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WO2017133994A1 - Dérivés à activité pesticide comportant des substituants contenant du soufre et du cyclopropyle - Google Patents

Dérivés à activité pesticide comportant des substituants contenant du soufre et du cyclopropyle Download PDF

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Publication number
WO2017133994A1
WO2017133994A1 PCT/EP2017/051879 EP2017051879W WO2017133994A1 WO 2017133994 A1 WO2017133994 A1 WO 2017133994A1 EP 2017051879 W EP2017051879 W EP 2017051879W WO 2017133994 A1 WO2017133994 A1 WO 2017133994A1
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spp
formula
cyano
ccn
methyl
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PCT/EP2017/051879
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English (en)
Inventor
Pierre Joseph Marcel Jung
Andrew Edmunds
Michel Muehlebach
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Syngenta Participations Ag
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Publication of WO2017133994A1 publication Critical patent/WO2017133994A1/fr

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    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D487/00—Heterocyclic compounds containing nitrogen atoms as the only ring hetero atoms in the condensed system, not provided for by groups C07D451/00 - C07D477/00
    • C07D487/02—Heterocyclic compounds containing nitrogen atoms as the only ring hetero atoms in the condensed system, not provided for by groups C07D451/00 - C07D477/00 in which the condensed system contains two hetero rings
    • C07D487/04—Ortho-condensed systems
    • 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
    • A01N43/00—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds
    • A01N43/90—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having two or more relevant hetero rings, condensed among themselves or with a common carbocyclic ring system

Definitions

  • the present invention relates to pesticidally active, in particular insecticidally active tetracyclic derivatives containing sulfur and cyclopropane substituents, to compositions comprising those compounds, and to their use for controlling animal pests (including arthropods and in particular insects or representatives of the order Acarina).
  • Heterocyclic compounds with pesticidal action are known and described, for example, in
  • the present invention accordingly relates to compounds of formula I,
  • A is CH or N
  • X is S, SO or S0 2 ;
  • Ri is C i-C6 alkyl , or is C3-C6cycloalkyl-Ci-C4alkyl witch can be mono- or polysubstituted by substituents selected from the group consisting of halogen, cyano, Ci-C4haloalkyl and Ci-C4alkyl ;
  • R2 is C i-C4haloalkylsulfanyl, Ci-C4haloalkylsulfinyl, Ci-C4haloalkylsulfonyl or Ci-C6haloalkyl; or
  • R2 is C3-C6cycloalkyl which can be mono - or polysubstituted by substituents selected from the group consisting of halogen, cyano, Ci-C4haloalkyl and Ci-C4alkyl ;
  • R4 is hydrogen, halogen, cyano, Ci-C4alkyl or Ci-C4haloalkyl
  • Re is C i-C 4 alkyl
  • Li , L2, L3 and L4 form together with the two carbon atoms to which Li and L4 are attached, an aromatic, partially saturated or fully saturated carbocyclic or heterocyclic ring system;
  • Li is nitrogen, S(0)n, oxygen, N-Rioa or C(Rio a ) m ;
  • l_2 is nitrogen, S(0)n, oxygen, N-Riob or C(Riot>)m
  • L3 is nitrogen, S(0)n, oxygen, N-Rioc, or C(Rioc) m ;
  • L4 is nitrogen, S(0)n, oxygen, a direct bond, N-Riod or C(Riod) m ; with the provisos that no more than 2 substituents selected from Li , L2, L3 and L4 can be oxygen or sulfur; and if two L groups are oxygen, they are not adjacent to each other; and no more than three L groups can be nitrogen;
  • n 0, 1 or 2;
  • n 1 or 2;
  • Rioa, Riob, Rioc, and R-iod independently from each other, are hydrogen, halogen, nitro, cyano, hydroxyl, Ci-C6alkyl, C2-C6alkenyl, C2-C6alkynyl, C3-C6cycloalkyl , Ci-C6haloalkyl, C2-C6haloalkenyl, C2- Cehaloalkynyl, C3-C6halocycloalkyl , Ci-C6alkoxy, Ci-C4alkoxyCi-C4alkyl, Ci-C6haloalkoxy, Ci-C6alkylthio, Ci-C6alkylsulfinyl , Ci-C6alkylsulfonyl , Ci-C6haloalkylthio, Ci-C6haloalkylsulfinyl , Ci-C6haloalkylsulfonyl , C2-C6alkylcarbonyl
  • one of Rioa, Riob, Rioc and Riod can be oxo; or
  • Rioa, Riot>, R100, and Riod independently from each other, are C3-C6cycloalkyl mono- to polysubstituted by substituents selected from the group consisting of halogen, Ci-C4 haloalkyl, Ci-C4alkyl and cyano;
  • Compounds of formula I which have at least one basic centre can form, for example, acid addition salts, for example with strong inorganic acids such as mineral acids, for example perchloric acid, sulfuric acid, nitric acid, a phosphorus acid or a hydrohalic acid, with strong organic carboxylic acids, such as Ci- C4alkanecarboxylic acids which are unsubstituted or substituted, for example by halogen, for example acetic acid, such as saturated or unsaturated dicarboxylic acids, for example oxalic acid, malonic acid, succinic acid, maleic acid, fumaric acid or phthalic acid, such as hydroxycarboxylic acids, for example ascorbic acid, lactic acid, malic acid, tartaric acid or citric acid, or such as benzoic acid, or with organic sulfonic acids, such as Ci-C4alkane- or arylsulfonic acids which are unsubstituted or substituted, for example by halogen, for
  • Compounds of formula I which have at least one acidic group can form, for example, salts with bases, for example mineral salts such as alkali metal or alkaline earth metal salts, for example sodium, potassium or magnesium salts, or salts with ammonia or an organic amine, such as morpholine, piperidine, pyrrolidine, a mono-, di- or tri-lower- alkylamine, for example ethyl-, diethyl-, triethyl- or dimethylpropylamine, or a mono-, di- or trihydroxy- lower-alkylamine, for example mono-, di- or triethanolamine.
  • m is 1 or 2 depending on the hybridization of the carbon atom.
  • Rioa can be the same or different; for example one Rioa can be hydrogen and the other methyl. This is also valid for the definitions of C(Rio_)m , C(Rioc)m and C(Riod)m.
  • alkyl groups occurring in the definitions of the substituents can be straight-chain or branched and are, but are not limited to, methyl, ethyl, n-propyl, isopropyl, n-butyl, sec-butyl, iso-butyl, tert-butyl, pentyl, hexyl, nonyl, decyl and their branched isomers.
  • Alkylsulfanyl, alkylsulfinyl, alkylsulfonyl, alkoxy, alkenyl and alkynyl radicals are derived from the alkyl radicals mentioned.
  • the alkenyl and alkynyl groups can be mono- or polyunsaturated.
  • Halogen is generally fluorine, chlorine, bromine or iodine. This also applies, correspondingly, to halogen in combination with other meanings, such as haloalkyl or halophenyl.
  • Haloalkyl groups preferably have a chain length of from 1 to 6 carbon atoms.
  • Haloalkyl is, but is not limited to, fluoromethyl, difluoromethyl, trifluoromethyl, chloromethyl, dichloromethyl, trichloromethyl, 2,2,2-trifluoroethyl, 2-fluoroethyl, 2-chloroethyl, pentafluoroethyl, 1 ,1 -difluoro-2,2,2-trichloroethyl, 2,2,3,3- tetrafluoroethyl and 2,2,2-trichloroethyl.
  • Alkoxy is, but is not limited to, methoxy, ethoxy, propoxy, i-propoxy, n-butoxy, isobutoxy, sec-butoxy and tert-butoxy and also the isomeric pentyloxy and hexyloxy radicals.
  • Alkoxyalkyl groups preferably have a chain length of 1 to 6 carbon atoms.
  • Alkoxyalkyl is, but are not limited to, methoxymethyl, methoxyethyl, ethoxymethyl, ethoxyethyl, n- propoxymethyl, n-propoxyethyl, isopropoxymethyl or isopropoxyethyl.
  • Alkoxycarbonyl is, but are not limited to, methoxycarbonyl (which is Cialkoxycarbonyl), ethoxycarbonyl, propoxycarbonyl, isopropoxycarbonyl, n-butoxycarbonyl, tert-butoxycarbonyl, n-pentoxycarbonyl or hexoxycarbonyl.
  • the cycloalkyl groups preferably have from 3 to 6 ring carbon atoms and are, for example, cyclopropyl, cyclobutyl, cyclopentyl and cyclohexyl.
  • C2-C6 alkynyl refers to a straight or branched hydrocarbon chain radical group consisting solely of carbon and hydrogen atoms, containing at least one triple bond, having from two to six carbon atoms, and which is attached to the rest of the molecule by a single bond.
  • C2-C4 alkynyl and “C2-C3 alkynyl” can be formed accordingly.
  • Examples of C2-C6 alkynyl include, but are not limited to, ethynyl, prop-1 -ynyl, but-1 -ynyl, but-2-ynyl.
  • C2-C6alkenyl refers to a straight or branched hydrocarbon chain radical group consisting solely of carbon and hydrogen atoms, containing at least one double bond, having from two to six carbon atoms, and which is attached to the rest of the molecule by a single bond.
  • C2-C4alkenyl and “C2-C3alkenyl” can be formed accordingly.
  • Examples of C2-C6 alkenyl include, but are not limited to, prop-1 -enyl, but-1 -enyl, but-2-enyl.
  • an aromatic, partially saturated or fully saturated heterocyclic ring system'Mhe heterocyclic ring system is preferably a group comprising 5 to 6 carbon atoms in the ring, which are saturated, unsaturated or partially saturated, for example, but are not limited to phenyl, cyclopentyl and cyclohexenyl , pyrrolyl; pyrazolyl; isoxazolyl; furanyl; thienyl; imidazolyl; oxazolyl; thiazolyl; isothiazolyl; triazolyl; oxadiazolyl; thiadiazolyl; tetrazolyl; furyl; pyridyl; pyrimidyl;
  • pyrazinyl pyridazinyl; triazinyl, pyranyl; pyrrolidinyl, piperidinyl; pyrrol id inyl-2-one; piperidinyl-2-one.
  • "mono- to polysubstituted" in the definition of the substituents means typically, depending on the chemical structure of the substituents, monosubstituted to seven-times substituted, preferably monosubstituted to five-times substituted, more preferably mono-, di- or tri- substituted.
  • An example for an aromatic, partially saturated or fully saturated carbocyclic or heterocyclic ring system wherein one of Rio a , Riot>, Rioc or R-iod can represent oxo is the following group:
  • the compounds of formula I according to the invention also include hydrates which may be formed during the salt formation.
  • A is C-H or N ;
  • Ri is Ci-C4alkyl or C3-C6cycloalkyl-Ci-C4alkyl ;
  • R2 is Ci-C4haloalkyl, cyano or is C3-C6cycloalkyl which can be mono - or polysubstituted by substituents selected from the group consisting of halogen, Ci-C4 haloalkyl , cyano and Ci-C4alkyl;
  • Li, L2, L3 and L4 are as defined under formula I above;
  • Rioa, Riob, Rioc, and R-iod independently from each other, are hydrogen, halogen, nitro, cyano, hydroxyl,
  • Ci-C6alkyl C2-C6alkenyl, C2-C6alkynyl, C3-C6cycloalkyl , C3-C6cycloalkyl-Ci-C4alkyl, Ci-C6haloalkyl, C2-
  • J is selected from the group consisting of
  • Embodiment (A3) Ri, R2, R4, Re, X, Rioa, Riot>, Rio c and Riod are as defined under Embodiment (A1 ).
  • J is as defined under Embodiment (A2);
  • A is C-H or N ;
  • Ri is Ci-C 4 alkyl
  • R2 is Ci-C4haloalkylsulfanyl, Ci-C4haloalkylsulfinyl, Ci-C4haloalkylsulfonyl, Ci-C4haloalkyl, or is
  • X, R4 and R6 are as defined under formula I above;
  • R-ioa, Riot > , Rioc and Riod independently from each other, are hydrogen, halogen, nitro, cyano, hydroxyl , Ci-C6alkyl, C2-C6alkenyl, C2-C6alkynyl, C3-C6cycloalkyl, C3-C6cycloalkyl-Ci-C4alkyl, Ci-C6haloalkyl, C2- Cehaloalkenyl, C2-C6haloalkynyl, C3-C6halocycloalkyl, C3-C6cyclohaloalkyl-Ci-C4 cycloalkyi, Ci-C4alkoxy, Ci-C4haloalkoxy, Ci-C4alkylthio, Ci-C4alkylsulfinyl, Ci-C4alkylsulfonyl, Ci-C4haloalkylthio, Ci- C4haloalkylsulfinyl or Ci-
  • Embodiment (A4) is a diagrammatic representation of Embodiment (A4):
  • J is as defined under Embodiment (A2);
  • A is C-H or N ;
  • Ri is Ci-C 4 alkyl
  • R2 is Ci-C4haloalkylsulfanyl, Ci-C4haloalkylsulfinyl, Ci-C4haloalkylsulfonyl or Ci-C4haloalkyl;
  • R-ioa, Riot > , Rioc and Riod independently from each other, are hydrogen, halogen, nitro, cyano, hydroxyl , Ci-C6alkyl, C2-C6alkenyl, C2-C6alkynyl, C3-C6cycloalkyl, C3-C6cycloalkyl-Ci-C4alkyl, Ci-C6haloalkyl, C2- Cehaloalkenyl, C2-C6haloalkynyl, C3-C6halocycloalkyl, C3-C6cyclohaloalkyl-Ci-C4 cycloalkyi, Ci-C4alkoxy, Ci-C4haloalkoxy, Ci-C4alkylthio, Ci-C4alkylsulfinyl, Ci-C4alkylsulfonyl, Ci-C4haloalkylthio, Ci- C4haloalkylsulfinyl or Ci-
  • Embodiment (A5) is a diagrammatic representation of Embodiment (A5):
  • J is as defined under Embodiment (A2);
  • A is C-H or N
  • Ri is Ci-C 4 alkyl
  • R 2 is -OCF3, -SCF3, -S(0)CF 3 , -S(0) 2 CF 3 or CF 3 ;
  • X, R4 and R6 are as defined under formula I above;
  • R-ioa, Riot>, Rioc and Riod independently from each other, are hydrogen, halogen, cyano, Ci-C6alkyl, C2- Cealkenyl, C2-C6alkynyl, Ci-C6haloalkyl, Ci-C4alkoxy, Ci-C4haloalkoxy, Ci-C4alkylthio, Ci-C4alkylsulfinyl, Ci-C4alkylsulfonyl, Ci-C4haloalkylthio, Ci-C4haloalkylsulfinyl or Ci-C4haloalkylsulfonyl.
