WO2012150208A1 - Utilisation d'esters d'alcools benzyliques substitués de l'acide cyclopropane carboxylique pour lutter contre des insectes résistants aux insecticides - Google Patents

Utilisation d'esters d'alcools benzyliques substitués de l'acide cyclopropane carboxylique pour lutter contre des insectes résistants aux insecticides Download PDF

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WO2012150208A1
WO2012150208A1 PCT/EP2012/057889 EP2012057889W WO2012150208A1 WO 2012150208 A1 WO2012150208 A1 WO 2012150208A1 EP 2012057889 W EP2012057889 W EP 2012057889W WO 2012150208 A1 WO2012150208 A1 WO 2012150208A1
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spp
nmr
ppm
mhz
biphenyl
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PCT/EP2012/057889
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German (de)
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Peter Jeschke
Ralf Nauen
Arnd Voerste
Neil Berry
Naomi DYER
Weiqian David HONG
Hyder ZEYNAB
Louise LA PENSEE
Paul O´NEILL
Sunil SABBANI
Stephen Ward
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Bayer Cropscience Ag
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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
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C69/00—Esters of carboxylic acids; Esters of carbonic or haloformic acids
    • C07C69/74—Esters of carboxylic acids having an esterified carboxyl group bound to a carbon atom of a ring other than a six-membered aromatic ring
    • C07C69/753—Esters of carboxylic acids having an esterified carboxyl group bound to a carbon atom of a ring other than a six-membered aromatic ring of polycyclic acids
    • 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
    • C07D333/14—Radicals substituted by singly bound hetero atoms other than halogen
    • C07D333/16—Radicals substituted by singly bound hetero atoms other than halogen by oxygen atoms

Definitions

  • the present application relates to the use of substituted benzyl alcohol esters of cyclopropanecarboxylic acid 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
  • cross-resistance Whether a resistance mechanism responsible for the resistance of a pest to a particular insecticide makes this pest resistant to a new insecticide (cross-resistance) is difficult to predict due to the various mechanisms of resistance. In particular, in cases where the mechanism of action of the novel insecticide is unknown or in which resistance is mediated by mechanisms other than alteration of the binding site, for example by metabolic resistance, it is difficult to predict cross-resistance.
  • 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
  • alkyl stands in which is alkyl, alkoxy, haloalkyl, alkylthio, alkylsulfoxyl, alkylsulfonyl, haloalkoxy, haloalkylthio, haloalkylsulfoxyl, haloalkylsulfonyl, alkylamino, dialkylamino, cyano, halogen or hydroxy and p is a number from 0 to 2, optionally substituted hetaryl, preferably pyridine-2 -yl or pyridin-3-yl, or for one of the radicals from the series
  • Xi, ⁇ ', Xi are independently alkyl, haloalkyl, cycloalkyl, halocycloalkyl, alkenyl, haloalkenyl, alkynyl, alkoxy, haloalkoxy, alkoxycarbonyl, alkoxyalkyl, haloalkoxyalkyl, alkylthio, haloalkylthio, alkylsulfinyl, haloalkylsulfinyl, alkylsulfonyl, haloalkylsulfonyl, Fluorine, bromine, chlorine, iodine, nitro, cyano, amino, alkylamino, dialkylamino, is methyl, cyano, halogen or haloalkyl, preferably halogen is fluorine, preferably haloalkyl is fluoromethyl, and Yi and Y 2 are each independently halogen or haloalkyl
  • 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 (I-a), (I-b), (I-c) or (I-d) 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), (I-b), (Ic) or (I-d) can be separated by physical methods, for example by chromatographic methods.
  • Yi and Y2 are each independently halogen or haloalkyl, preferably halogen is selected from the group of bromine or chlorine, preferably haloalkyl is trifluoromethyl and
  • LG for an in situ generated nucleofuge leaving group is, a) in a first reaction step with compounds of the general formula ( ⁇ - ⁇ )
  • Hal is halogen, such as iodine or bromine, preferably iodine,
  • Z is alkyl, alkoxy, haloalkyl, alkylthio, alkylsulfoxyl, alkylsulfonyl, haloalkoxy, haloalkylthio, haloalkylsulfoxyl, haloalkylsulfonyl, alkylamino, dialkylamino, cyano, halogen or hydroxy and p is a number from 0 to 2,
  • R 2 is methyl, cyano, halogen or haloalkyl, preferably halogen is fluorine, preferably haloalkyl is fluoromethyl, if appropriate in the presence of a suitable acid binder and if appropriate in the presence of a suitable diluent to give compounds of the general formula (IA) - -
  • Hal is halogen, such as iodine or bromine, preferably iodine,
  • R is hydrogen or alkylene
  • Ri is optionally substituted hetaryl, preferably pyridin-2-yl or pyridin-3-yl, or one of the radicals from the series
  • Xi, ⁇ ', Xi are independently alkyl, haloalkyl, cycloalkyl, halogenocycloalkyl, alkenyl, haloalkenyl, alkynyl, alkoxy, haloalkoxy, alkoxycarbonyl, alkoxyalkyl, haloalkoxyalkyl, alkylthio, haloalkylthio, alkylsulfmyl, haloalkylsulfinyl, alkylsulfonyl, haloalkylsulfonyl, fluoro, Bromine, chlorine, iodine, nitro, cyano, amino, alkylamino, dialkylamino are optionally reacted in the presence of a suitable transition metal catalyst and optionally in the presence of a suitable diluent, or
  • R 2 is methyl, cyano, halogen or haloalkyl, preferably halogen is fluorine, preferably haloalkyl is fluoromethyl, if appropriate 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). Preferred substituents or ranges of the radicals listed in the formulas mentioned above and below are explained below.
