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WO2012150221A2 - Nouveaux esters d'alcools benzyliques halogénés de l'acide cyclopropancarboxique utilisés comme pesticides - Google Patents

Nouveaux esters d'alcools benzyliques halogénés de l'acide cyclopropancarboxique utilisés comme pesticides Download PDF

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Publication number
WO2012150221A2
WO2012150221A2 PCT/EP2012/057927 EP2012057927W WO2012150221A2 WO 2012150221 A2 WO2012150221 A2 WO 2012150221A2 EP 2012057927 W EP2012057927 W EP 2012057927W WO 2012150221 A2 WO2012150221 A2 WO 2012150221A2
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spp
haloalkyl
compounds
nmr
ppm
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PCT/EP2012/057927
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German (de)
English (en)
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WO2012150221A3 (fr
Inventor
Peter Jeschke
Arnd Voerste
Neil Berry
Naomi DYER
Weiqian David HONG
Zeynab HYDER
Louise LA PENSEE
Paul O´NEILL
Sunil SABBANI
Stephen Ward
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Bayer Cropscience Ag
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Publication of WO2012150221A2 publication Critical patent/WO2012150221A2/fr
Publication of WO2012150221A3 publication Critical patent/WO2012150221A3/fr

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    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D333/00—Heterocyclic compounds containing five-membered rings having one sulfur atom as the only ring hetero atom
    • C07D333/02—Heterocyclic compounds containing five-membered rings having one sulfur atom as the only ring hetero atom not condensed with other rings
    • C07D333/04—Heterocyclic compounds containing five-membered rings having one sulfur atom as the only ring hetero atom not condensed with other rings not substituted on the ring sulphur atom
    • C07D333/06—Heterocyclic compounds containing five-membered rings having one sulfur atom as the only ring hetero atom not condensed with other rings not substituted on the ring sulphur atom with only hydrogen atoms, hydrocarbon or substituted hydrocarbon radicals, directly attached to the ring carbon atoms
    • C07D333/08—Hydrogen atoms or radicals containing only hydrogen and carbon atoms
    • C07D333/10—Thiophene
    • 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
    • C07C69/743—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 acids with a three-membered ring and with unsaturation outside the ring
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C2601/00—Systems containing only non-condensed rings
    • C07C2601/02—Systems containing only non-condensed rings with a three-membered ring

Definitions

  • the present application relates to novel halogenated benzyl alcohol esters of cyclopropanecarboxylic acid, processes for their preparation and use for controlling animal pests, especially arthropods and in particular of insects, arachnids and nematodes.
  • R 1 and R 2 Cl or Br or F
  • the object of the present invention was to provide compounds which broaden the spectrum of pesticides from various aspects.
  • the problem is solved, as well as other tasks not explicitly mentioned, which can be derived or deduced from the relationships discussed herein, by novel compounds of the formula (I),
  • 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,
  • Ri 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, halocycloalkyl, alkenyl, haloalkenyl, alkynyl, alkoxy, haloalkoxy, alkoxycarbonyl, alkoxyalkyl, haloalkoxyalkyl, alkylthio, haloalkylthio, alkylsulfinyl, haloalkylsulfinyl, alkylsulfonyl, haloalkylsulfonyl, Fluorine, bromine, chlorine, iodine, nitro, cyano, amino, alkylamino, dialkylamino,
  • R 2 is cyano, halogen or haloalkyl, preferably halogen is fluorine, preferably haloalkyl is fluoromethyl, and
  • Y 1 and Y 2 independently of one another are halogen or haloalkyl, preferably halogen is selected from the series bromine or chlorine, preferably haloalkyl is trifluoromethyl.
  • Z is alkyl, alkoxy, haloalkyl, alkylthio, alkylsulfoxyl, alkylsulfonyl, haloalkoxy, haloalkylthio, haloalkylsulfoxyl, haloalkylsulfonyl, alkylamino, dialkylamino, cyano, halogen or hydroxyl and p is a number from 0 to 2,
  • R 2 is cyano, halogen or haloalkyl, preferably halogen is fluorine, preferably haloalkyl is fluoromethyl and
  • Yi and Y 2 are each independently halogen or haloalkyl, preferably halogen is selected from the group of bromine or chlorine, preferably haloalkyl is trifluoromethyl, wherein the aforementioned compounds (1) to (5) are excluded.
