WO2014167084A1 - Substituted pyrimidinium compounds and derivatives for combating animal pests - Google Patents

Substituted pyrimidinium compounds and derivatives for combating animal pests Download PDF

Info

Publication number
WO2014167084A1
WO2014167084A1 PCT/EP2014/057344 EP2014057344W WO2014167084A1 WO 2014167084 A1 WO2014167084 A1 WO 2014167084A1 EP 2014057344 W EP2014057344 W EP 2014057344W WO 2014167084 A1 WO2014167084 A1 WO 2014167084A1
Authority
WO
WIPO (PCT)
Prior art keywords
formula
compounds
ring
alkyl
substituted
Prior art date
Application number
PCT/EP2014/057344
Other languages
French (fr)
Inventor
Arun Narine
Nina Gertrud Bandur
Joachim Dickhaut
Swetlana DERKSEN
Raffael KOLLER
Wolfgang Von Deyn
Jean-Yves WACH
Deborah L. Culbertson
Original Assignee
Basf Se
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Priority to KR1020157032205A priority Critical patent/KR102223216B1/en
Priority to AU2014253086A priority patent/AU2014253086B2/en
Priority to CN201480020609.3A priority patent/CN105121441B/en
Priority to BR112015021863-6A priority patent/BR112015021863B1/en
Application filed by Basf Se filed Critical Basf Se
Priority to JP2016506980A priority patent/JP6449850B2/en
Priority to UAA201510934A priority patent/UA115904C2/en
Priority to CA2901559A priority patent/CA2901559C/en
Priority to EP14716829.8A priority patent/EP2984089B1/en
Priority to KR1020217005894A priority patent/KR20210024256A/en
Priority to US14/783,600 priority patent/US9730451B2/en
Priority to ES14716829T priority patent/ES2913139T3/en
Priority to MX2015014204A priority patent/MX2015014204A/en
Publication of WO2014167084A1 publication Critical patent/WO2014167084A1/en
Priority to CR20150610A priority patent/CR20150610A/en
Priority to US15/656,293 priority patent/US11019820B2/en

Links

Classifications

    • 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
    • A—HUMAN NECESSITIES
    • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61P—SPECIFIC THERAPEUTIC ACTIVITY OF CHEMICAL COMPOUNDS OR MEDICINAL PREPARATIONS
    • A61P33/00—Antiparasitic agents
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D471/00—Heterocyclic compounds containing nitrogen atoms as the only ring hetero atoms in the condensed system, at least one ring being a six-membered ring with one nitrogen atom, not provided for by groups C07D451/00 - C07D463/00
    • C07D471/02—Heterocyclic compounds containing nitrogen atoms as the only ring hetero atoms in the condensed system, at least one ring being a six-membered ring with one nitrogen atom, not provided for by groups C07D451/00 - C07D463/00 in which the condensed system contains two hetero rings
    • C07D471/04—Ortho-condensed systems
    • 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
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D498/00—Heterocyclic compounds containing in the condensed system at least one hetero ring having nitrogen and oxygen atoms as the only ring hetero atoms
    • C07D498/02—Heterocyclic compounds containing in the condensed system at least one hetero ring having nitrogen and oxygen atoms as the only ring hetero atoms in which the condensed system contains two hetero rings
    • C07D498/04—Ortho-condensed systems
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D513/00—Heterocyclic compounds containing in the condensed system at least one hetero ring having nitrogen and sulfur atoms as the only ring hetero atoms, not provided for in groups C07D463/00, C07D477/00 or C07D499/00 - C07D507/00
    • C07D513/02—Heterocyclic compounds containing in the condensed system at least one hetero ring having nitrogen and sulfur atoms as the only ring hetero atoms, not provided for in groups C07D463/00, C07D477/00 or C07D499/00 - C07D507/00 in which the condensed system contains two hetero rings
    • C07D513/04—Ortho-condensed systems

Definitions

  • the present invention relates to insecticidal substituted pyrimidinium compounds and/or to the compositions comprising such compounds for combating invertebrate pests.
  • the invention also relates to pesticidal methods, to uses and to applications of substituted pyrimidinium compounds as described in the present invention and the stereoisomers, salts, tautomers and N-oxides thereof as well as compositions comprising them.
  • Invertebrate pests and in particular insects, arthropods and nematodes destroy growing and harvested crops and attack wooden dwelling and commercial structures, thereby causing large economic loss to the food supply and to property.
  • substituted pyrimidinium compounds of the general formula (I), as defined below including their stereoisomers, their salts, in particular their agriculturally or veterinary acceptable salts, their tautomers and their N-oxides.
  • the present invention provides substituted pyrimidinium compounds of formula (I) or a composition comprising at least one substituted pyrimidinium compound of formula (I)
  • X, Y are each independently O or S;
  • o, q are each independently 0, 1 or 2, provided that the sum (o + q) is 0, 1 or 2 for each ring;
  • Ci-Cs-alkyl, C2-C8-alkenyl, C2-C8-alkynyl, C3-Cio-cycloalkyl, C 4 - Cio-cycloalkenyl, Cs-C-u-cycloalkylcycloalkyl or R 1 may form a three- to eleven-membered saturated, or partially unsaturated or aromatic carbo-or heterocyclic ring or ring system, which may contain 1 to 4 heteroatoms selected from N(R c )p, O, and S, wherein S may be oxidized, and wherein the aforementioned groups and the carbo- or heterocyclic rings system may be unsubstituted, partially or fully substituted by R a ; or
  • R aa is each independently halogen, Ci-C6-alkyl, C1-C6- haloalkyl, Ci-C6-alkoxy or Ci-C6-haloalkoxy;
  • R b is each independently hydrogen, Ci-C6-alkyl, Ci-C6-haloalkyl, C1-C6- alkoxy, Ci-C6-haloalkoxy or a three- to six-membered saturated, or partially unsaturated or aromatic carbo- or heterocyclic ring, which may contain 1 to 3 heteroatoms selected from N(R C ) P , O, and S, wherein S may be oxidized and which carbo- or heterocyclic ring may be partially or fully substituted by R aa ;
  • R c is each independently hydrogen, Ci-C4-alkyl, Ci-C4-haloalkyl, C1-C4- alkylcarbonyl, C1-C6 cycloalkyl, or a three- to six-membered saturated, partially unsaturated or aromatic carbo- or heterocyclic ring, which may contain 1 to 3 heteroatoms selected from N(R aa ) p , O and S, wherein S may be oxidized and wherein the carbo- or heterocyclic ring may be partially or fully substituted by R aa ;
  • R b R b , R c R b or R C R C together with the atom to which they are bound, may form a 3-, 4-, 5-, 6- or 7- mem- bered saturated, partially unsaturated or aromatic carbo- or heterocyclic ring, which may contain 1 to 2 heteroatoms or heteroatoms groups selected from N, O, S, NO, SO and SO2 and wherein the carbo- or heterocyclic ring may be partially or fully substituted by R 3 ;
  • R d is each independently hydrogen, phenyl, Ci-C6-alkyl, C2-C6-alkenyl, C2-C6-alkynyl, Cs-Cs-cycloalkyl, or Ci-C6-alkoxyalkyl, wherein the above mentioned groups may be substituted by one or more halogen;
  • R e is each independently, Ci-C4-alkyl, Ci-C4-haloalkyl, C1-C4- alkylcarbonyl, C1-C6 cycloalkyl, or a three- to six-membered saturated, partially unsaturated or aromatic carbo- or heterocyclic ring, which may contain 1 to 3 heteroatoms selected from N(R aa ) p , O and S, wherein S may be oxidized and wherein the carbo- or heterocyclic ring may be partially or fully substituted by R aa ;
  • n 0, 1 or 2;
  • n 0, 1 , or 2;
  • p O or l ;
  • R 2a may form a carbo-or heterocyclic three- to ten-membered ring or a seven- to eleven-membered rings system, which ring or ring system may be saturated, partially unsaturated, or aromatic, and which ring or ring system may contain 1 to 4 heteroatoms selected from N(R C ) P , O, and S, wherein S may be oxidized,
  • X 2 is independently O or S
  • the substituted pyrimidinium compounds of the formula (I), and their agriculturally acceptable salts are highly active against animal pest, i.e. harmful arthropodes and nematodes, especially against difficult to control insects and acaridae.
  • compositions comprising at least one compound of formula (I) as defined above; agricultural and veterinary compositions comprising an amount of at least one compound of formula (I) or an enantiomer, diasteromer or salt thereof as defined above;
  • a method for combating invertebrate pests, infestation, or infection by invertebrate pests comprises contacting said pest or its food supply, habitat or breeding grounds with a pesticidally effective amount of at least one compound of formula (I) as defined above or a composition thereof;
  • a method for controlling invertebrate pests, infestation, or infection by inverte- brate pests comprises contacting said pest or its food supply, habitat or breeding grounds with a pesticidally effective amount of at least one compound of formula (I) as defined above or a composition comprising at least one compound of formula (I);
  • a method for preventing or protecting against invertebrate pests comprising con- tacting the invertebrate pests, or their food supply, habitat or breeding grounds with a substituted pyrimidinium compounds of the general formula (I) as defined above or a composition comprising at least one compound of formula (I) as defined above or a composition comprising at least one compound of formula (I);
  • a method for protecting crops, plants, plant propagation material and/or growing plants from attack or infestation by invertebrate pests comprising contacting or treating the crops, plants, plant propagation material and growing plants, or soil, material, surface, space, area or water in which the crops, plants, plant propagation material is stored or the plant is growing, with a pesticidally effective amount of at least one compound of formula (I) as defined above or a composition comprising at least one com- pound of formula (I);
  • a non-therapeutic method method for treating animals infested or infected by parasites or preventing animals of getting infected or infested by parasites or protecting animals against infestation or infection by parasites which comprises orally, topically or parenterally administering or applying to the animals a parasiticidally effective amount of a compound of formula (I) as defined above or a composition comprising at least one compound of formula (I);
  • seed comprising a compound of formula (I) as defined above, in an amount of from 0.1 g to 10 kg per 100 kg of seed; the use of the compounds of formula (I) as defined above for protecting growing plants or plant propagation material from attack or infestation by invertebrate pests; the use of compounds of formula (I) or the enantiomers, diastereomers or veterinary acceptable salts thereof for combating parasites in and on animals;
  • a process for the preparation of a veterinary composition for treating, controlling, preventing or protecting animals against infestation or infection by parasites which comprises adding a parasiticidally effective amount of an compound of formula (I) or the enantiomers, diastereomers and/or veterinary acceptable salt thereof to a carrier composition suitable for veterinary use;
  • the invention relates to the use of a compound as disclosed in the present invention, for combating or controlling invertebrate pests, in particular invertebrate pests of the group of insects, arachnids or nema- todes.
  • compound(s) according to the invention or “compound(s) of formula (I)” as used in the present invention refers to and comprises the compound(s) as defined herein and/or stereoisomer(s), salt(s), tautomer(s) or N-oxide(s) thereof.
  • compound(s) of the present invention is to be understood as equivalent to the term “compound(s) according to the invention”, therefore also comprising stereoisomer(s), salt(s), tautomer(s) or N-oxide(s) of compounds of formula (I).
  • composition(s) according to the invention or “composition(s) of the present invention” encompasses composition(s) comprising at least one compound of formula (I) according to the invention as defined above, therefore also including a stereoisomer, an agriculturally or veterinary acceptable salt, tautomer or an N-oxide of the compounds of formula (I).
  • substituted pyrimidinium compounds of formula (I) according to the present invention have not yet been described for pesticidal uses or pesticidal applications in agricul- tural industry or veterinary practice.
  • Heterocyclic substituted pyridinium derivatives and their use as pesticides have been disclosed in WO 2009/099929 as well as in WO 201 1/017347 and in WO 201 1/017351.
  • the particularly substituted pyrimidinium compoundsof formula (I) with the characteristic substitution pattern as defined in the present invention have not yet been described.
  • the compounds of the formula (I) may have one or more centers of chirality, in which case they are present as mixtures of enantiomers or diastereomers.
  • the invention provides both the single pure enantiomers or pure dia- stereomers of the compounds of formula (I), and their mixtures and the use according to the invention of the pure enantiomers or pure diastereomers of the compound of formula (I) or its mixtures.
  • Suitable compounds of the formula (I) also include all possi- ble geometrical stereoisomers (cis/trans isomers) and mixtures thereof. Cis/trans isomers may be present with respect to an alkene, carbon-nitrogen double-bond or amide group.
  • stereoisomer(s) encompasses both optical isomers, such as enantiomers or diastereomers, the latter existing due to more than one center of chirality in the molecule, as well as geometrical isomers (cis/trans isomers).
  • the present invention relates to every possible stereoisomer of the compounds of formula (I), i.e. to single enantiomers or diastereomers, as well as to mixtures thereof.
  • the compounds of the formula (I) may be present in the form of their tautomers.
  • the invention also relates to the tautomers of the formula (I) and the stereoisomers, salts, tautomers and N-oxides of said tautomers.
  • the compounds of the present invention may be amorphous or may exist in one or more different crystalline states (polymorphs) or modifications which may have a different macroscopic properties such as stability or show different biological properties such as activities.
  • the present invention includes both amorphous and crystalline compounds of the formula (I), mixtures of different crystalline states or modifications of the respective compound I, as well as amorphous or crystalline salts thereof.
  • Salts of the compounds of the formula (I) are preferably agriculturally and/or veterinary acceptable salts. They can be formed in a customary method, e.g. by reacting the compound with an acid of the anion in question if the compound of formula (I) has a basic functionality or by reacting an acidic compound of formula (I) with a suitable base.
  • Suitable agriculturally or veterinary useful salts are especially the salts of those cations or the acid addition salts of those acids whose cations and anions, respectively, do not have any adverse effect on the action of the compounds according to the present invention.
  • Suitable cations are in particular the ions of the alkali metals, preferably lithi- urn, sodium and potassium, of the alkaline earth metals, preferably calcium, magnesium and barium, and of the transition metals, preferably manganese, copper, zinc and iron, and also ammonium (NhV) and substituted ammonium in which one to four of the hydrogen atoms are replaced by Ci-C4-alkyl, Ci-C4-hydroxyalkyl, Ci-C4-alkoxy, C1-C4- alkoxy-Ci-C4-alkyl, hydroxy-Ci-C4-alkoxy-Ci-C4-alkyl, phenyl or benzyl.
  • substituted ammonium ions comprise methylammonium, isopropylammonium, dime- thylammonium, diisopropylammonium, trimethylammonium, tetramethylammonium, tetraethylammonium, tetrabutylammonium, 2-hydroxyethylammonium, 2-(2- hydroxyethoxy)ethyl-ammonium, bis(2-hydroxyethyl)ammonium, benzyltrime- thylammonium and benzyltriethylammonium, furthermore phosphonium ions, sulfonium ions, preferably tri(Ci-C4-alkyl)sulfonium, and sulfoxonium ions, preferably tri(Ci-C4- alkyl)sulfoxonium.
  • Anions of useful acid addition salts are primarily chloride, bromide, fluoride, hydrogen sulfate, sulfate, dihydrogen phosphate, hydrogen phosphate, phosphate, nitrate, hy- drogen carbonate, carbonate, hexafluorosilicate, hexafluorophosphate, benzoate, and the anions of Ci-C4-alkanoic acids, preferably formate, acetate, propionate and butyr- ate. They can be formed by reacting the compounds of the formulae I with an acid of the corresponding anion, preferably of hydrochloric acid, hydrobromic acid, sulfuric acid, phosphoric acid or nitric acid.
  • N-oxide includes any compound of the present invention which has at least one tertiary nitrogen atom that is oxidized to an N-oxide moiety.
  • the organic moieties groups mentioned in the above definitions of the variables are - like the term halogen - collective terms for individual listings of the individual group members.
  • the prefix C n -C m indicates in each case the possible number of carbon atoms in the group.
  • Halogen will be taken to mean fluoro, chloro, bromo and iodo.
  • partially or fully halogenated will be taken to mean that 1 or more, e.g. 1 , 2, 3, 4 or 5 or all of the hydrogen atoms of a given radical have been replaced by a halogen atom, in particular by fluorine or chlorine.
  • C n -C m -alkyl refers to a branched or unbranched satu- rated hydrocarbon group having n to m, e.g.
  • 1 to 10 carbon atoms preferably 1 to 6 carbon atoms, for example methyl, ethyl, propyl, 1-methylethyl, butyl, 1 -methylpropyl, 2-methylpropyl, 1 ,1 -dimethylethyl, pentyl, 1 -methylbutyl, 2-methylbutyl, 3-methylbutyl, 2,2-dimethylpropyl, 1 -ethylpropyl, hexyl, 1 ,1 -dimethylpropyl, 1 ,2-dimethylpropyl, 1 - methylpentyl, 2-methylpentyl, 3-methylpentyl, 4-methylpentyl, 1 ,1 -dimethylbutyl, 1 ,2- dimethylbutyl, 1 ,3-dimethylbutyl, 2,2-dimethylbutyl, 2,3-dimethylbutyl, 3,3-dimethylbutyl, 1 -ethylbutyl, 2-e
  • C n -C m -haloalkyl refers to a straight-chain or branched alkyl group having n to m carbon atoms, e.g.
  • Ci-C4-haloalkyl such as chloromethyl, bro- momethyl, dichloromethyl, trichloromethyl, fluoromethyl, difluoromethyl, trifluoromethyl, chlorofluoromethyl, dichlorofluoromethyl, chlorodifluoromethyl, 1 -chloroethyl, 1 - bromoethyl, 1 -fluoroethyl, 2-fluoroethyl, 2,2-difluoroethyl, 2,2,2-trifluoroethyl, 2-chloro-
  • Ci-Cio-haloalkyl in particular comprises C1-C2- fluoroalkyl, which is synonym with methyl or ethyl, wherein 1 , 2, 3, 4 or 5 hydrogen atoms are substituted by fluorine atoms, such as fluoromethyl, difluoromethyl, trifluoromethyl, 1 -fluoroethyl, 2-fluoroethyl, 2,2-difluoroethyl, 2,2,2-trifluoroethyl and pentafluo- romethyl.
  • C n -C m -alkoxy and “C n -C m -alkylthio" refer to straight-chain or branched alkyl groups having n to m carbon atoms, e.g. 1 to 10, in particular 1 to 6 or 1 to 4 carbon atoms (as mentioned above) bonded through oxygen (or sulfur linkages, respectively) at any bond in the alkyl group.
  • Ci-C4-alkoxy such as methoxy, ethoxy, propoxy, isopropoxy, butoxy, sec-butoxy, isobutoxy and tert-butoxy
  • Ci-C4-alkylthio such as methylthio, ethylthio, propylthio, isopropylthio, and n-butylthio.
  • C n -C m -haloalkoxy and "C n -C m -haloalkylthio” (or C n -C m - haloalkylsulfenyl, respectively) refer to straight-chain or branched alkyl groups having n to m carbon atoms, e.g.
  • Ci-C2-haloalkoxy such as chloromethoxy, bromomethoxy, dichloromethoxy, trichloromethoxy, fluoromethoxy, difluoromethoxy, trifluoromethoxy, chlorofluoromethoxy, dichlorofluoromethoxy, chloro- difluoromethoxy, 1 -chloroethoxy, 1 -bromoethoxy, 1 -fluoroethoxy, 2-fluoroethoxy, 2,2- difluoroethoxy, 2,2,2-trifluoroethoxy, 2-chloro-2-fluoroethoxy, 2-chloro-2,2- difluoroethoxy, 2,2-dichloro-2-fluoroe
  • C2-C m -alkenyl intends a branched or unbranched unsaturated hydrocarbon group having 2 to m, e.g. 2 to 10 or 2 to 6 carbon atoms and a double bond in any position, such as ethenyl, 1 -propenyl, 2-propenyl, 1 -methyl-ethenyl, 1 - butenyl, 2-butenyl, 3-butenyl, 1 -methyl-1 -propenyl, 2-methyl-1 -propenyl, 1 -methyl-2- propenyl, 2-methyl-2-propenyl, 1 -pentenyl, 2-pentenyl, 3-pentenyl, 4-pentenyl, 1 - methyl-1 -butenyl, 2-methyl-1 -butenyl, 3-methyl-1 -butenyl, 1 -methyl-2-butenyl, 2-methyl- 2-butenyl, 3-methyl-2-butenyl, 1 -methyl-2-butenyl,
  • C2-C m -alkynyl refers to a branched or unbranched unsaturated hydrocarbon group having 2 to m, e.g. 2 to 10 or 2 to 6 carbon atoms and containing at least one triple bond, such as ethynyl, propynyl, 1 -butynyl, 2-butynyl, and the like.
  • C n -Cm-alkoxy-C n -Cm-alkyl refers to alkyl having n to m car- bon atoms, e.g. like specific examples mentioned above, wherein one hydrogen atom of the alkyl radical is replaced by an C n -C m -alkoxy group; wherein the value of n and m of the alkoxy group are independently chosen from that of the alkyl group .
  • aryl refers to a mono-, bi- or tricyclic aromatic hydrocarbon radical such as phenyl or naphthyl, in particular phenyl (also referred as to C6H 5 as subsitituent).
  • ring system denotes two or more directly connected rings.
  • C3-C m -cycloalkyl refers to a monocyclic ring of 3- to m- membered saturated cycloaliphatic radicals, e.g. cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, cycloheptyl, cyclooctyl and cyclodecyl.
  • alkylcycloalkyl denotes as well as the term " alkyl which may be substituted by cycloalkyi” an alkyl group which is substituted by a cycloalkyi ring, wherein alkyl and cycloakyl are as herein defined.