  • the compound has the general formula (1-2)
  • R 1 represents one of the radicals selected from the group (A), (B), (C), (D), (F), (G), (H), (M) and (T) stands and
  • Xi, ⁇ ', Xi are independently alkyl, haloalkyl, cycloalkyl, halogenocycloalkyl, alkenyl, haloalkenyl, alkynyl, alkoxy, haloalkoxy, alkoxycarbonyl, alkoxyalkyl, haloalkoxyalkyl, alkylthio, haloalkylthio, alkylsulfinyl, haloalkylsulfinyl, alkylsulfonyl, haloalkylsulfonyl, fluoro, Bromine, chlorine, iodine, nitro, cyano, amino, alkylamino, dialkylamino and
  • R 2 is methyl, fluorine or fluoromethyl
  • Yi and Y 2 are bromine, chlorine or trifluoromethyl.
  • the compounds have the general formula (1.3) or (1.4):
  • - - is alkyl, alkoxy, haloalkyl, alkylthio, alkylsulfoxyl, alkylsulfonyl, haloalkoxy, halo genalkylthio, haloalkylsulfoxyl, haloalkylsulfonyl, alkylamino, dialkylamino, cyano, halogen or hydroxy and p is a number from 0 to 2, for one of the radicals the series
  • R 1 represents one of the radicals selected from the group (A), (B), (C), (D), (F), (G), (H), (M) and (T) stands and
  • Xi, ⁇ ', Xi are independently alkyl, haloalkyl, cycloalkyl, halogenocycloalkyl, alkenyl, haloalkenyl, alkynyl, alkoxy, haloalkoxy, alkoxycarbonyl, alkoxyalkyl, haloalkoxyalkyl, alkylthio, haloalkylthio, alkylsulfmyl, haloalkylsulfinyl, alkylsulfonyl, haloalkylsulfonyl, fluorine, bromine, Chlorine, iodine, nitro, cyano, amino, alkylamino, dialkylamino,
  • R 2 is methyl, fluorine or fluoromethyl.
  • the compounds have the general formula (1.5) or (1.6)
  • R 1 represents one of the radicals selected from the group (A), (B), (C), (D), (F), (G), (H), (M) and (T) stands and
  • Xi, ⁇ ', Xi are independently alkyl, haloalkyl, cycloalkyl, halogenocycloalkyl, alkenyl, haloalkenyl, alkynyl, alkoxy, haloalkoxy, alkoxycarbonyl, alkoxyalkyl, haloalkoxyalkyl, alkylthio, haloalkylthio, alkylsulfmyl, haloalkylsulfinyl, alkylsulfonyl, haloalkylsulfonyl, fluoro, Bromine, chlorine, iodine, nitro, cyano, amino, alkylamino, dialkylamino and
  • R 2 is methyl, fluorine or fluoromethyl.
  • the compound has the general formula (1.7)
  • Xi, ⁇ ', Xi are independently alkyl, haloalkyl, cycloalkyl, halogenocycloalkyl, alkenyl, haloalkenyl, alkynyl, alkoxy, haloalkoxy, alkoxycarbonyl, alkoxyalkyl, haloalkoxyalkyl, alkylthio, haloalkylthio, alkylsulfmyl, haloalkylsulfinyl, alkylsulfonyl, haloalkylsulfonyl, fluoro, Bromine, chlorine, iodine, nitro, cyano, amino, alkylamino, dialkylamino, stands for methyl, fluorine or fluoromethyl and
  • Yi and Y 2 are bromine, chlorine or trifluoromethyl. - -
  • the compounds have the general formula (1.8) and (1.9),
  • Ri preferably represents one of the radicals selected from the group consisting of (A), (B), (C), (D), (F), (G), (H), (M) and (T), in which the arrow marks the binding to the adjacent ring and
  • Xi, ⁇ ', Xi are independently alkyl, haloalkyl, cycloalkyl, halogenocycloalkyl, alkenyl, haloalkenyl, alkynyl, alkoxy, haloalkoxy, alkoxycarbonyl, alkoxyalkyl, haloalkoxyalkyl, alkylthio, haloalkylthio, alkylsulfmyl, haloalkylsulfinyl, alkylsulfonyl, haloalkylsulfonyl, fluoro, Bromine, chlorine, iodine, nitro, cyano, amino, alkylamino, dialkylamino, preferably stand for fluorine and
  • R 2 is methyl, fluorine or fluoromethyl. Further very particularly preferred substituents of the radicals listed in the compounds of the formula (I) are explained in Table 1.
  • Very particularly preferred compounds of the formula (LI) are the following compounds: - -
  • step E 4-trifluoromethylphenyl-boronic acid, according to the manufacturing method (step E) is represented by the reaction scheme V mentioned below (see Preparation Examples, Example 1).
  • stage D, E The compounds required as starting materials for preparing the process according to the invention (stage D, E) are generally defined by the formulas (II) and (III-B) / (III-A).
  • the compounds of formula (II) may, for. T. commercially or by literature methods according to the reaction scheme I (step C, method I, II) are obtained from the corresponding 2,2-dimethyl-cyclopropanecarboxylic acids (A-l) (see also Preparation Example 1, step D).