  • 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.
  • Y 1 and Y 2 independently of one another are halogen or haloalkyl, preferably halogen is selected from the group of bromine or chlorine, preferably haloalkyl is trifluoromethyl and LG is a nucleofuge leaving group which may be generated in situ ("leaving group”), 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 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, Z and p are as defined above,
  • 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 if appropriate in the presence of a suitable diluent, or b with compounds of the general formula (III-B)
  • R 2 is 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 fluorine or fluoromethyl
  • Yi and Y 2 are bromine, chlorine or trifluoromethyl.
  • the compounds have the general formula (1.3) or (1.4):
  • 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, stands for fluorine or fluoromethyl.
  • the compounds have the general formula (1.5) or (1.6): in which
  • 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 "independently of one another are alkyl, haloalkyl, cycloalkyl, halogenocycloalkyl, alkenyl, haloalkenyl, alkynyl, alkoxy, haloalkoxy, alkoxycarbonyl, alkoxyalkyl,
  • R 2 is 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,
  • R 2 is fluorine or fluoromethyl
  • Yi and Y 2 are bromine, chlorine or trifluoromethyl.
  • the compounds have the general formula (1.8) and (1.9), in which
  • 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, alkylsulfinyl, haloalkylsulfinyl, alkylsulfonyl, haloalkylsulfonyl, fluoro, Bromine, chlorine, iodine, nitro, cyano, amino, alkylamino, dialkylamino, preferably stand for fluorine and
  • R 2 is 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:
  • 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 (Al) (see also Preparation Example 1, step D).
  • 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 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, Metode 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 Palladium-catalyzed cross-coupling (Suzuki coupling, Wang H.J., et al., Tetrahedron Lett., 2005, 46, 2631-2634 and literature cited therein)
  • a suitable coupling reaction eg Suzuki coupling in the presence of suitable transition metal catalysts, see Reaction Scheme I, Stefe E
  • Certain substituted benzoic acid esters of the formula (A-2) have already become known, for example: 2-fluoro-3-iodobenzoic acid (WO 2009/132774), 2,6-difluoro-3-iodo-benzoic acid (M. Sato et al. , J. Med. Chem. 2009, 52, 4869-4882), 2,4,5-trifluoro-3-iodo-benzoic acid (EP-A 357 047).
  • 2-fluoro-3-iodo-benzoic acid in Preparation Example 1 is described.
  • the preparation of the 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).
  • 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
  • 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. It can be worked under normal pressure in principle. Preferably, working at atmospheric pressure or at pressures up to 15 bar and optionally under a protective gas atmosphere (nitrogen, helium or argon).
  • a protective gas atmosphere nitrogen, helium or argon
  • acid binders such as amines, in particular tertiary amines and also alkali metal and alkaline earth metal compounds.
  • 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 and further basic compounds such as amidine bases or guanidine bases such as 7-methyl-l, 5,7-triaza-bicyclo (4.4.
  • 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. It can be worked under normal pressure in principle. Preferably, working at atmospheric pressure or at pressures up to 15 bar and optionally under a protective gas atmosphere (nitrogen, helium or argon).
  • a protective gas atmosphere nitrogen, helium or argon
  • 0.01 to 0.04 mol, preferably 0.01 to 0.03 mol, particularly preferably 0.02 mol of transition metal catalyst are generally used to carry out the process according to the invention per mole of compound of general formula (IA).
  • suitable 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 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:
  • Pests of the genus Arthropoda in particular of the class Arachnida eg Acarus spp., Aceria sheldoni, Aculops spp., Aculus spp., Amblyomma spp., Amphitetranychus viennensis, Ar gas spp., Boophilus spp., Brevipalpus spp., Bryobia graminum, Bryobia praetiosa, Centruroides spp., Chorioptes spp., Dermanyssus gallinae, Dermatophagoides pteronyssinus, Dermatophagoides farinae, Dermacentor spp., Eotetranychus spp., Epitrimerus pyri, Eutetranychus spp.
