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WO2012150207A1 - Utilisation de dérivés d'esters de l'acide cyclopropancarboxylique pour lutter contre les insectes résistants aux insecticides - Google Patents

Utilisation de dérivés d'esters de l'acide cyclopropancarboxylique pour lutter contre les insectes résistants aux insecticides Download PDF

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Publication number
WO2012150207A1
WO2012150207A1 PCT/EP2012/057888 EP2012057888W WO2012150207A1 WO 2012150207 A1 WO2012150207 A1 WO 2012150207A1 EP 2012057888 W EP2012057888 W EP 2012057888W WO 2012150207 A1 WO2012150207 A1 WO 2012150207A1
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WIPO (PCT)
Prior art keywords
spp
compounds
anopheles
ppm
nmr
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PCT/EP2012/057888
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German (de)
English (en)
Inventor
Peter Jeschke
Ralf Nauen
Arnd Voerste
Neil Berry
Naomi DYER
Peter Gibbons
Ian HALE
Weiqian David HONG
Chinyere OKPARA
Paul O´NEILL
Chandrakala Pidathala
Stephen Ward
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Bayer Cropscience Ag
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Publication of WO2012150207A1 publication Critical patent/WO2012150207A1/fr

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    • A—HUMAN NECESSITIES
    • A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
    • A01N—PRESERVATION OF BODIES OF HUMANS OR ANIMALS OR PLANTS OR PARTS THEREOF; BIOCIDES, e.g. AS DISINFECTANTS, AS PESTICIDES OR AS HERBICIDES; PEST REPELLANTS OR ATTRACTANTS; PLANT GROWTH REGULATORS
    • A01N53/00—Biocides, pest repellants or attractants, or plant growth regulators containing cyclopropane carboxylic acids or derivatives thereof
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D333/00—Heterocyclic compounds containing five-membered rings having one sulfur atom as the only ring hetero atom
    • C07D333/02—Heterocyclic compounds containing five-membered rings having one sulfur atom as the only ring hetero atom not condensed with other rings
    • C07D333/04—Heterocyclic compounds containing five-membered rings having one sulfur atom as the only ring hetero atom not condensed with other rings not substituted on the ring sulphur atom
    • C07D333/06—Heterocyclic compounds containing five-membered rings having one sulfur atom as the only ring hetero atom not condensed with other rings not substituted on the ring sulphur atom with only hydrogen atoms, hydrocarbon or substituted hydrocarbon radicals, directly attached to the ring carbon atoms
    • C07D333/08—Hydrogen atoms or radicals containing only hydrogen and carbon atoms
    • C07D333/10—Thiophene

Definitions

  • the present application relates to the use of derivatives of cyclopropanecarboxylic esters for controlling insecticide-resistant insects.
  • Resistance can be defined as an "inheritable change in the sensitivity of a pest population that is reflected in the repeated failure of a product to achieve the expected level of control when used against the pest species, according to the manufacturer's instructions.”
  • IRAC Insecticide Resistance Action Committee, IRAC, www Cross resistance occurs when resistance to one insecticide also leads to resistance to another insecticide, even if the insect has not come into contact with the latter due to the size and rapid generation sequence of populations of animal pests the risk of developing insecticide resistance, especially if insecticides are used incorrectly or too highly.
  • metabolic resistance There are several mechanisms of resistance development. The most common is metabolic resistance. For example, resistant insects can detoxify or destroy the insecticide faster, or they excrete it faster than normal sensitive insects. Insects use their internal enzyme systems to break down insecticides. Resistant insects have increased levels or more efficient forms of these enzymes. In addition to their higher efficiency, these enzymes can also have a broad spectrum of activity, ie reduce several different insecticides. Metabolic resistance depends on the structure of the drug. Therefore, metabolic resistance is most likely to be disrupted by drugs of different chemical structure. The second most common mechanism of resistance is a change in the target structure (protein, receptor, ion channel, etc.) of the insecticide.
  • target structure protein, receptor, ion channel, etc.
  • IRM Insecticide resistance management
  • IPM integrated pest management
  • the object of the present invention was to provide a class of compounds for controlling insecticide-resistant insects, in particular from the family of Culicidae.
  • the problem is solved, as well as other tasks not explicitly mentioned, which can be derived or deduced from the relationships discussed herein, by the use of the compounds of the formula
  • Ri is hydrogen, cyano, alkenyl or alkynyl
  • Y is CH or N
  • Z is halogen, n is 0, 1, 2 or 3,
  • M is oxygen, sulfur, methylene or oxymethylene
  • R 2 represents optionally substituted hetaryl, preferably pyridin-2-yl or pyridine-3 or one of the radicals from the series
  • the compounds of the formula (I) can also be present in different compositions as optical isomers or mixtures of isomers, which can optionally be separated in a customary manner.
  • the compounds of the formulas (Ia), (Ib), (Ic) or (Id) can be present both as mixtures and in the form of their pure isomers. If appropriate, mixtures of the compounds of the formulas (Ia), (Ib), (Ic) or (Id) can be separated by physical methods, for example by chromatographic methods. Furthermore, the compounds of the formula (I) can be present in the two isomeric forms of the formulas (IA) or (IB), depending on the position of the substituent Ri:
  • LG for an optionally in situ generated nucleofuge leaving group is, with compounds of the general formula (IV)
  • R 1, R 2, M, Y, Z and n have the meaning given above, optionally in the presence of a suitable acid binder and optionally in the presence of a suitable diluent.
  • the compounds of the invention are generally defined by the formula (I).
  • the compound has the general formula (II)
  • Y is CH or N
  • Z is halogen, n is 0, 1, 2 or 3,
  • R 2 represents optionally substituted hetaryl, preferably pyridin-2-yl or pyridin-3-yl, or one of the radicals from the series
  • Yi and Y 2 are bromine, chlorine or trifluoromethyl.