  • LG stands for an in situ generated nucleofuge leaving group ("Leaving Group").
  • Examples of compounds of the formula (II) having a nucleofugic leaving group LG are known;
  • reaction of compounds of the formula (II) with the compounds of the formula (III-B) / (III-A) 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, Methoden der Organischen Chemie, Volume 15/2; Bodansky et al., Peptide Synthesis 2 nd ed. (Wiley & Sons, New York 1976) or Gross, Meienhofer, The Peptides: Analysis, Synthesis, Biology (Academic Press, New York 1979).
  • radical R 1 is aryl or hetaryl
  • radical R 2 is fluorine or fluoromethyl (-CH 2 -F) and Z and p have the meaning mentioned above, this is correspondingly substituted 2-fluoro-benzyl alcohols or 2-fluoromethyl-benzyl alcohols.
  • compounds of the general formula (III-B) which are known are 2,4,5,6-tetrafluoro- [1,1-biphenyl] -3-methanol (US Pat. No. 4,329,518), 2,4,6-trifluoro [ 1, 1'-biphenyl] -3-methanol (US 4,402,973), 2-fluoro-2 ', 6'-dimethyl- [1, 1'-biphenyl] -3-methanol (WO 2007/123225) or 2-fluoro 3 ', 5'-difluoro [1, 1'-biphenyl] -3-methanol (see Preparation Example 35, Method II, Step B).
  • the compounds of the formula (III-B) / (III-A) can be obtained by known preparation methods, for example by reduction of the ester function from optionally substituted benzenecarboxylic acid esters (A-5) or from optionally substituted 3-halobenzoic acids (A-3).
  • Suitable reducing agents for the reduction of a carbonyl group are a wide variety of hydrogenating reagents, such as alkali metal hydrides, in particular sodium borohydride (NaBH i), lithium borohydride (L1BH4), lithium aluminum hydride (L1AIH4), lithium triethylborohydride (Li [Et3BH]), lithium tricarboxylic (Li [, yeoBu3BH], sodium bis (2-methoxyethoxy) aluminum hydride, alkylaluminum hydrides, in particular diisobutylaluminum hydride (DIBAL-H), or tetramethylammonium triacetoxyborohydride, inter alia, in question (see H.
  • alkali metal hydrides in particular sodium borohydride (NaBH i), lithium borohydride (L1BH4), lithium aluminum hydride (L1AIH4), lithium triethylborohydride (Li [Et3BH]),
  • borohydride resin for example "borohydride on Amberlite ® IRA-406", are used for the hydrogenation (cf.. AR Sande et al. Tetrahedron Lett. 1984, 25, 3501).
  • alkali metal hydrides in particular sodium borohydride (NaBH4) or lithium borohydride (L1BH4) (compare Preparation Example 1, Stage A).
  • the 2-bromomethyl-benzoic acid esters of the formulas (A-3a) and (A-5a) are first prepared from the optionally substituted 2-methyl-benzoic acid esters of the formulas (A-6) and (A-7) by means of radical bromination, the then in the presence of a suitable fluorinating agent in the 2-bromomethyl-benzoic acid ester of the formulas (A-3b) and (A-5b) can be converted (see Preparation Examples).
  • N-bromosuccinimide NB S
  • catalysts such as Azo in halogenated aromatic solvents, for example trifluorotoloul
  • AIBN bis-isobuyronitrile
  • ZrCl zirconium chloride
  • Certain substituted 2-methylbenzoic acid esters of the formulas (A-6) and (A-7) have already been disclosed, for example: 2-methyl-6- (methylsulfonyl) - [1,1'-biphenyl] -3-carboxylic acid methyl ester (JP 11193259) or 2-methyl-4- (methylsulfonyl) -3- (2-thienyl) benzoic acid methyl ester (WO 9626193).
  • the preparation of the 6-fluoro-2-methyl- [l, l'-biphenyl] -3-carboxylic acid methyl ester in Preparation Example 54 is described.
  • a suitable coupling reaction for example the palladium-catalyzed cross-coupling (Suzuki coupling; H.-J. Wang et al., Tetrahedron Lett. 2005, 46, 2631-2634 and references cited therein)
  • a suitable coupling reaction eg Suzuki coupling in the presence of suitable transition metal catalysts, see Reaction Scheme I, Stefe E
  • preparation routes for 2-fluoro-3-iodo-benzoic acid methyl ester and 2-fluoro-methyl-3-iodo-benzoic acid methyl ester are described in the Preparatory Examples.
  • halogenated benzoic acid esters of the formula (A-3) is possible by known process methods from optionally substituted 3-halobenzoic acids of the general formula (A-2), for example by means of an esterification reaction (compare also Preparation Example 1, Step A) ,
  • halogenated benzoic acid esters of the formula (A-3) can of course also be prepared by known procedures from optionally substituted 3-aminobenzoic acid esters of the general formula (A-8), for example by means of the known Sandmeyer reaction (cf. B. Houben-Weyl, Methods of Organic Chemistry, Volume VIII, page 311) possible (see reaction scheme VI).
  • Reaction scheme VI Reaction scheme VI
  • 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 in particular chlorohydrocarbons, 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
  • Preferred diluents for carrying out the process according to the invention are halogenated hydrocarbons, in particular chlorohydrocarbons, such as tetraethylene, tetrachloroethane, dichloroprone, methylene chloride, dichlorobutane or chloroform, in particular methylene chloride.