  • Eriophyes spp. Glycyphagus domesticus, Halotydeus destructor, Hemitarsonemus spp., Hyalomma spp., Ixodes spp., Latrodectus spp., Loxosceles spp., Metatetranychus spp., Neutrombicula autumnalis, Nuphersa spp., Oligonychus 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 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
  • Aedes spp. From the order of the Diptera, for example, Aedes spp., Agromyza spp., Anastrepha spp., Anopheles spp., Asphondylia spp., Bactrocera spp., Bibio hortulanus, Calliphora erythrocephala, Calliphora vicina, Ceritis capitata, Chironomus spp.
  • 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 ..
  • Eupoe cilia ambiguella Euproctis spp., Euxoa spp., Feltia spp., Galleria mellonella, Gracillaria spp., Grapholitha spp., Hedylepta spp., Helicoverpa spp., Heliothis spp., Hofmannophila pseudopetre- pretella, Homoeosoma spp., Homona Spp., Hyponomeuta padella, Kakivoria flavofasciata, Laphygma spp., Laspeyresia molesta, Leucinodes orbonalis, Leucoptera spp., Lithocolletis spp., Lithophane antennata, Lobesia spp., Loxagrotis albicosta, Lymantria spp., Lyonetia spp., Malacosoma neustria
  • ra praefica Stathmopoda spp., Stomopteryx subsecivella, Synanthedon spp., Tecia solanivora, Thermesia gemmatalis, Tinea cloacella, Tinea pellionella, Tineola bisselliella, Tortrix spp., Trichophaga tapetzella, Trichoplusia spp., Tryporyza incertulas, Tuta absoluta, Virachola spp.
  • Phthiraptera e.g. Damalinia spp., Haematopinus spp., Linognathus spp., Pediculus spp., Phylloera vastatrix, Phtirus pubis, Trichodectes spp.
  • siphonaptera e.g. Ceratophyllus spp., Ctenocephalides spp., Pulex irritans, Tunga penetrans, Xenopsylla cheopsis.
  • Thysanoptera e.g. Anaphothrips obscurus, Baliothrips biformis, Drepanothrips reuteri, Enneothrips flavens, Frankliniella spp., Heliothrips spp., Hercinothrips femoralis, Rhipropyrothrips cruentatus, Scirtothrips spp., Taeniothrips cardamomi, Thrips spp.
  • Anaphothrips obscurus e.g. Anaphothrips obscurus, Baliothrips biformis, Drepanothrips reuteri, Enneothrips flavens, Frankliniella spp., Heliothrips spp., Hercinothrips femoralis, Rhipropyrothrips 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 Plathelminthes and Nematoda strains eg Ancylostoma duodenale, Ancylostoma ceylanicum, Acylostoma braziliensis, Ancylostoma spp., Ascaris spp., Brugia malayi, Brugia timori, Bunostomum spp.
  • Plant pests from the strain of Nematoda, ie plant parasitic nematodes in particular Aphelenchoides spp., Bursaphelenchus spp., Ditylenchus spp., Globodera spp., Heterodera spp., Lon- gidorus 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., Rotylenchus spp., Neotylenchus spp., Paraphelenchus spp., Dolichodorus spp., Hoplolaimus spp., Punctodera spp., Criconemella spp., Quinisulcius spp.
  • Hemicycliophora spp. Anguina spp., Subanguina spp., Hemicriconemoides spp., Psilenchus spp., Pseudohalenchus spp., Criconemoides spp., Cacopaurus spp.
  • the order of coccidia can be determined, e.g. Fight Eimeria spp.
  • 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, e.g. by mixing the active compounds with extenders, ie liquid solvents and / or solid carriers, if appropriate using surface-active agents, ie emulsifiers and / or dispersants and / or foam-forming agents.
  • extenders ie liquid solvents and / or solid carriers
  • surface-active agents ie emulsifiers and / or dispersants and / or foam-forming agents.
  • the formulations are prepared either in suitable systems or else before or during use.
  • Adjuvants 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 liquors, seed dressing), such as certain technical properties and / or special biological properties.
  • Typical auxiliaries are: extenders, solvents and carriers.
  • Suitable extenders are, for example, water, polar and nonpolar organic chemical liquids, for example from the classes of aromatic and non-aromatic hydrocarbons (such as paraffins, alkylbenzenes, alkylnaphthalenes, chlorobenzenes), alcohols and polyols (which may also be substituted, rethert and / or esterified), ketones (such as acetone, cyclohexanone), esters (also 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, rether
  • 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.
