WO2012150223A1 - Nouveaux pyridinmethylesters de l'acide cyclopropancarboxylique utilisés comme pesticides - Google Patents

Nouveaux pyridinmethylesters de l'acide cyclopropancarboxylique utilisés comme pesticides Download PDF

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Publication number
WO2012150223A1
WO2012150223A1 PCT/EP2012/057931 EP2012057931W WO2012150223A1 WO 2012150223 A1 WO2012150223 A1 WO 2012150223A1 EP 2012057931 W EP2012057931 W EP 2012057931W WO 2012150223 A1 WO2012150223 A1 WO 2012150223A1
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spp
compounds
formula
radicals
cyano
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PCT/EP2012/057931
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German (de)
English (en)
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Peter Jeschke
Arnd Voerste
Neil Berry
Peter Gibbons
Weiqian David HONG
Paul O'neill
Stephen Ward
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Bayer Cropscience Ag
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Publication of WO2012150223A1 publication Critical patent/WO2012150223A1/fr

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    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D213/00—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members
    • C07D213/02—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members having three double bonds between ring members or between ring members and non-ring members
    • C07D213/04—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members having three double bonds between ring members or between ring members and non-ring members having no bond between the ring nitrogen atom and a non-ring member or having only hydrogen or carbon atoms directly attached to the ring nitrogen atom
    • C07D213/60—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members having three double bonds between ring members or between ring members and non-ring members having no bond between the ring nitrogen atom and a non-ring member or having only hydrogen or carbon atoms directly attached to the ring nitrogen atom with hetero atoms or with carbon atoms having three bonds to hetero atoms with at the most one bond to halogen, e.g. ester or nitrile radicals, directly attached to ring carbon atoms
    • C07D213/62—Oxygen or sulfur atoms
    • C07D213/63—One oxygen atom
    • C07D213/64—One oxygen atom attached in position 2 or 6
    • C07D213/647—One oxygen atom attached in position 2 or 6 and having in the molecule an acyl radical containing a saturated three-membered ring, e.g. chrysanthemumic acid esters
    • 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

Definitions

  • the present application relates to novel pyridinemethyl esters of cyclopropanecarboxylic acid, to processes for their preparation and to their use for controlling animal pests, in particular arthropods and in particular insects, arachnids and nematodes.
  • the object of the present invention was to provide compounds which broaden the spectrum of pesticides from various aspects.
  • Ri is hydrogen, cyano, alkenyl or akinyl
  • Z is halogen and 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
  • X, X 'and X "independently represent alkyl, haloalkyl, cycloalkyl, halocycloalkyl, alkenyl, haloalkenyl, alkynyl, alkoxy, haloalkoxy, alkoxycarbonyl, alkoxyalkyl, haloalkoxyalkyl, alkylthio Haloalkylthio, alkylsulfmyl, haloalkylsulfinyl, alkylsulfonyl, haloalkylsulfonyl, halogen, nitro, cyano, amino, alkylamino, dialkylamino, and Yi and Y2 independently of one another are halogen or haloalkyl, preferably halogen is selected from the series bromine or chlorine, preferably haloalkyl is trifluoromethyl where in the case of the phenyl, preferably haloalkyl is trifluoro
  • 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 formula (I) can be present in the two isomeric forms of the formulas (I-A) or (I-B), depending on the position of the substituent Ri:
  • the compounds of the formulas (I-A) or (I-B) can be present both as mixtures and in the form of their pure isomers. If desired, mixtures of the compounds of the formulas (I-A) and (I-B) can be separated by physical methods, for example by chromatographic methods.
  • Y 1 and Y 2 have the meaning given above, and
  • LG for an in situ generated nucleofuge leaving group is, with compounds of general formula (III)
  • R 1 , R 2 , Z and n have the meaning given above, if appropriate in the presence of a suitable acid binder and optionally in the presence of a suitable diluent.
  • novel compounds of the formula (I) have pronounced biological properties and, above all, for controlling animal pests, in particular insects, arachnids and nematodes, which are used in agriculture, in forestry, in the protection of stored products and materials, and on the hygiene sector are suitable.