  • chlorohydrocarbons such as tetraethylene, tetrachloroethane, dichloroprone, methylene chloride, dichlorobutane or chloroform, in particular methylene chloride.
  • the preparation of compounds of the formula (I) according to the preparation processes is carried out by reacting compounds of the formula (II) in the presence of compounds of the formula (IA) [Method I] or of the formula (III-B) [Method II], optionally in The presence of an acid binder and, if appropriate, be reacted 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.
  • Examples include the 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 bis-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, trimethyl - 5 - amine, tribenzylamine, triisopropyl
  • tertiary amines such as trimethylamine, triethylamine, N-ethyl-N, N-diisopropylamine or aromatic amines such as pyridine, 4-pyrrolidinopyridine, 4-dimethylamino-pyridine, quinoline, a-picoline, ß-picoline, in particular pyridine use.
  • Step E The preparation of compounds of the formula (I) according to Preparation Method I (Step E) is carried out by reacting compounds of the formula (IA) in the presence of compounds of the formula (A-4) by means of a palladium-catalyzed cross-coupling reaction (Suzuki coupling), in the presence of suitable transition metal catalysts and in the presence of one of the specified diluents.
  • a palladium-catalyzed cross-coupling reaction Sudzuki coupling
  • 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 150 ° C, more preferably 60 ° C to 120 ° C.
  • palladium catalysts for example palladium (II) acetate [Pd (ac) 2] or [1,1-bis (diphenylphosphino) ferrocenes] dichloropalladium (II) [PdCb (dppf)].
  • 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 compounds according to the invention can be present as geometrical and / or as optically active isomers or corresponding isomer mixtures in a different composition.
  • 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 the protection of 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 found in agriculture, horticulture, livestock, forests, gardens and recreational facilities, in supplies 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:
  • Anoplura eg Damalinia spp., Haematopinus spp., Linognathus spp., Pediculus spp., Trichodectes spp. - 7 -
  • 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.
  • From the class of Diplopoda e.g. Blaniulus guttulatus.
  • From the class of 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.
  • 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 and alis, Heterronychus arator, Heteronyx spp., Hylamorpha elegans, Hylotrupes bajulus, Hypera postica, Hypomeces squamosus, Hypothenemus spp., Lachnosterna consanguinea, Lasioderma serricorne, Latheticus oryzae, Lathridi spp., Lema spp., Leptinotarsa decem
  • Pentomidae Piesma quadrata, Piezodorus spp., Psallus spp., Pseudacysta persea, Rhodnius spp., Sahlbergella singularis, Scaptocoris castanea, Scotinophora spp., Stephanitis nashi, Tibraca spp., Triatoma 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 ..
  • Phthiraptera e.g. Damalinia spp., Haematopinus spp., Linognathus spp., Pediculus spp., Phylloera vastatrix, Phtirus pubis, Trichodectes spp.
  • Zygentoma e.g. , Ctenolepisma spp., Lepisma saccharina, Lepis- modes inquilinus, Thermobia domestica.
  • 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 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
  • insects of the Cuucidae family selected from the genera Aedes aegypti, Aedes albopictus, Anopheles stephensi, Culex quinquefasciatus, Anopheles albimanus, Anopheles funestus, Anopheles gambiae, Culex pipiens pallens, Anopheles minimus, Anopheles arabiensis and Anopheles sacharovi.
  • the insects are particularly preferably 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 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 the use of surface-active agents, ie emulsifiers and / or dispersants and / or foaming agents.
  • extenders ie liquid solvents and / or solid carriers
  • surface-active agents ie emulsifiers and / or dispersants and / or foaming agents.
  • surface-active agents ie emulsifiers and / or dispersants and / or foaming 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
  • 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, for example 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: 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 broken 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, arylsulfon
  • oligo- or polymers for example starting from vinylic monomers of Acrylic acid, from EO and / or PO alone or in combination with, for example, (poly) alcohols or (poly) amine.
  • lignin and its sulfonic acid derivatives simple and modified celluloses, aromatic and / or aliphatic sulfonic acids and their adducts with formaldehyde.
  • 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 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 and 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.
  • 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 substances, 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 in the form of insecticides in their commercial formulations and in the formulations 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 and in the formulations prepared from these formulations in mixtures with inhibitors that 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 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 that 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.
  • 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 seeds, 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, and plant cultivars and their parts are treated.
  • transgenic plants and plant cultivars which have been obtained by genetic engineering methods, if appropriate in combination with conventional methods (Genetically Modified Organisms), and their parts are treated.
  • the terms "parts” or “parts of plants” or “plant parts” have been explained above.
  • 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. These can be varieties, biotypes and genotypes. 5
  • 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 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 go beyond 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, 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 which are formed in the plants, in particular those which are 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 defense of plants against fungi, bacteria and viruses by systemic acquired resistance (SAR), systemin, phytoalexins, elicitors and resistance genes and correspondingly expressed proteins and toxins. Traits which are furthermore particularly emphasized are the increased tolerance of the plants to certain herbicidal active compounds, for example imidazolines, sulfonylureas, glyphosate or phosphinotricin (eg "PAT" gene).
  • herbicidal active compounds for example imidazolines, sulfonylureas, glyphosate or phosphinotricin (eg "PAT" gene).