  • Suitable solid carriers are: e.g. Ammonium salts and ground natural minerals, such as kaolins, clays, talc, chalk, quartz, attapulgite, montmorillonite or diatomaceous earth, and ground synthetic minerals, such as fumed silica, alumina and silicates, as solid carriers for granules are suitable: e.g.
  • emulsifiers and / or foam formers are: e.g. nonionic and anionic emulsifiers, such as polyoxyethylene fatty acid esters, polyoxyethylene fatty alcohol ethers, e.g.
  • Alkylaryl polyglycol ethers alkylsulfonates, alkyl sulfates, arylsulfonates and protein hydrolysates; suitable dispersants are non-ionic and / or ionic substances, e.g.
  • POE and / or POP ethers from the classes of alcohol POE and / or POP ethers, acid and / or POP-POE esters, alkyl-aryl and / or POP-POE ethers, fatty and / or POP-POE adducts, POE and / or POP polyol derivatives, POE and / or POP sorbitan or sugar adducts, alkyl or aryl sulfates, sulfonates and phosphates or the corresponding PO ether adducts.
  • suitable oligo- or polymers e.g. starting from vinylic monomers, from acrylic acid, from EO and / or PO alone or in combination with e.g.
  • Adhesives such as carboxymethylcellulose, natural and synthetic powdery, granular or latex-like polymers can be used in the formulations, such as gum arabic, polyvinyl alcohol, polyvinyl acetate, as well as natural phospholipids such as cephalins and lecithins and synthetic phospholipids.
  • Dyes such as inorganic pigments such as 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 can be used.
  • Other 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 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 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 produced by conventional breeding and optimization methods or by Technological and genetic engineering methods or combinations of these methods can be obtained, 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
  • plant cultivars and their parts are treated.
  • transgenic plants and plant cultivars obtained by genetic engineering if appropriate in combination with conventional methods (Genetically Modified Organisms), and parts thereof are treated.
  • the terms "parts” or “parts of plants” or “plant parts” have been explained above.
  • Plant varieties are 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.
  • the treatment according to the invention may also give rise to superadditive ("synergistic") effects.
  • superadditive for example, reduced application rates and / or extensions of the spectrum of action and / or an increase in the effect of the substances and agents usable in 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 power facilitated harvest, 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, which exceed the actual expected effects.
  • the preferred plants or plant varieties to be treated according to the invention to be treated include all plants which, as a result of the genetic engineering modification, obtained genetic material which gives these plants particularly advantageous valuable properties ("traits").
  • traits are better plant growth, increased tolerance to high or low temperatures, increased tolerance to dryness or to bottoms, increased flowering efficiency, easier harvesting, 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, such as against insects, mites, phytopathogenic fungi, bacteria and / or viruses as well as an increased tolerance of the plants to 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 particular 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
  • 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).
  • the genes which confer the desired properties (“traits") can also occur in combinations with one another in the transgenic plants.
  • Examples of “Bt plants” are maize varieties, cotton varieties, soybean varieties and potato varieties which are sold under the trade names YIELD GARD® (eg corn, cotton, soya), KnockOut® (eg maize), StarLink® (eg maize), Bollgard® ( Cotton), Nucotn® (cotton) and NewLeaf® (potato).
  • herbicide-tolerant plants cotton varieties and soybean are mentioned under the trade names Roundup Ready® (tolerance to glyphosate eg corn, cotton, soy), Liberty Link® (tolerance to phosphinotricin, eg rape), 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 rape
  • IMI® to imidazolinone
  • STS® tolerance to sulfonylureas eg corn.
  • Clearfield® eg maize
  • 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.
  • reaction mixture was cooled to -78 ° C and treated with 4.48 g (2.4 ml, 20.0 mmol) of 1-iodo-2-fluorobenzene.
  • the reaction mixture was stirred for a further 2 hours at -78.degree. Thereafter, the reaction mixture was carefully mixed with an excess freshly crushed dry ice (solid carbon dioxide) (quenching to -50 ° C).
  • the reaction mixture was brought to room temperature within 30 minutes. Thereafter, the solvent was removed in vacuo and the remaining residue was mixed with 50 ml of water.
  • 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. The combined organic phases were dried over magnesium sulfate, concentrated in vacuo and purified by flash chromatography using 5% ethyl acetate in hexane. This gives 7.82 g (83% of theory) of 2-bromomethyl-3-iodo-benzoic acid methyl ester as a colorless solid.