  • the compounds have the general formula (II.1) or (II.2):
  • Z is hydrogen or fluorine, n is 1, one of the radicals from the series
  • X 2, X 2 ', X 2 "independently of one another are C 1 -C -alkyl, C 1 -C -haloalkyl, C 1 -C 4 -alkoxy, C 1 -C 4 -halogenoalkoxy, C 1 -C 4 -haloalkylthio, C 1 -C 4 -haloalkylsulfmyl, C 1 -C 4 -alkyl C4- Halogenalkylsulfonyl, fluorine, chlorine, bromine, iodine or cyano, preferably trifluoromethyl, trifluoromethoxy, fluorine or chlorine, particularly preferably fluorine and chlorine.
  • the compounds have the general formula ( ⁇ .3),
  • Y is CH or N
  • Ri is hydrogen, cyano, alkenyl or alkynyl, preferably cyano, - -
  • Z is fluorine, chlorine, bromine or iodine, preferably fluorine
  • R 2 represents optionally substituted hetaryl, preferably pyridin-2-yl or pyridin-3-yl, or one of the radicals from the series
  • X 2 , X 2 ', X 2 are independently alkyl, haloalkyl, cycloalkyl, halogenocycloalkyl, alkenyl, haloalkenyl, alkynyl, alkoxy, haloalkoxy, alkoxycarbonyl, alkoxyalkyl, haloalkoxyalkyl, alkylthio, haloalkylthio, alkylsulfmyl, haloalkylsulfinyl, alkylsulfonyl, haloalkylsulfonyl , Halogen, nitro, cyano, amino, alkylamino, dialkylamino, and
  • Y 1 and Y 2 independently of one another are halogen or haloalkyl, preferably halogen is selected from the series bromine or chlorine, preferably haloalkyl is trifluoromethyl.
  • the determination of the absolute configuration can be made by X-ray structure analysis. - -
  • the compounds of formula (III) may, for. T. commercially or by literature methods according to the reaction scheme I (step C) are obtained from the corresponding 2,2-dimethyl-cyclopropanecarboxylic acids (A-l) (see also Preparation Example 1, step C).
  • LG stands for an in situ generated nucleofuge leaving group ("Leaving Group").
  • Examples of compounds of the formula (III) having a nucleofugic leaving group LG are known;
  • the compounds of the formula (IVa-1) are prepared from optionally Z-substituted 3-aryl (hetaryl) oxybenzaldehydes (A-4) which are obtainable by stage A / method I or stage A / method II, and the compounds of the formula (A-7a) are obtained by means of a suitable carbonyl reaction (see reaction scheme I, step B).
  • cyanohydrins 2-hydroxy-acetonitrile
  • IVa-1 2-hydroxy-acetonitrile
  • Cyanohydrin formation may be carried out in the presence of alkali metal cyanides (eg sodium cyanide, see K. Ozawa et al, Nippon Noyaku Gakkaishi 1986, 11, 169-174) or trimethylsilyl cyanide (TMS-CN, see LH McKendry, J. Labeled Comp., Radiopharm., 1984, 21, 401-408; U.S. Patent 4,221,799, see Preparation Example 1, Step B).
  • alkali metal cyanides eg sodium cyanide, see K. Ozawa et al, Nippon Noyaku Gakkaishi 1986, 11, 169-174
  • TMS-CN trimethylsilyl cyanide
  • a-ethynyl-3- (4-fluorophenoxy) -benzenemethanol (DE-OS 2,621,433) or a-ethynyl-4-fluoro-3-phenoxy) -benzenemethanol (WO 9408931) are known.
  • the optionally Z-substituted 3-aryl (hetaryl) oxybenzaldehydes (A-4) are either from optionally Z-substituted 3-formyl-phenylboronic acid derivatives of the formula (A-2) and (hetero) aromatic hydroxy compounds of the formula (A -3) (compare step A, method I) or from optionally Z-substituted 3-hydroxybenzaldehydes of the formula (A-5) and boronic acid derivatives of the formula (A-6) (compare step A, method II).
  • the optionally Z-substituted 3-formyl-phenylboronic acid derivatives of the formula (A-2) are known from the literature or accessible by methods known from the literature.
  • 4-ethoxy-3-formylphenylboronic acid WO 2008/057497
  • 4-fluoro-3-formylphenylboronic acid WO 2003/097576
  • the (hetero) aromatic hydroxy compounds of the formula (A-3) are known from the literature or can be obtained by methods known from the literature (for example preparation of phenols: see Houben-Weyl, Methoden der Organischen Chemie, Volume VI / 1c).
  • the optionally Z-substituted 3-hydroxybenzaldehydes of the formula (A-5) are known from the literature or can be obtained by methods known from the literature (for example preparation of aldehydes: see Houben-Weyl, Methoden der Organischen Chemie, Volume VII / 1, 2 Edition, p. 413).
  • boronic acid derivatives of the formula (A-6) are known from the literature or accessible by methods known from the literature (cf., Coupling Reactions with Boronic Acid Derivatives: Chem. Rev. 1995, 95, 2457-2483; Tetrahedron 2002, 58, 9633-9695, Metal-Catalyzed Cross- Coupling Reactions (Eds .: A. de Meijere, F. Diederich), 2 nd ed., Wiley-VCH, Weinheim, 2004).
  • step D The compounds required as starting materials for preparing the process (step D) according to the invention are generally defined by the formulas (III) and (IV).
  • the compounds of the formula (IVb-1) are prepared from optionally Z-substituted 3-aryl (hetaryl) methylbenzaldehydes (A-9) which are obtainable by stage A / method IV, and the compounds of the formula (A-7a ) by means of a suitable carbonyl reaction (compare Reaction Scheme IV, step B).
  • the radical R 1 is cyano
  • it is corresponding substituted 3- [hetaryl (aryl) methyl] -a-hydroxy-benzeneacetonitrile (cyanohydrins) (IVb-1), which are obtained by known preparation methods can.
  • Cyanohydrin formation can be carried out in the presence of alkali metal cyanides (eg sodium cyanide, see K. Ozawa et al, Nippon Noyaku Gakkishi 1986, 11, 169-174) or trimethylsilyl cyanide (TMS-CN, see LH McKendry, J. Biol. Labeled Comp., Radiopharm., 1984, 21, 401-408, U.S. Patent 4,221,799, see Preparation Example 1, Step B).