  • genes conferring 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 ® (eg - 5b -
  • herbicide-tolerant plants are maize varieties, cotton varieties and soybean varieties may be mentioned, under the trade names Roundup Ready ® (tolerance to glyphosate, for 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 ® tolerance to glyphosate, for 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. Of course, these statements also apply to future or future marketed plant varieties with these or future developed genetic traits.
  • 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.
  • N-bromo-succinimide N-bromo-succinimide (NBS) in 210 mL of ⁇ , ⁇ , ⁇ -trifluorotoluene was added under protective gas atmosphere (nitrogen) successively 297 mg (1.273 mmol) of zirconium Convene (IV) chloride (ZrC) and 7.34 g (26.6 mmol) of 3-iodo-2-methyl-benzoic acid methyl ester given. Subsequently, the reaction mixture was stirred for 24 hours at 105-108 ° C at reflux. After addition of saturated sodium bicarbonate solution (quenching), it was extracted three times with 50 ml of dichloromethane.
  • step A To a stirred solution of 4.34 g (15.5 mmol) 2-fluoro-3-iodo-benzoic acid methyl ester (step A) in 50 mL toluene at room temperature under a protective gas atmosphere (nitrogen) 7.8 mL (15.5 mmol) a 2.0 M solution of lithium borohydride in tetrahydrofuran (THF). Subsequently, the entire reaction mixture was stirred at 100 ° C for 30 minutes. Thereafter, 10 mL of an IM hydrochloric acid solution was added and the solvents were separated.
  • step A 2-fluoromethyl-3-iodo-benzoic acid methyl ester (step A) in 150 mL diethyl ether 661 mg lithium aluminum hydride were added at -42 ° C under a protective gas atmosphere (nitrogen) and the reaction mixture was stirred at this temperature. After two hours, the reaction mixture was quenched with hydrochloric acid solution and then extracted three times with 75 mL of diethyl ether. The organic phase was dried over magnesium sulfate, filtered off, concentrated in vacuo and purified by flash chromatography using a gradient (ethyl acetate / n-hexane).
  • Step C (method I. II): (1R, 3R) -3- (2,2-dibromethenyl) -2,2-dimethylcyclopropanecarb
  • Step D (Method I): (1R, 3R) -3- (2,2-dibromoethenyl) -2,2-dimethylcyclopropanecarb
  • the (1R, 3R) -3- (2,2-dibromethenyl) -2,2-dimethyl-cyclopropanecarboxylic acid chloride obtained in stage C was stirred in 40 ml of dichloromethane and admixed with 3.16 g (40 mmol) of pyridine. Subsequently, the reaction mixture was further stirred for one hour at room temperature and then treated with a solution of 4.56 g (18.1 mmol) (2-fluoro-3-iodo-phenyl) methanol (step C) in 20 mL dichloromethane. Thereafter, the reaction mixture was stirred for about 18 hours at room temperature. Subsequently, the solvent and excess pyridine were removed in vacuo.
  • the (1R, 3R) -3- (2-chloro-2-trifluoromethenyl) -2,2-dimethyl-cyclopropane-carboxylic acid 2-fluoro-3-iodo-benzyl ester was prepared in an analogous manner from (1R, 3R) -3 - (2-chloro-2-trifluoromethenyl) -2,2-dimethyl-cyclopropanecarboxylic acid chloride and (3-2-fluoro-3-iodo-phenyl) methanol.
  • the (1R, 3R) -3- (2,2-dibromoethenyl) -2,2-dimethyl-cyclopropane-carboxylic acid 2,6-difluoro-3-iodo-benzyl ester was prepared in an analogous manner from (1R, 3R) -3 - (2,2-Dibromethenyl) -2,2-dimethyl-cyclopropanecarboxylic acid chloride and (2,6-difluoro-3-iodo-phenyl) methanol.
  • the (1R, 3R) -3- (2,2-dibromoethenyl) -2,2-dimethyl-cyclopropane-carboxylic acid 2-fluoromethyl-3-iodobenzyl ester was prepared in an analogous manner from (1R, 3R) -3- ( 2,2-dibromethenyl) -2,2-dimethyl-cyclopropanecarboxylic acid chloride and (2-fluoromethyl-3-iodo-phenyl) methanol as a colorless solid.
  • Ci6Hi60 2 F 23 Na 79 Br 2 127 I calculates 566.8444.
  • the (1R, 3R) -3- (2-chloro-2-trifluoromethenyl) -2,2-dimethyl-cyclopropane-carboxylic acid 2-fluoromethyl-3-iodo-benzyl ester was prepared in an analogous manner from (1R, 3R) -3 - (2-chloro-2-trifluoromethenyl) -2,2-dimethyl-cyclo-propanecarboxylic acid chloride and (2-fluoromethyl-3-iodo-phenyl) methanol.
  • Example 6 was obtained at 16 hours reaction time at 70 ° C by means of Suzuki coupling (step E, method I).
  • examples 7 were obtained at 70 ° C. for 20 hours reaction time by means of Suzuki coupling (stage E, method I).
  • examples 8 were obtained at 18 hours reaction time at 100 ° C by means of Suzuki coupling (stage E, method I).
  • examples 9 to 11 were obtained at a reaction time of 24 hours at 70 ° C. by means of a Suzuki coupling (stage E, method I).