  • Embodiment (A6) is a diagrammatic representation of Embodiment (A6):
  • J is as defined under Embodiment (A2);
  • A is C-H or N
  • Ri is ethyl
  • R2 is -SCF3, -S(0)CF 3 , -S(0) 2 CF 3 or CF 3 ;
  • X, R4 and R6 are as defined under formula I above;
  • R-ioa, Riot>, R100, and Riod, independently from each other, are hydrogen, bromo, chloro, iodo, fluoro, cyano, methyl, ethyl, isopropyl, propyl, trifluoromethyl, CF 3 CH 2 -, CH 3 0, -SCF 3 , -S(0)CF 3 or -S(0) 2 CF 3 .
  • Embodiment (A7) Further preferred are compounds of formula 1-1 a
  • J is as defined under Embodiment (A2);
  • A is C-H or N
  • Ri is ethyl
  • R 2 is -SCF 3 , -S(0)CF 3 , -S(0) 2 CF 3 or CF 3 ;
  • X is as defined under formula I above;
  • R4 is hydrogen or cyano
  • R6 is methyl or ethyl
  • Rioa, Riob, Rioc and R-iod independently from each other, are hydrogen, bromo, chloro, iodo, fluoro, cyano, methyl or trifluoromethyl.
  • Embodiment (A8) is a diagrammatic representation of Embodiment (A8).
  • J is as defined under Embodiment (A2);
  • A is C-H or N
  • Ri is ethyl
  • R 2 is -SCF 3 , -S(0)CF 3 , -S(0) 2 CF 3 or CF 3 ;
  • X is as defined under formula I above;
  • R4 is hydrogen or cyano
  • R6 is methyl or ethyl
  • Rioa, Riot > , Rioc and Riod independently from each other, are hydrogen, bromo, chloro, iodo, fluoro, cyano, methyl or trifluoromethyl.
  • X is preferably S or SO2 and R6 is methyl.
  • J is preferably selected from Ji, J4 and J5.
  • R4 is preferably hydrogen.
  • Li is N-CH3
  • L2 is C-CF3
  • L3 is N
  • L4 is a direct bond.
  • WO 201 1/043404 WO 201 1/040629, WO 2010/125985, WO 2012/086848, WO 2013/018928,
  • Z is X-R1 or a leaving group, for example a halogen, and wherein X, Ri, Li , L2, L3, U and A are as described under formula I above, and wherein the arrow in the radical Q shows the point of attachment to the carbon atom of the carboxyl group in the compound of formula II,
  • R6, R2, Gi and G2 are as described under formula I above, in the presence of a dehydrating agent, such as for example polyphosphoric acid at temperature between 150°C to 250°C, to yield compounds of formula la, wherein the substituents are as described above and under formula I.
  • a dehydrating agent such as for example polyphosphoric acid at temperature between 150°C to 250°C
  • Compounds of the formula IV and/or IVa (or a mixture thereof), or a salt thereof, wherein Q is as defined above, and wherein R6, R2, G i and G2 are as described under formula I above, may be prepared by i) activation of compound of formula II, wherein Q is as defined above, by methods known to those skilled in the art and described in, for example, Tetrahedron, 2005, 61 (46), 10827-10852, to form an activated species lla, wherein Q is as defined above and wherein Xoo is halogen, preferably chlorine.
  • compounds lla where Xoo is halogen, preferably chlorine are formed by treatment of II with, for example, oxallyl chloride (COCI)2 or thionyl chloride SOCI2 in the presence of catalytic quantities of N,N- dimethylformamide DMF in inert solvents such as methylene chloride CH2CI2 or tetrahydrofuran THF at temperatures between 20 to 100°C, preferably 25°C.
  • COCI oxallyl chloride
  • SOCI2 thionyl chloride
  • Compounds of formula IV and/or IVa may further be converted into compounds of formula la, wherein Q is as defined above, and wherein R6, R2, G i and G2 are as described under formula I above, by dehydration, eg. by heating the compounds IV and/or IVa (or a mixture thereof) in the presence of an acid catalyst, such as for example methane sulfonic acid, or para-toluene sulfonic acid TsOH, in an inert solvent such as N-methyl pyrrolidine NMP at temperatures between 25-180°C, preferably 100-170°C, optionally under microwave conditions.
  • an acid catalyst such as for example methane sulfonic acid, or para-toluene sulfonic acid TsOH
  • an inert solvent such as N-methyl pyrrolidine NMP
  • solvent to be used examples include ethers such as THF, ethylene glycol dimethyl ether, tert-butylmethyl ether, and 1 ,4-dioxane, aromatic hydrocarbons such as toluene and xylene, nitriles such as acetonitrile or polar aprotic solvents such as N,N-dimethylformamide, N,N-dimethylacetamide, N-methyl-2-pyrrolidone or dimethyl sulfoxide. Similar chemistry has been previously described, as for example in WO2013/018928.
  • salts of the compound of formula V include compounds of the formula Va
  • this reaction can be carried out in the presence of a palladium catalyst, such as
  • a compound of formula lb above involving reagents such as, for example, m- chloroperoxybenzoic acid (mCPBA), hydrogen peroxide, oxone, sodium periodate, sodium hypochlorite or tert-butyl hypochlorite amongst other oxidants.
  • mCPBA m- chloroperoxybenzoic acid
  • hydrogen peroxide oxone
  • sodium periodate sodium hypochlorite
  • sodium hypochlorite or tert-butyl hypochlorite amongst other oxidants.
  • the oxidation reaction is generally conducted in the presence of a solvent.
  • the solvent to be used in the reaction include aliphatic halogenated hydrocarbons such as dichloromethane and chloroform; alcohols such as methanol and ethanol; acetic acid; water; and mixtures thereof.
  • Such oxidation reactions are disclosed, for example, in WO 2013/018928.
  • the sequence to prepare compounds of formula Ilia wherein R2, R4 and Re are as described under formula I above, from compounds of formula VIII may involve i. alkylation of compound VIII with R6-XLG, wherein R6 is as described under formula I above and wherein XLG is a leaving group, such as halogen, preferably iodine, bromine or chlorine, in presence of a base, such as sodium carbonate, potassium carbonate or cesium carbonate, or sodium hydride, in a appropriate solvent such as for example N ,N-dimethylformamide, ⁇ , ⁇ -dimethylacetamide or acetonitrile, to generate a compound of formula VII, wherein R6, R4 and R2 are as described under formula I above Alternatively, the alkylation could be realized via amino-reduction (see for example: Comprehensive Organic Transformations: A Guide to Functional Group Preparations.
  • Z is X-Ri or a leaving group or a group that could be transformed in leaving group such as, for example halogen, amine or nitro
  • X, Ri, Li , L2, L3, U and A are as described under formula I above, may be either known, commercially available or may be made by methods known to a person skilled in the art.
  • Ri is as defined in formula I, optionally in the presence of a suitable base, such as alkali metal carbonates, for example sodium carbonate and potassium carbonate, or alkali metal hydrides such as sodium hydride, or alkali metal hydroxides such as sodium hydroxide and potassium hydroxide, in an inert solvent at temperatures preferably between 25-120°C, to generate compounds of formula lid, wherein R is alkyl or hydrogen, Ri is as described under formula I above, and in which A, Li , l_2 , L3 and L4 are as described under formula I above.
  • a suitable base such as alkali metal carbonates, for example sodium carbonate and potassium carbonate, or alkali metal hydrides such as sodium hydride, or alkali metal hydroxides such as sodium hydroxide and potassium hydroxide
  • solvent to be used examples include ethers such as THF, ethylene glycol dimethyl ether, tert-butylmethyl ether, and 1 ,4-dioxane, aromatic hydrocarbons such as toluene and xylene, nitriles such as acetonitrile or polar aprotic solvents such as ⁇ , ⁇ -dimethylformamide, N,N-dimethylacetamide, N-methyl-2-pyrrolidone or dimethyl sulfoxide.
  • salts of the compound of formula V include compounds of the formula Va
  • compounds of formula lie, wherein Z is a amine and wherein A, Li , l_2 , L3 and L4 are as described under formula I above, and wherein R is alkyl or hydrogen can be transformed to compounds of formula lid via diazotation and reaction with dialkyldisulfide.
  • This transformation is well known and could be made by methods known to a person skilled in the art (see for example : Synthetic
  • Compound of formula (II) may be prepared by reaction of a compound of formula (lid), wherein R is alkyl via hydrolysis.
  • R is methyl or ethyl
  • the hydrolysis can be done with water and a base, such as potassium hydroxide or lithium hydroxide, in the absence or in the presence of a solvent, such as, for instance, tetrahydrofuran or methanol.
  • a solvent such as, for instance, tetrahydrofuran or methanol.
  • the hydrolysis is done in the presence of acid, such as trifluoroacetic acid or hydrochloric acid.
  • the reaction is carried out at a temperature of from -120°C to +130°C, preferably from -100°C to 100°C. See scheme 8.
  • compound of formula II may be prepared by reaction of a compound of formula (XIII) wherein Z is a leaving group as nitro or halogen such as fluorine and wherein A, Li , L.2, L.3 and L.4 are as described under formula I above by reaction of a compound of formula V or Va
  • X and Ri is as defined in formula I and in which A, Li , L.2 , L.3 and L4 are as described under formula I above, optionally in the presence of a suitable base, such as alkali metal carbonates, for example sodium carbonate and potassium carbonate, or alkali metal hydrides such as sodium hydride, or alkali metal hydroxides such as sodium hydroxide and potassium hydroxide, in an inert solvent at temperatures preferably between 25-120°C.
  • a suitable base such as alkali metal carbonates, for example sodium carbonate and potassium carbonate, or alkali metal hydrides such as sodium hydride, or alkali metal hydroxides such as sodium hydroxide and potassium hydroxide, in an inert solvent at temperatures preferably between 25-120°C.
  • solvent to be used examples include ethers such as THF, ethylene glycol dimethyl ether, tert-butylmethyl ether, and 1 ,4-dioxane, aromatic hydrocarbons such as toluene and xylene, nitriles such as acetonitrile or polar aprotic solvents such as N,N-dimethylformamide, N,N-dimethylacetamide, N-methyl-2-pyrrolidone or dimethyl sulfoxide.
  • ethers such as THF, ethylene glycol dimethyl ether, tert-butylmethyl ether, and 1 ,4-dioxane
  • aromatic hydrocarbons such as toluene and xylene
  • nitriles such as acetonitrile or polar aprotic solvents
  • N,N-dimethylformamide, N,N-dimethylacetamide, N-methyl-2-pyrrolidone or dimethyl sulfoxide examples
  • Compounds of formula II may be prepared by hydrolysis of the cyano of compound of formula XlVa in acidic or basic conditions. This transformation is well known and could be made by methods known to a person skilled in the art (see for example : Comprehensive Organic Transformations: A Guide to Functional Group Preparations. Edited by Richard C. Larock 1989 p 993, VCH publishers).
  • Compounds of formula XlVa may be prepared by deplacement of the Z, a leaving group such as halogen in compounds of formula XIV via similar process as described in scheme 6 or 7. This is illustrated for compounds of formula II in scheme 9.
  • compound of formula II may be prepared by reaction of a compound of formula (XlVb) where in Z is a leaving group as nitro or halogen such as fluorine and wherein A, Li, l_2, L3 and L4 are as described under formula I above by oxidation in presence of a oxidant such as oxygen, hydrogen peroxide or an metal oxide such as chromium trioxide with or without acid such as sulphuric acid with or without metal catalyst.
  • a oxidant such as oxygen, hydrogen peroxide or an metal oxide such as chromium trioxide with or without acid such as sulphuric acid with or without metal catalyst.
  • This transformation is well known and could be made by methods known to a person skilled in the art (see for example : Comprehensive Organic Transformations: A Guide to Functional Group Preparations. Edited by Richard C. Larock 1989 p 823, VCH publishers). This is illustrated for compounds of formula II in scheme 10.