  • the compounds of the invention are generally defined by the formula (I).
  • the compound has the general formula (IV)
  • Z is fluorine or chlorine, n is 0, 1 or 2, R2 is one of the radicals from the series
  • X, X 'and X are each, independently of one another, C 1 -C -alkyl, C 1 -C -haloalkyl, C 3 -C -cycloalkyl, C 3 -C 5 -halocycloalkyl, C 3 -C -alkenyl, C 2 -C -haloalkenyl, C 2 -C 4 -alkynyl, C 1 -C 4 -alkoxy, C 1 -C 4 -haloalkoxy, C 1 -C 4 -alkoxycarbonyl, C 1 -C 4 -alkoxy-C 1 -C 4 -alkyl, C 1 -C 4 -haloalkoxy-C 1 -C 4 -alkyl, C 4 -alkylthio, C 1 -C 4 -haloalkylthio, C 1 -C 4 -alkylsulfmyl, C 1 -C 4 -hal
  • R2 (A) the radicals Yi and Y2 are identical.
  • Z is fluorine, n is 0 or 1,
  • X, X 'and X "independently of one another are C 1 -C -alkyl, C 1 -C -haloalkyl, C 1 -C -alkoxy, C 1 -C 4 -halogenoalkoxy, C 1 -C 4 -haloalkylthio, C 1 -C 4 -haloalkylsulfmyl, C 1 -C4-
  • Halogenalkylsulfonyl, fluorine, chlorine, bromine, iodine or cyano, wherein in the case of the phenyl ring R2 (A) the radicals Yi and Y2 are identical.
  • the compounds have the general formula (VII)
  • the compounds have the general formula (IX)
  • R 1 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, X 'and X are each 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, stand, and Y 1 and Y 2 independently of one another are halogen or haloalkyl, preferably halogen is selected from the group bromine or chlorine, preferably haloalkyl is trifluoromethyl.
  • the compounds of the formula (I) according to the invention can be prepared by customary methods known to the person skilled in the art.
  • the compounds required as starting materials for preparing the process (stage E) according to the invention are generally defined by the formulas (II) and (III).
  • Yi, Y2, Z n, Ri and R2 preferably represent those radicals which have already been mentioned in connection with the description of the substances of the general formula (I) according to the invention as preferred substituents.
  • the compounds of formula (II) may, for. T. commercially or by literature methods according to the reaction scheme I (step D) are obtained from the corresponding 2,2-dimethyl-cyclopropanecarboxylic acids (Al) (see also Preparation Example 1, step D).
  • LG represents an optionally in-situ generated nucleofuge leaving group ("Leaving Group").
  • reaction of compounds of (II) with the compounds of 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).
  • the compounds of the formula (III) are known or can be obtained by methods known from the literature in accordance with reaction scheme I (cf., Preparation Example 1, Steps A to C).
  • the compounds of formula (III) are obtained from Z-substituted-6-aryloxypyridine-2-carboxylic acid aldehydes (A-5) and the compounds of formula (A-6) by means of suitable carbonyl reaction.
  • R i is cyano
  • Cyanohydrin formation can 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. Chem Labeled Comp. Radiopharm., 1984, 21, 401-408, US 4,221,799, see Preparation Example 1, Step C).
  • alkali metal cyanides eg sodium cyanide, see K. Ozawa et al, Nippon Noyaku Gakkaishi 1986, 11, 169-174
  • TMS-CN trimethylsilyl cyanide
  • the radical R 1 is ethynyl
  • 6- (4-fluorophenoxy) -2-pyridine-carboxaldehyde US 4,281,133
  • 6- (2-fluorophenoxy) -2-pyridine-carboxaldehyde 6- (2-fluorophenoxy) -2-pyridine-carboxaldehyde
  • 6- (3-fluorophenoxy) - 2-pyridine-carboxaldehyde 6- (3-difluoromethoxyphenoxy) -2-pyridine-carboxaldehyde or 6- (3-trifluoromethyl-phenoxy) -2-pyridine-carboxaldehyde
  • DE-OS 3200963 6- (4-fluorophenoxy) -2-pyridine-carboxaldehyde (US 4,281,133)
  • 6- (2-fluorophenoxy) -2-pyridine-carboxaldehyde 6- (3-fluorophenoxy) - 2-pyridine-carboxaldehyde
  • a formamide such as NN-dimethylformamide or N-methylformanilide, or an ester such as orthoformic acid ester or ethyl formate. Particularly preferred is N, N-dimethylformamide.