  • Step E Method I
  • (1R, 3R) -3- (2,2-dibromoethenyl) -2,2-dimethyl-cyclopropanecarboxylic acid 2,6-difluoro-3-iodo-b enzylester and the corresponding arylboronic acids in the presence of 2 mol% [l, l-bis (diphenylphosphino) ferrocenes] dichloropalladium (II) (PdCl2 (dppf)), potassium phosphate and 16 hours reaction time at 70 ° C in toluene, Examples 20 and 21 ,
  • Step E Method I
  • (1R, 3R) -3- (2-chloro-2-trifluoromethenyl) -2,2-dimethyl-cyclopropanecarboxylic acid 2-fluoromethyl-3-iodo-benzyl ester and corresponding arylboronic acids in the presence of 2 mol% palladium (II) acetate (Pd (ac) 2), 5 mol% triphenylpine potassium phosphate and 6 hours reaction time at 70 ° C in toluene, Examples 30 and 35.
  • Step A (Method II): 2-fluoro-3-iodo-benzoic acid methyl ester (known from Step A, Method I)
  • Step E (Method II): 2, 3 ', 5'-trifluoro [l, - biphenyl] -3-carbon Acidmethylester - -
  • Step B (Method II): (2, 3 ', 5'-trifluoro [1, 1'-biphenyl] methanol, see Step B, Method I
  • Step D (Method II): (1R, 3R) -3- (2,2-dibromoethenyl) -2,2-dimethyl-cyclopropanecarboxylic acid (2, 3 ', 5'-trifluoro [1, l' -] biphenyl] -3-yl) methylester; see. Stage D, Method I
  • Step A (Method II): 2-Fluoro-3-iodo-benzoic acid methyl ester (known from Step A, Method I)
  • Step E (Method II): 2, 2 ', 3'-trifluoro [1, 1 '-biphenyl] -3-carboxylic acid methyl ester; see. Level E,
  • Step B (2, 2 ', 3'-trifluoro [1, 1'-biphenyl] methanol, see Step B, Method I;
  • Step D (Method II): (1R, 3R) -3- (2,2-dibromoethenyl) -2,2-dimethyl-cyclopropanecarboxylic acid (2, 2 ', 3'-trifluoro [1, l' -] biphenyl] -3-yl) methylester; see .
  • S tu fe D method I
  • Step A (Method II): 2-fluoro-3-iodo-benzoic acid methyl ester (known from Step A, Method I)
  • Step E (Method II): 2, 2 ', 5'-trifluoro [l, - biphenyl] -3-carbon Acidmethylester; see. Level E,
  • Step B (2, 2 ', 5'-trifluoro [1, 1'-biphenyl] methanol, see Step B, Method I;
  • Step D (Method II): (1R, 3R) -3- (2,2-dibromethenyl) -2,2-dimethyl-cyclopropanecarboxylic acid
  • Step A (Method II): 2-Fluoro-3-iodo-benzoic acid methyl ester (known from Step A, Method I)
  • Step E (Method II): 2,4 '-difluoro- [1,1'-biphenyl ] -3-carboxylic acid methyl ester, see step E,
  • Step B (2, 4'-difluoro [1, 1'-biphenyl] methanol, see Step B, Method I, Yield obtained: 90% (of theory)
  • Step D (Method II): (1R, 3R) -3- (2,2-dibromethenyl) -2,2-dimethyl-cyclopropanecarboxylic acid
  • Step A (Method II): 2-Fluoro-3-iodo-benzoic acid methyl ester (known from Step A, Method I)
  • Step E (Method II): 2-Fluoro [1, 1'-biphenyl] -3 -carboxylate; see. Stage E, Method II; Example 35; Yield obtained: 95% (of theory)
  • Step B (2-Fluoro [1, 1'-biphenyl] methanol, see Step B, Method I;
  • Step D (Method II): (1R, 3R) -3- (2,2-dibromethenyl) -2,2-dimethyl-cyclopropanecarboxylic acid
  • Step A (Method II): 2-fluoro-3-iodo-benzoic acid methyl ester (known from Step A, Method I)
  • Step E (Method II): 2, 3 ', 5'-trifluoro [l, - biphenyl] -3-carbon Acidmethylester; see. Level E,
  • Step B (2, 3 ', 5'-trifluoro [1, 1'-biphenyl] methanol, see Step B, Method I;
  • Step D (Method II): (1R, 3R) -3- (2,2-dibromethenyl) -2,2-dimethyl-cyclopropanecarboxylic acid
  • Step A (Method II): 2,6-Difluoro-3-iodo-benzoic acid methyl ester (known from
  • Step B (Method II): 2,6-difluoro [1, 1'-biphenyl] methanol; see. Stage B, Method I; obtained
  • Step D (Method II): (1R, 3R) -3- (2,2-dibromethenyl) -2,2-dimethylcyclopropanecarboxylic acid (2,6-difluoro [1, 1'-biphenyl] -3 yl) methylester; see. Stage D, Method I; Yield: 87% (ie theory)
  • Step A (Method II): 2,6-Difluoro-3-iodo-benzoic acid methyl ester (known from