  • the reactants can be reacted in the presence of a base.
  • suitable bases are alkali metal or alkaline earth metal hydroxides, alkali metal or alkaline earth metal hydrides, alkali metal or alkaline earth metal amides, alkali metal or alkaline earth metal alkoxides, alkali metal or alkaline earth metal acetates, alkali metal or alkaline earth metal carbonates, alkali metal or alkaline earth metal dialkylamides or alkali metal or alkaline earth metal alkylsilylamides, alkylamines, alkylenediamines, free or N-alkylated saturated or unsaturated cycloalkylamines, basic heterocycles, ammonium hydroxides and carbocyclic amines.
  • Examples which may be mentioned are sodium hydroxide, sodium hydride, sodium amide, sodium methoxide, sodium acetate, sodium carbonate, potassium tert-butoxide, potassium hydroxide, potassium carbonate, potassium hydride, lithium diisopropylamide, potassium bis(trimethylsilyl)amide, calcium hydride, triethylamine, diisopropylethylamine, triethylenediamine, cyclohexylamine, N-cyclohexyl- N,N-dimethylamine, ⁇ , ⁇ -diethylaniline, pyridine, 4-(N,N-dimethylamino)pyridine, quinuclidine, N- methylmorpholine, benzyltrimethylammonium hydroxide and 1 ,8-diazabicyclo[5.4.0]undec-7-ene (DBU).
  • the reactants can be reacted with each other as such, i.e. without adding a solvent or diluent. In most cases, however, it is advantageous to add an inert solvent or diluent or a mixture of these. If the reaction is carried out in the presence of a base, bases which are employed in excess, such as triethylamine, pyridine, N-methylmorpholine or ⁇ , ⁇ -diethylaniline, may also act as solvents or diluents.
  • reaction is advantageously carried out in a temperature range from approximately -80°C to approximately +140°C, preferably from approximately -30°C to approximately +100°C, in many cases in the range between ambient temperature and approximately +80°C.
  • a compound of formula I can be converted in a manner known per se into another compound of formula I by replacing one or more substituents of the starting compound of formula I in the customary manner by (an)other substituent(s) according to the invention.
  • Salts of compounds of formula I can be prepared in a manner known per se.
  • acid addition salts of compounds of formula I are obtained by treatment with a suitable acid or a suitable ion exchanger reagent and salts with bases are obtained by treatment with a suitable base or with a suitable ion exchanger reagent.
  • Salts of compounds of formula I can be converted in the customary manner into the free compounds I, acid addition salts, for example, by treatment with a suitable basic compound or with a suitable ion exchanger reagent and salts with bases, for example, by treatment with a suitable acid or with a suitable ion exchanger reagent.
  • Salts of compounds of formula I can be converted in a manner known per se into other salts of compounds of formula I, acid addition salts, for example, into other acid addition salts, for example by treatment of a salt of inorganic acid such as hydrochloride with a suitable metal salt such as a sodium, barium or silver salt, of an acid, for example with silver acetate, in a suitable solvent in which an inorganic salt which forms, for example silver chloride, is insoluble and thus precipitates from the reaction mixture.
  • a salt of inorganic acid such as hydrochloride
  • a suitable metal salt such as a sodium, barium or silver salt
  • the compounds of formula I which have salt- forming properties, can be obtained in free form or in the form of salts.
  • the compounds of formula I and, where appropriate, the tautomer's thereof, in each case in free form or in salt form, can be present in the form of one of the isomers which are possible or as a mixture of these, for example in the form of pure isomers, such as antipodes and/or diastereomers, or as isomer mixtures, such as enantiomer mixtures, for example racemates, diastereomer mixtures or racemate mixtures, depending on the number, absolute and relative configuration of asymmetric carbon atoms which occur in the molecule and/or depending on the configuration of non-aromatic double bonds which occur in the molecule; the invention relates to the pure isomers and also to all isomer mixtures which are possible and is to be understood in each case in this sense hereinabove and hereinbelow, even when stereochem al details are not mentioned specifically in each case.
  • Diastereomer mixtures or racemate mixtures of compounds of formula I, in free form or in salt form, which can be obtained depending on which starting materials and procedures have been chosen can be separated in a known manner into the pure diasteromers or racemates on the basis of the
  • Enantiomer mixtures such as racemates, which can be obtained in a similar manner can be resolved into the optical antipodes by known methods, for example by recrystallization from an optically active solvent, by chromatography on chiral adsorbents, for example high-performance liquid chromatography (HPLC) on acetyl cellulose, with the aid of suitable microorganisms, by cleavage with specific, immobilized enzymes, via the formation of inclusion compounds, for example using chiral crown ethers, where only one enantiomer is complexed, or by conversion into diastereomeric salts, for example by reacting a basic end-product racemate with an optically active acid, such as a carboxylic acid, for example camphor, tartaric or malic acid, or sulfonic acid, for example camphorsulfonic acid, and separating the diastereomer mixture which can be obtained in this manner, for example by fractional crystallization based on their differing solubilities, to give the di
  • Pure diastereomers or enantiomers can be obtained according to the invention not only by separating suitable isomer mixtures, but also by generally known methods of diastereoselective or enantioselective synthesis, for example by carrying out the process according to the invention with starting materials of a suitable stereochemistry.
  • N-oxides can be prepared by reacting a compound of the formula I with a suitable oxidizing agent, for example the H202 urea adduct in the presence of an acid anhydride, e.g. trifluoroacetic anhydride.
  • a suitable oxidizing agent for example the H202 urea adduct
  • an acid anhydride e.g. trifluoroacetic anhydride.
  • the compounds of formula I and, where appropriate, the tautomers thereof, in each case in free form or in salt form, can, if appropriate, also be obtained in the form of hydrates and/or include other solvents, for example those which may have been used for the crystallization of compounds which are present in solid form.
  • Table 1 This table discloses the 64 compounds of the formula 1-1 b:
  • the compounds of formula I according to the invention are preventively and/or curatively valuable active ingredients in the field of pest control, even at low rates of application, which have a very favorable biocidal spectrum and are well tolerated by warm-blooded species, fish and plants.
  • the active ingredients according to the invention act against all or individual developmental stages of normally sensitive, but also resistant, animal pests, such as insects or representatives of the order Acarina.
  • the insecticidal or acaricidal activity of the active ingredients according to the invention can manifest itself directly, i. e. in destruction of the pests, which takes place either immediately or only after some time has elapsed, for example during ecdysis, or indirectly, for example in a reduced oviposition and/or hatching rate.
  • Haematopinus spp. Linognathus spp., Pediculus spp., Pemphigus spp. and Phylloxera spp.;
  • Agriotes spp. Amphimallon majale, Anomala orientalis, Anthonomus spp., Aphodius spp, Astylus atromaculatus, Ataenius spp, Atomaria linearis, Chaetocnema tibialis, Cerotoma spp, Conoderus spp, Cosmopolites spp., Cotinis nitida, Curculio spp., Cyclocephala spp, Dermestes spp., Diabrotica spp., Diloboderus abderus, Epilachna spp., Eremnus spp., Heteronychus arator, Hypothenemus hampei, Lagria vilosa, Leptinotarsa decemLineata, Lissorhoptrus spp., Liogenys spp, Maecolaspis spp, Maladera castanea, Megas
  • Aleurocanthus spp Aleurolobus barodensis, Aleurothrixus floccosus, Aleyrodes brassicae, Amarasca biguttula, Amritodus atkinsoni, Aonidiella spp., Aphididae, Aphis spp., Aspidiotus spp., Aulacorthum solani, Bactericera cockerelli, Bemisia spp, Brachycaudus spp, Brevicoryne brassicae, Cacopsylla spp, Cavariella aegopodii Scop., Ceroplaster spp., Chrysomphalus aonidium, Chrysomphalus dictyospermi, Cicadella spp, Cofana spectra, Cryptomyzus spp, Cicadulina spp, Coccus hesperidum, Dalbulus maidis, Dialeurodes spp, Diaphorin
  • Hymenoptera for example, Acromyrmex, Arge spp, Atta spp., Cephus spp., Diprion spp., Diprionidae, Gilpinia polytoma, Hoplocampa spp., Lasius spp., Monomorium pharaonis, Neodiprion spp., Pogonomyrmex spp, Slenopsis invicta, Solenopsis spp. and Vespa spp.;
  • Coptotermes spp Corniternes cumulans, Incisitermes spp, Macrotermes spp, Mastotermes spp, Microtermes spp, Reticulitermes spp.; Solenopsis geminate
  • Blatta spp. Blattella spp., Gryllotalpa spp., Leucophaea maderae, Locusta spp., Neocurtilla hexadactyla, Periplaneta spp. , Scapteriscus spp, and Schistocerca spp.;
  • the active ingredients according to the invention can be used for controlling, i. e. containing or destroying, pests of the abovementioned type which occur in particular on plants, especially on useful plants and ornamentals in agriculture, in horticulture and in forests, or on organs, such as fruits, flowers, foliage, stalks, tubers or roots, of such plants, and in some cases even plant organs which are formed at a later point in time remain protected against these pests.
  • Suitable target crops are, in particular, cereals, such as wheat, barley, rye, oats, rice, maize or sorghum; beet, such as sugar or fodder beet; fruit, for example pomaceous fruit, stone fruit or soft fruit, such as apples, pears, plums, peaches, almonds, cherries or berries, for example strawberries, raspberries or blackberries; leguminous crops, such as beans, lentils, peas or soya; oil crops, such as oilseed rape, mustard, poppies, olives, sunflowers, coconut, castor, cocoa or ground nuts; cucurbits, such as pumpkins, cucumbers or melons; fibre plants, such as cotton, flax, hemp or jute; citrus fruit, such as oranges, lemons, grapefruit or tangerines; vegetables, such as spinach, lettuce, asparagus, cabbages, carrots, onions, tomatoes, potatoes or bell peppers; Lauraceae, such as avocado, Cinnamonium or camphor; and also tobacco, nuts,
  • compositions and/or methods of the present invention may be also used on any ornamental and/or vegetable crops, including flowers, shrubs, broad-leaved trees and evergreens.
  • the invention may be used on any of the following ornamental species: Ageratum spp., Alonsoa spp., Anemone spp., Anisodontea capsenisis, Anthemis spp., Antirrhinum spp., Aster spp., Begonia spp. (e.g. B. elatior, B. semperflorens, B. tubereux), Bougainvillea spp., Brachycome spp., Brassica spp.
  • Ageratum spp. Ageratum spp., Alonsoa spp., Anemone spp., Anisodontea capsenisis, Anthemis spp., Antirrhinum spp., Aster spp., Begonia spp. (e.g. B. elatior, B. semperflorens, B. tubereux), Bougainvillea spp., Brachycome spp.
  • Coreopsis spp. Crassula coccinea, Cuphea ignea, Dahlia spp., Delphinium spp., Dicentra spectabilis, Dorotheantus spp., Eustoma grandiflorum, Forsythia spp., Fuchsia spp., Geranium gnaphalium, Gerbera spp., Gomphrena globosa, Heliotropium spp., Helianthus spp., Hibiscus spp., Hortensia spp., Hydrangea spp., Hypoestes phyllostachya, Impatiens spp. (/.
  • Iresines spp. Kalanchoe spp., Lantana camara, Lavatera trimestris, Leonotis leonurus, Lilium spp., Mesembryanthemum spp., Mimulus spp., Monarda spp.,
  • Rhododendron spp. Rosa spp. (rose), Rudbeckia spp., Saintpaulia spp., Salvia spp., Scaevola aemola, Schizanthus wisetonensis, Sedum spp., Solanum spp., Surfinia spp., Tagetes spp., Nicotinia spp., Verbena spp., Zinnia spp. and other bedding plants.
  • the invention may be used on any of the following vegetable species: Allium spp. (A.
  • Cyanara spp. (C. scolymus, C. cardunculus), Daucus carota, Foeniculum vulgare, Hypericum spp., Lactuca sativa, Lycopersicon spp. (L. esculentum, L. lycopersicum), Mentha spp., Ocimum basilicum, Petroselinum crispum, Phaseolus spp. (P. vulgaris, P.
  • Preferred ornamental species include African violet, Begonia, Dahlia, Gerbera, Hydrangea, Verbena, Rosa, Kalanchoe, Poinsettia, Aster, Centaurea, Coreopsis, Delphinium, Monarda, Phlox, Rudbeckia, Sedum, Petunia, Viola, Impatiens, Geranium, Chrysanthemum, Ranunculus, Fuchsia, Salvia, Hortensia, rosemary, sage, St. Johnswort, mint, sweet pepper, tomato and cucumber.
  • the active ingredients according to the invention are especially suitable for controlling Aphis craccivora, Diabrotica balteata, Heliothis virescens, Myzus persicae, Plutella xylostella and Spodoptera littoralis in cotton, vegetable, maize, rice and soya crops.