  • alkali metal cyanides eg sodium cyanide, see K. Ozawa et al, Nippon Noyaku Gakkishi 1986, 11, 169-174
  • TMS-CN trimethylsilyl cyanide
  • EP-A 18 315 3 - [(4-fluorophenyl) methyl] -a-hydroxybenzene acetonitrile
  • EP-A 227 415 4-fluoro- ⁇ -hydroxy-3- (phenylmethyl) benzene acetonitrile
  • EP-A 253 536 3 - [(4-fluorophenyl) methyl] -a-hydroxybenzene acetonitrile
  • EP-A 227 415 4-fluoro- ⁇ -hydroxy-3- (phenylmethyl) benzene acetonitrile
  • the (hetero) aromatic hydroxy compounds of the formula (A-2) are known from the literature or according to the methods described above, literature accessible.
  • the optionally Z-substituted halomethyl compounds of the formula (A-8) in which halogen may be chlorine, bromine or iodine are commercially available or obtainable by the methods known from the literature (for example bromomethylation: see Houben-Weyl, Methoden Chemische Chemie, Vol. V / 4, p. 784; chloromethylation of non-activated arenes: see H. Suzuki Bull. Chem. Soc., Japan, 1970, 43, 3299).
  • step D The compounds required as starting materials for preparing the process (step D) according to the invention are generally defined by the formulas (III) and (IV).
  • the compounds of the formula (IVc-1) are prepared from optionally Z-substituted 3-hydroxybenzaldehydes (A-5) which are obtainable by stage A / method V, and the compounds of formula (A-7a) by means of a suitable carbonyl reaction obtained (see Reaction Scheme V, step B).
  • cyanohydrins a-hydroxy-3- (phenylmethoxy) -benzeneacetonitriles
  • IVc-1 cyanohydrins
  • Cyanohydrin formation may be carried out in the presence of alkali metal cyanides (eg sodium cyanide, see K. Ozawa et al, Nippon Noyaku Gakkaishi 1986, 11, 169-174) or trimethylsilyl cyanide (TMS-CN, see LH McKendry, J. Labeled Comp. Ratiopharm 1984, 21, 401-408, U.S. Patent 4,221,799, see Preparation Example 1, Step B) ,
  • alkali metal cyanides eg sodium cyanide, see K. Ozawa et al, Nippon Noyaku Gakkaishi 1986, 11, 169-174
  • TMS-CN trimethylsilyl cyanide
  • halomethyl compounds of the formula (A-8), in which halogen may be chlorine, bromine or iodine are commercially available or obtainable in accordance with the methods described above and known from the literature.
  • reaction of compounds of the formula (IV) with the compounds of the formula (III) can also be carried out in the presence of a coupling agent for the carboxylic acid and optionally in the presence of a basic reaction auxiliary in one of the diluents given below.
  • Suitable coupling agents for carrying out the preparation process are all those which are suitable for the preparation of an amide bond (cf., for example, Houben-Weyl, Methods of Organic Chemistry, Volume 15/2; Bodansky et al., Peptide Synthesis 2nd ed. (Wiley & Sons, New York 1976) or Gross, Meierhofer, The Peptides: Analysis, Synthesis, Biology (Academic Press, New York 1979).
  • diluents are advantageously used in such an amount that the reaction mixture remains easy to stir throughout the process.
  • Suitable diluents for carrying out the process according to the invention are all inert organic solvents.
  • halogenated hydrocarbons especially chlorinated hydrocarbons such as tetraethylene, tetrachloroethane, dichloropropane, methylene chloride, dichlorobutane, chloroform, carbon tetrachloride, trichloroethane, trichlorethylene, pentachloroethane, difluorobenzene, 1,2-dichloroethane, chlorobenzene, bromobenzene, dichlorobenzene, chlorotoluene, trichlorobenzene; Alcohols, such as methanol, ethanol, isopropanol, butanol; Ethers such as ethyl propyl ether, methyl tert-butyl ether, n-butyl ether, anisole, phenol, cyclohexyl methyl ether, dimethyl ether, diethyl ether, dipropyl ether, diisopropyl ether
  • Mixtures of the solvents and diluents mentioned can also be used for the process according to the invention.
  • Preferred diluents for carrying out the process according to the invention are ethers, such as methyl tert-butyl ether, tetrahydrofuran or dioxane, in particular tetrahydrofuran.
  • the preparation of compounds of the formula (I) according to the preparation process is carried out by reacting compounds of the formula (IV) in the presence of compounds of the formula (III), if appropriate in the presence of an acid binder and, if appropriate, in one of the diluents mentioned.
  • the reaction time is generally 10 minutes to 48 hours.
  • the reaction takes place at temperatures between -10.degree. C. and + 200.degree. C., preferably between + 10.degree. C. and 120.degree. C., more preferably at room temperature.
  • acid binders As basic reaction auxiliaries for carrying out the process according to the invention, it is possible to use all suitable acid binders, such as amines, in particular tertiary amines and also alkali metal and alkaline earth metal compounds.
  • hydroxides, hydrides, oxides and carbonates of lithium, sodium, potassium, magnesium, calcium and barium as well as other basic compounds such as amidine or guanine dinb as ene 7-methyl-l, 5,7-triaza bicyclo (4.4.0) dec-5-ene (MTBD); Diazabicyclo (4.3.0) nonene (DBN), diazabicyclo (2.2.2) octane (DABCO), 1,8-diazabicyclo (5.4.0) undecene (DBU), cyclohexyltetrabutyl-guanidine (CyTBG), cyclohexyltetramethylguanidine (CyTMG) , ⁇ , ⁇ , ⁇ -tetramethyl-l, 8-naphthalenediamine, pentamethylpiperidine, tertiary amines such as triethylamine, trimethylamine, tribenzylamine, triis
  • Tertiary amines such as trimethylamine, triethylamine or N-ethyl-N, N-diisopropylamine are preferably used.
  • the compounds according to the invention can be present as geometrical and / or as optically active isomers or corresponding isomer mixtures in different compositions.