  • Step E (Method II): 2,6-Difluoro-3-thien-2-yl-benzoic acid methyl ester; see. Level E, method
  • Step B (2,6-Difluoro-3-thien-2-yl) benzyl alcohol; see. Stage B, Method I; Yield obtained: 99% (of theory)
  • Step D (Method II): (1R, 3R) -3- (2,2-dibromethenyl) -2,2-dimethylcyclopropanecarboxylic acid (2,6-difluoro-3-thien-2-yl) benzyl ester; see. Stage D, Method I; Yield: 85% (ie theory) - 7 -
  • Step A (Method II): 2-fluoromethyl-3-iodo-benzoic acid methyl ester (known from Step A,
  • Step B (2-fluoromethyl-3-thien-2-yl) benzyl alcohol; see. Stage B, Method I;
  • Step D (Method II): (1R, 3R) -3- (2,2-dibromethenyl) -2,2-dimethylcyclopropanecarboxylic acid (2-fluoromethyl-3-thien-2-yl) benzyl ester; see. Stage D, Method I; Output: 95% (ie theory)
  • Step A (Method II): 2-fluoromethyl-3-iodo-benzoic acid methyl ester (known from Step A,
  • Step B 2-fluoromethyl- [1,1'-biphenyl] -methanol; see. Stage B, Method I; Yield obtained: 89% (of theory) - 7 -
  • Step D (Method II): (1R, 3R) -3- (2,2-dibromethenyl) -2,2-dimethyl-cyclopropanecarboxylic acid
  • Step A (Method II): 2-fluoromethyl-3-iodo-benzoic acid methyl ester (known from Step A,
  • Step B 2-fluoromethyl-4'-fluoro [1,1'-biphenyl] -methanol; see. Stage B, Method I;
  • Step D (Method II): (1R, 3R) -3- (2,2-dibromethenyl) -2,2-dimethyl-cyclopropanecarboxylic acid
  • Step A (Method II): 2-fluoromethyl-3-iodo-benzoic acid methyl ester (known from Step A,
  • Step B 2-fluoromethyl-3'-fluoro [1,1'-biphenyl] -methanol; see. Level B, method
  • Step D (Method II): (1R, 3R) -3- (2,2-dibromethenyl) -2,2-dimethyl-cyclopropanecarboxylic acid
  • Step A (Method II): 2-fluoromethyl-3-iodo-benzoic acid methyl ester (known from Step A,
  • Step B 2-fluoromethyl-2'-fluoro [1,1'-biphenyl] -methanol; see. Level B, method
  • Step D (Method II): (1R, 3R) -3- (2,2-dibromethenyl) -2,2-dimethyl-cyclopropanecarboxylic acid
  • Step A (Method II): 2-fluoromethyl-3-iodo-benzoic acid methyl ester (known from Step A,
  • Step B 2-fluoromethyl-2 ', 4'-difluoro [1, 1'-biphenyl] -methanol; see. Stage B, Method I; Yield obtained: 92% (theory)
  • Step D (Method II): (1R, 3R) -3- (2,2-dibromethenyl) -2,2-dimethyl-cyclopropanecarboxylic acid
  • Step A (Method II): 2-fluoromethyl-3-iodo-benzoic acid methyl ester (known from Step A,
  • Step B 2-fluoromethyl-4'-chloro [ ⁇ , ⁇ -biphenyl] -methanol; see. Level B, method
  • Step D (Method II): (1R, 3R) -3- (2,2-dibromethenyl) -2,2-dimethyl-cyclopropanecarboxylic acid
  • Step A (Method II): 6-fluoro-3-iodo-benzoic acid methyl ester (known from WO 2009/058237)
  • Step E (Method II): 6-fluoro-2-fluoromethyl- [1, ⁇ -biphenyl] 3 -carboxylic acid methyl ester
  • the preparation is carried out from 6-fluoro-3-iodo-benzoic acid methyl ester and phenylboronic acid (compare Example 35b, step E, method II) in the presence of palladium (II) acetate, triphenylphosphine and potassium phosphate in a reaction in toluene at 70 for 6 hours ° C.
  • 3rd step 6-Fluoro-2-fluoromethyl [1, ⁇ -biphenyl] -3-carboxylic acid methyl ester: The preparation is carried out from 2-bromomethyl-6-fluoro- [1,1'-biphenyl] -3-carboxylic acid methyl ester (2 Step) and TBAF (1.0 M in THF) (see Example a-2, Step A, Method I) within 4 hours of stirring at room temperature.
  • Step B Method B (Method II): (4-Fluoro-2-fluoromethyl [1, 1'-biphenyl] -3-yl) methanol; see. Level B,
  • Step D (Method II): (1R, 3R) -3- (2-chloro-2-trifluoromethenyl) -2,2-dimethyl-cyclopropanecarboxylic acid (6-fluoro-2-fluoromethyl- [1, 1 '-] biphenyl] -3-yl) methyl ester, colorless oil; see. Stage D, Method I; Yield: 79% (of theory) ES HRMS: m / z found: 481.0987.