  • the active ingredients according to the invention are further especially suitable for controlling Mamestra (preferably in vegetables), Cydia pomonella
  • the invention may also relate to a method of controlling damage to plant and parts thereof by plant parasitic nematodes (Endoparasitic-, Semiendoparasitic- and Ectoparasitic nematodes), especially plant parasitic nematodes such as root knot nematodes, Meloidogyne hapla, Meloidogyne incognita, Meloidogyne javanica, Meloidogyne arenaria and other Meloidogyne species; cyst-forming nematodes, Globodera rostochiensis and other Globodera species; Heterodera avenae, Heterodera glycines, Heterodera schachtii, Heterodera trifolii, and other Heterodera species; Seed gall nematodes, Anguina species; Stem and foliar nematodes, Aphelenchoides species; Sting nematodes, Belonolai
  • Heliocotylenchus multicinctus and other Helicotylenchus species Sheath and sheathoid nematodes, Hem ycliophora species and Hemicriconemoides species; Hirshmanniella species; Lance nematodes, Hoploaimus species; false rootknot nematodes, Nacobbus species; Needle nematodes, Longidorus elongatus and other Longidorus species; Pin nematodes, Pratylenchus species; Lesion nematodes, Pratylenchus neglectus, Pratylenchus penetrans, Pratylenchus curvitatus, Pratylenchus goodeyi and other Pratylenchus species; Burrowing nematodes, Radopholus similis and other Radopholus species; Reniform nematodes, Rotylenchus robustus, Rotylenchus reniformis and other Rotylenchus species
  • the compounds of the invention may also have activity against the molluscs.
  • examples of which include, for example, Ampullariidae; Arion (A. ater, A. circumscriptus, A. hortensis, A. rufus);
  • Bradybaenidae (Bradybaena fruticum); Cepaea (C. hortensis, C. Nemoralis); ochlodina; Deroceras (D. agrestis, D. empiricorum, D. laeve, D. reticulatum); Discus (D. rotundatus); Euomphalia; Galba (G.
  • Helicelia H. itala, H. obvia
  • Helicidae Helicigona arbustorum Helicodiscus
  • Helix H.
  • Limax L. cinereoniger, L. flavus, L. marginatus, L. maximus, L. tenellus
  • Lymnaea Milax (M. gagates, M. marginatus, M. sowerbyi); Opeas; Pomacea (P. canaticulata); Vallonia and Zanitoides.
  • crops is to be understood as including also crop plants which have been so transformed by the use of recombinant DNA techniques that they are capable of synthesising one or more selectively acting toxins, such as are known, for example, from toxin-producing bacteria, especially those of the genus Bacillus.
  • Toxins that can be expressed by such transgenic plants include, for example, insecticidal proteins, for example insecticidal proteins from Bacillus cereus or Bacillus popilliae; or insecticidal proteins from Bacillus thuringiensis, such as ⁇ -endotoxins, e.g. CrylAb, CrylAc, Cryl F, Cry1 Fa2, Cry2Ab, Cry3A, Cry3Bb1 or Cry9C, or vegetative insecticidal proteins (Vip), e.g. Vip1 , Vip2, Vip3 or Vip3A; or insecticidal proteins of bacteria colonising nematodes, for example Photorhabdus spp.
  • insecticidal proteins for example insecticidal proteins from Bacillus cereus or Bacillus popilliae
  • Bacillus thuringiensis such as ⁇ -endotoxins, e.g. CrylAb, CrylAc, Cryl F, Cry1 Fa2, Cry2Ab,
  • Xenorhabdus spp. such as Photorhabdus luminescens, Xenorhabdus nematophilus
  • toxins produced by animals such as scorpion toxins, arachnid toxins, wasp toxins and other insect-specific neurotoxins
  • toxins produced by fungi such as Streptomycetes toxins, plant lectins, such as pea lectins, barley lectins or snowdrop lectins;
  • agglutinins agglutinins
  • proteinase inhibitors such as trypsin inhibitors, serine protease inhibitors, patatin, cystatin, papain inhibitors
  • ribosome-inactivating proteins RIP
  • steroid metabolism enzymes such as 3-hydroxysteroidoxidase, ecdysteroid-UDP-glycosyl- transferase, cholesterol oxidases, ecdysone inhibitors, HMG-COA-reductase, ion channel blockers, such as blockers of sodium or calcium channels, juvenile hormone esterase, diuretic hormone receptors, stilbene synthase, bibenzyl synthase, chitinases and glucanases.
  • proteinase inhibitors such as trypsin inhibitors, serine protease inhibitors, patatin, cystatin, papain inhibitors
  • RIP ribosome-inactivating proteins
  • steroid metabolism enzymes such as 3-hydroxy
  • ⁇ -endotoxins for example CrylAb, CrylAc, Cryl F, Cry1 Fa2, Cry2Ab, Cry3A, Cry3Bb1 or Cry9C, or vegetative insecticidal proteins (Vip), for example Vip1 , Vip2, Vip3 or Vip3A, expressly also hybrid toxins, truncated toxins and modified toxins.
  • Hybrid toxins are produced recombinantly by a new combination of different domains of those proteins (see, for example, WO 02/15701 ).
  • Truncated toxins for example a truncated CrylAb, are known.
  • modified toxins one or more amino acids of the naturally occurring toxin are replaced.
  • amino acid replacements preferably non-naturally present protease recognition sequences are inserted into the toxin , such as, for example, in the case of Cry3A055, a cathepsin-G-recognition sequence is inserted into a Cry3A toxin (see WO 03/018810).
  • Examples of such toxins or transgenic plants capable of synthesising such toxins are disclosed, for example, in EP-A-0 374 753, WO 93/07278, WO 95/34656, EP-A-0 427 529, EP-A-451 878 and WO 03/052073.
  • Cryl-type deoxyribonucleic acids and their preparation are known, for example, from WO 95/34656, EP-A-0 367 474, EP-A-0 401 979 and WO 90/13651 .
  • the toxin contained in the transgenic plants imparts to the plants tolerance to harmful insects.
  • insects can occur in any taxonomb group of insects, but are especially commonly found in the beetles (Coleoptera), two-winged insects (Diptera) and moths (Lepidoptera).
  • Transgenic plants containing one or more genes that code for an insecticidal resistance and express one or more toxins are known and some of them are commercially available. Examples of such plants are: YieldGard® (maize variety that expresses a CrylAb toxin); YieldGard Rootworm® (maize variety that expresses a Cry3Bb1 toxin); YieldGard Plus® (maize variety that expresses a CrylAb and a Cry3Bb1 toxin); Starlink® (maize variety that expresses a Cry9C toxin); Herculex I® (maize variety that expresses a Cry1 Fa2 toxin and the enzyme phosphinothricine N-acetyltransferase (PAT) to achieve tolerance to the herbicide glufosinate ammonium); NuCOTN 33B® (cotton variety that expresses a Cry1 Ac toxin);
  • Bollgard I® (cotton variety that expresses a Cry1 Ac toxin);
  • Bollgard II® (cotton variety that expresses a Cry1 Ac and a Cry2Ab toxin);
  • VipCot® (cotton variety that expresses a Vip3A and a CrylAb toxin);
  • NewLeaf® (potato variety that expresses a Cry3A toxin); NatureGard®, Agrisure® GT Advantage (GA21 glyphosate-tolerant trait), Agrisure® CB Advantage (Bt11 com borer (CB) trait) and Protecta®.
  • transgenic crops are:
  • MIR604 Maize from Syngenta Seeds SAS, Chemin de I'Hobit 27, F-31 790 St. Sauveur, France, registration number C/FR/96/05/10. Maize which has been rendered insect-resistant by transgenic expression of a modified Cry3A toxin. This toxin is Cry3A055 modified by insertion of a cathepsin-G- protease recognition sequence. The preparation of such transgenic maize plants is described in WO 03/018810.
  • MON 863 Maize from Monsanto Europe S.A. 270-272 Avenue de Tervuren, B-1 150 Brussels, Belgium, registration number C/DE/02/9. MON 863 expresses a Cry3Bb1 toxin and has resistance to certain Coleoptera insects.
  • NK603 x MON 810 Maize from Monsanto Europe S.A. 270-272 Avenue de Tervuren, B-1 150 Brussels, Belgium, registration number C/GB/02/M3/03. Consists of conventionally bred hybrid maize varieties by crossing the genetically modified varieties NK603 and MON 810.
  • NK603 ⁇ MON 810 Maize transgenically expresses the protein CP4 EPSPS, obtained from Agrobacterium sp. strain CP4, which imparts tolerance to the herbicide Roundup® (contains glyphosate), and also a CrylAb toxin obtained from Bacillus thuringiensis subsp. kurstaki which brings about tolerance to certain Lepidoptera, include the European com borer.
  • Crops may also be modified for enhanced resistance to fungal (for example Fusarium, Anthracnose, or Phytophthora), bacterial (for example Pseudomonas) or viral (for example potato leafroll virus, tomato spotted wilt virus, cucumber mosaic virus) pathogens. Crops also include those that have enhanced resistance to nematodes, such as the soybean cyst nematode.
  • fungal for example Fusarium, Anthracnose, or Phytophthora
  • bacterial for example Pseudomonas
  • viral for example potato leafroll virus, tomato spotted wilt virus, cucumber mosaic virus pathogens.
  • Crops also include those that have enhanced resistance to nematodes, such as the soybean cyst nematode.
  • Crops that are tolerance to abiotic stress include those that have enhanced tolerance to drought, high salt, high temperature, chill, frost, or light radiation, for example through expression of NF-YB or other proteins known in the art.
  • Antipathogenic substances which can be expressed by such transgenic plants include, for example, ion channel blockers, such as blockers for sodium and calcium channels, for example the viral KP1 , KP4 or KP6 toxins; stilbene synthases; bibenzyl synthases; chitinases; glucanases; the so-called "pathogenesis- related proteins" (PRPs; see e.g. EP-A-0 392 225); antipathogenic substances produced by ion channel blockers, such as blockers for sodium and calcium channels, for example the viral KP1 , KP4 or KP6 toxins; stilbene synthases; bibenzyl synthases; chitinases; glucanases; the so-called "pathogenesis- related proteins" (PRPs; see e.g. EP-A-0 392 225); antipathogenic substances produced by PRPs; see e.g. EP-A-0 392 225; antipathogenic substances produced by
  • compositions according to the invention are the protection of stored goods and store rooms and the protection of raw materials, such as wood, textiles, floor coverings or buildings, and also in the hygiene sector, especially the protection of humans, domestic animals and productive livestock against pests of the mentioned type.
  • pests such as mosquitoes and other disease vectors; see also http://www.who.int/malaria/vector_control/irs/en/).
  • the method for controlling pests comprises applying the compositions of the invention to the target pests, to their locus or to a surface or substrate by brushing, rolling, spraying, spreading or dipping.
  • an IRS (indoor residual spraying) application of a surface such as a wall, ceiling or floor surface is contemplated by the method of the invention.
  • it is contemplated to apply such compositions to a substrate such as non-woven or a fabric material in the form of (or which can be used in the manufacture of) netting, clothing, bedding, curtains and tents.
  • a further object of the invention is therefore a substrate selected from nonwoven and fabric material comprising a composition which contains a compound of formula I.
  • the method for controlling such pests comprises applying a pesticidally effective amount of the compositions of the invention to the target pests, to their locus, or to a surface or substrate so as to provide effective residual pesticidal activity on the surface or substrate.
  • a pesticidally effective amount of the compositions of the invention to the target pests, to their locus, or to a surface or substrate so as to provide effective residual pesticidal activity on the surface or substrate.
  • Such application may be made by brushing, rolling, spraying, spreading or dipping the pesticidal composition of the invention.
  • an IRS application of a surface such as a wall, ceiling or floor surface is contemplated by the method of the invention so as to provide effective residual pesticidal activity on the surface.
  • it is contemplated to apply such compositions for residual control of pests on a substrate such as a fabric material in the form of (or which can be used in the manufacture of) netting, clothing, bedding, curtains and tents.
  • Substrates including non-woven, fabrics or netting to be treated may be made of natural fibres such as cotton, raffia, jute, flax, sisal, hessian, or wool, or synthetic fibres such as polyamide, polyester, polypropylene, polyacrylonitrile or the like.
  • the polyesters are particularly suitable.
  • the methods of textile treatment are known, e.g. WO 2008/151984, WO 2003/034823, US 5631072, WO 2005/64072, WO 2006/128870, EP 1724392, WO20051 13886 or WO 2007/090739.
  • Further areas of use of the compositions according to the invention are the field of tree injection/trunk treatment for all ornamental trees as well all sort of fruit and nut trees.
  • the compounds according to the present invention are especially suitable against wood-boring insects from the order Lepidoptera as mentioned above and from the order Coleoptera, especially against woodborers listed in the following tables A and B:
  • Agrilus sayi Bayberry, Sweetfern
  • Rhododendron Rhadodendron, Azalea, Laurel, Poplar, Willow, Mulberry
  • Phloeotribus liminaris Peach, Cherry, Plum, Black cherry,
  • the present invention may be also used to control any insect pests that may be present in turfgrass, including for example beetles, caterpillars, fire ants, ground pearls, millipedes, sow bugs, mites, mole crickets, scales, mealybugs ticks, spittlebugs, southern chinch bugs and white grubs.
  • the present invention may be used to control insect pests at various stages of their life cycle, including eggs, larvae, nymphs and adults.
  • the present invention may be used to control insect pests that feed on the roots of turfgrass including white grubs (such as Cyclocephala spp. (e.g. masked chafer, C. lurida), Rhizotrogus spp. (e.g. European chafer, R. majalis), Cotinus spp. (e.g. Green June beetle, C. nitida), Popillia spp. (e.g.