  • These stereoisomers are, for example, enantiomers, diastereomers, atropisomers or geometric isomers.
  • the invention thus comprises pure stereoisomers as well as any mixtures of these isomers.
  • the active compounds according to the invention are suitable for plant protection, favorable warm-blooded toxicity and good environmental compatibility for protecting plants and plant organs, for increasing crop yields, improving the quality of the crop and for controlling animal pests, in particular insects, arachnids, helminths, nematodes and mollusks found in agriculture, horticulture, livestock, forestry, gardens and recreational facilities, supplies and materials, and the sanitary sector.
  • animal pests in particular insects, arachnids, helminths, nematodes and mollusks found in agriculture, horticulture, livestock, forestry, gardens and recreational facilities, supplies and materials, and the sanitary sector.
  • They can preferably be used as crop protection agents. They are effective against normally sensitive and resistant species as well as against all or individual stages of development.
  • pests include: Pests of the genus Arthropoda, in particular of the class Arachnida eg Acarus spp., Aceria sheldoni, Aculops spp., Aculus spp., Amblyomma spp., Amphitetranychus viennensis, Argas spp., Boophilus spp., Brevipalpus spp., Bryobia graminum , Bryobia praetiosa, Centruroides spp., Chorioptes spp., Dermanyssus gallinae, Dermatophagoides pteronyssinus, Dermatophagoides farinae, Dermacentor spp., Eotetranychus spp., Epitrimerus pyri, Eutetranychus spp., Eriophyes spp., Glycyphagus domesticus, Halotydeus destructor, Hemit
  • Hyalomma spp. Ixodes spp., Latrodectus spp., Loxosceles spp., Metatetranychus spp., Neutrombicula autumnalis, Nuphersa spp., Oligonychus spp., Ornithodorus spp., Ornithonyssus spp., Panonychus spp., Phyllocoptruta oleivora, Polyphagotarsonemus latus, Psorop - Spp., Rhipicephalus spp., Rhizoglyphus spp., Sarcoptes spp., Scorpio maurus, Steneotarsonemus spp., Steneotarsonemus spinki, Tarsonemus spp., Tetranychus spp., Trombicula alfreddugesi, Vae jovis spp., Vasates lycopersici.
  • Insecta e.g. from the order of the Blattodea e.g. Blattella asahinai, Blattella germanica, Blatta orientalis, Leucophaea maderae, Panchlora spp., Parcoblatta spp., Periplaneta spp., Supella longipalpa.
  • the order of the Blattodea e.g. Blattella asahinai, Blattella germanica, Blatta orientalis, Leucophaea maderae, Panchlora spp., Parcoblatta spp., Periplaneta spp., Supella longipalpa.
  • Aedes spp. From the order of Diptera, for example, Aedes spp., Agromyza spp., Anastrepha spp., Anopheles spp., Asphondylia spp., Bactrocera spp., Bibio hortulanus, Calliphora erythrocephala, Calliphora vicina, Ceratitis - capitata, Chironomus spp., Chrysomyia spp., Chrysops spp., Chrysozona pluvialis, Cochliomyia spp., Contarinia spp., Cordylobia anthropophaga, Cricotopus sylvestris, Culex spp., Culicoides spp., Culiseta spp., Cuterebra spp., Dacus oleae, Dasyneura spp., Delia spp
  • Lucilla spp. Lutzomyia spp., Mansonia spp., Musca spp., Oestrus spp., Oscinella frit, Paratanytarsus spp., Paralauterbordiella subcincta, Pegomyia spp., Phlebotomus spp , Phorbia spp., Phormia spp., Piophila casei, Prodiplosis spp., Psila rosae, Rhagoletis spp., Sarcophaga spp., Simulium spp, Stomoxys spp., Tabanus spp., Tetanops spp., Tipula spp. ,
  • Hymenoptera e.g. Acromyrmex spp., Athalia spp., Atta spp., Diprion spp., Hoplo- campa spp., Lasius spp., Monomorium pharaonis, Sirex spp., Solenopsis invicta, Tapinoma spp., Uracus spp., Vespa spp., Xeris spp ..
  • Hofmannophila pseudospretella Homoeos oma spp., Homona spp., Hyponomeuta padella, Kakivoria flavofasciata, Laphygma spp., Laspeyresia mestela, Leucinodes orbonalis, Leucoptera spp., Lithocolletis spp., Lithophane antennata, Lobesia spp., Loxagrotis albicosta, Lymantria spp., Lyonetia spp , Malacosoma neustria, Maruca testulalis, Mamstra brassicae, Melanitis leda, Mocis spp., Monopis obviella, Mythimna separata, Nemapogon cloacellus, Nymphula spp., Oiketicus spp., Oria spp., Orthaga spp.,
  • Phthiraptera e.g. Damalinia spp., Haematopinus spp., Linognathus spp., Pediculus spp., Phylloera vastatrix, Phtirus pubis, Trichodectes spp.
  • siphonaptera e.g. Ceratophyllus spp., Ctenocephalides spp., Pulex irritans, Tunga penetrans, Xenopsylla cheopsis.
  • Thysanoptera e.g. Anaphothrips obscurus, Baliothrips biformis, Drepanothrips reuteri, Enneothrips hevens, Frankliniella spp., Heliothrips spp., Hercinothrips femoralis, Rhipiphorothrips cruentatus, Scirtothrips spp., Taeniothrips cardamomi, Thrips spp.
  • Symphyla e.g. Scutigerella spp ..
  • Pests of the Mollusca strain in particular of the bivalve class, e.g. Dreissena spp., As well as from the class Gastropoda e.g. Arion spp., Biomphalaria spp., Bulinus spp., Deroceras spp., Galba spp., Lymnaea spp., Oncomelania spp., Pomacea spp., Succinea spp.
  • Gastropoda e.g. Arion spp., Biomphalaria spp., Bulinus spp., Deroceras spp., Galba spp., Lymnaea spp., Oncomelania spp., Pomacea spp., Succinea spp.