  • cycloalkylalkyl denotes as well as the term "cycloalkyi which may be substituted by alkyl” a cycloalkyi ring which is substituted by an alkyl group, wherein alkyl and cycloakyl are as herein defined.
  • a I kyl cy cl oa I ky I a I ky I denotes as well as the term " alkylcycloalkyl which may be substituted by alkyl” an alkylcycloalkyl group which is substituted by an alkyl, wherein alkyl and alkylcycloakyl are as herein defined.
  • C3-C m -cycloalkenyl refers to a monocyclic ring of 3- to m- membered partially unsaturated cycloaliphatic radicals.
  • cycloalkylcycloalkyi denotes as well as the term "cycloalkyi which may be substituted by cycloalkyi” a cycloalkyi substitution on another cycloalkyi ring, wherein each cycloalkyi ring independently has from 3 to 7 carbon atom ring members and the cycloalkyls are linked through one single bond or have one common carbon atom.
  • Examples of cycloalkylcycloalkyi include cyclopropylcyclopropyl (e.g. 1 ,1 '-bicyclopropyl-2 - yl), cyclohexylcyclohexyl wherein the two rings are linked through one single common carbon atom (e.g.
  • cyclohexylcyclopentyl wherein the two rings are linked through one single bond (e.g. 4-cyclopentylcyclohexyl) and their different stereoisomers such as (1 R,2S)-1 , 1 '-bicyclopropyl-2-yl and (1 R,2R)-1 ,1 '-bicyclopropyl- 2-yl.
  • 3- to 6-membered carbocyclic ring refers to cyclopropane, cyclobutane, cyclopentane and cyclohexane rings.
  • heterocyclic radical 3-, 4-, 5-, 6- or 7-membered saturated, partially unsaturated or aromatic heterocyclic ring which may contain 1 , 2, 3 or 4 heteroatoms" or “containing heteroatom groups", wherein those heteroatom(s) (group(s)) are selected from N (N-substituted groups), O and S (S-substituted groups) as used herein refers to monocyclic radicals, the monocyclic radicals being saturated, partially unsaturated or aromatic (completely unsaturated).
  • the heterocyclic radical may be attached to the remainder of the molecule via a carbon ring member or via a nitrogen ring member.
  • Examples of 3-, 4-, 5-, 6- or 7-membered saturated heterocyclyl or heterocyclic rings include: oxiranyl, aziridinyl, azetidinyl, 2-tetrahydrofuranyl, 3-tetrahydrofuranyl, 2-tetra- hydrothienyl, 3-tetrahydrothienyl, 2-pyrrolidinyl, 3-pyrrolidinyl, 3-pyrazolidinyl, 4-pyrazo- lidinyl, 5-pyrazolidinyl, 2-imidazolidinyl, 4-imidazolidinyl, 2-oxazolidinyl, 4-oxazolidinyl, 5-oxazolidinyl, 3-isoxazolidinyl, 4-isoxazolidinyl, 5-isoxazolidinyl, 2-thiazolidinyl, 4-thia- zolidinyl, 5-thiazolidinyl, 3-isothiazolidinyl, 4-isothiazolidinyl, 5-
  • Examples of 3-, 4-, 5-, 6- or 7-membered partially unsaturated heterocyclyl or hetero- cyclic rings include: 2,3-dihydrofur-2-yl, 2,3-dihydrofur-3-yl, 2,4-dihydrofur-2-yl, 2,4-di- hydrofur-3-yl, 2,3-dihydrothien-2-yl, 2,3-dihydrothien-3-yl, 2,4-dihydrothien-2-yl, 2,4- dihydrothien-3-yl, 2-pyrrolin-2-yl, 2-pyrrolin-3-yl, 3-pyrrolin-2-yl, 3-pyrrolin-3-yl, 2-isoxa- zolin-3-yl, 3-isoxazolin-3-yl, 4-isoxazolin 3 yl, 2-isoxazolin-4-yl, 3-isoxazolin-4-yl, 4- isoxazolin-4-yl, 2-isoxa
  • Examples of 5- or 6-membered aromatic heterocyclic (hetaryl) or heteroaromatic rings are: 2-furyl, 3-furyl, 2-thienyl, 3-thienyl, 2-pyrrolyl, 3-pyrrolyl, 3-pyrazolyl, 4-pyrazolyl, 5- pyrazolyl, 2-oxazolyl, 4-oxazolyl, 5-oxazolyl, 2-thiazolyl, 4-thiazolyl, 5-thiazolyl, 2-imida- zolyl, 4-imidazolyl, 1 ,3,4-triazol-2-yl, 2-pyridinyl, 3-pyridinyl, 4-pyridinyl, 3-pyridazinyl, 4- pyridazinyl, 2-pyrimidinyl, 4-pyrimidinyl, 5-pyrimidinyl and 2-pyrazinyl.
  • a "C2-Cm-alkylene” is divalent branched or preferably unbranched saturated aliphatic chain having 2 to m, e.g. 2 to 7 carbon atoms, for example CH2CH2, -CH(CH3)-, CH2CH2CH2, CH(CH 3 )CH 2 , CH 2 CH(CH 3 ), CH2CH2CH2CH2, CH2CH2CH2CH2CH2, CH2CH2CH2CH2CH2CH2, and CH2CH2CH2CH2CH2CH2CH2.
  • Embodiments and preferred compounds of the present invention for use in pesticidal methods and for insecticidal application purposes are outlined in the following paragraphs.
  • variables of the compounds of formula (I) have the following meanings, these meanings, both on their own and in combination with one another, being particular embodiments of the compounds of the formula (I):
  • X is O. These compounds correspond to the compounds of formula (1.1 ).
  • X is S. These compounds correspond to the compounds of formula (1.2).
  • Y is S. These compounds respond to the compounds of formula (I.A). In another embodiment of the compounds of formula (I), Y is O. These compounds correspond to the compounds of formula (I.B).
  • Z is a direct bond or C(R a R aa )0. In a further embodiment of the compounds of formula (I), Z is a direct bond.
  • Z is O, S(0) m , or NR b .
  • X 1 is O.
  • X 1 is S.
  • X 1 is NR b . In an embodiment of the compounds of formula (I), Y 1 is O.
  • Y 1 is S.
  • Y 1 is NR C .
  • A is CH or N, and wherein the nitrogen of the pyrimidinium ring taken together with the contiguous linking carbon atom and A as depicted in formula (I), form a five or six membered ring, wherein each remaining ring member is selected from carbon atoms and up to one heteroatoms independently selected from O, S, and N(R C ) P , wherein each ring may be substituted with up to one R a , wherein R a has the meaning as hereunder described.
  • A is CH or N, and wherein the nitrogen of the pyrimidinium ring taken together with the contiguous linking carbon atom and A as depicted in formula (I), form a five membered ring, wherein each remaining ring member is selected from carbon atoms and up to one heteroatoms inde- pendently selected from O, S, and N(R C ) P .
  • A is CH or N, and wherein the nitrogen of the pyrimidinium ring taken together with the contiguous linking carbon atom and A as depicted in formula (I), form a six membered ring, wherein each remaining ring member is selected from carbon atoms and up to one heteroatoms independently selected from O, S, and N(R C ) P .
  • compounds of formula (I) are selected from the group of compounds of formulae 11-1 , II-2, II-3, II-4, II-5, II-6, II-7 and 11-15.
  • compounds of formula (I) are selected from the group of compounds of formulae 11-1 , II-2, II-3, II-4, II-5, II-6 and II-7.
  • the compounds of formula (I) is a compound of formula 11-1 .
  • the compound of formula (I) is a compound of formula 11-15.
  • the compound of formula (I) is a compound of formula 11-16.
  • R 1 is hydrogen, d-Cs-alkyl, C2-C8-alkenyl, C2-C8-alkynyl, C1-C6- alkoxy, C3-C6-cycloalkyl, C4-Cio-cycloalkenyl or Cs-Cn-cycloalkylcycloalkyl, wherein the C-atoms of the aforementioned groups may be unsubstituted, or partially or fully substituted by R a , wherein R a has the meaning as hereunder described.
  • R 1 is a three- to ten-membered saturated, or partially saturated or heterocyclic ring system, which may contain 1 to 3 heteroatoms selected from N(R c )p, O, and S, wherein S may be oxidized and which heterocyclic ring may be unsubstituted or substituted by R a .
  • R 1 is hydrogen, Ci-C4-alkyl, C2-Cs-alkenyl, Ci-C6-alkoxy, C3- C6-cycloalkyl or Cs-Cn-cycloalkylcycloalkyl, wherein the C-atoms of the aforementioned groups may be unsubstituted, or partially or fully substituted by halogen.
  • R 1 is Ci-C4-alkyl, C2-Cs-alkenyl, C3-C6-cycloalkyl, phenyl or benzyl, wherein the C-atoms of the aforementioned groups may be unsubstituted, or partially or fully substituted by R a , wherein R a has the meaning as hereunder described.
  • R 1 is Ci-C4-alkyl, C3-C6-cycloalkyl or phenyl, wherein the C- atoms of the aforementioned groups may be unsubstituted, or partially or fully substituted by halogen or Ci-C4-alkyl.
  • R 1 is Ci-C4-alkyl, C2-C4-alkenyl, phenyl or benzyl, wherein the c-atoms of the aforementioned groups may be partially or fully substituted with halo- gen, preferably CI or F.
  • R 1 is Ci-C4-alkyl, C3-C6-cycloalkyl or phenyl, preferably CH3, CH2CH3, CH(CH3)2, cyclopropyl or phenyl.
  • R 1 is Ci-C3-alkyl, preferably CH3, CH2CH3 or CH(CH3)2; particularly R is CH2CH3.
  • R 2 is hydrogen, halogen, CN, NO2, Ci-C6-alkyl, Ci-C6-haloalkyl, Ci- C6-haloalkoxy, Ci-C6-alkoxy, C2-C6-alkenyl, C2-C6-alkynyl, C3-C6-cycloalkyl, C5-C6- cycloalkenyl, Cs-Cu-cycloalkylcycloalkyl or S(0) m R b , wherein the C-atoms of the aforementioned groups may be unsubstituted, or partially or fully substituted by R 2a .
  • R 2 is hydrogen, halogen, CN, Ci-C6-alkyl, Ci-C2-alkoxy-Ci-C2-alkyl or C3-C6-cycloalkyl, wherein the C-atoms of the aforementioned groups may be substituted by halogen or CN.
  • R 2 is hydrogen, halogen, CN or Ci-C4-alkyl which may be substitut- ed by halogen.
  • R 2 is CN
  • R 2 is hydrogen or Ci-C2-alkyl, particularly CH3.
  • R 2 is Ci-C6-haloalkyl, preferably Ci-C2-haloalkyl, particularly halomethyl, such as CFs or CHF2.
  • R 2 is Ci-C2-alkoxy-Ci-C2-alkyl, preferably Ci-C2-alkoxy-methyl, particularly CH2OCH3.
  • R 2 is C3-C6-cycloalkyl, preferably cyclopropyl which may be substituted, preferably by halogen or cyano.
  • R 2 is C2-C6-alkyl, preferably C2-C4-alkyl, particularly CH2CH3 or C(CH 3 ) 3 .
  • R 2 is Ci-C6-alkyl, preferably Ci-C2-alkyl, particularly CH3.
  • R 2 is halogen, preferably CI or F, particularly F.
  • R 2 is phenyl which may be substituted by halogen, C1-C6- haloalkyl or Ci-C6-haloalkoxy.
  • R 2 is phenyl which may be substituted with phenyl.
  • R 2 is a six-membered heterocyclic ring, which contains 1 or 2, preferably 1 , heteroatom(s) selected from N-R c , O, and S, wherein S may be oxidised, which heterocyclic ring is unsubstituted or substituted by one or more groups R 2a , wherein R 2a is as hereunder defined.
  • R a is halogen, Ci-C6-alkyl, Ci-C6-haloalkyl, Ci-C6-alkoxy, C1-C6- haloalkoxy, C 3 -C 6 -cycloalkyl, CN, OR c , NR b R c , N0 2 , phenyl, pyridyl, thiazyl, furanyl, pyrimidinyl or thienyl, wherein the C-atoms aforementioned which groups may be un- substituted or substituted by one or more R aa , wherein R aa is as hereunder defined.
  • R a is halogen, Ci-C4-alkyl, Ci-C4-haloalkyl or C3-C6-cycloalkyl. In a further embodiment, R a is halogen, Ci-C4-alkyl, Ci-C4-haloalkyl or C3-C6-cycloalkyl. In a further embodiment, R a is halogen.
  • R a is halogen, CN, Ci-C6-alkyl, C3-C6-cycloalkyl, C2-C6- alkenyl, C2-C6-alkynyl, Ci-C6-alkoxy, C2-C6-alkenyloxy or C2-C6-alkynyloxy, which C- atoms of the aforementioned groups may be unsubstituted, partially or fully substituted by R aa , wherein R aa is as hereunder defined.
  • R a is halogen, CN, Ci-C6-alkyl, C3-C6-cycloalkyl, C2-C6- alkenyl, C2-C6-alkynyl, Ci-C6-alkoxy, C2-C6-alkenyloxy or C2-C6-alkynyloxy, wherein the C-atoms of the aforementioned groups may be unsubstituted, partially or fully substituted by halogen.
  • R a is halogen, Ci-C6-haloalkyl or Ci-C6-alkoxy.
  • R a is halogen, CN or Ci-C2-haloalkyl.
  • R a is halogen or Ci-C2-haloalkyl.
  • R a is halogen, preferably Br, CI or F, particularly CI.
  • R a is Ci-C2-haloalkyl, preferably halomethyl such as CHF2 or CF3, particularly CF3.
  • R b is hydrogen, Ci-C6-alkyl, Ci-C6-haloalkyl, Ci-C6-alkoxy, C1-C6- haloalkoxy, phenyl, pyridyl, thiazyl or thienyl, wherein the C-atoms of the aforementioned groups may be substituted by R aa , wherein R aa is as hereunder defined.
  • R b is hydrogen, Ci-C6-alkyl, Ci-C6-haloalkyl, Ci-C6-alkoxy or Ci- C6-haloalkoxy.
  • R b is hydrogen, Ci-C6-alkyl or Ci-C6-haloalkyl. In an embodiment, R b is Ci-C6-alkyl or Ci-C6-haloalkyl. In an embodiment, R b is H. In an embodiment, R c is hydrogen, Ci-C4-alkyl, Ci-C4-haloalkyl, Ci-C4-alkylcarbonyl, C1-C6 cycloalkyl, phenyl, pyridyl, thiazyl or thienyl wherein the C-atoms of the aforementioned groups may be substituted by R aa , wherein R aa is as hereunder defined.
  • R c is hydrogen, Ci-C4-alkyl, Ci-C4-haloalkyl, Ci-C4-alkylcarbonyl, or Ci-C6-cycloalkyl. In an embodiment, R c is hydrogen, Ci-C6-alkyl or Ci-C6-haloalkyl. In an embodiment, R c is Ci-C6-alkyl or Ci-C6-haloalkyl. In an embodiment, R c is H.
  • two geminally bound groups R b R b , R c R b or R C R C together with the atom to which they are bound, may form a 3-, 4-, 5-, 6- or 7- membered saturated, partially unsaturated or aromatic carbo- or heterocyclic ring, which may contain 1 to 2 heteroatoms or heteroatoms groups selected from N, O, S, NO, SO and SO2 and wherein the carbo- or heterocyclic ring may be partially or fully substituted by R 3 .
  • two geminally bound groups R b R b , R c R b or R C R C together with the atom to which they are bound may form a 5- or 6- membered saturated, partially unsaturated or aromatic carbocyclic ring, which ring may be partially or fully substituted by R 3 , and wherein R 3 is as hereunder defined.
  • two geminally bound groups R b R b , R c R b or R C R C together with the atom to which they are bound may form a 5- or 6- membered saturated, partially unsaturated or aromatic heterocyclic ring, which may contain 1 to 2 heteroatoms or heteroatoms groups selected from N, O, S, NO, SO and SO2, wherein the heterocyclic ring may be partially or fully substituted by R 3 , and wherein R 3 is as hereunder defined.
  • R d is hydrogen, phenyl, Ci-C4-alkyl or C2-C6-alkenyl, wherein the aforementioned groups may be substituted by one or more halogen.
  • R d is Ci-C4-alkyl or phenyl, which may be substituted by halogen.
  • R c Ci-C4-alkyl preferably CH3.
  • R e is Ci-C4-alkyl, Ci-C4-haloalkyl, Ci-C4-alkylcarbonyl, C1-C6 cycloalkyl, phenyl, pyridyl, thiazyl or thienyl wherein the aforementioned groups may be sub- stituted by R aa , wherein R aa is as hereunder defined.
  • R e is Ci- C4-alkyl, Ci-C4-haloalkyl, Ci-C4-alkylcarbonyl, or Ci-C6-cycloalkyl.
  • R e is Ci-C4-alkyl or Ci-C4-haloalkyl.
  • R aa is halogen, Ci-C6-alkyl or Ci-C6-haloalkyl. In another embodi- ment, R aa is Ci-C6-alkoxy or Ci-C6-haloalkoxy. In an embodiment, R aa is halogen.
  • R 2a is halogen, Ci-C6-alkyl, Ci-C6-haloalkyl, Ci-C6-alkoxy, C1-C6- haloalkoxy, C 3 -C 6 -cycloalkyl, CN, OR c , NR b R c , N0 2 , phenyl, pyridyl, thiazyl, furanyl, pyrimidinyl or thienyl, wherein the C-atoms of the aforementioned groups may be unsubstituted or substituted by one or more R 2aa , wherein R 2aa is as hereunder defined.
  • R 2a is halogen, Ci-C4-haloalkyl or C3-C6-haloalkoxy.
  • R 2a is phenyl which may be substituted by one or more R 2aa .
  • R 2a is halogen.
  • R 2a is C1-C6- haloalkyl.
  • R 2a is Ci-C6-haloalkoxy.
  • R 2a is halogen, CN, Ci-C6-alkyl, C3-C6-cycloalkyl, C2-C6- alkenyl, C2-C6-alkynyl, Ci-C6-alkoxy, C2-C6-alkenyloxy or C2-C6-alkynyloxy, which C- atoms of the aforementioned groups may be unsubstituted, partially or fully substituted by R 2aa , wherein R 2aa is as hereunder defined.
  • R 2a is Br, CI or F, particularly CI.
  • R 2a is Ci-C2-haloalkyl, preferably halomethyl such as CHF2 or
  • n is 0. In another embodiment, m is 1. In another embodiment, m is 2.
  • n is 0. In another embodiment, n is 1. In another embodiment, n is 2.
  • p is 0. In another embodiment, p is 1 .
  • Het is a five- or six-membered saturated, partially unsaturated or aromatic heterocyclic ring, which may contain 1 to 4 heteroatoms selected from N(R C ) P , O and S, wherein the heterocyclic ring is substituted by (R a ) n and the remaining variables in the meaning of Het are as above defined.
  • Het is a five- or six-membered saturated, partially unsaturated or aromatic heterocyclic ring, which may contain 1 to 2 heteroatoms selected from N(R C ) P , O and S, wherein the heterocyclic ring is substituted by (R a ) n .
  • Het is a five-membered aromatic heterocyclic ring, which contains 2 heteroatoms selected from N(R C ) P , O and S, wherein the heterocyclic ring is substituted by (R a ) n .
  • Het is a five-membered saturated heterocyclic ring, which contains 1 heteroatom selected from N(R C ) P , O and S, preferably O, wherein the heterocyclic ring is substituted by (R a ) n .
  • Het is a six-membered aromatic heterocyclic ring, which contains 2 heteroatoms selected from N(R C ) P , O and S, preferably N(R C ) P , wherein the heterocyclic ring is substituted by (R a ) n .
  • Het is a six-membered aromatic heterocyclic ring, which contains 1 heteroatom selected from N(R C ) P , O and S, preferably N(R C ) P , wherein the heterocyclic ring is substituted by (R a ) n .
  • Het is pyridyl which is substituted by (R a ) n .
  • Het is tetrahydrofuryl which is substituted by (R a ) n .
  • Het is selected from any one of the following ring systems D-1 to D-56:
  • Het is selected from the following rings systems D-2, D-9, D- 22, D-25, D-28, D-29 and D-54:
  • R a is halogen, Ci-C4-haloalkyl, CiC4-alkoxy or Ci-C4-alkylthio or phenyl; pref- erably R a is halogen or halomethyl.
  • Het is selected from the following rings systems D-2, D-9 and D-25:
  • R a is halogen, Ci-C4-haloalkyl, CiC4-alkoxy or Ci-C4-alkylthio or phenyl, pref- erably halogen or Ci-C4-haloalkyl; more preferably R a is CI, Br, F or CF3, most preferably R a is CI or CF 3 .
  • Het is selected from the following rings systems D-2, D-25 or D-54:
  • R a is halogen or Ci-C4-haloalkyl; preferably R a is CI, Br, F or CF3, most preferably R a is CI or CF 3 .
  • Het is selected from the following rings systems D-2a, D-2b, D- 2c, D-25a and D-54a:
  • R a are independently from each other selected from CI, Br, F and CF3.
  • Het is D-2, preferably D-2b or D-2c, particularly D-2b, wherein R a is CI or CF 3 .
  • Het is D-2a.
  • Het is D-25, preferably D-25a substituted by CI.
  • Het is D-9, preferably D-9a or D9b.
  • Het is D-56, preferably D-56a.