  • white grubs such as Cyclocephala spp. (e.g. masked chafer, C. lurida), Rhizotrogus spp. (e.g. European chafer, R. majalis), Cotinus spp. (e.g. Green June beetle, C. nitida), Popillia spp. (e.g.
  • Japanese beetle, P. japonica Phyllophaga spp. (e.g. May/June beetle), Ataenius spp. (e.g. Black turfgrass ataenius, A. spretulus), Maladera spp. (e.g. Asiatic garden beetle, M. castanea) and Tomarus spp.), ground pearls (Margarodes spp.), mole crickets (tawny, southern, and short-winged; Scapteriscus spp., Gryllotalpa africana) and leatherjackets (European crane fly, Tipula spp.).
  • Phyllophaga spp. e.g. May/June beetle
  • Ataenius spp. e.g. Black turfgrass ataenius, A. spretulus
  • Maladera spp. e.g. Asiatic garden beetle, M. castanea
  • the present invention may also be used to control insect pests of turfgrass that are thatch dwelling, including armyworms (such as fall armyworm Spodoptera frugiperda, and common armyworm
  • the present invention may also be used to control insect pests of turfgrass that live above the ground and feed on the turfgrass leaves, including chinch bugs (such as southern chinch bugs, Blissus insularis), Bermudagrass mite (Eriophyes cynodoniensis) , rhodesgrass mealybug (Antonina graminis), two-lined spittlebug (Propsapia bicincta), leafhoppers, cutworms (Noctuidae family), and greenbugs.
  • the present invention may also be used to control other pests of turfgrass such as red imported fire ants (Solenopsis invicta) that create ant mounds in turf.
  • compositions according to the invention are active against ectoparasites such as hard ticks, soft ticks, mange mites, harvest mites, flies (biting and licking), parasitic fly larvae, lice, hair lice, bird lice and fleas.
  • ectoparasites such as hard ticks, soft ticks, mange mites, harvest mites, flies (biting and licking), parasitic fly larvae, lice, hair lice, bird lice and fleas.
  • Anoplurida Haematopinus spp., Linognathus spp., Pediculus spp. and Phtirus spp., Solenopotes spp..
  • Mallophagida Trimenopon spp., Menopon spp., Trinoton spp., Bovicola spp., Werneckiella spp., Lepikentron spp., Damalina spp., Trichodectes spp. and Felicola spp..
  • Nematocerina and Brachycerina for example Aedes spp., Anopheles spp., Culex spp., Simulium spp., Eusimulium spp., Phlebotomus spp., Lutzomyia spp., Culicoides spp., Chrysops spp., Hybomitra spp., Atylotus spp., Tabanus spp., Haematopota spp.,
  • Philipomyia spp. Braula spp., Musca spp., Hydrotaea spp., Stomoxys spp., Haematobia spp., Morellia spp., Fannia spp., Glossina spp., Calliphora spp., Lucilia spp., Chrysomyia spp., Wohlfahrtia spp., Sarcophaga spp., Oestrus spp., Hypoderma spp., Gasterophilus spp., Hippobosca spp., Lipoptena spp. and Melophagus spp..
  • Siphonaptrida for example Pulex spp., Ctenocephalides spp., Xenopsylla spp.,
  • Heteropterida for example Cimex spp., Triatoma spp., Rhodnius spp., Panstrongylus spp..
  • Actinedida Prostigmata
  • Acaridida Acaridida
  • Acarapis spp. Cheyletiella spp., Ornitrocheyletia spp., Myobia spp., Psorergatesspp., Demodex spp., Trombicula spp., Listrophorus spp., Acarus spp., Tyrophagus spp., Caloglyphus spp., Hypodectes spp., Pterolichus spp., Psoroptes spp., Chorioptes spp., Otodectes spp., Sarcoptes spp., Notoedres spp., Knemidocoptes spp., Cytodites spp. and Laminosioptes spp..
  • compositions according to the invention are also suitable for protecting against insect infestation in the case of materials such as wood, textiles, plastics, adhesives, glues, paints, paper and card, leather, floor coverings and buildings.
  • compositions according to the invention can be used, for example, against the following pests: beetles such as Hylotrupes bajulus, Chlorophorus pilosis, Anobium punctatum, Xestobium rufovillosum, Ptilinuspecticornis, Dendrobium pertinex, Ernobius mollis, Priobium carpini, Lyctus brunneus, Lyctus africanus, Lyctus planicollis, Lyctus linearis, Lyctus pubescens, Trogoxylon aequale, Minthesrugicollis, Xyleborus spec.Tryptodendron spec, Apate monachus, Bostrychus capucins, Heterobostrychus brunneus, Sinoxylon spec, and Dinoderus minutus, and also hymenopterans such as Sirex juvencus, Urocerus gigas, Urocerus gigas taignus and
  • the compounds according to the invention can be used as pesticidal agents in unmodified form, but they are generally formulated into compositions in various ways using formulation adjuvants, such as carriers, solvents and surface-active substances.
  • formulation adjuvants such as carriers, solvents and surface-active substances.
  • the formulations can be in various physical forms, e.g.
  • Such formulations can either be used directly or diluted prior to use.
  • the dilutions can be made, for example, with water, liquid fertilisers, micronutrients, biological organisms, oil or solvents.
  • the formulations can be prepared e.g. by mixing the active ingredient with the formulation adjuvants in order to obtain compositions in the form of finely divided solids, granules, solutions, dispersions or emulsions.
  • the active ingredients can also be formulated with other adjuvants, such as finely divided solids, mineral oils, oils of vegetable or animal origin, modified oils of vegetable or animal origin, organic solvents, water, surface-active substances or combinations thereof.
  • the active ingredients can also be contained in very fine microcapsules.
  • Microcapsules contain the active ingredients in a porous carrier. This enables the active ingredients to be released into the environment in controlled amounts (e.g. slow-release).
  • Microcapsules usually have a diameter of from 0.1 to 500 microns. They contain active ingredients in an amount of about from 25 to 95 % by weight of the capsule weight.
  • the active ingredients can be in the form of a monolithic solid, in the form of fine particles in solid or liquid dispersion or in the form of a suitable solution.
  • the encapsulating membranes can comprise, for example, natural or synthetic rubbers, cellulose, styrene/butadiene copolymers, polyacrylonitrile, polyacrylate, polyesters, polyamides, polyureas, polyurethane or chemically modified polymers and starch xanthates or other polymers that are known to the person skilled in the art.
  • very fine microcapsules can be formed in which the active ingredient is contained in the form of finely divided particles in a solid matrix of base substance, but the microcapsules are not themselves encapsulated.
  • the formulation adjuvants that are suitable for the preparation of the compositions according to the invention are known per se.
  • liquid carriers there may be used: water, toluene, xylene, petroleum ether, vegetable oils, acetone, methyl ethyl ketone, cyclohexanone, acid anhydrides, acetonitrile, acetophenone, amyl acetate, 2-butanone, butylene carbonate, chlorobenzene, cyclohexane, cyclohexanol, alkyl esters of acetic acid, diacetone alcohol, 1 ,2-dichloropropane, diethanolamine, p-diethylbenzene, diethylene glycol, diethylene glycol abietate, diethylene glycol butyl ether, diethylene glycol ethyl ether, diethylene glycol methyl ether, A/.W-dimethylformamide, dimethyl sulfoxide, 1 ,4-dioxane, dipropylene glycol, dipropylene glycol methyl ether, dipropylene glycol dibenz
  • perchloroethylene perchloroethylene, ethyl acetate, amyl acetate, butyl acetate, propylene glycol methyl ether, diethylene glycol methyl ether, methanol, ethanol, isopropanol, and alcohols of higher molecular weight, such as amyl alcohol, tetrahydrofurfuryl alcohol, hexanol, octanol, ethylene glycol, propylene glycol, glycerol, N- methyl-2-pyrrolidone and the like.
  • alcohols of higher molecular weight such as amyl alcohol, tetrahydrofurfuryl alcohol, hexanol, octanol, ethylene glycol, propylene glycol, glycerol, N- methyl-2-pyrrolidone and the like.
  • Suitable solid carriers are, for example, talc, titanium dioxide, pyrophyllite clay, silica, attapulgite clay, kieselguhr, limestone, calcium carbonate, bentonite, calcium montmorillonite, cottonseed husks, wheat flour, soybean flour, pumice, wood flour, ground walnut shells, lignin and similar substances.
  • a large number of surface-active substances can advantageously be used in both solid and liquid formulations, especially in those formulations which can be diluted with a carrier prior to use.
  • Surface- active substances may be anionic, cationic, non-ionic or polymeric and they can be used as emulsifiers, wetting agents or suspending agents or for other purposes.
  • Typical surface-active substances include, for example, salts of alkyl sulfates, such as diethanolammonium lauryl sulfate; salts of alkylarylsulfonates, such as calcium dodecylbenzenesulfonate; alkylphenol/alkylene oxide addition products, such as nonylphenol ethoxylate; alcohol/alkylene oxide addition products, such as tridecylalcohol ethoxylate; soaps, such as sodium stearate; salts of alkylnaphthalenesulfonat.es, such as sodium dibutylnaphthalenesulfonate; dialkyl esters of sulfosuccinate salts, such as sodium di(2- ethylhexyl)sulfosuccinate; sorbitol esters, such as sorbitol oleate; quaternary amines, such as lauryltrimethylammonium chloride, polyethylene glycol est
  • Further adjuvants that can be used in pesticidal formulations include crystallisation inhibitors, viscosity modifiers, suspending agents, dyes, anti-oxidants, foaming agents, light absorbers, mixing auxiliaries, antifoams, complexing agents, neutralising or pH-modifying substances and buffers, corrosion inhibitors, fragrances, wetting agents, take-up enhancers, micronutrients, plasticisers, glidants, lubricants, dispersants, thickeners, antifreezes, microbicides, and liquid and solid fertilisers.
  • compositions according to the invention can include an additive comprising an oil of vegetable or animal origin, a mineral oil, alkyl esters of such oils or mixtures of such oils and oil derivatives.
  • the amount of oil additive in the composition according to the invention is generally from 0.01 to 10 %, based on the mixture to be applied.
  • the oil additive can be added to a spray tank in the desired concentration after a spray mixture has been prepared.
  • Preferred oil additives comprise mineral oils or an oil of vegetable origin, for example rapeseed oil, olive oil or sunflower oil, emulsified vegetable oil, alkyl esters of oils of vegetable origin, for example the methyl derivatives, or an oil of animal origin, such as fish oil or beef tallow.
  • Preferred oil additives comprise alkyl esters of C8-C22 fatty acids, especially the methyl derivatives of C12-C18 fatty acids, for example the methyl esters of lauric acid, palmitic acid and oleic acid (methyl laurate, methyl palmitate and methyl oleate, respectively).
  • Many oil derivatives are known from the Compendium of Herbicide Adjuvants, 10 th Edition, Southern Illinois University, 2010.
  • the inventive compositions generally comprise from 0.1 to 99 % by weight, especially from 0.1 to 95 % by weight, of compounds of the present invention and from 1 to 99.9 % by weight of a formulation adjuvant which preferably includes from 0 to 25 % by weight of a surface-active substance. Whereas commercial products may preferably be formulated as concentrates, the end user will normally employ dilute formulations.
  • the rates of application vary within wide limits and depend on the nature of the soil, the method of application, the crop plant, the pest to be controlled, the prevailing climatic conditions, and other factors governed by the method of application, the time of application and the target crop.
  • a general guideline compounds may be applied at a rate of from 1 to 2000 l/ha, especially from 10 to 1000 l/ha.
  • Preferred formulations can have the following compositions (weight %):
  • Emulsifiable concentrates are:
  • active ingredient 1 to 95 %, preferably 60 to 90 %
  • surface-active agent 1 to 30 %, preferably 5 to 20 %
  • liquid carrier 1 to 80 %, preferably 1 to 35 %
  • Dusts active ingredient: 0.1 to 10 %, preferably 0.1 to 5 %
  • solid carrier 99.9 to 90 %, preferably 99.9 to 99 %
  • active ingredient 5 to 75 %, preferably 10 to 50 %
  • surface-active agent 1 to 40 %, preferably 2 to 30 %
  • active ingredient 0.5 to 90 %, preferably 1 to 80 %
  • surface-active agent 0.5 to 20 %, preferably 1 to 15 %
  • solid carrier %, preferably 15 to 90 %
  • active ingredient 0.1 to 30 %, preferably 0.1 to 15 %
  • solid carrier 99.5 to 70 %, preferably 97 to 85 %
  • the combination is thoroughly mixed with the adjuvants and the mixture is thoroughly ground in a suitable mill, affording wettable powders that can be diluted with water to give suspensions of the desired concentration.
  • Talcum - 20 % The combination is thoroughly mixed with the adjuvants and the mixture is thoroughly ground in a suitable mill, affording powders that can be used directly for seed treatment.
  • Emulsions of any required dilution which can be used in plant protection, can be obtained from this concentrate by dilution with water.
  • Ready-for-use dusts are obtained by mixing the combination with the carrier and grinding the mixture in a suitable mill. Such powders can also be used for dry dressings for seed.