  • Animal parasites from the strains of Plathelminthes and Nematoda e.g. Ancylostoma duodenale, Ancylostoma ceylanicum, Acylostoma braziliensis, Ancylostoma spp., Ascaris spp., Brugia malayi, Brugia timori, Bunostomum spp., Chabertia spp., Clonorchis spp., Cooperia spp., Dicrocoelium spp, Dictyocollus filaria, Diphyllobothrium latum, Dracunculus medinensis, Echinococcus granulosus, Echinococcus multilocularis, Enterobius vermicularis, Faciola spp., Haemonchus spp., Heterakis spp., Hymenolepis nana, Hyostrongulus spp., Loa Loa
  • Plant pests from the strain of Nematoda i. plant parasitic nematodes, in particular Aphelenchoides spp., Bursaphelenchus spp., Ditylenchus spp., Globodera spp., Heterodera spp., Longidorus spp., Meloidogyne spp., Pratylenchus spp., Radopholus spp., Trichodorus spp., Tylenchulus spp, Xiphinema Spp., Helicotylenchus spp., Tylenchorhynchus spp., Scutellonema spp., Paratrichodorus spp., Meloinema spp., Paraphelenchus spp., Aglenchus spp., Belonolaimus spp., Nacobbus spp, Rotylenchulus spp., Rotyle
  • the order of coccidia can be determined, e.g. Fight Eimeria spp.
  • the active compounds according to the invention are particularly suitable for controlling pyrethroid-resistant insects. Preference is given to pyrethroid-resistant insects which originate from the family of Culicidae, Muscidae or Blattidae. Particularly preferred are those insects which originate from the family of Culicidae. Most preferred are the insects selected from the genera group - -
  • insects are selected from the group of the genera Culex quinquefasciatus and Anopheles gambiae.
  • the compounds according to the invention can also be used in certain concentrations or application rates as herbicides, safeners, growth regulators or agents for improving plant properties, or as microbicides, for example as fungicides, antimycotics, bactericides, viricides (including anti-viral agents) or as anti-MLO agents (Mycoplasma -like-organism) and RLO (Rickettsia-like-organism). They can also be used as intermediates or precursors for the synthesis of other active ingredients.
  • the active compounds can be converted into the customary formulations, such as solutions, emulsions, wettable powders, water- and oil-based suspensions, powders, dusts, pastes, soluble powders, soluble granules, scattering granules, suspension-emulsion concentrates, active substance-impregnated natural products, active ingredient impregnated synthetic materials, fertilizers and microencapsules in polymeric materials.
  • customary formulations such as solutions, emulsions, wettable powders, water- and oil-based suspensions, powders, dusts, pastes, soluble powders, soluble granules, scattering granules, suspension-emulsion concentrates, active substance-impregnated natural products, active ingredient impregnated synthetic materials, fertilizers and microencapsules in polymeric materials.
  • formulations are prepared in a known manner, e.g. by mixing the active compounds with extenders, ie liquid solvents and / or solid carriers, if appropriate using surface-active agents, ie emulsifiers and / or dispersants and / or foam-forming agents.
  • extenders ie liquid solvents and / or solid carriers
  • surface-active agents ie emulsifiers and / or dispersants and / or foam-forming agents.
  • Excipients which can be used are those which are suitable for imparting special properties to the composition itself and / or preparations derived therefrom (for example spray liquor, seed dressing), such as certain technical properties and / or specific biological properties.
  • Typical auxiliaries are: extenders, solvents and carriers.
  • extender e.g. Water, polar and non-polar organic chemical liquids e.g.
  • aromatic and non-aromatic hydrocarbons such as paraffins, alkylbenzenes, alkylnaphthalenes, chlorobenzenes
  • alcohols and polyols which may also be substituted, etherified and / or esterified
  • ketones such as acetone, cyclohexanone
  • Esters including fats and oils
  • poly) ethers simple and substituted amines, amides, lactams (such as N-alkylpyrrolidones) and lactones, sulfones and sulfoxides (such as dimethyl sulfoxide).
  • organic solvents can also be used as auxiliary solvents.
  • Suitable liquid solvents are essentially: aromatics, such as xylene, toluene, or alkylnaphthalenes, chlorinated aromatics and chlorinated aliphatic hydrocarbons, such as chlorobenzenes, chloroethylenes or methylene chloride, aliphatic hydrocarbons, such as ?
  • Cyclohexane or paraffins e.g. Petroleum fractions, mineral and vegetable oils, alcohols, such as butanol or glycol, and their ethers and esters, ketones, such as acetone, methyl ethyl ketone, methyl isobutyl ketone or cyclohexanone, strongly polar solvents, such as dimethyl sulfoxide, and water.
  • Suitable solid carriers are: e.g. Ammonium salts and ground natural minerals, such as kaolins, clays, talc, chalk, quartz, attapulgite, montmorillonite or diatomaceous earth, and ground synthetic minerals, such as fumed silica, alumina and silicates, as solid carriers for granules are suitable: e.g. crushed and fractionated natural rocks such as calcite, marble, pumice, sepiolite, dolomite and synthetic granules of inorganic and organic flours and granules of organic material such as paper, sawdust, coconut shells, corn cobs and tobacco stalks; suitable emulsifiers and / or foam formers are: e.g.
  • nonionic and anionic emulsifiers such as polyoxyethylene fatty acid esters, polyoxyethylene fatty alcohol ethers, e.g. Alkylaryl polyglycol ethers, alkylsulfonates, alkyl sulfates, arylsulfonates and protein hydrolysates;
  • suitable dispersants are non-ionic and / or ionic substances, e.g.
  • POE and / or POP ethers from the classes of alcohol POE and / or POP ethers, acid and / or POP-POE esters, alkyl-aryl and / or POP-POE ethers, fatty and / or POP-POE adducts, POE and / or POP polyol derivatives, POE and / or POP sorbitol or sugar adducts, alkyl or aryl sulfates, sulfonates and phosphates or the corresponding PO ether adducts.
  • suitable oligo- or polymers e.g. starting from vinylic monomers, from acrylic acid, from EO and / or PO alone or in combination with e.g.