  • the compounds of the formula (I) compiled in the tables below which compounds correspond to the compounds of formulae I.1 .B (i.e. wherein X and Y are O) and to the preferred compounds of formula 11-1 , II-2, 11—3 , II-4, II-5, II-6, II-7, and 11-15.
  • Each of the groups mentioned for the substituents in the tables are furthermore per se, independently of the combination in which they are mentioned, a particularly preferred aspect of the substituent in question. Further, each individual meaning of a substituent in the tables constitutes a particularly preferred embodiment of the substituents in question.
  • Table 1 Compounds of the formula (111-1 ) corresponding to the compounds of the formula 11-1 , in which X and Y are O, Het is D-2b wherein R a is CI, and the combination of R 1 , ZR 2 for a compound corresponds in each case to one line of Table A:
  • Table 2 Compounds of the formula (III-2) corresponding to the compounds of the formula II-2, in which X and Y are O, Het is D-2b wherein R a is CI, and the combination of R 1 , ZR 2 for a compound corresponds in each case to one line of Table A:
  • Table 3 Compounds of the formula (III-3) corresponding to the compounds of the formula 11—3 , in which X and Y are O, Het is D-2b wherein R a is CI, and the combination of R 1 , ZR 2 for a compound corresponds in each case to one line of Table A.
  • Table 4 Compounds of the formula (III-4) corresponding to the compounds of the formula II-4, in which X and Y are O, Het is D-2b wherein R a is CI, and the combination of R 1 , ZR 2 for a compound corresponds in each case to one line of Table A.
  • Table 5 Compounds of the formula (III-5) corresponding to the compounds of the formula II-5, in which X and Y are O, Het is D-2b wherein R a is CI, and the combination of R 1 , ZR 2 for a compound cor line of Table A.
  • Table 6 Compounds of the formula (III-6) corresponding to the compounds of the formula II-6, in which X and Y are O, Het is D-2b wherein R a is CI, and the combination of R 1 , ZR 2 for a compound corresponds in each case to one line of Table A.
  • Table 7 Compounds of the formula (III-7) corresponding to the compounds of the formula II-7, in which X and Y are O, Het is D-2b wherein R a is CI, and the combination of R 1 , ZR 2 for a compound corresponds in each case to one line of Table A.
  • Table 8 Compounds of the formula (III-8) corresponding to the compounds of the formula 11-15, in which X and Y are O, Het is D-2b wherein R a is CI, and the combination of R 1 , ZR 2 for a compound to one line of Table A.
  • Table 9 Compounds of the formula (III-9) corresponding to the compounds of the formula 11-1 , in which X and Y are O, Het is D-25a wherein R a is CI, and the combination of R 1 , ZR 2 for a compound o one line of Table A:
  • Table 10 Compounds of the formula (111-10) corresponding to the compounds of the formula II-2, in which X and Y are O, Het is D-25a wherein R a is CI, and the combination of R 1 , ZR 2 for a compound corresponds in each case to one line of Table A.
  • Table 1 1 Compounds of the formula (111-1 1 ) corresponding to the compounds of the formula 11—3 , in which X and Y are O, Het is D-25a wherein R a is CI, and the combination of R 1 , ZR 2 for a compound corresponds in each case to one line of Table A.
  • Table 12 Compounds of the formula (111-12) corresponding to the compounds of the formula II-4, in which X and Y are O, Het is D-25a wherein R a is CI, and the combination of R 1 , ZR 2 for a compound corresponds in each case to one line of Table A.
  • Table 13 Compounds of the formula (111-13) corresponding to the compounds of the formula II-5, in which X and Y are O, Het is D-25a wherein R a is CI, and the combination of R 1 , ZR 2 for a compound one line of Table A..
  • Table 14 Compounds of the formula (111-14) corresponding to the compounds of the formula II-6, in which X and Y are O, Het is D-25a wherein R a is CI, and the combination of R 1 , ZR 2 for a compound corresponds in each case to one line of Table A.
  • Table 15 Compounds of the formula (111-15) corresponding to the compounds of the formula II-7, in which X and Y are O, Het is D-25a wherein R a is CI, and the combination of R 1 , ZR 2 for a compoun one line of Table A.
  • Table 16 Compounds of the formula (111-16) corresponding to the compounds of the formula 11-15, in which X and Y are O, Het is D-25a wherein R a is CI, and the combination of R 1 , ZR 2 for a compoun to one line of Table A.
  • Table 17 Compounds of the formula (111-17) corresponding to the compounds of the formula 11-1 , in which X and Y are O, Het is D-2b wherein R a is CI, and the combination of R 1 , ZR 2 for a compound corre ne line of Table A:
  • Table 18 Compounds of the formula (111-18) corresponding to the compounds of the formula II-2, in which X and Y are O, Het is D-9b, and the combination of R 1 , ZR 2 for a compound corresponds in each case to one line of Table A:
  • Table 19 Compounds of the formula (111-19) corresponding to the compounds of the formula 11—3 , in which X and Y are O, Het is D-9b, and the combination of R 1 , ZR 2 for a compound corresponds in each case to one line of Table A.
  • Table 20 Compounds of the formula (III-20) corresponding to the compounds of the formula II-4, in which X and Y are O, Het is D-9b, and the combination of R 1 , ZR 2 for a compound corresponds in each .
  • Table 21 Compounds of the formula (111-21 ) corresponding to the compounds of the formula II-5, in which X and Y are O, Het is D-9b, and the combination of R 1 , ZR 2 for a compound corresponds in eac .
  • Table 22 Compounds of the formula (III-22) corresponding to the compounds of the formula II-6, in which X and Y are O, Het is D-9b, and the combination of R 1 , ZR 2 for a compound corresponds in each case to one line of Table A.
  • Table 23 Compounds of the formula (111-23) corresponding to the compounds of the formula 11-7, in which X and Y are O, Het is D-9b, and the combination of R 1 , ZR 2 for a compound corresponds in each case to one line of Table A.
  • Table 24 Compounds of the formula (III-24) corresponding to the compounds of the formula 11-15, in which X and Y are O, Het is D-9b, and the combination of R 1 , ZR 2 for a compound corresponds in each case to one line of Table A.
  • Table 25 Compounds of the formula (III-25) corresponding to the compounds of the formula 11-1 , in which X and Y are O, Het is D-25a wherein R a is S-CH3, and the combination of R 1 , ZR 2 for a compound corresponds in each case to one line of Table A:
  • Table 26 Compounds of the formula (III-26) corresponding to the compounds of the formula II-2, in which X and Y are O, Het is D-25a wherein R a is S-CH3, and the combination of R 1 , ZR 2 for a compound corresponds in each case to one line of Table A.
  • Table 27 Compounds of the formula (III-27) corresponding to the compounds of the formula 11—3 , in which X and Y are O, Het is D-25a wherein R a is S-CH3, and the combination of R 1 , ZR 2 for a compound corresponds in each case to one line of Table A.
  • Table 28 Compounds of the formula (III-28) corresponding to the compounds of the formula II-4, in which X and Y are O, Het is D-25a wherein R a is S-CH3, and the combination of R 1 , ZR 2 for a compound corresponds in each case to one line of Table A.
  • Table 29 Compounds of the formula (III-29) corresponding to the compounds of the formula II-5, in which X and Y are O, Het is D-25a wherein R a is S-CH3, and the combination of R 1 , ZR 2 for a comp o one line of Table A..
  • Table 30 Compounds of the formula (III-30) corresponding to the compounds of the formula II-6, in which X and Y are O, Het is D-25a wherein R a is S-CH3, and the combination of R 1 , ZR 2 for a compound corresponds in each case to one line of Table A.
  • Table 32 Compounds of the formula (III-32) corresponding to the compounds of the formula 11-15, in which X and Y are O, Het is D-25a wherein R a is S-CH3, and the combination of R 1 , ZR 2 for a compound corresponds in each case to one line of Table A.
  • Table 33 Compounds of the formula (III-33) corresponding to the compounds of the formula 11-1 , in which X and Y are O, Het is D-2c wherein R a is CI and Phenyl, and the combination of R 1 , ZR 2 for a compound corresponds in each case to one line of Table A:
  • Table 34 Compounds of the formula (III-34) corresponding to the compounds of the formula II-2, in which X and Y are O, Het is D-2c wherein R a is CI and Phenyl, and the combination of R 1 , ZR 2 for a compound corresponds in each case to one line of Table A:
  • Table 35 Compounds of the formula (111-35) corresponding to the compounds of the formula 11-3, in which X and Y are O, Het is D-2c wherein R a is CI and phenyl, and the combination of R 1 , ZR 2 for a compound corresponds in each case to one line of Table A.
  • Table 36 Compounds of the formula (III-36) corresponding to the compounds of the formula II-4, in which X and Y are O, Het is D-2c wherein R a is CI and phenyl, and the combination of R 1 , ZR 2 for a compound corresponds in each case to one line of Table A.
  • Table 37 Compounds of the formula (III-37) corresponding to the compounds of the formula II-5, in which X and Y are O, Het is D-2c wherein R a is CI and phenyl, and the combination of R 1 , ZR 2 for a compound corresponds in each case to one line of Table A.
  • Table 38 Compounds of the formula (III-38) corresponding to the compounds of the formula II-6, in which X and Y are O, Het is D-2c wherein R a is CI and phenyl, and the combination of R 1 , ZR 2 for a compound corresponds in each case to one line of Table A.
  • Table 39 Compounds of the formula (III-39) corresponding to the compounds of the formula II-7, in which X and Y are O, Het is D-2c wherein R a is CI and phenyl, and the combination of R 1 , ZR 2 for a compound corresponds in each case to one line of Table A.
  • Table 40 Compounds of the formula (III-40) corresponding to the compounds of the formula 11-15, in which X and Y are O, Het is D-2c wherein R a is CI and phenyl, and the combination of R 1 , ZR 2 for a compound corresponds in each case to one line of Table A.
  • Table 41 Compounds of the formula (111-41 ) corresponding to the compounds of the formula 11-1 , in which X and Y are O, Het is D-56a wherein R a is O-Me, and the combination of R 1 , ZR 2 for a to one line of Table A:
  • Table 42 Compounds of the formula (III-42) corresponding to the compounds of the formula II-2, in which X and Y are O, Het is D-56a wherein R a is O-Me, and the combination of R 1 , ZR 2 for a one line of Table A.
  • Table 43 Compounds of the formula (III-43) corresponding to the compounds of the formula 11—3 , in which X and Y are O, Het is D-56a wherein R a is O-Me, and the combination of R 1 , ZR 2 for a compound corresponds in each case to one line of Table A.
  • Table 44 Compounds of the formula (111-12) corresponding to the compounds of the formula II-4, in which X and Y are O, Het is D-56a wherein R a is O-Me, and the combination of R 1 , ZR 2 for a compound corresponds in each case to one line of Table A.
  • Table 45 Compounds of the formula (III-45) corresponding to the compounds of the formula II-5, in which X and Y are O, Het is D-56a wherein R a is O-Me, and the combination of R 1 , ZR 2 for a compound corresponds in each case to one line of Table A..
  • Table 46 Compounds of the formula (III-46) corresponding to the compounds of the formula II-6, in which X and Y are O, Het is D-56a wherein R a is O-Me, and the combination of R 1 , ZR 2 for a compound corresponds in each case to one line of Table A.
  • Table 47 Compounds of the formula (111-47) corresponding to the compounds of the formula 11-7, in which X and Y are O, Het is D-56a wherein R a is O-Me, and the combination of R 1 , ZR 2 for a compound corresponds in each case to one line of Table A.
  • Table 48 Compounds of the formula (III-48) corresponding to the compounds of the formula 11-15, in which X and Y are O, Het is D-56a wherein R a is O-Me, and the combination of R 1 , ZR 2 for a compound corresponds in each case to one line of Table A.
  • Table 49 Compounds of the formula (III-49) corresponding to the compounds of the formula 11-16, in which X and Y are O, Het is D-2b wherein R a is CI, and the combination of R 1 , ZR 2 for a co e of Table A:
  • Table 50 Compounds of the formula (III-50) corresponding to the compounds of the formula 11-16, in which X and Y are O, Het is D-25a wherein R a is CI, and the combination of R 1 , ZR 2 for a compound corresponds in each case to one line of Table A:
  • Table 51 Compounds of the formula (111-51 ) corresponding to the compounds of the formula 11-16, in which X and Y are O, Het is D-2c wherein R a is CI and Phenyl, and the combination of R 1 , ZR 2 for a compound corresponds in each case to one line of Table A:
  • Table 52 Compounds of the formula (III-52) corresponding to the compounds of the formula 11-16, in which X and Y are O, Het is D-25a wherein R a is S-Me, and the combination of R 1 , ZR 2 for a line of Table A:
  • Table 53 Compounds of the formula (III-53) corresponding to the compounds of the formula 11-16, in which X and Y are O, Het is D-9b, and the combination of R 1 , ZR 2 for a compound corresponds in each case to one line of Table A:
  • Table 54 Compounds of the formula (III-54) corresponding to the compounds of the formula 11-16, in which X and Y are O, Het is D-56a wherein R a is O-Me, and the combination of R 1 , ZR 2 for a compound corresponds in each case to one line of Table A:
  • the compound of formula (I) according to the present invention can be prepared according to the following syntheses routes, e.g. according to the preparation methods and preparation schemes as described below.
  • the compound of formula (I) according to the present invention can be prepared, according to the e.g. preparation methods and preparation schemes as described below.
  • the compounds used as starting materials for the syntheses of the compounds according to the present invention can generally be prepared by standard methods of organic chemistry. If not otherwise specified, the definitions of the variables such as X, Y, Het, R 1 and R 2 of the structures given in the schemes have the same meaning as defined above.
  • LG denotes a leaving group such as halogen (e.g. chlorine or bromine), OR' , or SR' , with R' being Ci-C6-alkyl, preferably chlorine methoxy ethoxy, methylthio or ethylthio (Scheme 2):
  • Lactams are widespread in organic chemistry and methods to produce them are well known. For example see: Smith, M. B, in Science of Synthesis, (2005) 21 , 653.
  • certain compounds of formula (I) can advantageously be prepared from other compounds of formula (I) by derivatization, e.g. by ester hydrolysis, amidation, esterification, ether cleavage, olefination, reduction, oxidation and the like, or by customary modifications of the synthesis routes described.
  • the reaction mixtures are worked up in the customary manner, for example by mixing with water, separating the phases, and, if appropriate, purifying the crude products by chromatography, for example on alumina or silica gel.
  • invertebrate pest encompasses animal populations, such as arthropod pests, including insects and arachnids, as well as nematodes, which may attack plants thereby causing substantial damage to the plants attacked, as well as ectoparasites which may infest animals, in particular warm blooded animals such as e.g. mammals or birds, or other higher animals such as reptiles, amphibians or fish, thereby causing substantial damage to the animals infested.
  • the compounds of formula (I) according to the present invention are in particular suitable for efficiently controlling arthropod pests such as arachnids, myriapedes and insects as well as nematodes.
  • the compounds of the formula (I) are especially suitable for efficiently combating the following pests:
  • Insects from the order of the lepidopterans for example Agrotis ypsilon, Agrotis segetum, Alabama argillacea, Anticarsia gemmatalis, Argyresthia conjugella, Autographa gamma, Bupalus piniarius, Cacoecia murinana, Capua reticulana, Chei- matobia brumata, Choristoneura fumiferana, Choristoneura occidentalis, Cirphis unipuncta, Cydia pomonella, Dendrolimus pini, Diaphania nitidalis, Diatraea grandiosel- la, Earias insulana, Elasmopalpus lignosellus, Eupoecilia ambiguella, Evetria bouliana, Feltia subterranea, Galleria mellonella, Grapholitha funebrana, Grapholitha molesta,
  • mosquitoes e.g. Aedes aegypti, Aedes albopictus, Aedes vexans, Anas- trepha ludens, Anopheles maculipennis, Anopheles crucians, Anopheles albimanus, Anopheles gambiae, Anopheles freeborni, Anopheles leucosphyrus, Anopheles minimus, Anopheles quadrimaculatus, Calliphora vicina, Ceratitis capitata, Chrysomya bezziana, Chrysomya hominivorax, Chrysomya macellaria, Chrysops discalis, Chrys- ops silacea, Chrysops atlanticus, Cochliomyia hominivorax, Contarinia sorghicola Cordylobia anthropophaga, Culicoides furens, Culex pipiens, Culex
  • Thrips thrips (Thysanoptera), e.g. Dichromothrips corbetti, Dichromothrips ssp., Frankliniella fusca, Frankliniella occidentalis, Frankliniella tritici, Scirtothrips citri, Thrips oryzae, Thrips palmi and Thrips tabaci, termites (Isoptera), e.g.
  • Calotermes flavicollis Leucotermes flavipes, Heterotermes aureus, Reticulitermes flavipes, Reticulitermes virginicus, Reticulitermes lucifugus, Re- ticulitermes santonensis, Reticulitermes grassei, Termes natalensis, and Coptotermes formosanus;
  • cockroaches e.g. Blattella germanica, Blattella asahinae, Peri- planeta americana, Periplaneta japonica, Periplaneta brunnea, Periplaneta fuligginosa, Periplaneta australasiae, and Blatta orientalis;
  • insects e.g. Acrosternum hilare, Blissus leucopterus, Cyrtopeltis notatus, Dysdercus cingulatus, Dysdercus intermedius, Eurygaster integriceps, Euschistus impictiventris, Leptoglossus phyllopus, Lygus lineolaris, Lygus pratensis, Nezara viridula, Piesma quadrata, Solu- bea insularis , Thyanta perditor, Acyrthosiphon onobrychis, Adelges laricis, Aphidula nasturtii, Aphis fabae, Aphis forbesi, Aphis pomi, Aphis gossypii, Aphis grossulariae, Aphis schneideri, Aphis
  • crickets grasshoppers, locusts (Orthoptera), e.g. Acheta domestica, Gryllotalpa gryllo- talpa, Locusta migratoria, Melanoplus bivittatus, Melanoplus femurrubrum, Melanoplus mexicanus, Melanoplus sanguinipes, Melanoplus spretus, Nomadacris septemfasciata, Schistocerca americana, Schistocerca gregaria, Dociostaurus maroccanus, Tachycines asynamorus, Oedaleus senegalensis, Zonozerus variegatus, Hieroglyphus daganensis, Kraussaria angulifera, Calliptamus italicus, Chortoicetes terminifera, and Locustana pardalina;
  • Orthoptera e.g. Acheta domestica, Gryllotalpa gryllo- talpa, Locusta
  • arachnoidea such as arachnids (Acarina), e.g. of the families Argasidae, Ixodidae and Sarcoptidae, such as Amblyomma americanum, Amblyomma variegatum, Ambryomma maculatum, Argas persicus, Boophilus annulatus, Boophilus decoloratus, Boophilus microplus, Dermacentor silvarum, Dermacentor andersoni, Dermacentor variabilis, Hy- alomma truncatum, Ixodes ricinus, Ixodes rubicundus, Ixodes scapularis, Ixodes holo- cyclus, Ixodes pacificus, Ornithodorus moubata, Ornithodorus hermsi, Ornithodorus turicata, Ornithonyssus bacoti, Otobius megnini, Dermanyss
  • Tetranychidae spp. such as Tetranychus cinnabarinus, Tetranychus kanzawai, Tetranychus pacificus, Tetranychus telarius and Tetranychus urticae, Panonychus ul- mi, Panonychus citri, and Oligonychus pratensis; Araneida, e.g. Latrodectus mactans, and Loxosceles reclusa;
  • fleas e.g. Ctenocephalides felis, Ctenocephalides canis, Xenopsylla cheopis, Pulex irritans, Tunga penetrans, and Nosopsyllus fasciatus,
  • silverfish, firebrat e.g. Lepisma saccharina and Thermobia domestica, centipedes (Chilopoda), e.g. Scutigera coleoptrata,
  • Earwigs e.g. forficula auricularia
  • Pthirus pubis Haematopinus eurysternus, Haematopinus suis, Linognathus vituli, Bo- vicola bovis, Menopon gallinae, Menacanthus stramineus and Solenopotes capillatus.
  • Collembola (springtails), e.g. Onychiurus ssp..
  • the compounds of formula (I) are also suitable for controlling Nematodes: plant para- sitic nematodes such as root knot nematodes, Meloidogyne hapla, Meloidogyne incognita, Meloidogyne javanica, 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 spe- cies; Sting nematodes, Belonolaimus longicaudatus and other Belonolaimus species; Pine nematodes, Bursaphelenchus xylophilus and other Bursaphelenchus species
  • the compounds of formula (I) are particularly useful for controlling, or combating, or treating, or preventing or protecting each of the individual group of target pests as above listed as well as each combination thereof.
  • the Compounds of the formula (I) are particularly useful for controlling insects, prefer- ably piercing-sucking insects such as insects from the genera Thysanoptera, Diptera and Hemiptera.
  • Compounds of the formula (I) are particularly useful for controlling insects of the orders Hemiptera and Thysanoptera.
  • the compounds of formula (I) can be converted into the customary formulations, e.g. solutions, emulsions, suspensions, dusts, powders, pastes, granules and directly sprayable solutions.
  • the use form depends on the particular purpose and application method. Formulations and application methods are chosen to ensure in each case a fine and uniform distribution of the compound of formula (I) according to the invention.
  • An agrochemical composition according to the present invention comprises a pesti- cidally effective amount of a compound of formula (I) according to the present invention.
  • effective amount denotes an amount of the composition or of the com- pounds of formula (I), which is sufficient for controlling animal pests on a locus, such as crops, cultivated plants or in the protection of materials and which does not result in a substantial damage to the treated plants.
