backlash, most visibly in Western Europe, as biotechnology continues to make inroads into the agricultural economy. As with the arguments against crop protection chemicals of the past, we can only assume that the antibiotech movement will continue to voice its concerns. It is incumbent on our industry to prove and defend the promise and benefits that biotech offers. And further, we must In Synthesis and Chemistry of Agrochemicals VI; Baker, D., et al.; ACS Symposium Series; American Chemical Society: Washington, DC, 2001. 3 meet public concern with open dialogue, significant education, and sound evidence regarding safety and quality of world food, specifically regarding implications of biotechnology. The Global Crop Protection Market The entire global crop protection market for the year 2000 was estimated to be about S31 billion and is not expected to grow substantially over the next bs.acs.org 800.ch001 tfohifv aetn h yis1e a0gr%lso. boaCfl otmhneva rektnoettti aowln iawtlh oc rraolgdpb ivpoartoleutceehc.n tioolHno egcryhb eiccmoindicterasil bsau crteicoponruesns tegenrdto ewdfo inrth gea, bbmouuat tj oat4r 5ple%asrs,t p://pu002-0 ifnrusietcs tiacnidde sv e2g2e%ta balneds, fuknegyi ccirdoepss ailnm othset 2w0o%rl do f cwonotrilnduwei dteo sbaele sc.e rAelaolsn,g cwoirtnh, 5, 2012 | htt0.1021/bk-2 fEsooury rbotepraaend, siE,t iaorsintc aeAl, sccioar otatpon ndp, Lrooaitltesince teiAdo mnr aepcreihc eaam.n diIc nsatulesgr aerrsebtmieneagtilsny. , NNKooerrytthh r eAAgmimoenersrii cciana , i tsh West iewlls otterhrledn 11 2 on June 001 | doi: malathjooru gmh afrakr edt isftaonr t binio staelcehsn (o2l)o. gy sales with Western Europe being second 42 163.35.uly 29, we'vDe uese ienn p aar t tcoo tnhtein rueelda tivdeelcyl isntaet icin s izthee o f nthuem gbleorb aol fc rompa jporro teacgtiroonc hmemarikceatl by 89.Date: J hcoavmep asneieens pprihnacrimpaalcleyu tthicroalu ghco mmepragneiress anedx ita ctqhuei siatigornosc. heSmimicuallt abnuesoiunselsys, wtoe oaded ation tchoen cinendtursattrey tohni st hheaisr cmreoartee dp rsoefvietarabll ea gprhoacrhmeamciecuatli ccaolm mpaanrkieests w. ithA at nt heex cteosps ooff wnlblic 10% global market share. The two largest of these being Syngenta (formed ou D P from the merger of Novartis and Zeneca) at 6.4 billion in 1999 annual sales (22% market share) and Aventis (formed from the mergef of Rhone-Poulenc and AgrEvo) at 4.1 billion in 1999 annual sales (15% market share). Top agrochemicals, with sales at or over a quarter billion dollars for the year 2000 were as follows: glyphosate, paraquat, acetochlor, atrazine, 2,4-D, metolachlor, pendimethalin and simazine (herbicides), chlorpyriphos and imidacloprid (insecticides) and azoxystrobin, mancozeb and tebuconazole (fungicides) (3). In Synthesis and Chemistry of Agrochemicals VI; Baker, D., et al.; ACS Symposium Series; American Chemical Society: Washington, DC, 2001. 4 Discovery of New Agrochemicals The discovery of new and useful agrochemicals continues to rely heavily on the discovery of high quality leads. The many and varied ways for new lead discovery and their optimization toward commercial agrochemicals has been detailed in this series of ACS books (4-8). Lead sources have included natural products, pharmaceutical compounds and synthesis and acquistion of novel compounds. In the search for novel leads the trend has been toward increased screening capacity particularly through the use of large compound libraries. And, the future is progressing toward focused compound libraries that input desirable chemical and physical property traits. org 001 Historically, natural products have served as a rich lead source and have acs.0.ch contributed significantly to many current commercial agrochemical products. bs.80 The pyrethroids provide the most striking example with over 30 registered p://pu002-0 pstrroidkuincgts .e vTidhee necveo oluf ttihoen wofi dsetr uracntugree -oafc ctihveimtyi cfoalr osypnptohretutinci tpyy rthetahtr oexidisst sp rforovmid eas 5, 2012 | htt0.1021/bk-2 csaiynndhg almleo atlherkariednt ,s robeuaqryuctiehr.er moNiedon tta sno dne lxybp iwfaenendrteeh drd irnpa)ym, rbeautthitc r ofriiandte e u aitmitltieptnyrt oiivonnetmo t oethn epts h syroesiail clia(ztlee pfdlr,u otph(eeri.rgnty.) 11 2 on June 001 | doi: and rIitc eis mpaerrkheatpss (ientshtorfuecntpivreo xt)o. look at some of the significant new products 42 163.35.uly 29, isnutcrcoedsuscfueld idni stchoe vmerayr ksettrpaltaecgeie os.v erL tihkee lpasytr eftivhero yidesa,r ss ttoro gbeiltu ari npsi chtuarvee ofa sr etcheenitr by 89.Date: J tgheen efsuins gliecaiddse fmroamrk enta wtuirtahl tphreo dleuacdtes.r , Satrzoobxiylustrrionbs ihna (vSey bnegceonmtae, m19a9jo7r) , palta yaenrnsu ianl ownloaded ublication hosafe ltetehsri osac tyb cooloivcke ,r r ea4pn0lda0 c demmemielnloitnosns t froainrte t 2ht0he0 e0 m.e evtohNlovexiwynga csrstytrroluabctietlu uarrerien adfcuetinsvcgiriticybi detderes n indc soa n ftcoahri anptihnteigsr DP class. The lepidopteran insecticide spinosyn (Dow, 1997) was discovered through fermentation technology, followed by extensive screening and characterization. Several chapters in this book detail synthetic modifications to spinosyn and link fermentation and synthetic technology as a discovery strategy. Imidacloprid (Bayer, 1991), a member of the neonicotinoid class of insecticides, and indoxacarb (DuPont, 2000), an oxadiazine insecticide share similar discovery histories. The leads for both were identified through random screening in the early 70fs. Both classes of chemistry were successfully optimized to higher active materials over the following decade, although In Synthesis and Chemistry of Agrochemicals VI; Baker, D., et al.; ACS Symposium Series; American Chemical Society: Washington, DC, 2001.
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