  • Adhesives such as carboxymethylcellulose, natural and synthetic powdery, granular or latex-like polymers can be used in the formulations, such as gum arabic, polyvinyl alcohol, polyvinyl acetate, as well as natural phospholipids such as cephalins and lecithins and synthetic phospholipids.
  • Dyes such as inorganic pigments, e.g. Iron oxide, titanium oxide, ferrocyan blue and organic dyes such as alizarin, azo and metal phthalocyanine dyes and trace nutrients such as salts of iron, manganese, boron, copper, cobalt, molybdenum and zinc.
  • inorganic pigments e.g. Iron oxide, titanium oxide, ferrocyan blue and organic dyes such as alizarin, azo and metal phthalocyanine dyes and trace nutrients such as salts of iron, manganese, boron, copper, cobalt, molybdenum and zinc.
  • additives may be fragrances, mineral or vegetable optionally modified oils, waxes and nutrients (also trace nutrients), such as salts of iron, manganese, boron, copper, cobalt, molybdenum and zinc.
  • Stabilizers such as low-temperature stabilizers, preservatives, antioxidants, light stabilizers or other agents which improve the chemical and / or physical stability, may furthermore be present.
  • the formulations generally contain between 0.01 and 98% by weight of active ingredient, preferably between 0.5 and 90%.
  • the active ingredient according to the invention may be present in its commercial formulations as well as in the formulations prepared from these formulations in admixture with other active ingredients such as insecticides, attractants, sterilants, bactericides, acaricides, nematicides, fungicides, growth regulators, herbicides, safeners, fertilizers or semiochemicals.
  • active ingredients such as insecticides, attractants, sterilants, bactericides, acaricides, nematicides, fungicides, growth regulators, herbicides, safeners, fertilizers or semiochemicals.
  • a mixture with other known active ingredients, such as herbicides, fertilizers, growth regulators, safeners, semiochemicals, or with agents for improving the plant properties is possible.
  • the active compounds according to the invention may also be present in the form of insecticides in their commercial formulations and in the forms prepared from these formulations in admixture with synergists.
  • Synergists are compounds which increase the effect of the active ingredients without the added synergist itself having to be active.
  • the active compounds according to the invention may furthermore, when used as insecticides in their commercial formulations and in the forms of use prepared from these formulations, be present in mixtures with inhibitors which reduce degradation of the active ingredient after application in the environment of the plant, on the surface of plant parts or in plant tissues ,
  • the active ingredient content of the application forms prepared from the commercial formulations can vary widely.
  • the active ingredient concentration of the application forms can be from 0.00000001 up to 95% by weight of active compound, preferably between 0.00001 and 1% by weight.
  • the application is done in a custom forms adapted to the application.
  • plants are understood as meaning all plants and plant populations, such as desired and undesired wild plants or crop plants (including naturally occurring crop plants).
  • Crop plants can be plants which can be obtained by conventional breeding and optimization methods or by biotechnological and genetic engineering methods or combinations of these methods, including the transgenic plants and including the plant varieties which can or can not be protected by plant breeders' rights.
  • Plant parts are understood to mean all aboveground and subterranean parts and organs of the plants, such as shoot, leaf, flower and root, examples of which include leaves, needles, stems, stems, flowers, fruiting bodies, fruits and seeds, as well as roots, tubers and rhizomes become.
  • the plant parts also include crops and vegetative and generative propagation material, such as cuttings, tubers, rhizomes, offshoots and seeds.
  • the treatment according to the invention of the plants and parts of plants with the active ingredients takes place directly or by acting on their environment, habitat or storage space according to the usual treatment methods, eg by dipping, spraying, evaporating, atomizing, spreading, brushing, injecting and in propagation material, in particular in seed, furthermore by single-layer or multi-layer encapsulation.
  • plants and their parts can be treated.
  • wild-type or plant species obtained by conventional biological breeding methods such as crossing or protoplast fusion
  • plant cultivars and their parts are treated.
  • transgenic plants and plant cultivars obtained by genetic engineering if appropriate in combination with conventional methods (Genetically Modified Organisms), and parts thereof are treated.
  • the terms "parts” or “parts of plants” or “plant parts” have been explained above.
  • Plant varieties are plants with new traits that have been bred either by conventional breeding, by mutagenesis or by recombinant DNA techniques. These can be varieties, biotypes and genotypes.
  • the treatment according to the invention may also give rise to superadditive ("synergistic") effects.
  • superadditive for example, reduced application rates and / or extents of the spectrum of action and / or enhancement of the effect of the substances and agents that can be used according to the invention, better plant growth, increased tolerance to high or low temperatures, increased tolerance to drought or to water or soil salt content, increased flowering efficiency, easier harvesting, acceleration of ripeness, higher crop yields, higher quality and / or higher nutritional value of the harvested products, higher shelf life and / or machinability of the harvested products possible, which exceed the actual expected effects.
  • the preferred plants or plant varieties to be treated according to the invention to be treated include all plants which, as a result of the genetic engineering modification, obtained genetic material which gives these plants particularly advantageous valuable properties ("traits").
  • traits are better plant growth, increased tolerance to high or low temperatures, increased tolerance to dryness or to bottoms salt, increased flowering, easier harvesting, acceleration of ripeness, higher crop yields, higher quality and / or higher nutritional value of the harvested products , higher shelf life and / or workability of the harvested products.
  • Further and particularly emphasized examples of such properties are an increased defense of the plants against animal and microbial pests, such as against insects, mites, phytopathogenic fungi, bacteria and / or viruses as well as an increased tolerance the plants against certain herbicidal active ingredients.
  • transgenic plants are the important crops such as cereals (wheat, rice), corn, soybeans, potatoes, sugar beets, tomatoes, peas and other vegetables, cotton, tobacco, oilseed rape and fruit plants (with the fruits apples, pears, citrus fruits and Grapes), with special emphasis on maize, soya, potato, cotton, tobacco and oilseed rape.
  • Traits which are particularly emphasized are the increased defense of the plants against insects, arachnids, nematodes and snails by toxins formed in the plants, in particular those produced by the genetic material from Bacillus thuringiensis (for example by the genes CrylA (cf.