  • Such an amount can vary in a broad range and is dependent on various factors, such as the animal pest species to be controlled, the treated cultivated plant or material, the climatic conditions and the specific compound of formula (I) used.
  • compositions e.g. solutions, emulsions, suspensions, dusts, powders, pastes, granules, pressings, capsules, and mixtures thereof.
  • composition types are suspensions (e.g. SC, OD, FS), emulsifiable concentrates (e.g. EC), emulsions (e.g. EW, EO, ES, ME), capsules (e.g. CS, ZC), pastes, pastilles, wettable powders or dusts (e.g. WP, SP, WS, DP, DS), pressings (e.g.
  • compositions types are defined in the " Catalogue of pesticide formulation types and international coding system" , Technical Monograph No. 2, 6th Ed. May 2008, CropLife International.
  • compositions are prepared in a known manner, such as described by Mollet and Grubemann, Formulation technology, Wiley VCH, Weinheim, 2001 ; or Knowles, New developments in crop protection product formulation, Agrow Reports DS243, T&F In- forma, London, 2005.
  • auxiliaries for the formulations and or the agrochemicals compositions according to the inventions are solvents, liquid carriers, solid carriers or fillers, surfactants, dispersants, emulsifiers, wetters, adjuvants, solubilizers, penetration en- hancers, protective colloids, adhesion agents, thickeners, humectants, repellents, at- tractants, feeding stimulants, compatibilizers, bactericides, antifreezing agents, anti- foaming agents, colorants, tackifiers and binders.
  • Suitable solvents and liquid carriers are water and organic solvents, such as mineral oil fractions of medium to high boiling point, e.g. kerosene, diesel oil; oils of vegetable or animal origin; aliphatic, cyclic and aromatic hydrocarbons, e. g. toluene, paraffin, tetra- hydronaphthalene, alkylated naphthalenes; alcohols, e.g. ethanol, propanol, butanol, benzylalcohol, cyclohexanol; glycols; DMSO; ketones, e.g. cyclohexanone; esters, e.g.
  • mineral oil fractions of medium to high boiling point e.g. kerosene, diesel oil
  • oils of vegetable or animal origin oils of vegetable or animal origin
  • aliphatic, cyclic and aromatic hydrocarbons e. g. toluene, paraffin, tetra- hydronaphthalene, alky
  • lactates carbonates, fatty acid esters, gammabutyrolactone; fatty acids; phosphonates; amines; amides, e.g. N-methylpyrrolidone, fatty acid dimethylamides; and mixtures thereof.
  • Suitable solid carriers or fillers are mineral earths, e.g. silicates, silica gels, talc, kaolins, lime-stone, lime, chalk, clays, dolomite, diatomaceous earth, bentonite, calcium sulfate, magnesium sulfate, magnesium oxide; polysaccharide powders, e.g. cellulose, starch; fertilizers, e.g. ammonium sulfate, ammonium phosphate, ammonium nitrate, ureas; products of vegetable origin, e.g. cereal meal, tree bark meal, wood meal, nutshell meal, and mixtures thereof.
  • mineral earths e.g. silicates, silica gels, talc, kaolins, lime-stone, lime, chalk, clays, dolomite, diatomaceous earth, bentonite, calcium sulfate, magnesium sulfate, magnesium oxide
  • polysaccharide powders e.g. cellulose
  • Suitable surfactants are surface active compounds, such as anionic, cationic, nonionic and amphoteric surfactants, block polymers, polyelectrolytes, and mixtures thereof. Such surfactants can be used as emulsifier, dispersant, solubilizer, wetter, penetration enhancer, protective colloid, or adjuvant. Examples of surfactants are listed in
  • McCutcheon' s, Vol.1 Emulsifiers & Detergents, McCutcheon' s Directories, Glen Rock, USA, 2008 (International Ed. or North American Ed.).
  • Suitable anionic surfactants are alkali, alkaline earth or ammonium salts of sulfonates, sulfates, phosphates, carboxylates, and mixtures thereof.
  • sulfonates are alkylarylsulfonates, diphenylsulfonates, alpha-olefin sulfonates, lignine sulfonates, sulfonates of fatty acids and oils, sulfonates of ethoxylated alkylphenols, sulfonates of alkoxylated arylphenols, sulfonates of condensed naphthalenes, sulfonates of dodecyl- and tridecylbenzenes, sulfonates of naphthalenes and alkylnaphthalenes, sulfosuccin- ates or sulfosuccinamates.
  • Examples of sulfates are sulfates of fatty acids and oils, of ethoxylated alkylphenols, of alcohols, of ethoxylated alcohols, or of fatty acid esters.
  • Examples of phosphates are phosphate esters.
  • Examples of carboxylates are alkyl carboxylates, and carboxylated alcohol or alkylphenol ethoxylates.
  • Suitable nonionic surfactants are alkoxylates, N-substituted fatty acid amides, amine oxides, esters, sugar based surfactants, polymeric surfactants, and mixtures thereof.
  • alkoxylates are compounds such as alcohols, alkylphenols, amines, amides, arylphenols, fatty acids or fatty acid esters which have been alkoxylated with 1 to 50 equivalents.
  • Ethylene oxide and/or propylene oxide may be employed for the alkoxylation, preferably ethylene oxide.
  • N-substituted fatty acid amides are fatty acid glucamides or fatty acid alkanolamides.
  • esters are fatty acid esters, glycerol esters or monoglycerides.
  • sugar-based surfactants are sorbitans, ethoxylated sorbitans, sucrose and glucose esters or alkylpolyglucosides.
  • polymeric surfactants are homo- or copolymers of vinylpyrrolidone, vinyl- alcohols, or vinylacetate.
  • Suitable cationic surfactants are quaternary surfactants, for example quaternary ammonium compounds with one or two hydrophobic groups, or salts of long chain primary amines.
  • Suitable amphoteric surfactants are alkylbetains and imidazolines.
  • Suitable block polymers are block polymers of the A-B or A-B-A type comprising blocks of poly- ethylene oxide and polypropylene oxide, or of the A-B-C type comprising alkanol, polyethylene oxide and polypropylene oxide.
  • Suitable polyelectrolytes are polyacids or pol- ybases. Examples of polyacids are alkali salts of polyacrylic acid or polyacid comb polymers. Examples of polybases are polyvinylamines or polyethyleneamines.
  • Suitable adjuvants are compounds, which have a neglectable or even no pesticidal activity themselves, and which improve the biological performance of the compound of formula (I) on the target.
  • examples are surfactants, mineral or vegetable oils, and other auxiliaries. Further examples are listed by Knowles, Adjuvants and additives, Agrow Reports DS256, T&F Informa UK, 2006, chapter 5.
  • Suitable thickeners are polysaccharides (e.g. xanthan gum, carboxymethylcellulose), anorganic clays (organically modified or unmodified), polycarboxylates, and silicates.
  • Suitable bactericides are bronopol and isothiazolinone derivatives such as alkylisothia- zolinones and benzisothiazolinones.
  • Suitable antifreezing agents are ethylene glycol, propylene glycol, urea and glycerine.
  • Suitable antifoaming agents are silicones, long chain alcohols, and salts of fatty acids.
  • Suitable colorants e.g. in red, blue, or green
  • Suitable colorants are pigments of low water solubility and water-soluble dyes. Examples are inorganic colorants (e.g. iron oxide, titan oxide, iron hexacyanoferrate) and organic colorants (e.g. alizarin-, azo- and phthalocyanine color- ants).
  • Suitable tackifiers or binders are polyvinylpyrrolidons, polyvinylacetates, polyvinyl alcohols, polyacrylates, biological or synthetic waxes, and cellulose ethers.
  • composition types and their preparation are:
  • a compound of formula (I) according to the invention 10-60 wt% of a compound of formula (I) according to the invention and 5-15 wt% wetting agent (e.g. alcohol alkoxylates) are dissolved in water and/or in a water- soluble solvent (e.g. alcohols) up to 100 wt%.
  • the active substance dissolves upon dilution with water.
  • a compound of formula (I) according to the invention 5-25 wt% of a compound of formula (I) according to the invention and 1 -10 wt% dispersant (e. g. polyvinylpyrrolidone) are dissolved in up to 100 wt% organic solvent (e.g. cyclohexanone). Dilution with water gives a dispersion.
  • dispersant e. g. polyvinylpyrrolidone
  • emulsifiers e.g. calcium dodecylbenzenesulfonate and castor oil ethoxylate
  • water insoluble organic solvent e.g. aromatic hydrocarbon
  • Emulsions (EW, EO, ES)
  • emulsifiers e.g. calcium dodecylbenzenesulfonate and castor oil ethoxylate
  • 20-40 wt% water insoluble organic solvent e.g. aromatic hydrocarbon
  • a compound of formula (I) in an agitated ball mill, 20-60 wt% of a compound of formula (I) according to the invention are comminuted with addition of 2-10 wt% dispersants and wetting agents (e.g. sodium lignosulfonate and alcohol ethoxylate), 0,1 -2 wt% thickener (e.g. xanthan gum) and up to 100 wt% water to give a fine active substance suspension. Dilution with water gives a stable suspension of the active substance. For FS type composition up to 40 wt% binder (e.g. polyvinylalcohol) is added.
  • WG, SG Water dispersible granules and water soluble granules
  • 50-80 wt% of a compound of formula (I) according to the invention are ground finely with addition of up to 100 wt% dispersants and wetting agents (e.g. sodium lignosulfonate and alcohol ethoxylate) and prepared as water dispersible or water soluble granules by means of technical appliances (e. g. extrusion, spray tower, fluidized bed). Dilution with water gives a stable dispersion or solution of the active substance.
  • dispersants and wetting agents e.g. sodium lignosulfonate and alcohol ethoxylate
  • wt% of a compound of formula (I) according to the invention are ground in a rotor stator mill with addition of 1 -5 wt% dispersants (e.g. sodium ligno- sufonate), 1 -3 wt% wetting agents (e.g. alcohol ethoxylate) and up to 100 wt% solid carrier, e.g. silica gel. Dilution with water gives a stable dispersion or solution of the active substance.
  • dispersants e.g. sodium ligno- sufonate
  • 1 wt% wetting agents e.g. alcohol ethoxylate
  • solid carrier e.g. silica gel
  • a compound of formula (I) according to the invention are comminuted with addition of 3-10 wt% dispersants (e.g. sodium lig- nosulfonate), 1 -5 wt% thickener (e.g. carboxymethylcellulose) and up to 100 wt% water to give a fine suspension of the active substance. Dilution with water gives a stable suspension of the active substance.
  • dispersants e.g. sodium lig- nosulfonate
  • 1 -5 wt% thickener e.g. carboxymethylcellulose
  • wt% of a compound of formula (I) according to the invention are added to 5- 30 wt% organic solvent blend (e.g. fatty acid dimethylamide and cyclohexanone), 10-25 wt% surfactant blend (e.g. alkohol ethoxylate and arylphenol ethoxylate), and water up to 100 %. This mixture is stirred for 1 h to produce spontaneously a thermodynamically stable microemulsion.
  • organic solvent blend e.g. fatty acid dimethylamide and cyclohexanone
  • surfactant blend e.g. alkohol ethoxylate and arylphenol ethoxylate
  • An oil phase comprising 5-50 wt% of a compound of formula (I) according to the invention, 0-40 wt% water insoluble organic solvent (e.g. aromatic hydrocarbon), 2-15 wt% acrylic monomers (e.g. methylmethacrylate, methacrylic acid and a di- or triacrylate) are dispersed into an aqueous solution of a protective colloid (e.g. polyvinyl alcohol). Radical polymerization initiated by a radical initiator results in the formation of poly(meth)acrylate microcapsules.
  • an oil phase comprising 5-50 wt% of a compound I according to the invention, 0-40 wt% water insoluble organic solvent (e.g.
  • an isocyanate mono- mer e.g. diphenylmethene-4,4' -diisocyanatae
  • a protective colloid e.g. polyvinyl alcohol
  • the addition of a polyam- ine results in the formation of a polyurea microcapsules.
  • the monomers amount to 1 -10 wt%. The wt% relate to the total CS composition.
  • 1 -10 wt% of a compound of formula (I) according to the invention are ground finely and mixed intimately with up to 100 wt% solid carrier, e.g. finely divided kaolin.
  • solid carrier e.g. finely divided kaolin.
  • 0.5-30 wt% of a compound of formula (I) according to the invention is ground finely and associated with up to 100 wt% solid carrier (e.g. silicate). Granulation is achieved by extrusion, spray drying or the fluidized bed.
  • solid carrier e.g. silicate
  • Ultra-low volume liquids (UL) 1 -50 wt% of a compound of formula (I) according to the invention are dissolved in up to 100 wt% organic solvent, e.g. aromatic hydrocarbon.
  • compositions types i) to xi) may optionally comprise further auxiliaries, such as 0,1 -1 wt% bactericides, 5-15 wt% antifreezing agents, 0,1 -1 wt% antifoaming agents, and 0,1 -1 wt% colorants.
  • auxiliaries such as 0,1 -1 wt% bactericides, 5-15 wt% antifreezing agents, 0,1 -1 wt% antifoaming agents, and 0,1 -1 wt% colorants.
  • the agrochemical compositions generally comprise between 0.01 and 95%, preferably between 0.1 and 90%, and most preferably between 0.5 and 75%, by weight of active substance i.e. the compounds of formula (I) according to the invention.
  • the active substances are generally employed in a purity of from 90% to 100%, preferably from 95% to 100% (according to NMR spectrum).
  • Water soluble concentrates (LS), Suspoemulsions (SE), flowable concentrates (FS), powders for dry treatment (DS), water dispersible powders for slurry treatment (WS), water soluble powders (SS), emulsions (ES), emulsifiable concentrates (EC) and gels (GF) are usually employed for the purposes of treatment of plant propagation materials, particularly seeds.
  • compositions according to the invention in question give, after two-to-tenfold dilution, concentrations of active substance of from 0.01 to 60% by weight, preferably from 0.1 to 40% by weight, in the ready-to-use preparations.
  • Methods for applying or treating compound of formula (I) and compositions thereof, respectively, on to plant propagation material, especially seeds include dressing, coating, pelleting, dusting, soaking and in furrow application methods of the propagation material.
  • compound of formula (I) or the compositions thereof, respectively are applied on to the plant propa- gation material by a method such that germination is not induced, e.g. by seed dressing, pelleting, coating and dusting.
  • the amounts of active substances applied are, depending on the kind of effect desired, from 0.001 to 2 kg per ha, preferably from 0.005 to 2 kg per ha, more preferably from 0.05 to 0.9 kg per ha, in particular from 0.1 to 0.75 kg per ha.
  • amounts of active substance In treatment of plant propagation materials such as seeds, e. g. by dusting, coating or drenching seed, amounts of active substance of from 0.1 to 1000 g, preferably from 1 to 1000 g, more preferably from 1 to 100 g and most preferably from 5 to 100 g, per 100 kilogram of plant propagation material (preferably seed) are generally required.
  • the amount of active substance applied depends on the kind of application area and on the desired effect.
  • Amounts customarily applied in the protection of materials are 0.001 g to 2 kg, preferably 0.005 g to 1 kg, of active substance per cubic meter of treated material.
  • oils, wetters, adjuvants, fertilizer, or micronutrients, and other pesti- cides may be added to the active substances or the compositions comprising them as premix or, if appropriate not until immediately prior to use (tank mix).
  • pesti- cides e.g. herbicides, insecticides, fungicides, growth regulators, safeners
  • These agents can be admixed with the compositions according to the invention in a weight ratio of 1 :100 to 100:1 , preferably 1 :10 to 10:1.
  • the user applies the composition according to the invention usually from a predosage device, a knapsack sprayer, a spray tank, a spray plane, or an irrigation system.
  • the agrochemical composition is made up with water, buffer, and/or further auxiliaries to the desired application concentration and the ready-to-use spray liquor or the agrochemical composition according to the invention is thus obtained.
  • 20 to 2000 liters, preferably 50 to 400 liters, of the ready-to-use spray liquor are applied per hectare of agricultural useful area.
  • composition according to the invention such as parts of a kit or parts of a binary or ternary mixture may be mixed by the user himself in a spray tank and further auxiliaries may be added, if appropriate.
  • either individual components of the composition according to the invention or partially premixed components e. g. components comprising compounds of formula (I) and/or additional active substances from the groups M.1 ) to M.26, including M-X or F.I to F.XII, may be mixed by the user in a spray tank and further auxiliaries and additives may be added, if appropriate.
  • either individual components of the composition according to the invention or partially premixed components e. g. components comprising compounds of formula (I) and/or active substances from the groups M.1 to M.26, including M-X or F.I to F.XII, can be applied jointly (e.g. after tank mix) or consecutively.