  • the combination is mixed and ground with the adjuvants, and the mixture is moistened with water.
  • the mixture is extruded and then dried in a stream of air.
  • the finely ground combination is uniformly applied, in a mixer, to the kaolin moistened with polyethyl glycol. Non-dusty coated granules are obtained in this manner.
  • nonylphenol polyethylene glycol ether (15 mol of ethylene oxide) 6 %
  • silicone oil (in the form of a 75 % emulsion in water) 1 %
  • the finely ground combination is intimately mixed with the adjuvants, giving a suspension concentrate from which suspensions of any desired dilution can be obtained by dilution with water.
  • a suspension concentrate from which suspensions of any desired dilution can be obtained by dilution with water.
  • living plants as well as plant propagation material can be treated and protected against infestation by microorganisms, by spraying, pouring or immersion.
  • the finely ground combination is intimately mixed with the adjuvants, giving a suspension concentrate from which suspensions of any desired dilution can be obtained by dilution with water.
  • a suspension concentrate from which suspensions of any desired dilution can be obtained by dilution with water.
  • living plants as well as plant propagation material can be treated and protected against infestation by microorganisms, by spraying, pouring or immersion.
  • 28 parts of the combination are mixed with 2 parts of an aromatic solvent and 7 parts of toluene diisocyanate/polymethylene-polyphenylisocyanate-mixture (8:1 ).
  • This mixture is emulsified in a mixture of 1 .2 parts of polyvinylalcohol, 0.05 parts of a defoamer and 51.6 parts of water until the desired particle size is achieved.
  • a mixture of 2.8 parts 1 ,6-diaminohexane in 5.3 parts of water is added.
  • the mixture is agitated until the polymerization reaction is completed.
  • the obtained capsule suspension is stabilized by adding 0.25 parts of a thickener and 3 parts of a dispersing agent.
  • the capsule suspension formulation contains 28% of the active ingredients.
  • the medium capsule diameter is 8-15 microns.
  • the resulting formulation is applied to seeds as an aqueous suspension in an apparatus suitable for that purpose.
  • Formulation types include an emulsion concentrate (EC), a suspension concentrate (SC), a suspo- emulsion (SE), a capsule suspension (CS), a water dispersible granule (WG), an emulsifiable granule (EG), an emulsion, water in oil (EO), an emulsion, oil in water (EW), a micro-emulsion (ME), an oil dispersion (OD), an oil miscible flowable (OF), an oil miscible liquid (OL), a soluble concentrate (SL), an ultra-low volume suspension (SU), an ultra-low volume liquid (UL), a technical concentrate (TK), a dispersible concentrate (DC), a wettable powder (WP), a soluble granule (SG) or any technically feasible formulation in combination with agriculturally acceptable adjuvants.
  • EC emulsion concentrate
  • SC suspension concentrate
  • SE suspo- emulsion
  • CS capsule suspension
  • WG water dispersible granule
  • Mp melting point in °C. Free radicals represent methyl groups. H and 9 F NMR measurements were recorded on Brucker 400MHz or 300MHz spectrometers, chemical shifts are given in ppm relevant to a TMS standard. Spectra measured in deuterated solvents as indicated.
  • Step C Synthesis of 6-ethylsulfanyl-1 -methyl-2-(trifluoromethyl)benzimidazole-5-carboxylic acid
  • Residue was purified by flash chromatography to give 6-ethylsulfanyl-1 -methyl-2- (trifluoromethyl)benzimidazole-5-carboxylic acid (0.14 g, 0.46 mmol, 39.3% Yield) .
  • Step A 1 - cvclopropyl -3-(amino)-6-(trifluoromethyl)pyridin-2-one
  • N-[1 -cyclopropyl-2-hydroxy-6-oxo-2-(trifluoromethyl)-3H-pyridin-5-yl]benzamide was dissolved in hydrogen chloride (563 g, 473.1 mL, 5710 mmol) and the mixture was stirred at 100°C for Over Night. The precipitate of Benzoic acid was filtered off and the filtrate was basified to pH 7-8 with a solution of sodium hydroxyl cone.
  • Step B 1 -cyclopropyl -3-(methylamino)-6-(trifluoromethyl)pyridin-2-one
  • Step C 1 - cyclopropyl -3-(methylamino)-4-nitro-6-(trifluoromethyl)pyridin-2-one
  • Step D 4-amino-1 - cyclopropyl -3-(methylamino)-6-(trifluoromethyl) pyridin-2-one
  • Step A Synthesis of methyl 5-[(2 ⁇ -dimethoxyphenyl)methylamino1-3-ethylsulfanyl-pyridine-2-carboxylate
  • Methyl 5-bromo-3-ethylsulfanyl-pyridine-2-carboxylate (Intermediate 9, 5. mmol, 1380.75 mg) was dissolved in dried toluene (35 ml) and cesium carbonate (7.5 mmol) was then added. The mixture was degassed with argon and then tris(dibenzylideneacetone)dipalladium(0) (0.1 1 mmol) , 2,2'- bis(diphenylphosphino)-1 ,1 '-binaphtyle (0.2 mmol) and 2,4-Dimethoxybenzylamine (5 mmol) were added. The mixture was stirred under argon at 105°C (bath).
  • Step B Synthesis of methyl 5-amino-3-ethylsulfanyl-pyridine-2-carboxylate
  • Step C Synthesis of methyl 5-amino-6-bromo-3-ethylsulfanyl-pyridine-2-carboxylate
  • Methyl 5-amino-3-ethylsulfanyl-pyridine-2-carboxylate (0.93mmol) was dissolved in acetic acid glacial (10 ml) and then anhydrous sodium acetate (1 .22 mmol) was added. Then bromine (0.93 mmol) was added dropwise at ambient temperature. The orange mixture was stirred at ambient temperature for 2 hours. TLC showed no more starting material. The volatiles were removed under reduced pressure and the residue was dissolved in ethyl acetate. The organic phase was washed with sodium hydrogen carbonate solution followed by sodium thiosulfate solution and finally with water. The organic phase was dried and concentrated.
  • Step D Synthesis of methyl 6-bromo-3-ethylsulfanyl-5-[(2,2,2-trifluoroacetyl)aminolpyridine-2-carboxylate
  • Step E Synthesis of methyl 6-bromo-3-ethylsulfanyl-5-[methyl-(2,2,2-trifluoroacetyl)aminolpyridine-2- carboxylate
  • Step F Synthesis of methyl 6-bromo-3-ethylsulfonyl-5-[methyl-(2,2,2-trifluoroacetyl)aminolpyridine-2- carboxylate
  • Step G Synthesis of methyl 6-ethylsulfonyl-1 -methyl-2-(trifluoromethyl)imidazo[4,5-blpyridine-5- carboxylate
  • Step H Synthesis of 6-ethylsulfonyl-1 -methyl-2-(trifluoromethyl)imidazo[4,5-blpyridine-5-carboxylic acid
  • Step A N-[1 -cvclopropyl-3-(methylamino)-2-oxo-6-(trifluoromethyl)-4-pyridyl1-6-ethylsulfanyl-1 -methyl-2- (trifluoromethyl)imidazo[4,5-blpyridine-5-carboxamideand N-[4-amino-1 -cvclopropyl-2-oxo-6- (trifluoromethyl)-3-pyridyl1-6-ethylsulfanyl-N,1 -dimethyl-2-(trifluoromethyl)imidazo[4,5-blpyridine-5- carboxamide:
  • the 6-ethylsulfanyl-1 -methyl-2-(trifluoromethyl)benzimidazole-5-carbonyl chloride was diluted in 3 mL of tetrahydrofuran and added to a solution of 4-amino-1 -cyclopropyl-3-(methylamino)-6- (trifluoromethyl)pyridin-2-one (Intermediate 2, 0.129 g, 0.533 mmol) in ethyl acetate (5 mL) and N,N- diethylethanamine (0.184 mL, 1 .31 mmol). The mixture was stirred at reflux for 1 hour.
  • Step F 5-cyclopropyl-2-[6-ethylsulfanyl-1 -methyl-2-(trifluoromethyl)benzimidazol-5-yll-3-methyl-6- (trifluoromethyl)imidazo[4,5-clpyridin-4-one A1
  • Step A N-H -cvclopropyl-3-(methylamino)-2-oxo-6-(trifluoromethyl)-4-pyridyl1-6-ethylsulfonyl-1 -methyl-2- (trifluoromethyl)imidazo[4,5-blpyridine-5-carboxamide and N-[4-amino-1 -cvclopropyl-2-oxo-6- (trifluoromethyl)-3-pyridyl1-6-ethylsulfonyl-N,1 ⁇
  • the 6-ethylsulfonyl-1 -methyl-2-(trifluoromethyl)imidazo[4,5-b]pyridine-5-carbonyl chloride was diluted in 3 mL of tetrahydrofuran and added to a solution of 4-amino-1 - cyclopropyl -3-(methylamino)-6- (trifluoromethyl)pyridin-2-one (Intermediate 2, 0.120 g, 0.481 mmol) in ethyl acetate (5 mL) and N,N- diethylethanamine (0.169 mL, 1 .2 mmol). The mixture was stirred at reflux for 1 hour.
  • Step B 5-cvclopropyl-2-[6-ethylsulfonyl-1 -methyl-2-(trifluoromethyl)imidazo[4,5-blpyridin-5-yl1-3-methyl-6-
  • compositions according to the invention can be broadened considerably, and adapted to prevailing circumstances, by adding other insecticidally, acaricidally and/or fungicidally active ingredients.
  • mixtures of the compounds of formula I with other insecticidally, acaricidally and/or fungicidally active ingredients may also have further surprising advantages which can also be described, in a wider sense, as synergistic activity. For example, better tolerance by plants, reduced phytotoxicity, insects can be controlled in their different development stages or better behaviour during their production, for example during grinding or mixing, during their storage or during their use.
  • Suitable additions to active ingredients here are, for example, representatives of the following classes of active ingredients: organophosphorus compounds, nitrophenol derivatives, thioureas, juvenile hormones, formamidines, benzophenone derivatives, ureas, pyrrole derivatives, carbamates, pyrethroids, chlorinated hydrocarbons, acylureas, pyridylmethyleneamino derivatives, macrolides, neonicotinoids and Bacillus thuringiensis preparations.