  • Bt plants are produced in the plants (hereinafter "Bt plants”. Traits also highlight the increased resistance of plants to fungi, bacteria and viruses by systemic acquired resistance (SAR), systemin, phytoalexins, elicitors and resistance genes and correspondingly expressed proteins and toxins. Traits that are also particularly emphasized are the increased tolerance of the plants to certain herbicidal active compounds, for example imidazolinones, sulfonylureas, glyphosate or phosphinotricin (eg "PAT" gene).
  • SAR systemic acquired resistance
  • PAT phosphinotricin
  • genes which confer the desired properties can also occur in combinations with one another in the transgenic plants.
  • “Bt plants” are maize varieties, cotton varieties, soya bean varieties and potato varieties which are sold under the trade names YIELD GARD ® (for example maize, cotton, soya beans), KnockOut ® (for example maize), StarLink ® (for example maize), Bollgard ® ( cotton), NuCOTN ® (cotton) and NewLeaf ® (KAR toffel) are sold.
  • herbicide-tolerant plants are maize varieties, cotton varieties and soybean varieties may be mentioned, under the trade names Roundup Ready ® (tolerance to Gly phosate example maize, cotton, soya bean), Liberty Link ® (tolerance to phosphinotricin, for example oilseed rape), IMI ® (Tolerance to imidazolinone) and STS ® (tolerance to sulfonylureas eg corn).
  • Roundup Ready ® to Gly phosate example maize, cotton, soya bean
  • Liberty Link ® tolerance to phosphinotricin, for example oilseed rape
  • IMI ® Tolerance to imidazolinone
  • STS ® tolerance to sulfonylureas eg corn
  • Clearfield ® varieties eg corn
  • Step A (Method I): 3- (4-fluorophenoxy) benzaldehyde (cf also DE-OS 2 615 435)
  • step A 0.19 g (0.9 mmol) of 3- (4-fluorophenoxy) benzaldehyde (step A) were stirred in 5 ml of dry dichloromethane under an inert gas atmosphere (nitrogen). Thereafter, 0.34 ml (2.7 mmol) of trimethylsilyl cyanide and 0.013 ml (0.09 mmol) of triethylamine were added, and the reaction mixture was stirred at room temperature for 2 hours. Subsequently, the reaction mixture was dissolved in 2 ml of THF. After addition of 2 ml of 2N hydrochloric acid was stirred for a further two hours at room temperature. The THF was distilled off in vacuo and the remaining residue was diluted with water.
  • Step C (1R, 3R) -3- (2,2-dibromethenyl) -2,2-dimethylcyclopropanecarboxylic acid chloride (also see
  • Step D (1R, 3R) -3- (2,2-Dibromoethenyl) -2,2-dimethyl-cyclopropanecarboxylic acid cyano [3- (4-fluorophenoxy) phenyl] methyl ester 327 mg (1.1 mmol) of the product obtained in step C (1R, 3R) -3- (2,2-dibromethenyl) -2,2-dimethyl-cyclopropanecarboxylic acid chloride was stirred under inert gas atmosphere in 2 ml of THF and added dropwise at 0 ° C with a solution of 243 mg (1.0 mmol ) 2- (3- (4-fluorophenoxy) phenyl) -2-hydroxy-acetonitrile in 3 mL of anhydrous THF and then with 153 mL (1.1 mmol) of triethylamine.
  • reaction mixture was stirred for 2 hours at room temperature, then treated with saturated brine and extracted with ethyl acetate.
  • the organic extracts were combined and washed successively with 1N hydrochloric acid, saturated sodium bicarbonate solution and saturated brine. Subsequently, the separated organic phase was dried over magnesium sulfate, and after filtration from filtered under reduced pressure.
  • a yellow oil is obtained which is purified by column chromatography (silica gel, eluent: 5% ethyl acetate: hexane) 460 mg (80% of theory) (1R, 3R) -3- (2,2-dibromethenyl) -2,2-dimethyl- cyclopropanecarboxylic acid cyano [3- (4-fluorophenoxy) phenyl] methyl ester as a colorless oil.
  • the (1: 1) mixture of diastereomers can be separated by preparative HPLC (column Knauer, normal phase, dimension: 250 ⁇ 20 mm, filling: Eurosper 100-5 Si, detection of the wavelength at 254 nm).
  • the column was eluted with 8% ethyl acetate / hexane at a flow rate of 5 mL / min.
  • Example 4a (1R, 3R) -3- (2-chloro-2-trifluoromethenyl) -2,2-dimethyl-cyclopropanecarboxylic acid (R) -cyan [3- (3-fluorophenoxy) phenyl] methyl ester - 5 -
  • X-ray structure determination of a suitable single crystal of example 5b was carried out with a Bruker D8 diffractometer with APEX CCD detector and a 1.5 kW graphite monochromatic Mo radiation. Structure resolution was performed using X-SEED (Barbour, LJ "X-Seed - A Software tool for supramolecular crystallography" J. Supramol. Chem., 2001, 1, 1 89-191), a graphical interface to SHELX97 (G. Sheldrick, SHELX-97 Programs for Solving and Refining Crystal Structures, Institute of Inorganic Chemistry, University of Tammanstrasse 4, D-3400 Gottingen, Germany, 1997). The value of the absolute structure parameters (0.01 (1)) confirms the absolute configuration of Example 5b.