  • Acetylcholine esterase (AChE) inhibitors from the class of
  • M.1A carbamates, for example aldicarb, alanycarb, bendiocarb, benfuracarb, butocar- boxim, butoxycarboxim, carbaryl, carbofuran, carbosulfan, ethiofencarb, fenobucarb, formetanate, furathiocarb, isoprocarb, methiocarb, methomyl, metolcarb, oxamyl, pi- rimicarb, propoxur, thiodicarb, thiofanox, trimethacarb, XMC, xylylcarb and triazamate; or from the class of
  • M.1 B organophosphates for example acephate, azamethiphos, azinphos-ethyl, az- inphosmethyl, cadusafos, chlorethoxyfos, chlorfenvinphos, chlormephos, chlorpyrifos, chlorpyrifos-methyl, coumaphos, cyanophos, demeton-S-methyl, diazinon, dichlorvos/ DDVP, dicrotophos, dimethoate, dimethylvinphos, disulfoton, EPN, ethion, ethopro- phos, famphur, fenamiphos, fenitrothion, fenthion, fosthiazate, heptenophos, imicyafos, isofenphos, isopropyl O- (methoxyaminothio-phosphoryl) salicylate, isoxathion, mala- thion, mecarbam, me
  • GABA-gated chloride channel antagonists such as:
  • M.2A cyclodiene organochlorine compounds as for example endosulfan or chlordane; or
  • M.2B fiproles phenylpyrazoles
  • fipronil phenylpyrazoles
  • flufiprole pyra- fluprole
  • pyriprole phenylpyrazoles
  • M.3A pyrethroids for example acrinathrin, allethrin, d-cis-trans allethrin, d-trans alle- thrin, bifenthrin, bioallethrin, bioallethrin S-cylclopentenyl, bioresmethrin, cycloprothrin, cyfluthrin, beta-cyfluthrin, cyhalothrin, lambda-cyhalothrin, gamma-cyhalothrin, cyper- methrin, alpha-cypermethrin, beta-cypermethrin, theta-cypermethrin, zeta- cypermethrin, cyphenothrin, deltamethrin, empenthrin, esfenvalerate, etofenprox, fenpropathrin, fenvalerate
  • Nicotinic acetylcholine receptor agonists from the class of
  • M.4A neonicotinoids for example acteamiprid, chlothianidin, cycloxaprid, dinotefuran, imidacloprid, nitenpyram, thiacloprid and thiamethoxam; or the compounds
  • M4.A.3 1 -[(6-Chloropyridin-3-yl)methyl]-7-methyl-8-nitro-5-propoxy-1 ,2,3,5,6,7- hexahydroimidazo[1 ,2-a]pyridine;
  • M.4B nicotine or from the class M.4B nicotine;
  • M.6 Chloride channel activators from the class of avermectins and milbemycins, for example abamectin, emamectin benzoate, ivermectin, lepimectin or milbemectin;
  • M.7A juvenile hormone analogues as hydroprene, kinoprene and methoprene; or others as M.7B fenoxycarb or M.7C pyriproxyfen; M.8 miscellaneous non-specific (multi-site) inhibitors, for example
  • M.8A alkyl halides as methyl bromide and other alkyl halides, or
  • M.1 1 Microbial disruptors of insect midgut membranes, for example bacillus thuringiensis or bacillus sphaericus and the insecticdal proteins they produce such as bacillus thuringiensis subsp. israelensis, bacillus sphaericus, bacillus thuringiensis subsp. aizawai, bacillus thuringiensis subsp. kurstaki and bacillus thuringiensis subsp. tenebri- onis, or the Bt crop proteins: CrylAb, CrylAc, Cryl Fa, Cry2Ab, mCry3A, Cry3Ab, Cry3Bb and Cry34/35Ab1 ;
  • M.12 Inhibitors of mitochondrial ATP synthase for example
  • M.12B organotin miticides such as azocyclotin, cyhexatin or fenbutatin oxide, or M.12C propargite, or M.12D tetradifon;
  • M.14 Nicotinic acetylcholine receptor (nAChR) channel blockers for example nereis- toxin analogues as bensultap, cartap hydrochloride, thiocyclam or thiosultap sodium;
  • M.16 Inhibitors of the chitin biosynthesis type 1 as for example buprofezin;
  • Ecdyson receptor agonists such as diacylhydrazines, for example methoxyfeno- zide, tebufenozide, halofenozide, fufenozide or chromafenozide;
  • Octopamin receptor agonists as for example amitraz
  • M.20 Mitochondrial complex III electron transport inhibitors for example M.20A hydramethylnon, or M.20B acequinocyl, or M.20C fluacrypyrim;
  • M.21A METI acaricides and insecticides such as fenazaquin, fenpyroximate, pyrimidif- en, pyridaben, tebufenpyrad or tolfenpyrad, or M.21 B rotenone;
  • M.22A indoxacarb, or M.22B metaflumizone, or M.22B.1 2-[2-(4-Cyanophenyl)-1 -[3- (trifluoromethyl)phenyl]ethylidene]-N-[4-(difluoromethoxy)phenyl]- hydrazinecarboxamide or M.22B.2: N-(3-Chloro-2-methylphenyl)-2-[(4-chlorophenyl)[4- [methyl(methylsulfonyl)amino]phenyl]methylene]-hydrazinecarboxamide;
  • M.23 Inhibitors of the of acetyl CoA carboxylase such as Tetronic and Tetramic acid derivatives, for example spirodiclofen, spiromesifen or spirotetramat;
  • M.24A phosphine such as aluminium phosphide, calcium phosphide, phosphine or zinc phosphide, or M.24B cyanide
  • M.25 Mitochondrial complex II electron transport inhibitors such as beta-ketonitrile derivatives, for example cyenopyrafen or cyflumetofen
  • M.28 Ryanodine receptor-modulators from the class of diamides as for example flubendiamide, chlorantraniliprole (rynaxypyr®), cyantraniliprole (cyazypyr®), or the phthalamide compounds
  • M.28.4 methyl-2-[3,5-dibromo-2-( ⁇ [3-bromo-1 -(3-chlorpyridin-2-yl)-1 H-pyrazol-5- yl]carbonyl ⁇ amino)benzoyl]-1 ,2-dimethylhydrazinecarboxylate; or a compound selected from M.28.5a) to M.28.5I):
  • M.UN. insecticidal active compounds of unknown or uncertain mode of action as for example afidopyropen, afoxolaner, azadirachtin, amidoflumet, benzoximate, bifena- zate, bromopropylate, chinomethionat, cryolite, dicofol, flufenerim, flometoquin, fluen- sulfone, fluopyram, flupyradifurone, fluralaner, metoxadiazone, piperonyl butoxide, pyflubumide, pyridalyl, pyrifluquinazon, sulfoxaflor, tioxazafen, triflumezopyrim, or the compounds
  • M.UN.5 1 -[2-fluoro-4-methyl-5-[(2,2,2-trifluoroethyl)sulfinyl]phenyl]-3-(trifluoromethyl)- 1 H-1 ,2,4-triazole-5-amine, or actives on basis of bacillus firmus (Votivo, 1-1582); or a compound selected from the group of M.UN.6, wherein the compound is selected from M.UN.6a) to M.UN.6k): M.UN.6a) (E/Z)-N-[1 -[(6-chloro-3-pyridyl)methyl]-2-pyridylidene]-2,2,2-trifluoro- acetamide;
  • M.UN.6f E/Z-N-[1 -[(6-chloro-3-pyndyl)methyl]-2-pyridylidene]-2,2-difluoro-acetamide
  • M.UN.6g E/Z-2-chloro-N-[1 -[(6-chloro-3-pyridyl)methyl]-2-pyridylidene]-2,2-difluoro- acetamide
  • M.UN.8 8-chloro-N-[2-chloro-5-methoxyphenyl)sulfonyl]-6-trifluoromethyl)-imidazo[1 ,2- a]pyridine-2-carboxamide; or
  • M.UN.9 4-[5-(3,5-dichlorophenyl)-5-(trifluoromethyl)-4H-isoxazol-3-yl]-2-methyl-N-(1 - oxothietan-3-yl)benzamide; or
  • M.UN.10 5-[3-[2,6-dichloro-4-(3,3-dichloroallyloxy)phenoxy]propoxy]-1 H-pyrazole; or a compound selected from the group of M.UN.1 1 , wherein the compound is selected from M. UN.1 1 a) to M.UN.1 1 p):
  • M.UN.1 1. a) 3-[benzoyl(methyl)amino]-N-[2-bromo-4-[1 ,2,2,2-tetrafluoro-1 -
  • M.UN.1 1.c) 3-(benzoylmethylamino)-2-fluoro-N-[2-iodo-4-[1 ,2,2,2-tetrafluoro-1 - (trifluoromethyl)ethyl]-6-(trifluoromethyl)phenyl]-benzamide;
  • M.UN.1 1 .1) N-[5-[[2-bromo-6-chloro-4-[2,2,2-trifluoro-1 -hydroxy-1 - (trifluoromethyl)ethyl]phenyl]carbamoyl]-2-cyano-phenyl]-4-cyano-2-methyl-ben
  • M.UN.1 1 .m) N-[5-[[2-bromo-6-chloro-4-[1 ,2,2,3,3,3-hexafluoro-1 -
  • M.UN.1 1.o) 4-cyano-N-[2-cyano-5-[[2,6-dichloro-4-[1 ,2,2,2-tetrafluoro-1 - (trifluoromethyl)ethyl]phenyl]carbamoyl]phenyl]-2-methyl-benzamide;
  • M.UN.1 1.p) N-[5-[[2-bromo-6-chloro-4-[1 ,2,2,2-tetrafluoro-1 - (trifluoromethyl)ethyl]phenyl]carbamoyl]-2-cyano-phenyl]-4-cyano-2-methyl-ben or a compound selected from the group of M.UN.12, wherein the compound is selected from M. UN.12a) to M. UN.12m):
  • M.UN.12.1) N-[4-Chloro-2-(3-pyridyl)thiazol-5-yl]-N-methyl-3-methylthio-propanamide
  • M.UN.12.m N-[4-Chloro-2-(3-pyridyl)thiazol-5-yl]-N-ethyl-3-methylthio-propanamide; or the compound M.UN.13: 2-(4-methoxyiminocyclohexyl)-2-(3,3,3-trifluoropropylsulfonyl)acetonitrile; or the compounds
  • M.UN.15 1 -[(2-Chloro-1 ,3-thiazol-5-yl)methyl]-3-(3,5-dichlorophenyl)-9-methyl-4-oxo- 4H-pyrido[1 ,2-a]pyrimidin-1 -ium-2-olate.
  • the commercially available compounds of the group M listed above may be found in The Pesticide Manual, 15th Edition, C. D. S. Tomlin, British Crop Protection Council (201 1 ) among other publications.
  • the neonicotinoid cycloxaprid is known from WO20120/069266 and WO201 1/06946, and the neonicotinoid compound M.4A.2, sometimes also to be named as Guadipyr, is known from WO2013/003977, and the neonicotinoid compound M.4A.3. (approved as paichongding in China) is known from WO2010/069266.
  • the Metaflumizone analogue M.22B.1 is described in CN 10171577 and the analogue M.22B.2 in CN102126994.
  • the phthalamides M.28.1 and M.28.2 are both known from WO 2007/101540.
  • the an- thranilamide M.28.3 has been described in WO2005/077934.
  • the hydrazide compound M.28.4 has been described in WO 2007/043677.
  • the anthranilamides M.28.5a) to M.28.5h) can be prepared as described in WO 2007/006670, WO2013/024009 and WO2013/024010, the anthranilamide compound ⁇ .28.5 ⁇ ) is described in
  • WO201 1/085575 the compound M.28.5j) in WO2008/134969, the compound M.28.5k) in US201 1/046186 and the compound M.28.5I) in WO2012/034403.
  • the diamide compounds M.28.6 and M.28.7 can be found in CN102613183.
  • the anthranilamide compounds M.28.8a) and M.28.8b) are known from WO2010/069502.
  • the quinoline derivative flometoquin is shown in WO2006/013896.
  • the aminofuranone compounds flupyradifurone is known from WO 2007/1 15644.
  • the sulfoximine compound sulfoxaflor is known from WO2007/149134.
  • mom- fluorothrin is known from US6908945 and heptafluthrin from W010133098.
  • the oxadiazolone compound metoxadiazone can be found in JP13/166707.
  • the pyrazole acaricide pyflubumide is known from WO2007/020986.
  • the isoxazoline compounds have been described in following publications: fluralaner in WO2005/085216, afoxolan- er in WO2009/002809 and in WO201 1/149749 and the isoxazoline compound M.UN.9 in WO2013/050317.
  • the pyripyropene derivative afidopyropen has been described in WO 2006/129714.
  • the nematicide tioxazafen has been disclosed in WO09023721 and nematicide fluopyram in WO2008126922, nematicidal mixtures comprising flupyram in WO2010108616.
  • the triflumezopyrim compound was described in WO2012/0921 15.
  • the spiroketal-substituted cyclic ketoenol derivative M.UN.3 is known from
  • WO2006/089633 and the biphenyl-substituted spirocyclic ketoenol derivative M.UN.4 from WO2008/06791 1.
  • the triazoylphenylsulfide M.UN.5 has been described in WO2006/043635, and biological control agents on basis of bacillus firmus in
  • the compounds M.UN.6a) to M.UN.6i) listed under M.UN.6 have been described in WO2012/029672 and compounds M.UN.6j) and M.UN.6k) in WO2013129688.
  • the carboxamide compounds M. UN.1 1 . a) to M.UN.H .h) can be prepared as described in WO 2010/018714 and the carboxamide M.UN.1 1 i) to M.UN.1 1.p) are described WO2010/127926.
  • the pyridylthiazoles M.UN.12.a) to M.UN.12.C) are known from WO2010/006713, M.UN.12.C) and M.UN.12.d)
  • the malononitrile compound M.UN.13 was described in WO2009/0051 10.
  • the compounds M. UN.14a) and M. UN.14b) are known from WO2007/101369.
  • the compound M.UN.15 can be found in WO 2013/192035.
  • strobilurins azoxystrobin, coumethoxystrobin, coumoxystrobin, dimoxystrobin, ene- stroburin, fluoxastrobin, kresoxim-methyl, metominostrobin, orysastrobin, picoxystrobin, pyraclostrobin, pyrametostrobin, pyraoxystrobin, pyribencarb, triclopy- ricarb/chlorodincarb, trifloxystrobin, 2-[2-(2,5-dimethyl-phenoxymethyl)-phenyl]-3- methoxy-acrylic acid methyl ester and 2 (2-(3-(2,6-dichlorophenyl)-1 -methyl- allylideneaminooxymethyl)-phenyl)-2-methoxyimino-N methyl-acetamide;
  • oxazolidinediones and imidazolinones famoxadone, fenamidone;
  • Inhibitors of complex II e.g. carboxamides
  • carboxanilides benodanil, benzovindiflupyr, bixafen, boscalid, carboxin, fenfuram, fenhexamid, fluopyram, flutolanil, furametpyr, isopyrazam, isotianil, mepronil, oxycar- boxin, penflufen, penthiopyrad, sedaxane, tecloftalam, thifluzamide, tiadinil, 2-amino-4 methyl-thiazole-5-carboxanilide, N-(3',4',5' trifluorobiphenyl-2 yl)-3-difluoromethyl-1 - methyl-1 H-pyrazole-4 carboxamide (fluxapyroxad), N-(4'-trifluoromethylthiobiphenyl-2- yl)-3 difluoromethyl-1 -methyl-1 H pyrazole-4-carboxamide, N-(2-(1 ,3,3-
  • Inhibitors of complex III at Qi site cyazofamid, amisulbrom, [(3S,6S,7R,8R)-8- benzyl-3-[(3-acetoxy-4-methoxy-pyridine-2-carbonyl)amino]-6-methyl-4,9-dioxo-1 ,5-di- oxonan-7-yl] 2-methylpropanoate, [(3S,6S,7R,8R)-8-benzyl-3-[[3-(acetoxymethoxy)-4- methoxy-pyridine-2-carbonyl]amino]-6-methyl-4,9-dioxo-1 ,5-dioxonan-7-yl]
  • respiration inhibitors diflumetorim; (5,8-difluoro- quinazolin-4-yl)- ⁇ 2-[2-fluoro-4-(4-trifluoromethylpyridin-2-yloxy)-phenyl]-ethyl ⁇ -amine; tecnazen; ferimzone; ametoctradin; silthiofam; nitrophenyl derivates: binapacryl, dino- buton, dinocap, fluazinam, nitrthal-isopropyl, and
  • organometal compounds including organometal compounds: fentin salts, such as fentin-acetate, fentin chloride or fentin hydroxide;
  • F.II-1 C14 demethylase inhibitors (DMI fungicides, e.g. triazoles, imidazoles) triazoles: azaconazole, bitertanol, bromuconazole, cyproconazole, difenoconazole, diniconazole, diniconazole-M, epoxiconazole, fenbuconazole, fluquinconazole, flusi- lazole, flutriafol, hexaconazole, imibenconazole, ipconazole, metconazole, myclobu- tanil, paclobutrazole, penconazole, propiconazole, prothioconazole, simeconazole, tebuconazole, tetraconazole, triadimefon, triadimenol, triticonazole, uniconazole, , 1 - [re/-(2S;3R
  • imidazoles imazalil, pefurazoate, oxpoconazole, prochloraz, triflumizole;
  • pyrimidines, pyridines and piperazines fenarimol, nuarimol, pyrifenox, triforine, 1 -[rel- (2S;3R)-3-(2-chlorophenyl)-2-(2,4-difluorophenyl)-oxiranylmethyl]-5-thiocyanato-1 H- [1 ,2,4]triazole, 2-[rel-(2S;3R)-3-(2-chlorophenyl)-2-(2,4-difluorophenyl)-oxiranylmethyl]- 2H-[1 ,2,4]triazole-3-thiol;
  • morpholines aldimorph, dodemorph, dodemorph-acetate, fenpropimorph, tridemorph; piperidines: fenpropidin, piperalin; spiroketalamines: spiroxamine;
  • phenylamides or acyl amino acid fungicides benalaxyl, benalaxyl-M, kiralaxyl, met- alaxyl, metalaxyl-M (mefenoxam), ofurace, oxadixyl;
  • Tubulin inhibitors benzimidazoles and thiophanates: benomyl, carbendazim, fuberidazole, thiabendazole, thiophanate-methyl;
  • triazolopyrimidines 5-chloro-7 (4-methylpiperidin-1 -yl)-6-(2,4,6-trifluorophenyl)- [1 ,2,4]triazolo[1 ,5 a]pyrimidine;
  • benzamides and phenyl acetamides diethofencarb, ethaboxam, pencycuron, fluopico- lide, zoxamide;
  • Actin inhibitors benzophenones: metrafenone, pyriofenone;
  • anilino-pyrimidines cyprodinil, mepanipyrim, nitrapyrin, pyrimethanil;
  • F.V-2 Protein synthesis inhibitors (anilino-pyrimidines)
  • antibiotics blasticidin-S, kasugamycin, kasugamycin hydrochloride-hydrate, mildiomy- cin, streptomycin, oxytetracyclin, polyoxine, validamycin A;
  • MAP / Histidine kinase inhibitors e.g. anilino-pyrimidines
  • dicarboximides fluoroimid, iprodione, procymidone, vinclozolin;
  • phenylpyrroles fenpiclonil, fludioxonil;
  • F.VI-2 G protein inhibitors: quinolines: quinoxyfen;
  • organophosphorus compounds edifenphos, iprobenfos, pyrazophos;
  • dithiolanes isoprothiolane
  • Lipid peroxidation aromatic hydrocarbons: dicloran, quintozene, tecnazene, tolclofos-methyl, biphenyl, chloroneb, etridiazole;
  • cinnamic or mandelic acid amides dimethomorph, flumorph, mandiproamid, pyrimorph; valinamide carbamates: benthiavalicarb, iprovalicarb, pyribencarb, valifenalate and N-
  • F.VII-5 fatty acid amide hydrolase inhibitors 1 -[4-[4-[5-(2,6-difluorophenyl)-4,5- dihydro-3-isoxazolyl]-2-thiazolyl]-1 -piperidinyl]-2-[5-methyl-3-(trifluoromethyl)-1 H- pyrazol-1 -yl]ethanone;
  • F.VI 11-1 Inorganic active substances: Bordeaux mixture, copper acetate, copper hydroxide, copper oxychloride, basic copper sulfate, sulfur; F.VIII-2) Thio- and dithiocarbamates: ferbam, mancozeb, maneb, metam,
  • Organochlorine compounds e.g. phthalimides, sulfamides, chloronitriles: anilazine, chlorothalonil, captafol, captan, folpet, dichlofluanid, dichlorophen, flusulfa- mide, hexachlorobenzene, pentachlorphenole and its salts, phthalide, tolylfluanid, N-(4- chloro-2-nitro-phenyl)-N-ethyl-4-methyl-benzenesulfonamide;
  • phthalimides e.g. phthalimides, sulfamides, chloronitriles
  • Inhibitors of glucan synthesis validamycin, polyoxin B;
  • F.IX-2 Melanin synthesis inhibitors: pyroquilon, tricyclazole, carpropamide, dicyclomet, fenoxanil;
  • phosphonates fosetyl, fosetyl-aluminum, phosphorous acid and its salts;
  • F.XI Growth regulators: abscisic acid, amidochlor, ancymidol, 6-benzylaminopurine, brassinolide, butralin, chlormequat (chlormequat chloride), choline chloride, cyclanilide, daminozide, dikegulac, dimethipin, 2,6-dimethylpuridine, ethephon, flumetralin, flur- primidol, fluthiacet, forchlorfenuron, gibberellic acid, inabenfide, indole-3-acetic acid, maleic hydrazide, mefluidide, mepiquat (mepiquat chloride), naphthaleneacetic acid, N 6-benzyladenine, paclobutrazol, prohexadione (prohexadione-calcium), prohydro- jasmon, thidiazuron, triapenthenol, tributyl phosphorotrithioate
  • Ampelomyces quisqualis e.g. AQ 10 ® from Intrachem Bio GmbH & Co. KG, Germany
  • Aspergillus flavus e.g. AFLAGUARD ® from Syngenta, CH
  • Aureobasidium pullulans e.g. BOTECTOR ® from bio-ferm GmbH, Germany
  • Bacillus pumilus e.g. NRRL Ac- cession No. B-30087 in SONATA ® and BALLAD ® Plus from AgraQuest Inc., USA
  • Bacillus subtilis e.g. isolate NRRL-Nr.
  • Clonostachys rosea f. catenula- ta also named Gliocladium catenulatum (e.g. isolate J 1446: PRESTOP ® from Verdera, Finland), Coniothyrium minitans (e.g. CONTANS ® from Prophyta, Germany),
  • Cryphonectria parasitica e.g. Endothia parasitica from CNICM, France
  • Cryptococcus albidus e.g. YIELD PLUS ® from Anchor Bio-Technologies, South Africa
  • Fusarium oxysporum e.g. BIOFOX ® from S.I.A.P.A., Italy, FUSACLEAN ® from Natural Plant Protection, France
  • Metschnikowia fructicola e.g. SHEMER ® from Agrogreen, Israel
  • Microdochium dimerum e.g. ANTIBOT ® from Agrauxine, France
  • Phlebiopsis gigantea e.g.
  • ROTSOP ® from Verdera, Finland
  • Pseudozyma flocculosa e.g. SPORODEX ® from Plant Products Co. Ltd., Canada
  • Pythium oligandrum DV74 e.g. POLYVER- SUM ® from Remeslo SSRO, Biopreparaty, Czech Rep.
  • Reynoutria sachlinensis e.g. REGALIA ® from Marrone Biolnnovations, USA
  • Talaromyces f/avus VH 7b e.g. PRO- TUS ® from Prophyta, Germany
  • Trichoderma asperellum SKT-1 e.g.
  • T. atroviride LC52 e.g. SENTINEL ® from Agrimm Technologies Ltd, NZ
  • T. harzianum T-22 e.g. PLANTSHIELD ® der Fir- ma BioWorks Inc., USA
  • T. harzianum JH 35 e.g. ROOT PRO ® from Mycontrol Ltd., Israel
  • T. harzianum T-39 e.g. TRICHODEX ® and TRICHODERMA 2000 ® from Mycontrol Ltd., Israel and Makhteshim Ltd., Israel
  • T. harzianum and T. viride e.g.
  • T. harzianum ICC012 and T. viride ICC080 e.g. REMEDIER ® WP from Isagro Ricerca, Italy
  • T. polysporum and T. harzianum e.g. BINAB ® from BINAB Bio-Innovation AB, Sweden
  • T. stromaticum e.g. TRICOVAB ® from C.E.P.L.A.C., Brazil
  • T. virens GL-21 e.g. SOILGARD ® from Certis LLC, USA
  • T. viride TV1 e.g. T. viride TV1 from Ag- ribiotec srl, Italy
  • Ulocladium oudemansii HRU3 e.g. BOTRY-ZEN ® from Botry-Zen Ltd, NZ.
  • the animal pest i.e. the insects, arachnids and nematodes, the plant, soil or water in which the plant is growing can be contacted with the present compounds of formula (I) or composition(s) containing them by any application method known in the art.
  • contacting includes both direct contact (applying the compounds/compositions direct- ly on the animal pest or plant, typically to the foliage, stem or roots of the plant) and indirect contact (applying the compounds/compositions to the locus of the animal pest or plant).
  • the compounds of formula (I) or the pesticidal compositions comprising them may be used to protect growing plants and crops from attack or infestation by animal pests, especially insects, acaridae or arachnids by contacting the plant/crop with a pesticidally effective amount of compounds of formula (I).
  • crop refers both to growing and harvested crops.
  • the compounds of the present invention and the compositions comprising them are particularly important in the control of a multitude of insects on various cultivated plants, such as cereal, root crops, oil crops, vegetables, spices, ornamentals, for example seed of durum and other wheat, barley, oats, rye, maize (fodder maize and sugar maize / sweet and field corn), soybeans, oil crops, crucifers, cotton, sunflowers, ba- nanas, rice, oilseed rape, turnip rape, sugar beet, fodder beet, eggplants, potatoes, grass, lawn, turf, fodder grass, tomatoes, leeks, pumpkin/squash, cabbage, iceberg lettuce, pepper, cucumbers, melons, Brassica species, melons, beans, peas, garlic, onions, carrots, tuberous plants such as potatoes, sugar cane, tobacco, grapes, petunias, geranium/pelargoniums, pansies and impatiens.