  • Step 2 Methyl 2-fluoromethyl-3-iodobenzoate 73.44 ml (73.44 mmol) of tetra-n-butylammonium fluoride (TBAF, 1.0 M in THF) was converted into a stirred solution of 1 l under a protective gas atmosphere (nitrogen), 85 g (33.4 mmol) of 2-bromomethyl-3-iodobenzoic acid ester (see step 1) in THF. Thereafter, the reaction mixture was stirred at room temperature for 24 hours. The solvent was then removed in vacuo and the remaining residue was purified by flash chromatography using 5% ethyl acetate in hexane.
  • TBAF tetra-n-butylammonium fluoride
  • Step B (2-fluoro-3-iodophenyl) methanol (see also WO 2009/132774)
  • 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.
  • (2,6-Difluoro-3-iodo-phenyl) methanol was prepared analogously from 2,6-difluoro-3-iodo-benzoic acid methyl ester (cf., WO 2009/076747) by means of lithium borohydride reduction in toluene / tetrahydrofuran in 87%. iger yield (ie theory) as a colorless, crystalline solid.
  • Step C (method I. II): (1R, 3R) -3- (2,2-dibromethenyl) -2,2-dimethylcyclopropanecarb
  • Step E the solvent was removed in vacuo and the crude (1R, 3R) -3- (2,2-dibromethenyl) -2,2-dimethyl-cyclopropanecarboxylic acid chloride (yellowish oil) for the next reaction step (Step E). used.
  • d-1) Step D Method D (Method I): (1R, 3R) -3- (2,2-dibromethenyl) -2,2-dimethyl-cyclopropanecarboxylic acid
  • the (1R, 3R) -3- (2,2-dibromoethenyl) -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 admixed with a solution of 4.56 g (18.1 mmol) of (2-fluoro-3-iodo-phenyl) -methanol (step C) in 20 ml of dichloromethane. Thereafter, the reaction mixture was stirred for about 18 hours at room temperature.
  • 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.
  • Step D (Method I): (1R, 3R) -3- (2-chloro-2-trifluoromethenyl) -2,2-dimethyl-cyclopropanecarboxylic acid 2,6-difluoro-3-iodo-benzyl ester
  • the (1R, 3R) -3- (2-chloro-2-trifluoromethenyl) -2,2-dimethyl-cyclopropane-carboxylic acid 2,6-difluoro-3-iodobenzyl ester was prepared in an analogous manner (IR, 3R).
  • 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.
  • 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.
  • examples 4 were obtained at 6 hours reaction time at 75 ° C by means of Suzuki coupling (stage E, method I).
  • stage E, method I Suzuki coupling
  • Example 4 (1R, 3R) -3- (2,2-Dibromoethenyl) -2,2-dimethylcyclopropanecarboxylic acid (2, 3'-difluoro [1, 1'-biphenyl] -3-yl) methyl ester
  • Example 6 was obtained at 16 hours reaction time at 70 ° C by means of Suzuki coupling (step E, method I).
  • step E, method I Example 6 (1R, 3R) -3- (2,2-dibromethenyl) -2,2-dimethyl-cyclopropanecarboxylic acid (2-fluoro-3-thienoyl)
  • 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).
  • stage E, method I Suzuki coupling
  • Example 8 (1R, 3R) -3- (2,2-Dibromoethenyl) -2,2-dimethyl-cyclopropanecarboxylic acid (2-fluoro-2'-trifluoromethoxy- [1, ⁇ -biphenyl] -3-yl) methyl ester
  • Example 19 was obtained.
  • Example 19 (1R, 3R) -3- (2,2-dibromethenyl) -2,2-dimethylcyclopropanecarboxylic acid (2,2 ', 4'-trifluoromethane)
  • Step E Method I
  • (1R, 3R) -3- (2,2-dibromoethenyl) -2,2-dimethyl-cyclopropanecarboxylic acid 2,6-difluoro-3-iodo-b enyl ester and 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. Level D,
  • 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 [l, - biphenyl] -3-carbon Acidmethylester; 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) methyl ester; see .
