Modern Crop Protection Compounds, Volumes 1-3, Second Edition

1550 Pages·2011·11.17 MB·English

Editedby
WolfgangKra¨mer,UlrichSchirmer,
PeterJeschke,andMatthiasWitschel
ModernCropProtectionCompounds
Furtherreading
Wiley-VCH(ed.) Ziska,LewisH./Dukes,Jeffrey
Ullmann’sAgrochemicals WeedBiologyandClimate
Change
2Volumes
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ISBN:978-3-527-31604-5 ISBN:978-0-8138-1417-9
Walters,Dale Tadros,T.F.(ed.)
PlantDefense ColloidsinAgrochemicals
WardingoffAttackbyPathogens,
ColloidsandInterfaceScience
HerbivoresandParasiticPlants
Volume5ofthe‘‘ColloidsandInterface
2010
ScienceSeries”
ISBN:978-1-4051-7589-0
2009
ISBN:978-3-527-31465-2
Edited by Wolfgang Kra¨mer, Ulrich Schirmer, Peter Jeschke,
and Matthias Witschel
Modern Crop Protection Compounds
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XXIII
PrefacetotheSecondEdition
ManyofthechallengesforhumanitydefinedintheUnitedNations‘‘millennium
goals,’’ such as population growth, energy sustainability and public health, can
only be mastered by further significant improvements in agriculture. A major
contribution will have to come from better crops by breeding and/or genetic
modification,andinthefuturetheprotectionofthesehighlyvaluablecropsbythe
useofagrochemicalswillbeevenmoreimportantthanitistoday.
In this Second Edition of Modern Crop Protection Compounds, we discuss the
newdevelopmentsinchemicalcropprotectionandtheircontributiontoimproved
agriculture,asexemplifiedbythemostrecentlycommercializedagrochemicals.
In order to achieve the necessary progress in chemical crop protection, we are
facedwithseveralmajorchallenges.Currently,thelossofactiveingredientsdueto
newregulatoryrequirementsishigherthanthenumberofnewactiveingredients
beingintroducedintothemarket.Thesenewhurdlesalsodramaticallyincreasethe
attritionrateofnewcandidatesunderdevelopment,andtherebyreducetheoutput
ofnewagrochemicalsfurthermore.Inallindications,thediminishednumberof
available active ingredients in the market results in fewer options for resistance
management. Furthermore, the observed dramatic increases in the resistance of
fungi,weedsandinsectstoagrochemicalsoftenleavesonlyaveryfewsolutionsto
theproblemforthefarmerand,inmanycases,nosolutionatall.Thistrendwill
accelerateasfewerdifferentagrochemicalsbecomeavailable.
Duringthepastfewdecades,amajorconsolidationintheagrochemicalmarket
has taken place, whereby the number of companies conducting research in all
agrochemicalindicationshasbeenreducedfromover20duringthe1980stoabout
fivetoday;moreover,furtherconsolidation,especiallyalsointheareaofgenerics,is
highlyprobable.Onereasonforthistrendistheincreasingcostsinvolvedtobring
anewagrochemicaltothemarket.Suchincreasesindevelopmentcostsresultin
higherprojectedmarketvaluesnecessaryforprojectdecisionstobemade,whichin
turnwillresultinfeweravailableagrochemicals,especiallyformanyofthesmaller
markets.
The changing environmental conditions will also influence future agriculture,
duetotheexpectedincreasesindrought,flooding,andsalination.Moreintensive
farming on less available land will bring additional challenges and require the
provisionofspecialcropprotectionsolutions.
XXIV PrefacetotheSecondEdition
Itis,therefore,extremelyimportantthatcropprotectionresearchaddsnewand
better agrochemicals to the farmers’ toolboxes. The aim of this book is to stim-
ulate this process, by bringing together knowledge gained from modern biology,
biochemistryandchemistry,andbydiscussingtherationaleintheinventionand
developmentofmoderncropprotectioncompounds.
Each of the main sections, ‘‘Herbicides’’, ‘‘Fungicides’’, and ‘‘Insecticides’’, is
introducedbyacontributionfromtheauthorsoftherespectiveResistanceAction
Committee,reflectingthecommonresponsibilitiesofthecrop-protectionindustry
to maintain the efficacy of agrochemicals and to support sustainable agriculture
and public health. These introductory chapters allow us to mention those older
compoundsthatarenotdescribedindetailbecausetheyaredealtwithinextensoin
standardbooks,suchasChemistryofPlantProtection(Springer,Berlin,Heidelberg,
NewYork,Tokyo)andChemistryofPesticides(JohnWileyandSons).