  • the compounds of the present invention are employed as such or in form of compositions by treating the insects or the plants, plant propagation materials, such as seeds, soil, surfaces, materials or rooms to be protected from insecticidal attack with an insec- ticidally effective amount of the compound of formula (I).
  • the application can be carried out both before and after the infection of the plants, plant propagation materials, such as seeds, soil, surfaces, materials or rooms by the insects.
  • the present invention also includes a method of combating animal pests which comprises contacting the animal pests, their habit, breeding ground, food supply, cultivated plants, seed, soil, area, material or environment in which the animal pests are growing or may grow, or the materials, plants, seeds, soils, surfaces or spaces to be protected from animal attack or infestation with a pesticidally effective amount of a mixture of at least one compound of formula (I).
  • animal pests may be controlled by contacting the target pest, its food supply, habitat, breeding ground or its locus with a pesticidally effective amount of compounds of formula (I).
  • the application may be carried out before or after the infection of the locus, growing crops, or harvested crops by the pest.
  • the compounds of the invention can also be applied preventively to places at which occurrence of the pests is expected.
  • the compounds of formula (I) may be also used to protect growing plants from attack or infestation by pests by contacting the plant with a pesticidally effective amount of compounds of formula (I).
  • "contacting” includes both direct contact (applying the compounds/compositions directly on the pest and/or plant - typically to the foliage, stem or roots of the plant) and indirect contact (applying the compounds/compositions to the locus of the pest and/or plant).
  • “Locus” means a habitat, breeding ground, plant, seed, soil, area, material or environment in which a pest or parasite is growing or may grow.
  • plant propagation material is to be understood to denote all the generative parts of the plant such as seeds and vegetative plant material such as cuttings and tubers (e. g. potatoes), which can be used for the multiplication of the plant. This includes seeds, roots, fruits, tubers, bulbs, rhizomes, shoots, sprouts and other parts of plants. Seedlings and young plants, which are to be transplanted after germination or after emergence from soil, may also be included. These plant propagation materials may be treated prophylactically with a plant protection compound either at or before planting or transplanting.
  • cultivadas plants is to be understood as including plants which have been modified by breeding, mutagenesis or genetic engineering.
  • Genetically modified plants are plants, which genetic material has been so modified by the use of recombinant DNA techniques that under natural circumstances cannot readily be obtained by cross breeding, mutations or natural recombination.
  • one or more genes have been integrated into the genetic material of a genetically modified plant in order to improve certain properties of the plant.
  • Such genetic modifications also include but are not lim- ited to targeted post-transtional modification of protein(s) (oligo- or polypeptides) poly for example by glycosylation or polymer additions such as prenylated, acetylated or farnesylated moieties or PEG moieties(e.g. as disclosed in Biotechnol Prog. 2001 Jul- Aug;17(4):720-8., Protein Eng Des Sel. 2004 Jan;17(1 ):57-66, Nat Protoc.
  • cultivar plants are to be understood also including plants that have been rendered tolerant to applications of specific classes of herbicides, such as hy- droxy-phenylpyruvate dioxygenase (HPPD) inhibitors; acetolactate synthase (ALS) inhibitors, such as sulfonyl ureas (see e. g. US 6,222,100, WO 01/82685, WO
  • EP-A-0242236, EP-A-242246) or oxynil herbicides see e. g. US 5,559,024) as a result of conventional methods of breeding or genetic engineering.
  • mutagenesis for example Clearfield® summer rape (Canola) being tolerant to imidazolinones, e. g. imazamox.
  • cultiva plants is to be understood also including plants that are by the use of recombinant DNA techniques capable to synthesize one or more insecticidal proteins, especially those known from the bacterial genus Bacillus, particularly from Bacillus thuringiensis, such as a-endotoxins, e. g. CrylA(b), CrylA(c), CrylF, CrylF(a2), CryllA(b), CrylllA, CrylllB(bl ) or Cry9c; vegetative insecticidal proteins (VIP), e. g. VIP1 , VIP2, VIP3 or VIP3A; insecticidal proteins of bacteria colonizing nematodes, for example Photorhabdus spp.
  • VIP vegetative insecticidal proteins
  • toxins produced by animals such as scorpion toxins, arachnid toxins, wasp toxins, or other insect-specific neurotoxins
  • toxins produced by fungi such Streptomycetes toxins, plant lectins, such as pea or barley lectins; agglutinins
  • proteinase inhibitors such as trypsin inhibitors, serine protease inhibitors, patatin, cystatin or papain inhibitors
  • ribosome-inactivating proteins (RIP) such as ricin, maize-RIP, abrin, luffin, saporin or bryodin
  • steroid metabolism enzymes such as 3-hydroxysteroid oxidase, ecdysteroid-IDP-glycosyl-transferase, cholesterol oxidases, ecdysone inhibitors or HMG-CoA-reductase
  • ion channel blockers such as blockers of sodium or calcium channels
  • these insecticidal proteins or toxins are to be understood expressly also as pre-toxins, hybrid proteins, trun- cated or otherwise modified proteins.
  • Hybrid proteins are characterized by a new combination of protein domains, (see, for example WO 02/015701 ).
  • Further examples of such toxins or genetically-modified plants capable of synthesizing such toxins are dis-closed, for example, in EP-A 374 753, WO 93/007278, WO 95/34656, EP-A 427 529, EP-A 451 878, WO 03/018810 und WO 03/052073.
  • the methods for producing such genetically modified plants are generally known to the person skilled in the art and are described, for example, in the publications mentioned above.
  • insecticidal proteins contained in the genetically modified plants impart to the plants producing these proteins protection from harmful pests from certain taxonomic groups of arthropods, particularly to beetles (Coleoptera), flies (Diptera), and butterflies and moths (Lepidoptera) and to plant parasitic nematodes (Nematoda).
  • cultivars are to be understood also including plants that are by the use of recombinant DNA techniques capable to synthesize one or more proteins to increase the resistance or tolerance of those plants to bacterial, viral or fungal pathogens.
  • proteins are the so-called " pathogenesis-related proteins” (PR proteins, see, for example EP-A 0 392 225), plant disease resistance genes (for example potato cultivars, which express resistance genes acting against Phytophthora infestans derived from the mexican wild potato Solanum bulbocastanum) or T4- lyso-zym (e. g. potato cultivars capable of synthesizing these proteins with increased resistance against bacteria such as Erwinia amylvora).
  • PR proteins pathogenesis-related proteins
  • plant disease resistance genes for example potato cultivars, which express resistance genes acting against Phytophthora infestans derived from the mexican wild potato Solanum bulbocastanum
  • T4- lyso-zym e. g. potato
  • cultiva plants is to be understood also including plants that are by the use of recombinant DNA techniques capable to synthesize one or more proteins to increase the productivity (e. g. bio mass production, grain yield, starch content, oil content or protein content), tolerance to drought, salinity or other growth-limiting envi- ron-mental factors or tolerance to pests and fungal, bacterial or viral pathogens of those plants.
  • cultiva plants is to be understood also including plants that contain by the use of recombinant DNA techniques a modified amount of substances of content or new substances of content, specifically to improve human or animal nutrition, for ex-ample oil crops that produce health-promoting long-chain omega-3 fatty acids or unsaturated omega-9 fatty acids (e. g. Nexera® rape).
  • cultivación plants is to be understood also including plants that contain by the use of recombinant DNA techniques a modified amount of substances of content or new substances of content, specifically to improve raw material production, for example potatoes that produce increased amounts of amylopectin (e. g. Amflora® potato).
  • "pesticidally effective amount” means the amount of active ingredient (here of compound of formula (I)) needed to achieve an observable effect on growth, including the effects of necrosis, death, retardation, prevention, and removal, destruction, or otherwise diminishing the occurrence and activity of the target organism.
  • the pesticidally effective amount can vary for the various compounds/compositions used in the invention.
  • a pesticidally effective amount of the compositions will also vary according to the prevailing conditions such as desired pesticidal effect and duration, weather, target species, locus, mode of application, and the like.
  • the quantity of active ingredient ranges from 0.0001 to 500 g per 100 m 2 , preferably from 0.001 to 20 g per 100 m 2 .
  • Customary application rates in the protection of materials are, for example, from 0.01 g to 1000 g of active ingredient per m 2 treated material, desirably from 0.1 g to 50 g per m 2 .
  • Insecticidal compositions for use in the impregnation of materials typically contain from 0.001 to 95 weight %, preferably from 0.1 to 45 weight %, and more preferably from 1 to 25 weight % of at least one repellent and/or insecticide.
  • the rate of application of the active ingredients of this invention may be in the range of 0.1 g to 4000 g per hectare, desirably from 25 g to 600 g per hectare, more desirably from 50 g to 500 g per hectare.
  • the compounds of formula (I) are effective through both contact (via soil, glass, wall, bed net, carpet, plant parts or animal parts), and ingestion (bait, or plant part).
  • the compounds of the invention may also be applied against non-crop insect pests, such as ants, termites, wasps, flies, mosquitos, crickets, or cockroaches.
  • non-crop insect pests such as ants, termites, wasps, flies, mosquitos, crickets, or cockroaches.
  • compounds of formula (I) are preferably used in a bait composition.
  • the bait can be a liquid, a solid or a semisolid preparation (e.g. a gel).
  • Solid baits can be formed into various shapes and forms suitable to the respective application e.g. granules, blocks, sticks, disks.
  • Liquid baits can be filled into various devices to ensure proper application, e.g. open containers, spray devices, droplet sources, or evaporation sources.
  • Gels can be based on aqueous or oily matrices and can be formulated to par- ticular necessities in terms of stickiness, moisture retention or aging characteristics.
  • the bait employed in the composition is a product, which is sufficiently attractive to incite insects such as ants, termites, wasps, flies, mosquitos, crickets etc.
  • Food stimulants are chosen, for example, but not exclusively, from animal and/or plant proteins (meat-, fish- or blood meal, insect parts, egg yolk), from fats and oils of animal and/or plant origin, or mono-, oligo- or polyorganosaccharides, especially from sucrose, lactose, fructose, dextrose, glucose, starch, pectin or even molasses or honey.
  • Fresh or decaying parts of fruits, crops, plants, animals, insects or specific parts thereof can also serve as a feeding stimulant.
  • Sex pheromones are known to be more insect specific. Specific pheromones are described in the literature and are known to those skilled in the art.
  • the typical content of active ingredient is from 0.001 weight % to 15 weight %, desirably from 0.001 weight % to 5% weight % of active ingredient.
  • Formulations of compounds of formula (I) as aerosols are highly suitable for the non-professional user for controlling pests such as flies, fleas, ticks, mosquitos or cockroaches.
  • Aerosol recipes are preferably composed of the active ingredient, solvents such as lower alcohols (e.g. methanol, ethanol, propanol, butanol), ketones (e.g. acetone, methyl ethyl ketone), paraffin hydrocarbons (e.g.
  • kerosenes having boiling ranges of approximately 50 to 250 °C, dimethylforma- mide, N-methylpyrrolidone, dimethyl sulfoxide, aromatic hydrocarbons such as toluene, xylene, water, furthermore auxiliaries such as emulsifiers such as sorbitol monooleate, oleyl ethoxylate having 3-7 mol of ethylene oxide, fatty alcohol ethoxylate, perfume oils such as ethereal oils, esters of medium fatty acids with lower alcohols, aromatic car- bonyl compounds, if appropriate stabilizers such as sodium benzoate, amphoteric surfactants, lower epoxides, triethyl orthoformate and, if required, propellants such as propane, butane, nitrogen, compressed air, dimethyl ether, carbon dioxide, nitrous oxide, or mixtures of these gases.
  • emulsifiers such as sorbitol monooleate, oleyl ethoxylate having 3
  • the oil spray formulations differ from the aerosol recipes in that no propellants are used.
  • the content of active ingredient is from 0.001 to 80 weights %, preferably from 0.01 to 50 weight % and most preferably from 0.01 to 15 weight %.
  • the compound of formula (I) and its respective compositions can also be used in mosquito and fumigating coils, smoke cartridges, vaporizer plates or long-term vaporizers and also in moth papers, moth pads or other heat-independent vaporizer systems. Methods to control infectious diseases transmitted by insects (e.g.
  • Insecticidal compositions for application to fibers, fabric, knitgoods, nonwovens, netting material or foils and tarpaulins preferably comprise a mixture in- eluding the insecticide, optionally a repellent and at least one binder.
  • Suitable repellents for example are ⁇ , ⁇ -Diethyl-meta-toluamide (DEET), N,N-diethylphenylacetamide (DEPA), 1 -(3-cyclohexan-1 -yl-carbonyl)-2-methylpiperine, (2-hydroxymethylcyclohexyl) acetic acid lactone, 2-ethyl-1 ,3-hexandiol, indalone, Methylneodecanamide (MNDA), a pyrethroid not used for insect control such as ⁇ (+/-)-3-allyl-2-methyl-4-oxocyclopent-2- (+)-enyl-(+)-trans-chrysantemate (Esbiothrin), a repellent derived from or identical with plant extracts like limonene, eugenol, (+)-Eucamalol (1 ), (-)-l -epi-eucamalol or crude plant extracts from plants like
  • Suitable binders are selected for example from polymers and copolymers of vinyl esters of ali- phatic acids (such as such as vinyl acetate and vinyl versatate), acrylic and methacrylic esters of alcohols, such as butyl acrylate, 2-ethylhexylacrylate, and methyl acrylate, mono- and di-ethylenically unsaturated hydrocarbons, such as styrene, and aliphatic diens, such as butadiene.
  • vinyl esters of ali- phatic acids such as such as vinyl acetate and vinyl versatate
  • acrylic and methacrylic esters of alcohols such as butyl acrylate, 2-ethylhexylacrylate, and methyl acrylate
  • mono- and di-ethylenically unsaturated hydrocarbons such as styrene
  • aliphatic diens such as butadiene.
  • the impregnation of curtains and bednets is done in general by dipping the textile ma- terial into emulsions or dispersions of the insecticide or spraying them onto the nets.
  • the compound of formula (I) and its compositions can be used for protecting wooden materials such as trees, board fences, sleepers, etc. and buildings such as houses, outhouses, factories, but also construction materials, furniture, leathers, fibers, vinyl articles, electric wires and cables etc. from ants and/or termites, and for controlling ants and termites from doing harm to crops or human being (e.g. when the pests invade into houses and public facilities).
  • the compounds of formula (I) are applied not only to the surrounding soil surface or into the under-floor soil in order to protect wooden materials but it can also be applied to lumbered articles such as surfaces of the under-floor con- crete, alcove posts, beams, plywoods, furniture, etc., wooden articles such as particle boards, half boards, etc.
  • the ant controller of the present invention is applied to the crops or the surrounding soil, or is directly applied to the nest of ants or the like.
  • the compounds of formula (I) are also suitable for the treatment of seeds in order to protect the seed from insect pest, in particular from soil-living insect pests and the resulting plant' s roots and shoots against soil pests and foliar insects.
  • the compounds of formula (I) are particularly useful for the protection of the seed from soil pests and the resulting plant's roots and shoots against soil pests and foliar insects.
  • the protection of the resulting plant's roots and shoots is preferred. More preferred is the protection of resulting plant's shoots from piercing and sucking insects, wherein the protection from aphids is most preferred.
  • the present invention therefore comprises a method for the protection of seeds from insects, in particular from soil insects and of the seedling's roots and shoots from insects, in particular from soil and foliar insects, said method comprising contacting the seeds before sowing and/or after pregermination with a compound of the general formula (I) or a salt thereof.
  • a method wherein the plant's roots and shoots are protected, more preferably a method, wherein the plants shoots are protected from piercing and sucking insects, most preferably a method, wherein the plants shoots are protected from aphids.
  • seed embraces seeds and plant propagules of all kinds including but not limited to true seeds, seed pieces, suckers, corms, bulbs, fruit, tubers, grains, cuttings, cut shoots and the like and means in a preferred embodiment true seeds.
  • 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 present invention also comprises seeds coated with or containing the compound of formula (I).
  • coated with and/or containing generally signifies that the active ingredient is for the most part on the surface of the propagation product at the time of application, although a greater or lesser part of the ingredient may penetrate into the propagation product, depending on the method of application. When the said propagation product is (re)planted, it may absorb the active ingredient.
  • Suitable seed is seed of cereals, root crops, oil crops, vegetables, spices, ornamentals, for example seed of durum and other wheat, barley, oats, rye, maize (fodder maize and sugar maize / sweet and field corn), soybeans, oil crops, crucifers, cotton, sunflowers, bananas, rice, oilseed rape, turnip rape, sugar beet, fodder beet, eggplants, potatoes, grass, lawn, turf, fodder grass, tomatoes, leeks, pumpkin/squash, cabbage, iceberg lettuce, pepper, cucumbers, melons, Brassica species, melons, beans, peas, garlic, onions, carrots, tuberous plants such as potatoes, sugar cane, tobacco, grapes, petunias, geranium/pelargoniums, pansies and impatiens.
  • the compound of formula (I) may also be used for the treatment seeds from plants, which tolerate the action of herbicides or fungicides or insecticides owing to breeding, including genetic engineering methods.
  • the compound of formula (I) can be employed in treatment of seeds from plants, which are resistant to herbicides from the group consisting of the sulfonylureas, imidazolinones, glufosinate-ammonium or glyphosate-isopropylammonium and analogous active substances (see for example, EP-A-0242236, EP-A-242246) (WO
  • the compound of formula (I) can be used also for the treatment of seeds from plants, which have modified characteristics in comparison with existing plants consist, which can be generated for example by traditional breeding methods and/or the generation of mutants, or by recombinant procedures). For example, a number of cases have been described of recombinant modifications of crop plants for the purpose of modifying the starch synthesized in the plants (e.g.
  • WO 92/1 1376, WO 92/14827, WO 91/19806) or of transgenic crop plants having a modified fatty acid composition (WO 91/13972).
  • the seed treatment application of the compound of formula (I) is carried out by spraying or by dusting the seeds before sowing of the plants and before emergence of the plants.
  • compositions which are especially useful for seed treatment are e.g.:
  • a Soluble concentrates (SL, LS)
  • Conventional seed treatment formulations include for example flowable concentrates FS, solutions LS, powders for dry treatment DS, water dispersible powders for slurry treatment WS, water-soluble powders SS and emulsion ES and EC and gel formulation GF. These formulations can be applied to the seed diluted or undiluted. Application to the seeds is carried out before sowing, either directly on the seeds or after having pregerminated the latter
  • a FS formulation is used for seed treatment.
  • a FS formulation may comprise 1 -800 g/l of active ingredient, 1 -200 g/l Surfactant, 0 to 200 g/l antifreezing agent, 0 to 400 g/l of binder, 0 to 200 g/l of a pigment and up to 1 liter of a solvent, preferably water.
  • Especially preferred FS formulations of compounds of formula (I) for seed treatment usually comprise from 0.1 to 80% by weight (1 to 800 g/l) of the active ingredient, from 0.1 to 20 % by weight (1 to 200 g/l) of at least one surfactant, e.g. 0.05 to 5 % by weight of a wetter and from 0.5 to 15 % by weight of a dispersing agent, up to 20 % by weight, e.g. from 5 to 20 % of an anti-freeze agent, from 0 to 15 % by weight, e.g. 1 to 15 % by weight of a pigment and/or a dye, from 0 to 40 % by weight, e.g.
  • surfactant e.g. 0.05 to 5 % by weight of a wetter and from 0.5 to 15 % by weight of a dispersing agent, up to 20 % by weight, e.g. from 5 to 20 % of an anti-freeze agent, from 0 to 15 % by
  • a binder (sticker /adhesion agent), optionally up to 5 % by weight, e.g. from 0.1 to 5 % by weight of a thickener, optionally from 0.1 to 2 % of an anti-foam agent, and optionally a preservative such as a biocide, antioxidant or the like, e.g. in an amount from 0.01 to 1 % by weight and a filler/vehicle up to 100 % by weight.
  • a binder sticker /adhesion agent
  • a preservative such as a biocide, antioxidant or the like
  • Seed Treatment formulations may additionally also comprise binders and optionally colorants.
  • Binders can be added to improve the adhesion of the active materials on the seeds after treatment.
  • Suitable binders are homo- and copolymers from alkylene oxides like ethylene oxide or propylene oxide, polyvinylacetate, polyvinylalcohols, polyvinylpyrrolidones, and copolymers thereof, ethylene-vinyl acetate copolymers, acrylic homo- and copolymers, polyethyleneamines, polyethyleneamides and polyethyleneimines, polysaccharides like celluloses, tylose and starch, polyolefin homo- and copolymers like olefin/maleic anhydride copolymers, polyurethanes, polyesters, polystyrene homo and copolymers
  • colorants can be included in the formulation. Suitable colorants or dyes for seed treatment formulations are Rhodamin B, C.I. Pigment Red 1 12, C.I. Solvent Red 1 , pigment blue 15:4, pigment blue 15:3, pigment blue 15:2, pigment blue 15:1 , pigment blue 80, pigment yellow 1 , pigment yellow 13, pigment red 1 12, pigment red 48:2, pigment red 48:1 , pigment red 57:1 , pigment red 53:1 , pigment orange 43, pigment orange 34, pigment orange 5, pigment green 36, pigment green 7, pigment white 6, pigment brown 25, basic violet 10, basic violet 49, acid red 51 , acid red 52, acid red 14, acid blue 9, acid yellow 23, basic red 10, basic red 108.