  • step A To a solution stirred solution of 4.29 g (15.5 mmol) of 3-iodo-2-methyl-benzoic acid methyl ester (step A) in 50 mL toluene at room temperature under a protective gas atmosphere (nitrogen) 7.8 mL (15.5 mmol ) of a 2.0 M solution of lithium borohydride in tetrahydrofuran (THF). Subsequently, the entire reaction mixture was stirred at 100 ° C for 30 minutes. Thereafter, 10 mL of a 1M hydrochloric acid solution was added and the solvents were separated. The remaining residue was dissolved in 50 mL diethyl ether and washed successively with 20 mL saturated sodium thiosulfate solution, 20 mL saturated sodium bicarbonate solution and brine. 5
  • Step C (Method I, II): (1R, 3R) -3- (2,2-dibromethenyl) -2,2-dimethyl-cyclopropanecarboxylic acid chloride (see also US 4,342,770)
  • Step D (Method I): (1R, 3R) -3- (2,2-dibromethenyl) -2,2-dimethyl-cyclopropanecarboxylic acid
  • step C The (1R, 3R) -3- (2,2-dibromethenyl) -2,2-dimethyl-cyclopropanecarboxylic acid chloride obtained in step C was stirred in 40 ml of dichloromethane and 3.16 g (40 mmol) of pyridine were added. Subsequently, the reaction mixture was further stirred for one hour at room temperature and then treated with a solution of 4.49 g (18.1 mmol) of (3-iodo-2-methylphenyl) methanol (step C) in 20 ml of dichloromethane. Thereafter, the reaction mixture was stirred for about 18 hours at room temperature. Subsequently, the solvent and excess pyridine were removed in vacuo.
  • the (1R, 3R) -3- (2-chloro-2-trifluoromethenyl) -2,2-dimethyl-cyclopropane-carboxylic acid 3-iodo-2-methylbenzyl ester was prepared in an analogous manner from (1R, 3R) -3 - (2-chloro-2-trifluoromethenyl) -2,2-dimethyl-cyclopropanecarboxylic acid chloride (3-iodo-2-methylphenyl) methanol.
  • Example 9 was obtained at a reaction time of 12 hours at 70 ° C. by means of the Suzuki coupling (stage E, method I).
  • Step A Method I b
  • Step E Method II: Methyl 3 ', 5'-difluoro-2-methyl- [1, -biphenyl] -3-carboxylate
  • Step B (Method II): (3 ', 5'-Difluoro-2-methyl- [1, 1'-biphenyl] methanol, see Step B, Method
  • Step D (Method II): (1R, 3R) -3- (2,2-dibromethenyl) -2,2-dimethyl-cyclopropanecarboxylic acid (3 ', 5'- difluoro-2-methyl- [l, 1'-biphenyl] -3-yl) methyl ester; see. Level D,
  • examples 25 and 26 were obtained by means of stage D, method II (compare also stage D, method I).
  • Step A Methyl 3-iodo-2-methylbenzoate (known from Step A, Method
  • Step B (Method II): 2-methyl-3-thien-3-yl) benzyl alcohol; see. Stage B, Method I; obtained
  • Step D (Method II): (1R, 3R) -3- (2,2-dibromoethenyl) -2,2-dimethyl-cyclopropanecarboxylic acid [2-methyl-3- (thien-3-yl)] benzyl ester; see. Stage D, Method I; Yield: 92% (ie theory)
  • Step A (Method II): 6-fluoro-3-iodo-2-methyl-benzoic acid methyl ester (known from
  • 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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  • Pest Control & Pesticides (AREA)
  • Plant Pathology (AREA)
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Abstract

L'invention concerne l'utilisation d'esters d'alcools benzyliques substitués de l'acide cyclopropane carboxylique pour lutter contre des insectes résistants aux insecticides.
PCT/EP2012/057889 2011-05-04 2012-04-30 Utilisation d'esters d'alcools benzyliques substitués de l'acide cyclopropane carboxylique pour lutter contre des insectes résistants aux insecticides WO2012150208A1 (fr)

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Cited By (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2014079928A1 (fr) * 2012-11-23 2014-05-30 Bayer Cropscience Ag Utilisation d'un composé comprenant un fragment de polyfluorobenzyle contre des nuisibles résistants aux insecticides
CN109665962A (zh) * 2019-01-17 2019-04-23 广东工业大学 一种新型双卤代乙酰化杂环菊酯及其制备方法和应用
CN109896994A (zh) * 2019-03-26 2019-06-18 广东工业大学 一种新型含氯联苯菊酯、制备方法及其应用
CN110143869A (zh) * 2019-05-23 2019-08-20 广东工业大学 一种新型联苯菊酯衍生物及其制备方法和应用
CN114230540A (zh) * 2022-01-06 2022-03-25 西安爱德克美新材料有限公司 一种合成α-BPDA的方法

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Cited By (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2014079928A1 (fr) * 2012-11-23 2014-05-30 Bayer Cropscience Ag Utilisation d'un composé comprenant un fragment de polyfluorobenzyle contre des nuisibles résistants aux insecticides
JP2016503426A (ja) * 2012-11-23 2016-02-04 バイエル・クロップサイエンス・アクチェンゲゼルシャフト 殺虫剤抵抗性有害生物に対するポリフルオロベンジル部分を含む化合物の使用
CN109665962A (zh) * 2019-01-17 2019-04-23 广东工业大学 一种新型双卤代乙酰化杂环菊酯及其制备方法和应用
CN109896994A (zh) * 2019-03-26 2019-06-18 广东工业大学 一种新型含氯联苯菊酯、制备方法及其应用
CN109896994B (zh) * 2019-03-26 2022-09-16 广东工业大学 一种新型含氯联苯菊酯、制备方法及其应用
CN110143869A (zh) * 2019-05-23 2019-08-20 广东工业大学 一种新型联苯菊酯衍生物及其制备方法和应用
CN114230540A (zh) * 2022-01-06 2022-03-25 西安爱德克美新材料有限公司 一种合成α-BPDA的方法

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