Our general target for ‘‘new’’ crop protection compounds has been to include
thoseagrochemicalsthathavecometothemarketduringthepast20years,between
1990and2010.
This book would not have been realized without the support of all the major
agrochemicalcompaniesandtheirresearchanddevelopmentdivisions,norwithout
allthehighlycommittedauthorsfromthesecompaniesandtheuniversities.We
are fully appreciative of the tremendous workload involved in preparing the
manuscripts.
Wearesurethatthereaderswillenjoythisbookanduseitasacompendiumon
plantprotectionresearch,inmuchthesamewaythatweourselveshaveexperienced
researchoncropprotection,asstimulating,enjoyable,andalsochallenging.
Note
The authors have named the products/compounds preferably by their common
names.Although,occasionally,registeredtrademarksarecitedtheiruseisnotfree
foreveryone.Inviewofthenumberoftrademarksinvolved,itwasnotpossibleto
indicateeachparticularcaseineachtableandcontribution.Weacceptnoliability
forthis.
December2011 WolfgangKra¨mer
UlrichSchirmer
PeterJeschke
MatthiasWitschel
V
Contents
Volume1
Preface XXIII
ListofContributors XXV
I Herbicides 1
Overview 3
MatthiasWitschel
1 HRACClassificationofHerbicidesandResistanceDevelopment 5
HubertMenneandHelmutKo¨cher
1.1 Introduction 5
1.2 HRACClassificationSystemofHerbicides 7
1.3 HerbicideResistance 7
1.3.1 BiochemistryofHerbicideResistance 13
1.3.1.1 Target-SiteResistance 14
1.3.1.2 Non-Target-SiteResistancebyEnhancedMetabolicDetoxification 21
1.3.1.3 Non-Target-SiteResistancebyAlteredHerbicideDistribution 24
1.3.1.4 MultipleResistance 25
References 26
2 AcetohydroxyacidSynthaseInhibitors(AHAS/ALS) 29
2.1 BiochemistryoftheTargetandResistance 29
StevenGutteridgeandMarkE.Thompson
2.1.1 AcetohydroxyacidSynthase(AHAS) 29
2.1.2 Higher-OrderSubunitStructure 33
2.1.3 HerbicidesThatTargetAHAS 35
2.1.4 BindingSiteforAHAS-InhibitingHerbicides 36
2.1.5 MolecularBasisforResistancetoAHASInhibitors 41
2.1.6 ResistancetoAHAS-InhibitingHerbicidesinWeeds 43
VI Contents
2.1.7 EngineeredResistancetoAHAS-InhibitingHerbicidesinCrops 46
Acknowledgments 46
References 47
2.2 NewerSulfonylureas 50
OswaldOrt
2.2.1 Introduction 50
2.2.1.1 HistoryandDevelopment 52
2.2.1.2 Synthesis 56
2.2.2 AgriculturalUtility 56
2.2.2.1 Cereals 57
2.2.2.2 Rice 67
2.2.2.3 Maize 75
2.2.2.4 OtherCrops 78
2.2.3 SulfonylureaHerbicides:MetabolicFateandBehaviorintheSoil 81
2.2.4 ConcludingRemarks 83
Acknowledgments 83
References 83
2.3 ImidazolinoneHerbicides 88
DaleL.Shaner,MarkStidham,BijaySingh,andSiyuanTan
2.3.1 Overview 88
2.3.2 HistoryofDiscovery 90
2.3.3 Physico-chemicalProperties 91
2.3.4 StructuralFeaturesofHerbicidalImidazolinones 92
2.3.5 Imidazolinones:TheModeofAction 93
2.3.6 Imidazolinone-TolerantCrops 94
2.3.7 Imidazolinones:MechanismsofSelectivity 95
2.3.8 CommercialUsesoftheImidazolinoneHerbicides 96
2.3.9 Conclusion 98
References 98
2.4 Triazolopyrimidines 99
TimothyC.Johnson,RichardK.Mann,PaulR.Schmitzer,
RogerE.Gast,andGerritJ.deBoer
2.4.1 Introduction 99
2.4.2 N-Triazolo[1,5-c]PyrimidineSulfonanilide 100
2.4.2.1 Synthesis 100
2.4.2.2 Biology 100
2.4.2.3 Cloransulam-MethylandDiclosulamCropUtility 102