  • TX means "one compound selected from the group consisting of the compounds described in Table 1 and 2 of the present invention": an adjuvant selected from the group of substances consisting of petroleum oils (alternative name) (628) + TX,
  • an acaricide selected from the group of substances consisting of 1 ,1 -bis(4-chlorophenyl)-2-ethoxyethanol (lUPAC name) (910) + TX, 2,4-dichlorophenyl benzenesulfonate (lUPAC/Chemical Abstracts name) (1059) + TX, 2-fluoro- V-methyl- V-1 -naphthylacetamide (lUPAC name) (1295) + TX, 4-chlorophenyl phenyl sulfone (lUPAC name) (981 ) + TX, abamectin (1 ) + TX, acequinocyl (3) + TX, acetoprole [CCN] + TX, acrinathrin (9) + TX, aldicarb (16) + TX, aldoxycarb (863) + TX, alpha-cypermethrin (202) + TX, amidithion (870) + TX, amido
  • tetrachlorvinphos (777) + TX, tetradifon (786) + TX, tetranactin (alternative name) (653) + TX, tetrasul (1425) + TX, thiafenox (alternative name) + TX, thiocarboxime (1431 ) + TX, thiofanox (800) + TX, thiometon (801 ) + TX, thioquinox (1436) + TX, thuringiensin (alternative name) [CCN] + TX, triamiphos (1441 ) + TX, triarathene (1443) + TX, triazophos (820) + TX, triazuron (alternative name) + TX, trichlorfon (824) + TX, trifenofos (1455) + TX, trinactin (alternative name) (653) + TX, vamidothion (847) + TX
  • an algicide selected from the group of substances consisting of bethoxazin [CCN] + TX, copper dioctanoate (lUPAC name) (170) + TX, copper sulfate (172) + TX, cybutryne [CCN] + TX, dichlone (1052) + TX, dichlorophen (232) + TX, endothal (295) + TX, fentin (347) + TX, hydrated lime [CCN] + TX, nabam (566) + TX, quinoclamine (714) + TX, quinonamid (1379) + TX, simazine (730) + TX, triphenyltin acetate (lUPAC name) (347) and triphenyltin hydroxide (lUPAC name) (347) + TX, an anthelmintic selected from the group of substances consisting of abamectin (1 ) + TX, crufomate (101 1 ) + TX,
  • a bactericide selected from the group of substances consisting of 1 -hydroxy-1 - -pyridine-2-thione (lUPAC name) (1222) + TX, 4-(quinoxalin-2-ylamino)benzenesulfonamide (lUPAC name) (748) + TX, 8- hydroxyquinoline sulfate (446) + TX, bronopol (97) + TX, copper dioctanoate (lUPAC name) (170) + TX, copper hydroxide (lUPAC name) (169) + TX, cresol [CCN] + TX, dichlorophen (232) + TX, dipyrithione (1105) + TX, dodicin (11 12) + TX, fenaminosulf (1144) + TX, formaldehyde (404) + TX, hydrargaphen (alternative name) [CCN] + TX, kasugamycin (483) + TX, kasugamycin hydrochloride hydrate
  • a biological agent selected from the group of substances consisting of Adoxophyes orana GV (altemative name) (12) + TX, Agrobacterium radiobacter (alternative name) (13) + TX, Amblyseius spp. (alternative name) (19) + TX, Anagrapha falcifera NPV (alternative name) (28) + TX, Anagrus atomus (alternative name) (29) + TX, Aphelinus abdominalis (alternative name) (33) + TX, Aphidius colemani (alternative name) (34) + TX, Aphidoletes aphidimyza (alternative name) (35) + TX, Autographs californica NPV (alternative name) (38) + TX, Bacillus firmus (alternative name) (48) + TX, Bacillus sphaehcus Neide (scientific name) (49) + TX, Bacillus thuringiensis Hopkins (scientific name)
  • Steinernema carpocapsae (alternative name) (742) + TX, Steinernema feltiae (alternative name) (742) + TX, Steinernema glaseri (alternative name) (742) + TX, Steinernema riobrave (alternative name) (742) + TX, Steinernema riobravis (alternative name) (742) + TX, Steinernema scapterisci (alternative name) (742) + TX, Steinernema spp. (alternative name) (742) + TX, Trichogramma spp. (alternative name) (826) + TX, Typhlodromus occidentalis (alternative name) (844) and Verticillium lecanii (alternative name) (848) + TX,
  • a soil sterilant selected from the group of substances consisting of iodomethane (lUPAC name) (542) and methyl bromide (537) + TX,
  • a chemosterilant selected from the group of substances consisting of apholate [CCN] + TX, bisazir (alternative name) [CCN] + TX, busulfan (alternative name) [CCN] + TX, diflubenzuron (250) + TX, dimatif (alternative name) [CCN] + TX, hemel [CCN] + TX, hempa [CCN] + TX, metepa [CCN] + TX, methiotepa [CCN] + TX, methyl apholate [CCN] + TX, morzid [CCN] + TX, penfluron (alternative name) [CCN] + TX, tepa [CCN] + TX, thiohempa (alternative name) [CCN] + TX, thiotepa (alternative name) [CCN] + TX, tretamine (alternative name) [CCN] and
  • an insect repellent selected from the group of substances consisting of 2-(octylthio)ethanol (lUPAC name) (591 ) + TX, butopyronoxyl (933) + TX, butoxy(polypropylene glycol) (936) + TX, dibutyl adipate (lUPAC name) (1046) + TX, dibutyl phthalate (1047) + TX, dibutyl succinate (lUPAC name) (1048) + TX, diethyltoluamide [CCN] + TX, dimethyl carbate [CCN] + TX, dimethyl phthalate [CCN] + TX, ethyl hexanediol (1 137) + TX, hexamide [CCN] + TX, methoquin-butyl (1276) + TX, methylneodecanamide [CCN] + TX, oxamate [CCN] and picaridin [CCN] + TX,
  • an insecticide selected from the group of substances consisting of 1 -dichloro-1 -nitroethane
  • a molluscicide selected from the group of substances consisting of bis(tributyltin) oxide (lUPAC name) (913) + TX, bromoacetamide [CCN] + TX, calcium arsenate [CCN] + TX, cloethocarb (999) + TX, copper acetoarsenite [CCN] + TX, copper sulfate (172) + TX, fentin (347) + TX, ferric phosphate (lUPAC name) (352) + TX, metaldehyde (518) + TX, methiocarb (530) + TX, niclosamide (576) + TX, niclosamide-olamine (576) + TX, pentachlorophenol (623) + TX, sodium pentachlorophenoxide (623) + TX, tazimcarb (1412) + TX, thiodicarb (799) + TX, tributyltin oxide (913)
  • a nematicide selected from the group of substances consisting of AKD-3088 (compound code) + TX, 1 ,2- dibromo-3-chloropropane (lUPAC/Chemical Abstracts name) (1045) + TX, 1 ,2-dichloropropane (lUPAC/ Chemical Abstracts name) (1062) + TX, 1 ,2-dichloropropane with 1 ,3-dichloropropene (lUPAC name) (1063) + TX, 1 ,3-dichloropropene (233) + TX, 3,4-dichlorotetrahydrothiophene 1 ,1 -dioxide
  • tetrachlorothiophene (lUPAC/ Chemical Abstracts name) (1422) + TX, thiafenox (alternative name) + TX, thionazin (1434) + TX, triazophos (820) + TX, triazuron (alternative name) + TX, xylenols [CCN] + TX, YI-5302 (compound code) and zeatin (alternative name) (210) + TX, fluensulfone [318290-98-1 ] + TX, a nitrification inhibitor selected from the group of substances consisting of potassium ethylxanthate [CCN] and nitrapyrin (580) + TX,
  • a plant activator selected from the group of substances consisting of acibenzolar (6) + TX, acibenzolar-S- methyl (6) + TX, probenazole (658) and Reynoutria sachalinensis extract (alternative name) (720) + TX
  • a rodenticide selected from the group of substances consisting of 2-isovalerylindan-1 ,3-dione (lUPAC name) (1246) + TX, 4-(quinoxalin-2-ylamino)benzenesulfonamide (lUPAC name) (748) + TX, alpha- chlorohydrin [CCN] + TX, aluminium phosphide (640) + TX, antu (880) + TX, arsenous oxide (882) + TX, barium carbonate (891 ) + TX, bisthiosemi (912) + TX, brodifacoum (89) + TX, bromadiolone (91 ) + TX,
  • a synergist selected from the group of substances consisting of 2-(2-butoxyethoxy)ethyl piperonylate (lUPAC name) (934) + TX, 5-(1 ,3-benzodioxol-5-yl)-3-hexylcyclohex-2-enone (lUPAC name) (903) + TX, farnesol with nerolidol (alternative name) (324) + TX, MB-599 (development code) (498) + TX, MGK 264 (development code) (296) + TX, piperonyl butoxide (649) + TX, piprotal (1343) + TX, propyl isomer (1358) + TX, S421 (development code) (724) + TX, sesamex (1393) + TX, sesasmolin (1394) and sulfoxide (1406) + TX,
  • an animal repellent selected from the group of substances consisting of anthraquinone (32) + TX, chloralose (127) + TX, copper naphthenate [CCN] + TX, copper oxychloride (171 ) + TX, diazinon (227) + TX, dicyclopentadiene (chemical name) (1069) + TX, guazatine (422) + TX, guazatine acetates (422) + TX, methiocarb (530) + TX, pyridin-4-amine (lUPAC name) (23) + TX, thiram (804) + TX, trimethacarb (840) + TX, zinc naphthenate [CCN] and ziram (856) + TX,
  • a virucide selected from the group of substances consisting of imanin (alternative name) [CCN] and ribavirin (alternative name) [CCN] + TX,
  • a wound protectant selected from the group of substances consisting of mercuric oxide (512) + TX, octhilinone (590) and thiophanate-methyl (802) + TX,
  • azaconazole 60207-31 -0] + TX, bitertanol [70585-36-3] + TX, bromuconazole [116255-48-2] + TX, cyproconazole [94361 -06-5] + TX, difenoconazole [1 19446-68-3] + TX, diniconazole [83657-24-3] + TX, epoxiconazole [106325-08-0] +
  • TX TX
  • Bacillus subtilis strain AQ178 + TX Bacillus subtilis strain QST 713 (CEASE® + TX, Serenade® + TX, Rhapsody®) + TX, Bacillus subtilis strain QST 714 (JAZZ®) + TX, Bacillus subtilis strain AQ153 + TX, Bacillus subtilis strain AQ743 + TX, Bacillus subtilis strain QST3002 + TX, Bacillus subtilis strain
  • Bradyrhizobium japonicum (TerraMax®) + TX, Brevibacillus brevis + TX, Bacillus thuringiensis tenebrionis (Novodor®) + TX, BtBooster + TX, Burkholderia cepacia (Deny® + TX, Intercept® + TX, Blue Circle®) + TX, Burkholderia gladii + TX, Burkholderia gladioli + TX, Burkholderia spp.
  • TX Canadian thistle fungus (CBH Canadian Bioherbicide®) + TX, Candida butyri + TX, Candida famata + TX, Candida fructus + TX, Candida glabrata + TX, Candida guilliermondii + TX, Candida melibiosica + TX, Candida oleophila strain O + TX, Candida parapsilosis + TX, Candida pelliculosa + TX, Candida pulcherrima + TX, Candida reuêtii + TX, Candida saitoana (Bio-Coat® + TX, Biocure®) + TX, Candida sake + TX, Candida spp.
  • TX Filobasidium floriforme + TX, Fusarium acuminatum + TX, Fusarium chlamydosporum + TX, Fusarium oxysporum (Fusaclean® / Biofox C®) + TX, Fusarium proliferatum + TX, Fusarium spp. + TX,
  • Lecanicillium longisporum (Vertiblast®) + TX, Lecanicillium muscarium (Vertikil®) + TX, Lymantria Dispar nucleopolyhedrosis virus (Disparvirus®) + TX, Marinococcus halophilus + TX, Meira geulakonigii + TX, Metarhizium anisopliae (Met52®) + TX, Metarhizium anisopliae (Destruxin WP®) + TX, Metschnikowia fruticola (Shemer®) + TX, Metschnikowia pulcherrima + TX, Microdochium dimerum (Antibot®) + TX, Micromonospora coerulea + TX, Microsphaeropsis ochracea + TX, Muscodor albus 620 (Muscudor®) + TX, Muscodor roseus strain A3-5 + TX, Mycorrhizae spp.
  • TX Penicillium viridicatum + TX, Phlebiopsis gigantean (Rotstop®) + TX, phosphate solubilizing bacteria (Phosphomeal®) + TX, Phytophthora cryptogea + TX, Phytophthora palmivora (Devine®) + TX, Pichia anomala + TX, Pichia guilermondii + TX, Pichia membranaefaciens + TX, Pichia onychis + TX, Pichia stipites + TX, Pseudomonas aeruginosa + TX, Pseudomonas aureofasciens (Spot- Less Biofungicide®) + TX, Pseudomonas cepacia + TX, Pseudomonas chlororaphis (AtEze®) + TX, Pseudomonas corrugate + TX, Pse
  • Trichoderma asperellum T34 Biocontrol®
  • Trichoderma gamsii TX
  • Trichoderma atroviride Plantmate®
  • Trichoderma harzianum rifai Mycostar®
  • Trichoderma harzianum T-22 Trianum-P® + TX, PlantShield HC® + TX, RootShield® + TX, Trianum-G®) + TX, Trichoderma harzianum T-39
  • Trichodex® Trichoderma inhamatum + TX, Trichoderma koningii + TX, Trichoderma spp.
  • LC 52 (Sentinel®) + TX, Trichoderma lignorum + TX, Trichoderma longibrachiatum + TX, Trichoderma polysporum (Binab T®) + TX, Trichoderma taxi + TX, Trichoderma virens + TX, Trichoderma virens (formerly Gliocladium virens GL-21 ) (SoilGuard®) + TX, Trichoderma viride + TX, Trichoderma viride strain ICC 080 (Remedier®) + TX, Trichosporon pullulans + TX, Trichosporon spp.
  • TX Trichothecium spp. + TX, Trichothecium roseum + TX, Typhula phacorrhiza strain 94670 + TX, Typhula phacorrhiza strain 94671 + TX, Ulocladium atrum + TX, Ulocladium oudemansii (Botry-Zen®) + TX, Ustilago maydis + TX, various bacteria and supplementary micronutrients (Natural II®) + TX, various fungi (Millennium
  • Microbes® + TX, Verticillium chlamydosporium + TX, Verticillium lecanii (Mycotal® + TX, Vertalec®) + TX, Vip3Aa20 (VIPtera®) + TX, Virgibaclillus marismortui + TX, Xanthomonas campestris pv. Poae (Camperico®) + TX, Xenorhabdus bovienii + TX, Xenorhabdus nematophilus; and
  • Plant extracts including: pine oil (Retenol®) + TX, azadirachtin (Plasma Neem Oil® + TX, AzaGuard® + TX, MeemAzal® + TX, Molt-X® + TX, Botanical IGR (Neemazad® + TX, Neemix®) + TX, canola oil (Lilly Miller Vegol®) + TX, Chenopodium ambrosioides near ambrosioides (Requiem®) + TX, Chrysanthemum extract (Crisant®) + TX, extract of neem oil (Trilogy®) + TX, essentials oils of Labiatae (Botania®) + TX, extracts of clove rosemary peppermint and thyme oil (Garden insect killer®) + TX, Glycinebetaine (Greenstim®) + TX, garlic + TX, lemongrass oil (GreenMatch®) + TX, neem oil +
  • pheromones including: blackheaded fireworm pheromone (3M Sprayable Blackheaded Fireworm
  • Macrobials including: Aphelinus abdominalis + TX, Aphidius ervi (Aphelinus-System®) + TX,
  • Macrolophus caliginosus (Mirical-N® + TX, Macroline c® + TX, Mirical®) + TX, Mesoseiulus longipes + TX, Metaphycus flavus + TX, Metaphycus lounsburyi + TX, Micromus angulatus (Milacewing®) + TX, Microterys flavus + TX, Muscidifurax raptorellus and Spalangia cameroni (Biopar®) + TX, Neodryinus typhlocybae + TX, Neoseiulus californicus + TX, Neoseiulus cucumeris (THRYPEX®) + TX, Neoseiulus fallacis + TX, Nesideocoris tenuis (NesidioBug® + TX, Nesibug®) + TX, Ophyra aenescens (Biofly®) + TX, Orius insidiosus
  • TX Steinernematid spp. (Guardian Nematodes®) + TX, Stethorus punctillum (Stethorus®) + TX, Tamarixia radiate + TX, Tetrastichus setifer + TX, Thripobius semiluteus + TX, Torymus sinensis + TX, Trichogramma brassicae (Tricholine b®) + TX, Trichogramma brassicae (Tricho-Strip®) + TX, Trichogramma evanescens + TX, Trichogramma minutum + TX, Trichogramma ostriniae + TX, Trichogramma platneri + TX, Trichogramma pretiosum + TX, Xanthopimpla stemmator; and
  • the active ingredient mixture of the compounds of formula I selected from Table 1 and 2 with active ingredients described above comprises a compound selected from Table 1 and 2 and an active ingredient as described above preferably in a mixing ratio of from 100:1 to 1 :6000, especially from 50:1 to 1 :50, more especially in a ratio of from 20:1 to 1 :20, even more especially from 10:1 to 1 :10, very especially from 5:1 and 1 :5, special preference being given to a ratio of from 2:1 to 1 :2, and a ratio of from 4:1 to 2:1 being likewise preferred, above all in a ratio of 1 :1 , or 5:1 , or 5:2, or 5:3, or 5:4, or 4:1 , or 4:2, or 4:3, or 3:1 , or 3:2, or 2:1 , or 1 :5, or 2:5, or 3:5, or 4:5, or 1 :4, or 2:4, or 3:4, or 1 :3, or 2:3, or 1 :2, or 1 :600, or 1 :300, or 1 :150
  • the mixtures as described above can be used in a method for controlling pests, which comprises applying a composition comprising a mixture as described above to the pests or their environment, with the exception of a method for treatment of the human or animal body by surgery or therapy and diagnostic methods practised on the human or animal body.