  • gelling agent examples include carrageen (Satiagel ® )
  • the application rates of the compounds I are generally from 0.1 g to 10 kg per 100 kg of seed, preferably from 1 g to 5 kg per 100 kg of seed, more preferably from 1 g to 1000 g per 100 kg of seed and in particular from 1 g to 200 g per 100 kg of seed.
  • the invention therefore also relates to seed comprising a compound of the formula (I), or an agriculturally useful salt of I, as defined herein.
  • the amount of the compound I or the agriculturally useful salt thereof will in general vary from 0.1 g to 10 kg per 100 kg of seed, preferably from 1 g to 5 kg per 100 kg of seed, in particular from 1 g to 1000 g per 100 kg of seed. For specific crops such as lettuce the rate can be higher.
  • the compounds of formula (I) or the enantiomers or veterinary acceptable salts thereof are in particular also suitable for being used for combating parasites in and on animals.
  • An object of the present invention is therefore also to provide new methods to control parasites in and on animals.
  • Another object of the invention is to provide safer pesticides for animals.
  • Another object of the invention is further to provide pesticides for animals that may be used in lower doses than existing pesticides.
  • Another object of the invention is to provide pesticides for animals, which provide a long residual con- trol of the parasites.
  • the invention also relates to compositions containing a parasiticidally effective amount of compounds of formula (I) or the enantiomers or veterinarily acceptable salts thereof and an acceptable carrier, for combating parasites in and on animals.
  • the present invention also provides a method for treating, controlling, preventing and protecting animals against infestation and infection by parasites, which comprises orally, topically or parenterally administering or applying to the animals a parasiticidally effective amount of a compound of formula (I) or the enantiomers or veterinarily acceptable salts thereof or a composition comprising it.
  • the invention also provides a process for the preparation of a composition for treating, controlling, preventing or protecting animals against infestation or infection by parasites which comprises a parasiticidally effective amount of a compound of formula (I) or the enantiomers or veterinarily acceptable salts thereof or a composition comprising it.
  • Activity of compounds against agricultural pests does not suggest their suitability for control of endo- and ectoparasites in and on animals which requires, for example, low, non-emetic dosages in the case of oral application, metabolic compatibility with the animal, low toxicity, and a safe handling.
  • Compounds of formula (I) or the enantiomers or veterinarily acceptable salts thereof and compositions comprising them are preferably used for controlling and preventing infestations and infections animals including warm-blooded animals (including humans) and fish. They are for example suitable for controlling and preventing infestations and infections in mammals such as cattle, sheep, swine, camels, deer, horses, pigs, poultry, rabbits, goats, dogs and cats, water buffalo, donkeys, fallow deer and reindeer, and also in fur-bearing animals such as mink, chinchilla and raccoon, birds such as hens, geese, turkeys and ducks and fish such as fresh- and salt-water fish such as trout, carp and eels.
  • mammals such as cattle, sheep, swine, camels, deer, horses, pigs, poultry, rabbits, goats, dogs and cats, water buffalo, donkeys, fallow deer and reindeer
  • fur-bearing animals such
  • Compounds of formula (I) or the enantiomers or veterinarily acceptable salts thereof and compositions comprising them are preferably used for controlling and preventing infestations and infections in domestic animals, such as dogs or cats.
  • Infestations in warm-blooded animals and fish include, but are not limited to, lice, biting lice, ticks, nasal bots, keds, biting flies, muscoid flies, flies, myiasitic fly larvae, chig- gers, gnats, mosquitoes and fleas.
  • the compounds of formula (I) or the enantiomers or veterinarily acceptable salts thereof and compositions comprising them are suitable for systemic and/or non- systemic control of ecto- and/or endoparasites. They are active against all or some stages of development.
  • the compounds of formula (I) are especially useful for combating ectoparasites.
  • the compounds of formula (I) are especially useful for combating parasites of the following orders and species (e.g. as above previously listed in the target pests if not explicitly listed hereunder), respectively:
  • Anoplurida e.g. Haematopinus spp., Linognathus spp., Pediculus spp., Phtirus spp., and Solenopotes spp; Mallophagida (suborders Arnblycerina and Ischnocerina), e.g.
  • Trimenopon spp. Menopon spp., Trinoton spp., Bovicola spp., Werneckiella spp.,
  • Lepikentron spp. Trichodectes spp., and Felicola spp;
  • Roundworms Nematoda e.g. Wipeworms and Trichinosis (Trichosyringida), e.g.
  • Trichinellidae Trichinella spp.
  • Trichuridae Trichuris spp., Capillaria spp; Rhabditida, e.g. Rhabditis spp, Strongyloides spp., Helicephalobus spp,
  • Strongylida e.g. Strongylus spp., Ancylostoma spp., Necator americanus, Bunosto- mum spp. (Hookworm), Trichostrongylus spp., Haemonchus contortus., Ostertagia spp., Cooperia spp., Nematodirus spp., Dictyocaulus spp., Cyathostoma spp., Oe- sophagostomum spp., Stephanurus dentatus, Ollulanus spp., Chabertia spp., Stepha- nurus dentatus , Syngamus trachea, Ancylostoma spp., Uncinaria spp., Globocephalus spp., Necator spp., Metastrongylus spp., Muellerius capillaris, Protostrongylus spp., Angiostrongylus spp.,
  • Intestinal roundworms (Ascaridida), e.g. Ascaris lumbricoides, Ascaris suum, Ascaridia galli, Parascaris equorum, Enterobius vermicularis (Threadworm), Toxocara canis, Toxascaris leonine, Skrjabinema spp., and Oxyuris equi,
  • Ascaridida e.g. Ascaris lumbricoides, Ascaris suum, Ascaridia galli, Parascaris equorum, Enterobius vermicularis (Threadworm), Toxocara canis, Toxascaris leonine, Skrjabinema spp., and Oxyuris equi
  • Ascaridida e.g. Ascaris lumbricoides, Ascaris suum, Ascaridia galli, Parascaris equorum, Enterobius vermicularis (Threadworm), Toxocara canis, Toxascar
  • Camallanida e.g. Dracunculus medinensis (guinea worm)
  • Spirurida e.g. Thelazia spp. Wuchereria spp., Brugia spp., Onchocerca spp., Dirofilari spp. a, Dipetalonema spp., Setaria spp., Elaeophora spp., Spirocerca lupi, and Habro- nema spp;
  • Planarians (Plathelminthes):
  • Flukes e.g. Faciola spp., Fascioloides magna, Paragonimus spp., Dicro- coelium spp., Fasciolopsis buski, Clonorchis sinensis, Schistosoma spp., Trichobilhar- zia spp., Alaria alata, Paragonimus spp., and Nanocyetes spp,
  • Cercomeromorpha in particular Cestoda (Tapeworms), e.g. Diphyllobothrium spp., Tenia spp., Echinococcus spp., Dipylidium caninum, Multiceps spp., Hymenolepis spp.,
  • the compounds of formula (I) also are especially useful for combating endoparasites (roundworms nematoda, thorny headed worms and planarians).
  • Administration can be carried out both prophylactically and therapeutically.
  • Administra- tion of the active component(s) is carried out directly or in the form of suitable preparations, orally, topically/dermally or parenterally.
  • the term active component(s) as used above mean comprising at least one compound of formula (I) and eventually further active compound(s).
  • the compounds of formula (I) may be formulated as animal feeds, animal feed premixes, animal feed concentrates, pills, solutions, pastes, suspensions, drenches, gels, tablets, boluses and capsules.
  • the compounds of formula (I) may be administered to the animals in their drinking water.
  • the dosage form chosen should provide the animal with 0.01 mg/kg to 100 mg/kg of animal body weight per day of the formula (I) compound, preferably with 0.5 mg/kg to 100 mg/kg of animal body weight per day.
  • the compounds of formula (I) may be administered to animals parenterally, for example, by intraruminal, intramuscular, intravenous or subcutaneous injection.
  • the compounds of formula (I) may be dispersed or dissolved in a physiologically acceptable carrier for subcutaneous injection.
  • the compounds of formula (I) may be formulated into an implant for subcutaneous administration.
  • the compound of formula (I) may be transdermally administered to animals.
  • the dosage form chosen should provide the animal with 0.01 mg/kg to 100 mg/kg of animal body weight per day of the compound of formula (I).
  • the compounds of formula (I) may also be applied topically to the animals in the form of dips, dusts, powders, collars, medallions, sprays, shampoos, spot-on and pour-on formulations and in ointments or oil-in-water or water-in-oil emulsions.
  • dips and sprays usually contain 0.5 ppm to 5,000 ppm and preferably 1 ppm to 3,000 ppm of the compound of formula (I).
  • the compounds of formula (I) may be formulated as ear tags for animals, particularly quadrupeds such as cattle and sheep. Suitable preparations are:
  • Solutions such as oral solutions, concentrates for oral administration after dilution, solutions for use on the skin or in body cavities, pouring-on formulations, gels; - Emulsions and suspensions for oral or dermal administration; semi-solid preparations;
  • Solid preparations such as powders, premixes or concentrates, granules, pellets, tab- lets, boluses, capsules; aerosols and inhalants, and active component containing shaped articles.
  • compositions suitable for injection are prepared by dissolving the active ingredient in a suitable solvent and optionally adding further ingredients such as acids, bases, buffer salts, preservatives, and solubilizers.
  • the solutions are filtered and filled sterile.
  • Suitable solvents are physiologically tolerable solvents such as water, alkanols such as ethanol, butanol, benzyl alcohol, glycerol, propylene glycol, polyethylene glycols, N- methyl-pyrrolidone, 2-pyrrolidone, and mixtures thereof.
  • the active component(s) can optionally be dissolved in physiologically tolerable vege- table or synthetic oils which are suitable for injection.
  • Suitable solubilizers are solvents which promote the dissolution of the active component in the main solvent or prevent its precipitation.
  • examples are polyvinylpyrrolidone, polyvinyl alcohol, polyoxyethylated castor oil, and polyoxyethylated sorbitan ester.
  • Suitable preservatives are benzyl alcohol, trichlorobutanol, p-hydroxybenzoic acid es- ters, and n-butanol.
  • Oral solutions are administered directly. Concentrates are administered orally after prior dilution to the use concentration. Oral solutions and concentrates are prepared according to the state of the art and as described above for injection solutions, sterile procedures not being necessary.
  • Solutions for use on the skin are trickled on, spread on, rubbed in, sprinkled on or sprayed on.
  • Solutions for use on the skin are prepared according to the state of the art and according to what is described above for injection solutions, sterile procedures not being necessary.
  • parasiticidally effective amount means the amount of active ingredient needed to achieve an observable effect on growth, including the effects of necrosis, death, retardation, prevention, and removal, destruction, or otherwise diminishing the occurrence and activity of the target organism.
  • the parasiticidally effective amount can vary for the various compounds/compositions used in the invention.
  • a parasiticidally effective amount of the compositions will also vary according to the prevailing conditions such as desired parasiticidal effect and duration, target species, mode of application, and the like.
  • compositions which can be used in the invention can comprise generally from about 0.001 to 95% of the compound of formula (I).
  • Ready-to-use preparations contain the compounds acting against parasites, preferably ectoparasites, in concentrations of 10 ppm to 80 per cent by weight, preferably from 0.1 to 65 per cent by weight, more preferably from 1 to 50 per cent by weight, most preferably from 5 to 40 per cent by weight.
  • Preparations which are diluted before use contain the compounds acting against ectoparasites in concentrations of 0.5 to 90 per cent by weight, preferably of 1 to 50 per cent by weight.
  • the preparations comprise the compounds of formula (I) against endo- parasites in concentrations of 10 ppm to 2 per cent by weight, preferably of 0.05 to 0.9 per cent by weight, very particularly preferably of 0.005 to 0.25 per cent by weight.
  • compositions comprising the compounds of formula (I) are applied dermally / topically.
  • the topical application is conducted in the form of compound-containing shaped articles such as collars, medallions, ear tags, bands for fixing at body parts, and adhesive strips and foils.
  • solid formulations which release compounds of formula (I) in total amounts of 10 mg/kg to 300 mg/kg, preferably 20 mg/kg to 200 mg/kg, most preferably 25 mg/kg to 160 mg/kg body weight of the treated animal in the course of three weeks.
  • thermoplastic and flexible plastics as well as elastomers and thermoplastic elastomers are used.
  • Suitable plastics and elastomers are polyvinyl resins, polyurethane, polyacrylate, epoxy resins, cellulose, cellulose de- rivatives, polyamides and polyester which are sufficiently compatible with the compounds of formula (I).
  • a detailed list of plastics and elastomers as well as preparation procedures for the shaped articles is given e.g. in WO 03/086075.
  • Step 1 Methyl 4-(6-chloro-3-pyridyl)-4-oxo-butanoate
  • Step 1 .4 5-(6-chloro-3-pyridyl) pyrrolidin-2-one
  • Step 1 5-(6-chloro-3-pyridyl) pyrrolidine-2-thione
  • Step 1 .6 2-chloro-5-(5-methylsulfanyl-3,4-dihydro-2H-pyrrol-2-yl)pyridine
  • Step 1 2-(6-chloro-3-pyridyl)-N-isopropyl-3,4-dihydro-2H-pyrrol-5-amine
  • Step 1 .8 3-(6-chloro-3-pyridyl)-8-(dimethylamino)-5-oxo-6-phenyl-1 ,2,3,8- tetrahydroindolizin-4-ium-7-olate.
  • Step 2.4 2-chloro-5-(6-methylsulfanyl-2,3,4,5-tetrahydropyridin-2-yl)pyridine
  • Step 2.6 6-(6-chloro-3-pyridyl)-1 -methyl-4-oxo-3-phenyl-6,7,8,9-tetrahydropyrido[1 ,2- a]pyrimidin-5-ium-2-olate
  • Compounds can in general be characterized e.g. by coupled High Performance Liquid Chromatography / mass spectrometry (HPLC/MS), by 1 H-NMR and/or by their melting points.
  • HPLC/MS High Performance Liquid Chromatography / mass spectrometry
  • r.t. HPLC retention time (RT) in minutes; m/z of the [M+H]+, [M+Na]+ or [M+K]+ peaks.
  • Analytical HPLC column 2 Phenomenex Kinetex 1 ,7 ⁇ XB-C18 100A; 50 x 2,1 mm Elution: A: acetonitrile + 0.1 % trifluoroacetic acid (TFA) / water + 0.1 % trifluoroacetic acid (TFA) in a ratio of from 5:95 to 95:5 in 1.5 minutes at 50 °C.
  • the active compound is dissolved at the desired concentration in a mixture of 1 :1 (vohvol) distilled water : acetone.
  • the test solution is prepared at the day of use.
  • Test solutions are prepared in general at concentrations of 2500 ppm, 1000 ppm, 500 ppm, 300 ppm, 100 ppm and 30 ppm (wt/vol).
  • test unit For evaluating control of boll weevil (Anthonomus grandis) the test unit consisted of 96- well-microtiter plates containing an insect diet and 5-10 A. grandis eggs.
  • the compounds were formulated using a solution containing 75% v/v water and 25% v/v DMSO. Different concentrations of formulated compounds were sprayed onto the insect diet at 5 ⁇ , using a custom built micro atomizer, at two replications.
  • microtiter plates were incubated at about 25 + 1 °C and about 75 + 5 % relative humidity for 5 days. Egg and larval mortality was then visually assessed.
  • test unit For evaluating control of green peach aphid (Myzus persicae) through systemic means the test unit consisted of 96-well-microtiter plates containing liquid artificial diet under an artificial membrane.
  • the compounds were formulated using a solution containing 75% v/v water and 25% v/v DMSO. Different concentrations of formulated compounds were pipetted into the aphid diet, using a custom built pipetter, at two replications. After application, 5 - 8 adult aphids were placed on the artificial membrane inside the microtiter plate wells. The aphids were then allowed to suck on the treated aphid diet and incubated at about 23 + 1 °C and about 50 + 5 % relative humidity for 3 days. Aphid mortality and fecundity was then visually assessed.
  • Dichromothrips corbetti adults used for bioassay were obtained from a colony maintained continuously under laboratory conditions.
  • the test compound is diluted in a 1 :1 mixture of acetone:water (vohvol), plus 0.01 % vol/vol Al- kamuls ® EL 620 surfactant.
  • Thrips potency of each compound was evaluated by using a floral-immersion technique.
  • Plastic petri dishes were used as test arenas. All petals of individual, intact orchid flowers were dipped into treatment solution and allowed to dry. Treated flowers were placed into individual petri dishes along with about 20 adult thrips. The petri dishes were then covered with lids. All test arenas were held under continuous light and a temperature of about 28°C for duration of the assay. After 3 days, the numbers of live thrips were counted on each flower, and along inner walls of each petri dish. The percent mortality was recorded 72 hours after treatment.
  • Rice seedlings were cleaned and washed 24 hours before spraying.
  • the active compounds were formulated in 50:50 acetone:water (vohvol), and 0.1 % vol/vol surfactant (EL 620) was added.
  • Potted rice seedlings were sprayed with 5 ml test solution, air dried, placed in cages and inoculated with 10 adults. Treated rice plants were kept at about 28-29°C and relative humidity of about 50-60%. Percent mortality was recorded after 72 hours.
  • Rice seedlings were cleaned and washed 24 hours before spraying.
  • the active compounds were formulated in 50:50 acetone:water (vohvol) and 0.1 % vol/vol surfactant (EL 620) was added.
  • Potted rice seedlings were sprayed with 5 ml test solution, air dried, placed in cages and inoculated with 10 adults. Treated rice plants were kept at about 28-29°C and relative humidity of about 50-60%. Percent mortality was recorded after 72 hours.
  • compounds C-1 , C-6, C-24, C-28, C-29, C-42 and C-38 at 500 ppm showed over 75 % mortality in comparison with untreated controls.
  • Spider Mite (Tetranychus spp.)
  • the active compound is dissolved at the desired concentration in a mixture of 1 :1 (vohvol) distilled water : acetone.
  • the test solution is prepared at the day of use.
  • Potted cotton plants at two weeks of age were cleaned, air dried and inoculated with approximately 50 mites of various stages.
  • the potted plants are sprayed after the pest population has been recorded. Percent mortality is recorded 72 hours after treatment. In this test, compounds C-9 and C-42 at 500 ppm showed over 75 % mortality in comparison with untreated controls.
  • Tobacco budworm Heliothis virescens
  • test unit For evaluating control of tobacco budworm (Heliothis virescens) the test unit consisted of 96-well-microtiter plates containing an insect diet and 15-25 H. virescens eggs.
  • the compounds were formulated using a solution containing 75% v/v water and 25% v/v DMSO. Different concentrations of formulated compounds were sprayed onto the insect diet at 10 ⁇ , using a custom built micro atomizer, at two replications.
  • microtiter plates were incubated at about 28 + 1 °C and about 80 + 5 % relative humidity for 5 days. Egg and larval mortality was then visually assessed.
  • test unit For evaluating control of vetch aphid (Megoura viciae) through contact or systemic means the test unit consisted of 24-well-microtiter plates containing broad bean leaf disks.
  • the compounds were formulated using a solution containing 75% v/v water and 25% v/v DMSO. Different concentrations of formulated compounds were sprayed onto the leaf disks at 2.5 ⁇ , using a custom built micro atomizer, at two replications.
  • the leaf disks were air-dried and 5 - 8 adult aphids placed on the leaf disks inside the microtiter plate wells. The aphids were then allowed to suck on the treated leaf disks and incubated at about 23 + 1 °C and about 50 + 5 % relative humidity for 5 days. Aphid mortality and fecundity was then visually assessed.

Landscapes

  • Organic Chemistry (AREA)
  • Chemical & Material Sciences (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Health & Medical Sciences (AREA)
  • General Health & Medical Sciences (AREA)
  • Dentistry (AREA)
  • Environmental Sciences (AREA)
  • Zoology (AREA)
  • Wood Science & Technology (AREA)
  • Engineering & Computer Science (AREA)
  • Plant Pathology (AREA)
  • Pest Control & Pesticides (AREA)
  • Agronomy & Crop Science (AREA)
  • Veterinary Medicine (AREA)
  • General Chemical & Material Sciences (AREA)
  • Animal Behavior & Ethology (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Pharmacology & Pharmacy (AREA)
  • Tropical Medicine & Parasitology (AREA)
  • Public Health (AREA)
  • Nuclear Medicine, Radiotherapy & Molecular Imaging (AREA)
  • Medicinal Chemistry (AREA)
  • Pharmaceuticals Containing Other Organic And Inorganic Compounds (AREA)
  • Agricultural Chemicals And Associated Chemicals (AREA)
  • Nitrogen Condensed Heterocyclic Rings (AREA)
  • Nitrogen And Oxygen Or Sulfur-Condensed Heterocyclic Ring Systems (AREA)
  • Catching Or Destruction (AREA)

Abstract

The present invention relates to substituted pyrimidinium compounds of formula (I), to the stereoisomers, salts, tautomers and N-oxides thereof and to compositions comprising such compounds. The invention also relates to methods and uses of these substituted pyrimidinium compounds and of compositions thereof, for combating and controlling animal pests. Furthermore the invention relates also to pesticidal methods of applying such substituted pyrimidinium compounds. The substituted pyrimidinium compounds of the present invention are defined by the following general formula (I) wherein X, Y, Z, R1, R2, A and Het are defined as in the description.