  • the optionally Z-substituted 2-halo-6-aryloxypyridines of the formula (A-4) are obtained from corresponding 2,6-dihalopyridines (A-2) and hydroxylated aromatic compounds (A-3),
  • phenols according to methods known in the literature accessible (step A, see, for example, 2-bromo-6- (4-fluorophenoxy) pyridine: J Street, et al., Neth Recueil des Travaux Chimiques des Pays- Bas 1969, 88, 1391-412) ,
  • suitable starting compounds for the preparation of the compounds of the formula (A-5) are, for example, 6-aryloxypyridine-2-carboxylic acid alkyl esters (A-7). These starting compounds can be obtained by methods known from the literature and can then be reduced to give the compounds (A-5), for example in the presence of diisobutylaluminum hydride (compare US Pat. Nos. 5,013,352, 4,228,172) (see reaction scheme III).
  • compounds of the formula (A-8) can also be converted into aldehydes (A-5) by oxidation, for example with sodium periodate (cf., WO 2010/042646).
  • 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 (II) 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 ° C and + 200 ° C, preferably between + 10 ° C and 120 ° C, more preferably at room temperature.
  • 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 further basic compounds such as amidine bases or guanidine salts such as 7-methyl-l, 5,7-triaza-bicyclo ( 4.4.0) dec-5-en (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, triiso
  • 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 geometric 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 compounds of the invention may optionally be present in different polymorphic forms or as a mixture of different polymorphic forms. Both the pure polymorphs and the polymorph mixtures are the subject of the invention and can be used according to the invention.
  • the active compounds according to the invention are suitable for plant tolerance, 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 molluscs which are found in agriculture, horticulture, livestock, forests, gardens and recreational facilities, in the protection of materials and materials and in the hygiene 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.
  • the above mentioned pests include:
  • Pests of the Arthropoda strain in particular of the class Arachnida, e.g. 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.
  • 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.
  • Curculio spp. Cryptolestes ferruginus, Cryptorhynchus lapathi, Cylindrocopturus spp., Dermestes spp., Diabrotica spp., Dichocrocis spp., Dicladispa armigera, Diloboderus spp., Epilachna spp., Epitrix spp., Faustinus spp., Gibbium psylloides, Gnathocerus cornutus , Hellula undalis, Hete ronychus arator, Heteronyx spp., Hylamorpha elegans, Hylotrupes bajulus, Hypera postica, Hypomeces squamosus, Hypothenemus spp., Lachnosterna consanguinea, Lasioderma serricorne, Latheticus oryzae, Lathridius spp., Lema spp., Leptinotarsa
  • Euphyllura spp. Euscelis bilobatus, Ferrisia spp., Geococcus coffeae, Glycaspis spp., Heteropsylla cubana, Heteropsylla spinulosa, Homalodisca coagulata, Hyalopterus arundinis, Icerya spp., Idiocerus spp., Idioscopus spp., Laodelphax striatellus, Lecanium spp ., Lepidosaphes spp., Lipaphis erysimi, Macrosiphum spp., Macrosteies facifrons, Mahanarva spp., Melanaphis sacchari, Metcalfiella spp., Metopolophium dirhodum, Monellia costalis, Monelliopsis peca Nysonovia ribisnigri, Nephotettix spp., Nettigonic
  • 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 ..
  • Phthiraptera e.g. Damalinia spp., Haematopinus spp., Linognathus spp., Pediculus spp., Phylloera vastatrix, Phtirus pubis, Trichodectes spp ..
  • Psocoptera e.g. Lepinotus spp., Liposcelis 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, Rhiprophorothrips cruentatus, Scirtothrips spp., Taeniothrips cardamomi, Thrips spp.
  • Symphyla e.g. Scutigerella spp ..