  • Step A (Method II): 4-fluoro-3- (4-fluorophenoxy) benzaldehyde (cf also DE-OS 2,739,854)
  • Example 7b (1R, 3R) -3- (2,2-Dibromoethenyl) -2,2-dimethylcyclopropanecarboxylic acid (S) -cyano [4-fluoro-3- (4-chlorophenoxy) phenyl] methyl ester
  • Example 10b (1R, 3R) -3- (2-chloro-2-trifluoromethenyl) -2,2-dimethyl-cyclopropanecarboxylic acid (S) -cyano [4-fluoro-3- (4-chlorophenoxy) phenyl] methyl ester - -
  • Step A It is 4-fluoro-3- (4-fluorophenoxy) benzaldehyde (see also DE-OS 2,739,854) g
  • Step B 3- (4-Fluorophenoxy) phenyl) -a-ethynyl-4-fluorobenzenemethanol
  • Step A 0.59 g (2.53 mmol) of 3- (fluorophenoxy) benzaldehyde (Step A, Method II) were stirred in 10 ml of dry tetrahydrofuran under an inert gas atmosphere (nitrogen). Thereafter, with stirring, 7.6 ml (3.8 mmol) of lithium tetramethylsilyl-acetylene (as a 0.5 M solution in THF) was added at a temperature of -78 ° C and heated to 0 ° C within 3 hours. Subsequently, the reaction mixture was treated with a saturated ammonium chloride solution and extracted with ethyl acetate. The organic phase was dried over magnesium sulfate and concentrated in vacuo.
  • reaction mixture is mixed with 50 ml of 1N hydrochloric acid and extracted three times with 30 ml of ethyl acetate.
  • the combined organic phases are dried over magnesium sulfate, filtered and concentrated in vacuo.
  • the remaining crude product was purified by flash chromatography (silica gel, eluent: 10% ethyl acetate: hexane). This gives 0.5 g (80% of theory) of pure 3 - [(4-fluorophenyl) methyl] benzaldehyde which can be reacted further in accordance with Example 1 (see stages BD). - -
  • Step A 4-Fluoro-3- (4-fluorophenylmethoxy) -benzaldehyde
  • Example 18 was obtained. - -
  • Step A 2-bromo-6- (4-fluorophenoxy) pyridine (see also J.W. Street et al., Neth. Recueil des
  • Step B 6- (4-fluorophenoxy) -2-pyridine-carboxaldehyde (see also US 4,281,133)
  • Step C 2- (6- (4-Fluoro-phenoxy) -2-pyridinyl) -2-hydroxy-acetonitrile (see also US-P 4,221,799)
  • reaction solution was made alkaline with about 20 ml of saturated aqueous sodium bicarbonate solution (pH 8) and extracted three times with 50 ml of ethyl acetate.
  • the combined organic phases were washed with 50 ml of saturated brine. Subsequently, the separated organic phase was dried over magnesium sulfate, and concentrated after filtering in vacuo.
  • a clear oil is obtained, which is purified by column chromatography (eluent: 25% ethyl acetate: hexanes) 0.50 g (59% of theory) of 2- (6- (4-fluorophenoxy) -2-pyridinyl) -2-hydroxy-acetonitrile clear oil results.
  • Step D (1R, 3R) -3- (2,2-dibromethenyl) -2,2-dimethylcyclopropanecarboxylic acid chloride (also see
  • Step E (1R, 3R) -3- (2,2-Dibromoethenyl) -2,2-dimethylcyclopropanecarboxylic acid cyano [6- (4-fluoro-phenoxy-2-pyridinyl) methyl ester
  • the (1R, 3R) -3- (2,2-dibromoethenyl) -2,2-dimethyl-cyclopropanecarboxylic acid chloride obtained in step D was stirred under inert gas atmosphere in 30 ml of THF. Thereafter, with a solution of 0.30 g (1.23 mmol) of 2- (6- (4-fluorophenoxy) -2-pyridinyl) -2-hydroxy-acetonitrile (see step C), in 5.0 ml of THF and 0.21 ml (1.48 mmol) of triethylamine. After two hours of stirring at room temperature, the entire reaction mixture was mixed with 50 ml of ethyl acetate.
  • a yellow oil is obtained which is purified by column chromatography (eluent: 15% ethyl acetate: hexanes) 0.36 g (56% of theory) (1R, 3R) -3- (2,2-dibromethenyl) -2,2-dimethyl- cyclopropanecarboxylic acid cyano [6- (4-fluoro-phenoxy-2-pyridinyl) methyl ester as a pale yellow oil.
  • the (l: l) mixture of diastereomers can be separated by column chromatography.
  • Diastereomer I ES HRMS: m / z found: 544.9523 C2iHi 7 N 2 03F 23 Na 79 Br2 calculates: 544.9488.
  • Examples 20 to 24 can be obtained.
  • Solvent 2 Dow Corning 556 Silicone Fluid To prepare the active compound preparations according to the invention, the amount of active compound required for the desired concentration (%> m / v) is dissolved in 0.7 ml of solvent 1 and then mixed with 0.7 ml of solvent 2.
  • Each 1.4 ml of a drug solution are dropped onto a filter paper and the soaked papers dried overnight.
  • Each 20 non-blood-fed, 3-5 day old female mosquitoes [Anopheles funestus FANG (sensitive) or Anopheles funestus FUMOZ (resistant)] are brought into contact with one of the soaked filter papers for 60 minutes. Subsequently, the mosquitoes are removed from the filter paper and supplied with sugar water.
  • the mean lethal concentration LC50 is the statistically calculated concentration of a substance that is expected to be 50% of the exposed animals within the study period afterwards leads to death.).
  • the quotient "LC50 (FUMOZ-R) / LC50 (FANG)" represents the resistance ratio RR and is then determined accordingly from the LC50 values.

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Abstract

La présente demande concerne l'utilisation de dérivés d'esters de l'acide cyclopropancarboxylique pour lutter contre les insectes résistants aux insecticides.
PCT/EP2012/057888 2011-05-04 2012-04-30 Utilisation de dérivés d'esters de l'acide cyclopropancarboxylique pour lutter contre les insectes résistants aux insecticides WO2012150207A1 (fr)

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CN104649908A (zh) * 2013-11-18 2015-05-27 江苏扬农化工股份有限公司 一种单一立体构型的拟除虫菊酯化合物及其制备方法和应用

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Cited By (2)

* Cited by examiner, † Cited by third party
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CN104649908A (zh) * 2013-11-18 2015-05-27 江苏扬农化工股份有限公司 一种单一立体构型的拟除虫菊酯化合物及其制备方法和应用
CN104649908B (zh) * 2013-11-18 2016-08-24 江苏扬农化工股份有限公司 一种单一立体构型的拟除虫菊酯化合物及其制备方法和应用

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