2.4.2.4 MechanismofCropSelectivity 103
2.4.2.5 EnvironmentalDegradation,Ecotoxicology,andToxicology 104
2.4.3 N-Triazolo[1,5-c]PyrimidineSulfonamides 105
Contents VII
2.4.3.1 Synthesis 106
2.4.3.2 Biology 107
2.4.3.3 PenoxsulamCropUtility 109
2.4.3.4 Penoxsulam:MechanismofCropSelectivity 109
2.4.3.5 Penoxsulam:EnvironmentalDegradation,Ecotoxicology,and
Toxicology 110
2.4.4 N-Triazolo[1,5-a]PyrimidineSulfonamides 111
2.4.4.1 Synthesis 111
2.4.4.2 Biology 111
2.4.4.3 Pyroxsulam:CropUtility 112
2.4.4.4 Pyroxsulam:MechanismofCropSelectivity 112
2.4.4.5 Pyroxsulam:EnvironmentalDegradation,Ecotoxicology,and
Toxicology 113
2.4.5 AHASInhibition 114
2.4.6 Conclusions 115
References 115
2.5 PyrimidinylcarboxylatesandSulfonanilides 117
TakumiYoshimura,RyoHanai,andTsutomuShimizu
2.5.1 Introduction 117
2.5.2 DiscoveryofthePCsHerbicides 118
2.5.3 Structure–ActivityRelationshipsofPCsHerbicides 120
2.5.3.1 EffectsofBenzeneRingSubstituentsintheO-Pyrimidinylsalicylic
Acids 122
2.5.3.2 EffectofaBridgeAtominthePyrimidinylsalicylates 123
2.5.3.3 Pyrimidinylglycolates 123
2.5.4 ‘‘Pyrithiobac-Sodium’’:CottonHerbicide 125
2.5.4.1 Discovery 125
2.5.4.2 Biology 126
2.5.5 ‘‘Bispyribac-Sodium’’:HerbicideinDirect-SeededRice 128
2.5.5.1 Discovery 128
2.5.5.2 Biology 128
2.5.6 ‘‘Pyriminobac-Methyl’’:RiceHerbicide 129
2.5.6.1 Discovery 129
2.5.6.2 Biology 131
2.5.7 ModeofActionofthePCsHerbicides 132
2.5.8 ModeofSelectivityofthePCsHerbicidesinCrops 133
2.5.9 DiscoveryoftheSulfonanilides 134
2.5.10 Structure–ActivityRelationships 135
2.5.10.1 EffectoftheSulfonamideMoietyintheSulfonanilides 136
2.5.10.2 EffectsoftheBridgeMoietyintheSulfonanilides 136
2.5.10.3 EffectsofBenzeneRingSubstitutioninthe
Sulfonanilides 137
2.5.11 ‘‘Pyrimisulfan’’:RiceHerbicide 139
VIII Contents
2.5.11.1 Biology 139
Abbreviations 140
References 140
2.6 Sulfonylaminocarbonyl-Triazolinones 142
Klaus-HelmutMu¨ller,Ernst-RudolfF.Gesing,andHans-JoachimSantel
2.6.1 Introduction 142
2.6.2 DiscoveryoftheLeadStructure 143
2.6.3 OptimizationoftheLeadStructure 143
2.6.4 DiscoveryofThiencarbazone-Methyl(TCM) 146
2.6.5 Synthesis 148
2.6.5.1 SulfonylComponents 149
2.6.5.2 TriazolinoneSynthesis 150
2.6.6 Biology 151
2.6.7 Conclusions 158
References 158
3 ProtoporphyrinogenIXOxidaseInhibitors 163
GeorgeTheodoridis,RexLiebl,andCyrillZagar
3.1 Introduction 163
3.2 HistoricalDevelopment 165
3.2.1 DiphenylEther 165
3.2.2 PhenylRingAttachedtoHeterocycle 166
3.2.3 PhenylTetrahydrophthalimide 168
3.3 Non-ClassicalProtoxChemistries 171
3.3.1 N-PhenylHeterocycles:NewHeterocyclicSystems 172
3.3.2 PhenoxyphenylandBenzyloxyphenylAttachedtoHeterocycle 176
3.3.3 BenzoheterocyclicAttachedtoHeterocycle 178
3.3.4 BenzylAttachedtoHeterocycle 181
3.3.5 ReplacementofPhenylRingwithPyrazole 182
3.4 RecentDevelopments 182
3.5 Toxicology 190
3.6 Summary 190
References 191
4 HerbicideswithBleachingProperties 197
4.1 PhytoeneDesaturaseInhibitors 197
GerhardHamprechtandMatthiasWitschel
4.1.1 Introduction 197
4.1.2 CarotenoidBiosynthesisandPhytotoxicEffectsofBleaching
Herbicides 197
4.1.2.1 TargetsforBleachingHerbicides 197