  • Pests from the strain of Mollusca in particular from the class of bivalvia, eg Dreissena spp., And from the class of Gastropoda eg 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 eg Ancylostoma duodenale, Ancylostoma ceylanicum, Acylostoma braziliensis, Ancylostoma spp., Ascaris spp., Brugia malayi, Brugia timori, Bunostomum spp., Chabertia spp., Clonorchis spp., Cooperia spp.
  • Dicrocoelium 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, Nematodirus spp.
  • 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, Rotylenchus spp., Rotylench
  • 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 agents against viroids) or as anti-MLO agents (Mycoplasma-like-organism) and RLO (Rickettsia-like-organism) are used. 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 Feinstverkapselitch in polymeric materials.
  • 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 Feinstverkapselitch in polymeric materials.
  • formulations are prepared in a known manner, for example by mixing the active compounds with extenders, ie liquid solvents and / or solid carriers, optionally with use of 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.
  • polar and non-polar organic chemical liquids e.g. from the classes of 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) and (poly) ethers, the simple and substituted amines, amides, lactams (such as N-alkylpyrrolidones) and lactones, the sulfones and sulfoxides (such as dimethyl sulfoxide).
  • aromatic and non-aromatic hydrocarbons such as paraffins, alkylbenzenes, alkylnaphthalenes, chlorobenzenes
  • alcohols and polyols which may also be substituted, etherified and / or esterified
  • 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.
  • alcohols such as butanol or glycol
  • 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: for example, ammonium salts and ground natural minerals, such as kaolins, clays, talc, chalk, quartz, attapulgite, montmorillonite or diatomaceous earth, and ground synthetic minerals, such as finely divided silica, alumina and silicates, as solid carriers for granules: eg fractured 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: for example nonionic and anionic emulsifiers, such as polyoxyethylene fatty acid esters, polyoxyethylene fatty alcohol ethers, for example alkylaryl polyglycol ethers, alkylsulfonates, alkyl sulfates, arylsulf
  • oligomers or polymers for example starting from vinylic monomers, from acrylic acid, from EO and / or PO alone or in combination with, for example, (poly) alcohols or (poly) amine.
  • lignin and its sulphonic acid derivatives simple and modified celluloses, aromatic and / or aliphatic sulphonic acids and also adducts thereof with formaldehyde.
  • adhesives such as carboxymethylcellulose, natural and synthetic powdery, gromige or latex-shaped polymers, such as gum arabic, polyvinyl alcohol, polyvinyl acetate, and 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 cold stabilizers, preservatives, antioxidants, light stabilizers or other agents which improve the chemical and / or physical stability can also 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 can 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-regulating substances, 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 can furthermore be present when used as insecticides in their commercial formulations and in the forms of use 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 can also be used as insecticides in their commercial formulations as well as in the formulations prepared from these formulations in mixtures with inhibitors which are a degradation of the active ingredient after application in the environment of the plant, on the surface of plant parts or in plant tissues Reduce.
  • the active ingredient content of the application forms prepared from the commercial formulations can vary widely.
  • the active ingredient concentration of the use forms may 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 and parts of plants can be treated.
  • 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 protectable or non-protectable plant varieties by plant breeders.
  • Plant parts are to be understood as meaning all aboveground and underground parts and organs of the plants, such as shoot, leaf, flower and root, by way of example leaves, needles, stems, stems, flowers, fruiting bodies, fruits and seeds and roots, tubers and rhizomes.
  • 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 plant parts with the active ingredients is carried out directly or by acting on their environment, habitat or storage space according to the usual treatment methods, e.g. by dipping, spraying, evaporating, atomizing, spreading, brushing, injecting and in propagating material, in particular in seed, further by single or multilayer coating.
  • 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. It is particularly preferred according to the invention to treat plants of the respective commercially available or in use plant cultivars. Plant varieties are understood as meaning plants with new traits that have been bred either by conventional breeding, by mutagenesis or by recombinant DNA techniques.
  • the treatment according to the invention may also give rise to superadditive ("synergistic") effects.