  • the mixtures comprising a compound of formula I selected from Table 1 and 2 and one or more active ingredients as described above can be applied, for example, in a single "ready-mix” form, in a combined spray mixture composed from separate formulations of the single active ingredient components, such as a "tank-mix", and in a combined use of the single active ingredients when applied in a sequential manner, i.e. one after the other with a reasonably short period, such as a few hours or days.
  • the order of applying the compounds of formula I selected from Table 1 and 2 and the active ingredients as described above is not essential for working the present invention.
  • compositions according to the invention can also comprise further solid or liquid auxiliaries, such as stabilizers, for example unepoxidized or epoxidized vegetable oils (for example epoxidized coconut oil, rapeseed oil or soya oil), antifoams, for example silicone oil, preservatives, viscosity regulators, binders and/or tackifiers, fertilizers or other active ingredients for achieving specific effects, for example bactericides, fungicides, nematocides, plant activators, molluscicides or herbicides.
  • auxiliaries such as stabilizers, for example unepoxidized or epoxidized vegetable oils (for example epoxidized coconut oil, rapeseed oil or soya oil), antifoams, for example silicone oil, preservatives, viscosity regulators, binders and/or tackifiers, fertilizers or other active ingredients for achieving specific effects, for example bactericides, fungicides, nematocides
  • compositions according to the invention are prepared in a manner known per se, in the absence of auxiliaries for example by grinding, screening and/or compressing a solid active ingredient and in the presence of at least one auxiliary for example by intimately mixing and/or grinding the active ingredient with the auxiliary (auxiliaries).
  • auxiliaries for example by grinding, screening and/or compressing a solid active ingredient and in the presence of at least one auxiliary for example by intimately mixing and/or grinding the active ingredient with the auxiliary (auxiliaries).
  • compositions that is the methods of controlling pests of the
  • Typical rates of concentration are between 0.1 and 1000 ppm, preferably between 0.1 and 500 ppm, of active ingredient.
  • the rate of application per hectare is generally 1 to 2000 g of active ingredient per hectare, in particular 10 to 1000 g/ha, preferably 10 to 600 g/ha.
  • a preferred method of application in the field of crop protection is application to the foliage of the plants (foliar application), it being possible to select frequency and rate of application to match the danger of infestation with the pest in question.
  • the active ingredient can reach the plants via the root system (systemic action), by drenching the locus of the plants with a liquid composition or by
  • the active ingredient in solid form into the locus of the plants, for example into the soil, for example in the form of granules (soil application).
  • granules can be metered into the flooded paddy-field.
  • the compounds of the invention and compositions thereof are also be suitable for the protection of plant propagation material, for example seeds, such as fruit, tubers or kernels, or nursery plants, against pests of the abovementioned type.
  • the propagation material can be treated with the compound prior to planting, for example seed can be treated prior to sowing.
  • the compound can be applied to seed kernels (coating), either by soaking the kernels in a liquid composition or by applying a layer of a solid composition.
  • compositions when the propagation material is planted to the site of application, for example into the seed furrow during drilling.
  • These treatment methods for plant propagation material and the plant propagation material thus treated are further subjects of the invention.
  • Typical treatment rates would depend on the plant and pest/fungi to be controlled and are generally between 1 to 200 grams per 100 kg of seeds, preferably between 5 to 150 grams per 100 kg of seeds, such as between 10 to 100 grams per 100 kg of seeds.
  • seed embraces seeds and plant propagules of all kinds including but not limited to true seeds, seed pieces, suckers, corns, bulbs, fruit, tubers, grains, rhizomes, cuttings, cut shoots and the like and means in a preferred embodiment true seeds.
  • the present invention also comprises seeds coated or treated with or containing a compound of formula I.
  • coated or treated with and/or containing generally signifies that the active ingredient is for the most part on the surface of the seed at the time of application, although a greater or lesser part of the ingredient may penetrate into the seed material, depending on the method of application.
  • the present invention makes available a plant propagation material adhered thereto with a compound of formula I.
  • a composition comprising a plant propagation material treated with a compound of formula I.
  • Seed treatment comprises all suitable seed treatment techniques known in the art, such as seed dressing, seed coating, seed dusting, seed soaking and seed pelleting.
  • the seed treatment application of the compound formula I can be carried out by any known methods, such as spraying or by dusting the seeds before sowing or during the sowing/planting of the seeds.

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

Abstract

L'invention concerne des composés de formule (I) (R4 ) dans laquelle les substituants sont tels que définis dans la revendication 1, ainsi que les sels, stéréoisomères, énantiomères, tautomères et N-oxydes agrochimiquement acceptables de ces composés, qui peuvent être utilisés en tant qu'insecticides et peuvent être préparés de manière connue.
PCT/EP2017/051879 2016-02-04 2017-01-30 Dérivés à activité pesticide comportant des substituants contenant du soufre et du cyclopropyle WO2017133994A1 (fr)

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EP3268365B1 (fr) * 2015-03-12 2019-02-06 Syngenta Participations AG Dérivés tetracycliques actifs sur le plan pesticide avec des substituants contenant du soufre
WO2019162174A1 (fr) 2018-02-21 2019-08-29 Bayer Aktiengesellschaft Dérivés hétérocycliques bicycliques condensés utilisés comme pesticides
WO2019175046A1 (fr) 2018-03-12 2019-09-19 Bayer Aktiengesellschaft Dérivés hétérocycliques bicycliques condensés utilisés comme pesticides
WO2019219689A1 (fr) 2018-05-18 2019-11-21 Syngenta Participations Ag Dérivés hétérocycliques à activité pesticide incorporant des substituants contenant du sulfoximine
WO2019229089A1 (fr) 2018-05-31 2019-12-05 Syngenta Participations Ag Dérivés hétérocycliques à action pesticide comprenant des substituants contenant du soufre
WO2019234158A1 (fr) 2018-06-06 2019-12-12 Syngenta Crop Protection Ag Dérivés hétérocycliques à action pesticide comportant des substituants contenant de la sulfoximine
US10544163B2 (en) 2016-03-10 2020-01-28 Nissan Chemical Corporation Condensed heterocyclic compounds and pesticides
WO2020084075A1 (fr) 2018-10-24 2020-04-30 Syngenta Crop Protection Ag Dérivés hétérocycliques à action pesticide avec des substituants contenant de la sulfoximine
WO2020087765A1 (fr) * 2018-11-02 2020-05-07 广东药科大学 Pansement antibactérien à action prolongée
WO2020254530A1 (fr) 2019-06-18 2020-12-24 Syngenta Crop Protection Ag Dérivés de 7-sulfonyl-n-(1,3,4-thiadiazol-2-yl)-quinoxaline-6-carboxamide et dérivés respectifs de -benzimidazole-5-, -imidazo[4,5-b]pyridine-5-, -3h-furo[3,2b]pyridine-5-, -quinoléine-2- et -naphtalène-2-carboxamide utilisés en tant que pesticides
WO2021219810A1 (fr) 2020-04-30 2021-11-04 Syngenta Crop Protection Ag Dérivés hétérocycliques à action pesticide comprenant des substituants contenant du soufre
WO2024189139A1 (fr) 2023-03-14 2024-09-19 Syngenta Crop Protection Ag Lutte contre des nuisibles résistants aux insecticides

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WO2013018928A1 (fr) * 2011-08-04 2013-02-07 Sumitomo Chemical Company, Limited Composé hétérocyclique condensé et utilisation de celui-ci pour la lutte contre les organismes nuisibles
EP2857397A1 (fr) * 2012-05-30 2015-04-08 Sumitomo Chemical Company Limited Composé hétérocyclique condensé
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Cited By (20)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP3268365B1 (fr) * 2015-03-12 2019-02-06 Syngenta Participations AG Dérivés tetracycliques actifs sur le plan pesticide avec des substituants contenant du soufre
US10544163B2 (en) 2016-03-10 2020-01-28 Nissan Chemical Corporation Condensed heterocyclic compounds and pesticides
US10640518B2 (en) 2016-03-10 2020-05-05 Nissan Chemical Corporation Condensed heterocyclic compounds and pesticides
US10759815B2 (en) 2016-03-10 2020-09-01 Nissan Chemical Corporation Condensed heterocyclic compounds and pesticides
US11019821B2 (en) 2018-02-21 2021-06-01 Bayer Aktiengesellschaft Fused bicyclic heterocycle derivatives as pesticides
WO2019162174A1 (fr) 2018-02-21 2019-08-29 Bayer Aktiengesellschaft Dérivés hétérocycliques bicycliques condensés utilisés comme pesticides
WO2019175046A1 (fr) 2018-03-12 2019-09-19 Bayer Aktiengesellschaft Dérivés hétérocycliques bicycliques condensés utilisés comme pesticides
WO2019175045A1 (fr) 2018-03-12 2019-09-19 Bayer Aktiengesellschaft Dérivés hétérocycliques bicycliques condensés utilisés comme pesticides
US11414432B2 (en) 2018-03-12 2022-08-16 Bayer Aktiengesellschaft Condensed bicyclic heterocyclic derivatives as pest control agents
JP2021517148A (ja) * 2018-03-12 2021-07-15 バイエル・アクチエンゲゼルシヤフト 有害生物防除剤としての縮合二環式ヘテロ環式誘導体
JP2021515783A (ja) * 2018-03-12 2021-06-24 バイエル・アクチエンゲゼルシヤフト 害虫防除剤としての縮合二環式ヘテロ環式誘導体
WO2019219689A1 (fr) 2018-05-18 2019-11-21 Syngenta Participations Ag Dérivés hétérocycliques à activité pesticide incorporant des substituants contenant du sulfoximine
WO2019229089A1 (fr) 2018-05-31 2019-12-05 Syngenta Participations Ag Dérivés hétérocycliques à action pesticide comprenant des substituants contenant du soufre
WO2019234158A1 (fr) 2018-06-06 2019-12-12 Syngenta Crop Protection Ag Dérivés hétérocycliques à action pesticide comportant des substituants contenant de la sulfoximine
EP4342297A2 (fr) 2018-06-06 2024-03-27 Syngenta Crop Protection AG Dérivés hétérocycliques à activité pesticide comportant des substituants contenant de la sulfoximine
WO2020084075A1 (fr) 2018-10-24 2020-04-30 Syngenta Crop Protection Ag Dérivés hétérocycliques à action pesticide avec des substituants contenant de la sulfoximine
WO2020087765A1 (fr) * 2018-11-02 2020-05-07 广东药科大学 Pansement antibactérien à action prolongée
WO2020254530A1 (fr) 2019-06-18 2020-12-24 Syngenta Crop Protection Ag Dérivés de 7-sulfonyl-n-(1,3,4-thiadiazol-2-yl)-quinoxaline-6-carboxamide et dérivés respectifs de -benzimidazole-5-, -imidazo[4,5-b]pyridine-5-, -3h-furo[3,2b]pyridine-5-, -quinoléine-2- et -naphtalène-2-carboxamide utilisés en tant que pesticides
WO2021219810A1 (fr) 2020-04-30 2021-11-04 Syngenta Crop Protection Ag Dérivés hétérocycliques à action pesticide comprenant des substituants contenant du soufre
WO2024189139A1 (fr) 2023-03-14 2024-09-19 Syngenta Crop Protection Ag Lutte contre des nuisibles résistants aux insecticides

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