  • S tu fe D Method I Yield: 70% (ie theory)
  • 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 (2, 2 ', 5'-trifluoro [1, l' -] biphenyl] -3-yl) methylester; see. Level D,
  • 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 (2,4'-difluoro [1, 1'-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-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-dimethylcyclopropanecarboxylic acid (2-fluoro [l, 1'-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, 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 E (Method II): 2,6-difluoro [1, 1'-biphenyl] -3-carboxylic acid methyl ester; see. step
  • 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. Step D, Method I Yield: 87% (ie theory) ES HRMS: m / z calculated: 522.9515.
  • 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, build: 85% (ie theory)
  • 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) ES HRMS: m / z found: 524.9330. C2oHi 9 0 2 F 23 Na 79 SBr 81 Br [M + Na] + calcd: 524.9334.
  • Step A (Method II): 2-fluoromethyl-3-iodo-benzoic acid methyl ester (known from Step A,
  • Step B 2-fluoromethyl [1, biphenyl] methanol; see. Stage B, Method I; Yield obtained: 89% (of 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'-fluoro [1,1'-biphenyl] -methanol; see. Level B, method
  • 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 A (Method II): 2-fluoromethyl-3-iodo-benzoic acid methyl ester (known from Step A,
  • Step B 2-fluoromethyl-2'-fluoro [1-biphenyl] -methanol; see. Level B, method
  • Step D (Method II): (1R, 3R) -3- (2,2-dibromethenyl) -2,2-dimethylcyclopropanecarboxylic acid (2-fluoromethyl-2'-fluoro- [l, -biphenyl] - 3-yl) methylester; see. Stage D, Method I; Yield: 91% (ie theory)
  • 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 (2-fluoromethyl-2 ', 4'-difluoro [1, l '-biphenyl] -3-yl) methyl ester; see. Stage D, Method I; Yield: 84% (ie theory) ES HRMS: m / z found: [M + Na] + , 552.9603. C22Hi902F 3 23 Na 79 Br 2 Calculated: 552.9602.
  • Step A (Method II): 2-fluoromethyl-3-iodo-benzoic acid methyl ester (known from Step A,
  • Step B 2-fluoromethyl-4'-chloro [1,1'-biphenyl] -methanol; see. Level B, method
  • Step D (Method II): (1R, 3R) -3- (2,2-dibromethenyl) -2,2-dimethylcyclopropanecarboxylic acid (2-fluoromethyl-4'-chloro [1,1'-biphenyl ] -3-yl) methyl ester; see. Stage D, Method I; Yield: 66% (ie theory) ES HPvMS: m / z found: [M + Na] + , 550.9418.
  • 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
  • Step 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% (theory)
  • dimethylformamide emulsifier 1.5 parts by weight of dimethylformamide emulsifier: 0.5 part by weight of alkylaryl polyglycol ether
  • 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 with emulsifier-containing water to the desired concentration.
  • 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).
  • Emulsifier 0.5 part by weight of alkylaryl polyglycol ether
  • 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 with emulsifier-containing water to the desired concentration.
  • 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).
  • Emulsifier 0.5 part by weight of alkylaryl polyglycol ether
  • active compound preparation 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.
  • 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. Bean leaf discs (Phaseolus vulgaris) infected by all stages of the common spider mite (Tetranychus urticae) are sprayed with an active compound preparation of the desired concentration. After 6 days, 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)
  • Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
  • Agricultural Chemicals And Associated Chemicals (AREA)

Abstract

La présente invention concerne de nouveaux esters d'alcools benzyliques halogénés de l'acide cyclopropancarboxylique, leurs procédés de production et leur utilisation dans la lutte contre les animaux nuisibles, surtout les arthropodes et notamment les insectes, les arachnides et les nématodes.
PCT/EP2012/057927 2011-05-04 2012-04-30 Nouveaux esters d'alcools benzyliques halogénés de l'acide cyclopropancarboxique utilisés comme pesticides WO2012150221A2 (fr)

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Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN109651183A (zh) * 2019-01-18 2019-04-19 广东工业大学 一种新型酰胺菊酯类化学修饰物及其制备方法和应用

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DE2802962A1 (de) 1977-01-24 1978-07-27 Ici Ltd Halogenierte ester, verfahren zu ihrer herstellung und sie enthaltende insektizide zusammensetzungen
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Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN109651183A (zh) * 2019-01-18 2019-04-19 广东工业大学 一种新型酰胺菊酯类化学修饰物及其制备方法和应用

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