  • superadditive for example, reduced application rates and / or enhancements of the spectrum of action and / or an increase in the effect of the substances and agents which 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 go beyond the actual expected effects.
  • the preferred plants or plant cultivars to be treated according to the invention which are 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 drought or soil salt content, increased flowering efficiency, easier harvest, acceleration of ripeness, higher crop yields, higher quality and / or higher nutritional value 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, as against insects, mites, phytopathogenic fungi, bacteria and / or viruses as well as an increased tolerance of the plants against certain herbicidal active substances.
  • 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 produced in the plants, in particular those produced by the genetic material from Bacillus thuringiensis (eg by the genes CrylA (a) , CrylA (b), CrylA (c), CryllA, Cryll-IA, CryIIIB2, Cry9c Cry2Ab, Cry3Bb and CrylF and combinations thereof) 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.
  • SAR systemic acquired resistance
  • Plants are maize varieties, cottonseed varieties, soybean varieties and potato locations, which are sold under the trade names YIELD GARD® (eg maize, cotton, soya), KnockOut® (eg maize), StarLink® (eg maize), Bollgard® (cotton), Nucotn® (cotton) and NewLeaf® (potato).
  • YIELD GARD® eg maize, cotton, soya
  • KnockOut® eg maize
  • StarLink® eg maize
  • Bollgard® cotton
  • Nucotn® cotton
  • NewLeaf® potato
  • herbicide-tolerant plants maize varieties, cotton varieties and soybean varieties are mentioned under the trade names Roundup Ready® (tolerance to glyphosate eg corn, cotton, soy), Liberty Link® (tolerance to phosphinotricin, eg rapeseed), IMI® (tolerance to imidazolinone ) and STS® (tolerance to sulfonylureas eg corn).
  • Roundup Ready® tolerance to glyphosate eg corn, cotton, soy
  • Liberty Link® tolerance to phosphinotricin, eg rapeseed
  • IMI® to imidazolinone
  • STS® tolerance to sulfonylureas eg corn
  • Clearfield® varieties eg corn
  • the listed plants can be treated particularly advantageously according to the invention with the compounds of the general formula (I) or the active substance mixtures according to the invention.
  • the preferred ranges given above for the active compounds or mixtures also apply to the treatment of these plants. Particularly emphasized is the plant treatment with the compounds or mixtures specifically mentioned in the present text.
  • Step A 2-bromo-6- (4-fluorophenoxy) pyridine (see also J.W. Street et al., Neth. Recueil des
  • Step B 6- (4-fluorophenoxy) -pyridine-carboxaldehyde (see also US 4,281,133)
  • Step C 2- (6- (4-Fluoro-phenoxy) -2-pyridinyl) -2-hydroxy-acetonitrile (also see
  • 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.
  • Example 2 (1R, 3R) -3- (2,2-dibromethenyl) -2,2-dimethylcyclopropanecarboxylic acid cyan [6- (2-fluoro-phenoxy-2-pyridyl) methylester
  • Diastereomer I ES HRMS: m / z found: 544.9500 C2iHi 7 N 2 O 3 F 23 Na 79 Br 2 calcd: 544.9488.
  • Diastereomer I ES HRMS: m / z found: 560.9190 C2iHi 7 N 2 03 23 Na 35 Cl 79 Br2 Calculated: 560.9192.
  • Diastereomer II ES HRMS: m / z found: 491.0743 C22Hi 7 N 2 03F4 23 Na 35 Cl calcd: 491.0762.
  • Emulsifier 0.5 part by weight of alkylaryl polyglycol ether To prepare a suitable preparation of active compound, 1 part by weight of active compound is mixed with the stated amounts of solvent and emulsifier, and the concentrate is diluted to the desired concentration with emulsifier-containing water.
  • Chinese cabbage leaf discs (Brassica pekinensis) are sprayed with a preparation of active compound of the desired concentration and, after drying, are populated with larvae of the horseradish leaf beetle (Phaedon cochleariae). After the desired time, the effect is determined in%. 100% means that all beetle larvae have been killed; 0% means that no beetle larvae have been killed.
  • Emulsifier 0.5 part by weight of alkylaryl polyglycol ether To prepare a suitable preparation of active compound, 1 part by weight of active compound is mixed with the stated amounts of solvent and emulsifier, and the concentrate is diluted to the desired concentration with emulsifier-containing water. Corn-leaf disks (Zea mays) are sprayed with an active-substance preparation of the desired concentration and, after drying, are infested with caterpillars of the armyworm ⁇ Spodoptera frugiperda). After the desired time, the effect is determined in%. 100% means that all caterpillars have been killed; 0% means that no caterpillar has been killed. In this test, z. Example, the following compounds of the preparation examples effect of 100% at an application rate of 100g / ha:
  • Emulsifier 0.5 part by weight of alkylaryl polyglycol ether
  • active compound 1 part by weight of active compound is mixed with the stated amounts of solvent and emulsifier and the concentrate is diluted with emulsifier-containing water to the desired concentration.
  • Chinese cabbage leaf discs (Brassica pekinensis) infested with all stages of the green peach aphid (Myzus persicae) are sprayed with an active compound preparation of the desired concentration. After the desired time, the effect is determined in%. 100% means that all aphids have been killed; 0% means that no aphids have been killed.
  • dimethylformamide emulsifier 1.5 parts by weight of dimethylformamide emulsifier: 0.5 part by weight of alkylaryl polyglycol ether
  • active compound 1 part by weight of active compound is mixed with the stated amounts of solvent and emulsifier and the concentrate is diluted with emulsifier-containing water to the desired concentration.
  • Bean leaf discs Phaseolus vulgaris
  • infected by all stages of the common spider mite Tetranychus urticae
  • the effect is determined in%. 100% means that all spider mites have been killed; 0% means that no spider mites have been killed.

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Agronomy & Crop Science (AREA)
  • Pest Control & Pesticides (AREA)
  • Plant Pathology (AREA)
  • Health & Medical Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Dentistry (AREA)
  • General Health & Medical Sciences (AREA)
  • Wood Science & Technology (AREA)
  • Zoology (AREA)
  • Environmental Sciences (AREA)
  • Agricultural Chemicals And Associated Chemicals (AREA)
  • Pyridine Compounds (AREA)

Abstract

La présente invention concerne de nouveaux pyridinmethylesters de l'acide cyclopropancarboxylique, leur procédé de production et leur utilisation dans la lutte contre les animaux nuisibles, notamment les arthropodes et en particulier les insectes.
PCT/EP2012/057931 2011-05-04 2012-04-30 Nouveaux pyridinmethylesters de l'acide cyclopropancarboxylique utilisés comme pesticides WO2012150223A1 (fr)

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FR2289484A1 (fr) * 1974-10-24 1976-05-28 Sumitomo Chemical Co Esters d'acides cyclopropanecarboxyliques, leur procede de preparation et leur utilisation notamment comme insecticides
GB1446304A (en) 1972-05-25 1976-08-18 Nat Res Dev 3-substituted cyclopropane carboxylic acids and derivatives thereof
DE2621433A1 (de) * 1976-05-14 1977-12-01 Bayer Ag Substituierte phenoxybenzyloxycarbonylderivate, verfahren zu ihrer herstellung und ihre verwendung als insektizide und akarizide
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FR2383927A1 (fr) * 1977-03-14 1978-10-13 Dow Chemical Co Pyridylmethyl-esters substitues d'acides cyclopropanecarboxyliques utilisables comme insecticides
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FR2499567A2 (fr) 1979-08-30 1982-08-13 Roussel Uclaf Esters d'acides cyclopropane carboxyliques, leur procede de preparation et les compositions pesticides les renfermant
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US5013352A (en) 1990-03-30 1991-05-07 Dowelanco Substituted pyridyl-cyclohexanediones and their herbicidal uses
WO2003053905A1 (fr) 2001-12-20 2003-07-03 Syngenta Limited Procede pour la production d'esters pyrethroides ir
WO2010042646A1 (fr) 2008-10-10 2010-04-15 Amgen Inc. Composés d'aza- et de diaza-phtalazine en tant que modulateurs de map kinase p38 et procédés pour les utiliser

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