Description

Substituted pyrimidinium compounds and derivatives for combating animal pests
The present invention relates to insecticidal substituted pyrimidinium compounds and/or to the compositions comprising such compounds for combating invertebrate pests. The invention also relates to pesticidal methods, to uses and to applications of substituted pyrimidinium compounds as described in the present invention and the stereoisomers, salts, tautomers and N-oxides thereof as well as compositions comprising them. Invertebrate pests and in particular insects, arthropods and nematodes destroy growing and harvested crops and attack wooden dwelling and commercial structures, thereby causing large economic loss to the food supply and to property. While a large number of pesticidal agents are known, due to the ability of target pests to develop resistance to said agents, there is an ongoing need for new agents for combating invertebrate pests such as insects, arachnids and nematodes. It is therefore an object of the present invention to provide compounds having a good pesticidal activity and showing a broad activity spectrum against a large number of different invertebrate pests, especially against difficult to control insects, arachnids and nematodes. It has been found that these objectives can be achieved by substituted pyrimidinium compounds of the general formula (I), as defined below, including their stereoisomers, their salts, in particular their agriculturally or veterinary acceptable salts, their tautomers and their N-oxides.
Therefore, in a first aspect the present invention provides substituted pyrimidinium compounds of formula (I) or a composition comprising at least one substituted pyrimidinium compound of formula (I)
Figure imgf000002_0001
wherein
X, Y are each independently O or S;
Z is a direct bond, O, S(0)m, NRb, C(RaRaa)0, C(=X1), C(=X1)Y1,or Y C(=X1); is O, S, or NRb;
is O, S, or NRC;
A is CH or N and, wherein the nitrogen of the pyrimidinium ring taken together with the contiguous linking carbon atom and A as depicted in formula (I), form a four- to seven-membered ring, wherein each remaining ring member is selected from carbon atoms and up to 3 heteroatoms independently selected from up to 2 O, up to 2 S, and up to 3 N(RC)P, wherein up to 2 carbon atom ring members are independently selected from C(=0) and C(=S), and the sulfur atom ring members are independently selected from S(=0)m, wherein each ring may be substituted with up to 3 Ra;
is a three- to ten-membered heterocyclic ring or a seven- to eleven- membered heterocyclic ring system, each ring or ring system member selected from carbon atoms and up to 4 heteroatoms independently selected from up to 2 O, up to 2 S, and up to 4 N(RC)P, wherein up to 3 carbon atom ring members are independently selected from C(=0) and C(=S) and the sulfur atom ring members are independently selected from S(=0)0(=NRb)q, each ring or ring system optionally substituted with up to 5 Ra;
o, q are each independently 0, 1 or 2, provided that the sum (o + q) is 0, 1 or 2 for each ring;
is hydrogen, Ci-Cs-alkyl, C2-C8-alkenyl, C2-C8-alkynyl, C3-Cio-cycloalkyl, C4- Cio-cycloalkenyl, Cs-C-u-cycloalkylcycloalkyl or R1 may form a three- to eleven-membered saturated, or partially unsaturated or aromatic carbo-or heterocyclic ring or ring system, which may contain 1 to 4 heteroatoms selected from N(Rc)p, O, and S, wherein S may be oxidized, and wherein the aforementioned groups and the carbo- or heterocyclic rings system may be unsubstituted, partially or fully substituted by Ra; or
R1 is C(=0)Rb, C(=0)ORe, NRbRc, C(=0)NR Rc, C(=S)NR Rc, S02NR Rc, OC(=0)Rc, OC(=0)ORe, OC(=0)NR Re, N(Rc)C(=0)Rc, N(Rc)C(=0)ORe, N(Rc)C(=0)NR Rc, NRcS02R , NRcS02NR Rc, Si(Rd)3, C(=NRC)RC,
C(=NORc)Rc', C(=NNR Rc)Rc, C(=NN(C(=0)R )Rc)Rc
Figure imgf000003_0001
Ra is each independently halogen, Ci-C6-alkyl, Ci-C6-haloalkyl, C1-C6- alkoxy, Ci-C6-haloalkoxy, C2-C4-alkenyl, C2-C4-alkynyl, C3-C6- cycloalkyl, CN, ORc, NRbRc, N02, C(=0)(0)PRc, OC(=0)(0)PRe, C(=0)NR Rc, OC(=0)NR Re, NR C(=0)(0)PRe , NRbC(=0)NRbRc, C(=S)NR Rc, S(0)mR , S02NR Rc, OS02Rc, OS02NR Rc, NR S02Rc, NRbS02NRbRc, N=S(=0)PRcRc, S(=0)0(=NR )qRc, SF5, OCN, SCN, Si(Rd)3 or a three- to six-membered saturated, or partially unsaturated or aromatic carbo- or heterocyclic ring, which may contain 1 to 3 heteroatoms selected from N-(RC)P, O, and S which may be oxidized, and wherein the aforementioned groups and the carbo- or heterocyclic ring may be partially or fully substituted by Raa, or
two geminally bound groups Ra together may form a group selected from =0, =S, =CR Rc, =NRC, =NORc, and =NNRCRC;
Raa is each independently halogen, Ci-C6-alkyl, C1-C6- haloalkyl, Ci-C6-alkoxy or Ci-C6-haloalkoxy;
Rb is each independently hydrogen, Ci-C6-alkyl, Ci-C6-haloalkyl, C1-C6- alkoxy, Ci-C6-haloalkoxy or a three- to six-membered saturated, or partially unsaturated or aromatic carbo- or heterocyclic ring, which may contain 1 to 3 heteroatoms selected from N(RC)P, O, and S, wherein S may be oxidized and which carbo- or heterocyclic ring may be partially or fully substituted by Raa;
Rc is each independently hydrogen, Ci-C4-alkyl, Ci-C4-haloalkyl, C1-C4- alkylcarbonyl, C1-C6 cycloalkyl, or a three- to six-membered saturated, partially unsaturated or aromatic carbo- or heterocyclic ring, which may contain 1 to 3 heteroatoms selected from N(Raa)p, O and S, wherein S may be oxidized and wherein the carbo- or heterocyclic ring may be partially or fully substituted by Raa;
wherein two geminally bound groups RbRb, RcRb or RCRC together with the atom to which they are bound, may form a 3-, 4-, 5-, 6- or 7- mem- bered saturated, partially unsaturated or aromatic carbo- or heterocyclic ring, which may contain 1 to 2 heteroatoms or heteroatoms groups selected from N, O, S, NO, SO and SO2 and wherein the carbo- or heterocyclic ring may be partially or fully substituted by R3;
Rd is each independently hydrogen, phenyl, Ci-C6-alkyl, C2-C6-alkenyl, C2-C6-alkynyl, Cs-Cs-cycloalkyl, or Ci-C6-alkoxyalkyl, wherein the above mentioned groups may be substituted by one or more halogen;
Re is each independently, Ci-C4-alkyl, Ci-C4-haloalkyl, C1-C4- alkylcarbonyl, C1-C6 cycloalkyl, or a three- to six-membered saturated, partially unsaturated or aromatic carbo- or heterocyclic ring, which may contain 1 to 3 heteroatoms selected from N(Raa)p, O and S, wherein S may be oxidized and wherein the carbo- or heterocyclic ring may be partially or fully substituted by Raa;
n is 0, 1 or 2;
m is 0, 1 , or 2;
p is O or l ;
is H, halogen, CN, Ci-Cs alkyl, C2-C8 alkenyl, C2-C8 alkynyl, C3-C10 cycloalkyl, C4-C10 alkylcycloalkyl, C4-C10 cycloalkylalkyl, C6-C14 cycloalkylcycloal- kyl, C5-C10 alkylcycloalkylalkyl, or C3-C6 cycloalkenyl, wherein the aforementioned groups may be unsubstituted, partially, or fully substituted with R2a, or R2 may form a carbo-or heterocyclic three- to ten-membered ring or a seven- to eleven-membered rings system, which ring or ring system may be saturated, partially unsaturated, or aromatic, and which ring or ring system may contain 1 to 4 heteroatoms selected from N(RC)P, O, and S, wherein S may be oxidized, and wherein the carbo- or heterocyclic ring or rings system may be unsubstituted, partially, or fully substituted by R2a;
with the proviso that if R2 is halogen or CN, then Z is a direct bond;
R2a is each independently halogen, Ci-C6-alkyl, Ci-C6-haloalkyl, C1-C6- alkoxy, Ci-C6-haloalkoxy, C2-C4-alkenyl, C2-C4-alkynyl, C3-C6- cycloalkyl, CN, ORc, NRbRc, N02, C(=0)(0)PRc, OC(=0)(0)PRe, C(=0)NR Rc, OC(=0)NR Re, NR C(=0)(0)PRe , NRbC(=0)NRbRc, C(=S)NR Rc, S(0)mR , S02NR Rc, OS02Rc, OS02NR Rc, NR S02Rc, NR S02NR Rc, SF5, OCN, SCN, Si(Rd)3, C(=N(0)PR ) R ,
C(=NNRbRc)Rb, C(=NN(C(=0)0PRc)Rc)R , ON=CR Rc, ONRbRc,
Figure imgf000005_0001
OP(=X2)(ORc)2, N=CRbRc, NRbN=CRbRc, NRbNRbRc, NRbC(=S)NRbR , NRbC(=NRb)NRbRc, N RbN RbC(=X2) N RbRc, NR NR S02NR Rc, N=S(=0)pRcRc, or a three- to six-membered saturated, or partially unsaturated or aromatic carbo- or heterocyclic ring, which may contain 1 to 3 heteroatoms selected from N-(RC)P, O, and S, wherein S may be oxidized, and wherein the aforementioned groups and the carbo- or heterocyclic ring may be partially or fully substituted by R2aa;or
two geminally bound groups R2a together may form a group selected from =0, =S, =CR Rc, =NRC, =NORc, and =NNRCRC;
R2aa is each independently halogen, Ci-C6-alkyl, Ci-C6-haloalkyl, Ci C6-alkoxy, Ci-C6-haloalkoxy, C2-C4-alkenyl, C2-C4-alkynyl, C3- Ce-cycloalkyl, CN, ORc, NRbRc, N02, C(=0)(0)PRc,
OC(=0)(0)PRe, C(=0)NR Rc, OC(=0)NR Re, NR C(=0)(0)PRe NRbC(=0)NRbRc, C(=S)NR Rc, S(0)mR , S02NR Rc, OS02Rc, OS02NR Rc, NR S02Rc, NRbS02NRbRc, SF5, OCN, SCN, Si(Rd)3, C(=N(0)PR )R , C(=NNRbRc)Rb,
C(=NN(C(=0)0PRc)R )R , ON=CR Rc, ONRbRc,
Figure imgf000005_0002
OP(=X2)(0PRc)R , OP(=X2)(ORc)2, N=CRbRc, NRbN=CRbRc, NRbNRbRc, NRbC(=S)NRbRc, NRbC(=NRb)NRbRc, NR "
NR C(=X2)NR Rc, N RbN RbS02N RbRc, or N=S(=0)PRcRc, or two geminally bound groups R2aa together may form a group selected from =0, =S,=CR Rc, =NRC, =NORc, and =NNRCRC;
X2 is independently O or S;
is each independently halogen, Ci-C6-alkyl, Ci-C6-haloalkyl, C1-C6- alkoxy, Ci-C6-haloalkoxy, C2-C4-alkenyl, C2-C4-alkynyl, C3-C6- cycloalkyl, CN, ORc, NRbRc, N02, C(=0)(0)PRc, OC(=0)(0)PRe, C(=0)NR Rc, OC(=0)NR Re, NR C(=0)(0)PRe , NRbC(=0)NRbRc, C(=S)NR Rc, S(0)mR , S02NR Rc, OS02Rc, OS02NR Rc, NR S02Rc, NRbS02NRbRc, SF5, OCN, SCN, Si(Rd)3, C(=N(0)PR )R ,
C(=NNRbRc)Rb, C(=NN(C(=0)0PRc)R )R , ON=CR Rc, ONRbRc,
Figure imgf000005_0003
OP(=X2)(ORc)2, N=CRbRc, NRbN=CRbRc, NRbNRbRc, NRbC(=S)NRbR , NRbC(=NRb)NRbRc, N RbN RbC(=X2) N RbRc, N RbN RbS02N RbRc, or N=S(=0)PRcRc, or
two geminally bound groups R3 together may form a group selected from =0, =S, =CR Rc, =NRC, =NORc, and =NNRCRC; and/or stereoisomer or agriculturally or veterinary acceptable salts or tautomers or N- oxides thereof. The substituted pyrimidinium compounds of the formula (I), and their agriculturally acceptable salts are highly active against animal pest, i.e. harmful arthropodes and nematodes, especially against difficult to control insects and acaridae. Moreover, the present invention relates to and includes the following embodiments: compositions comprising at least one compound of formula (I) as defined above; agricultural and veterinary compositions comprising an amount of at least one compound of formula (I) or an enantiomer, diasteromer or salt thereof as defined above;
- a method for combating invertebrate pests, infestation, or infection by invertebrate pests, which method comprises contacting said pest or its food supply, habitat or breeding grounds with a pesticidally effective amount of at least one compound of formula (I) as defined above or a composition thereof;
a method for controlling invertebrate pests, infestation, or infection by inverte- brate pests, which method comprises contacting said pest or its food supply, habitat or breeding grounds with a pesticidally effective amount of at least one compound of formula (I) as defined above or a composition comprising at least one compound of formula (I);
a method for preventing or protecting against invertebrate pests comprising con- tacting the invertebrate pests, or their food supply, habitat or breeding grounds with a substituted pyrimidinium compounds of the general formula (I) as defined above or a composition comprising at least one compound of formula (I) as defined above or a composition comprising at least one compound of formula (I);
a method for protecting crops, plants, plant propagation material and/or growing plants from attack or infestation by invertebrate pests comprising contacting or treating the crops, plants, plant propagation material and growing plants, or soil, material, surface, space, area or water in which the crops, plants, plant propagation material is stored or the plant is growing, with a pesticidally effective amount of at least one compound of formula (I) as defined above or a composition comprising at least one com- pound of formula (I);
a non-therapeutic method method for treating animals infested or infected by parasites or preventing animals of getting infected or infested by parasites or protecting animals against infestation or infection by parasites which comprises orally, topically or parenterally administering or applying to the animals a parasiticidally effective amount of a compound of formula (I) as defined above or a composition comprising at least one compound of formula (I);
a method for treating, controlling, preventing or protecting animals against infestation or infection by parasites by administering or applying orally, topically or parenterally to the animals a substituted pyrimidinium compound of the general formula (I) as defined above or a composition comprising at least one compound of formula (I);
seed comprising a compound of formula (I) as defined above, in an amount of from 0.1 g to 10 kg per 100 kg of seed; the use of the compounds of formula (I) as defined above for protecting growing plants or plant propagation material from attack or infestation by invertebrate pests; the use of compounds of formula (I) or the enantiomers, diastereomers or veterinary acceptable salts thereof for combating parasites in and on animals;
- a process for the preparation of a veterinary composition for treating, controlling, preventing or protecting animals against infestation or infection by parasites which comprises adding a parasiticidally effective amount of an compound of formula (I) or the enantiomers, diastereomers and/or veterinary acceptable salt thereof to a carrier composition suitable for veterinary use;
- the use of a compound of formula (I) or the enantiomers, diastereomers and/or veterinary acceptable salt thereof for the preparation of a medicament for treating, controlling, preventing or protecting animals against infestation or infection by parasites.
All the compounds of the present invention including if applicable their stereoisomers, their tautomers, their salts or their N-oxides as well as compositions thereof are particularly useful for controlling invertebrate pests, in particular for controlling arthropods and nematodes and especially insects. Therefore, the invention relates to the use of a compound as disclosed in the present invention, for combating or controlling invertebrate pests, in particular invertebrate pests of the group of insects, arachnids or nema- todes.
The term "compound(s) according to the invention" or "compound(s) of formula (I)" as used in the present invention refers to and comprises the compound(s) as defined herein and/or stereoisomer(s), salt(s), tautomer(s) or N-oxide(s) thereof. The term "compound(s) of the present invention" is to be understood as equivalent to the term "compound(s) according to the invention", therefore also comprising stereoisomer(s), salt(s), tautomer(s) or N-oxide(s) of compounds of formula (I).
The term "composition(s) according to the invention" or "composition(s) of the present invention" encompasses composition(s) comprising at least one compound of formula (I) according to the invention as defined above, therefore also including a stereoisomer, an agriculturally or veterinary acceptable salt, tautomer or an N-oxide of the compounds of formula (I).
The substituted pyrimidinium compounds of formula (I) according to the present invention have not yet been described for pesticidal uses or pesticidal applications in agricul- tural industry or veterinary practice.
Heterocyclic substituted pyridinium derivatives and their use as pesticides have been disclosed in WO 2009/099929 as well as in WO 201 1/017347 and in WO 201 1/017351. However, the particularly substituted pyrimidinium compoundsof formula (I) with the characteristic substitution pattern as defined in the present invention have not yet been described.
Depending on the substitution pattern, the compounds of the formula (I) may have one or more centers of chirality, in which case they are present as mixtures of enantiomers or diastereomers. The invention provides both the single pure enantiomers or pure dia- stereomers of the compounds of formula (I), and their mixtures and the use according to the invention of the pure enantiomers or pure diastereomers of the compound of formula (I) or its mixtures. Suitable compounds of the formula (I) also include all possi- ble geometrical stereoisomers (cis/trans isomers) and mixtures thereof. Cis/trans isomers may be present with respect to an alkene, carbon-nitrogen double-bond or amide group. The term "stereoisomer(s)" encompasses both optical isomers, such as enantiomers or diastereomers, the latter existing due to more than one center of chirality in the molecule, as well as geometrical isomers (cis/trans isomers). The present invention relates to every possible stereoisomer of the compounds of formula (I), i.e. to single enantiomers or diastereomers, as well as to mixtures thereof.
Depending on the substitution pattern, the compounds of the formula (I) may be present in the form of their tautomers. Hence the invention also relates to the tautomers of the formula (I) and the stereoisomers, salts, tautomers and N-oxides of said tautomers. The compounds of the present invention may be amorphous or may exist in one or more different crystalline states (polymorphs) or modifications which may have a different macroscopic properties such as stability or show different biological properties such as activities. The present invention includes both amorphous and crystalline compounds of the formula (I), mixtures of different crystalline states or modifications of the respective compound I, as well as amorphous or crystalline salts thereof.
Salts of the compounds of the formula (I) are preferably agriculturally and/or veterinary acceptable salts. They can be formed in a customary method, e.g. by reacting the compound with an acid of the anion in question if the compound of formula (I) has a basic functionality or by reacting an acidic compound of formula (I) with a suitable base.
Suitable agriculturally or veterinary useful salts are especially the salts of those cations or the acid addition salts of those acids whose cations and anions, respectively, do not have any adverse effect on the action of the compounds according to the present invention. Suitable cations are in particular the ions of the alkali metals, preferably lithi- urn, sodium and potassium, of the alkaline earth metals, preferably calcium, magnesium and barium, and of the transition metals, preferably manganese, copper, zinc and iron, and also ammonium (NhV) and substituted ammonium in which one to four of the hydrogen atoms are replaced by Ci-C4-alkyl, Ci-C4-hydroxyalkyl, Ci-C4-alkoxy, C1-C4- alkoxy-Ci-C4-alkyl, hydroxy-Ci-C4-alkoxy-Ci-C4-alkyl, phenyl or benzyl. Examples of substituted ammonium ions comprise methylammonium, isopropylammonium, dime- thylammonium, diisopropylammonium, trimethylammonium, tetramethylammonium, tetraethylammonium, tetrabutylammonium, 2-hydroxyethylammonium, 2-(2- hydroxyethoxy)ethyl-ammonium, bis(2-hydroxyethyl)ammonium, benzyltrime- thylammonium and benzyltriethylammonium, furthermore phosphonium ions, sulfonium ions, preferably tri(Ci-C4-alkyl)sulfonium, and sulfoxonium ions, preferably tri(Ci-C4- alkyl)sulfoxonium.
Anions of useful acid addition salts are primarily chloride, bromide, fluoride, hydrogen sulfate, sulfate, dihydrogen phosphate, hydrogen phosphate, phosphate, nitrate, hy- drogen carbonate, carbonate, hexafluorosilicate, hexafluorophosphate, benzoate, and the anions of Ci-C4-alkanoic acids, preferably formate, acetate, propionate and butyr- ate. They can be formed by reacting the compounds of the formulae I with an acid of the corresponding anion, preferably of hydrochloric acid, hydrobromic acid, sulfuric acid, phosphoric acid or nitric acid.
The term " N-oxide" includes any compound of the present invention which has at least one tertiary nitrogen atom that is oxidized to an N-oxide moiety.
The organic moieties groups mentioned in the above definitions of the variables are - like the term halogen - collective terms for individual listings of the individual group members. The prefix Cn-Cm indicates in each case the possible number of carbon atoms in the group.
"Halogen" will be taken to mean fluoro, chloro, bromo and iodo.
The term "partially or fully halogenated" will be taken to mean that 1 or more, e.g. 1 , 2, 3, 4 or 5 or all of the hydrogen atoms of a given radical have been replaced by a halogen atom, in particular by fluorine or chlorine.
The term "Cn-Cm-alkyl" as used herein (and also in Cn-Cm-alkylamino, di-Cn-Cm- alkylamino, Cn-Cm-alkylaminocarbonyl, di-(Cn-Cm-alkylamino)carbonyl, Cn-Cm-alkylthio, Cn-Cm-alkylsulfinyl and Cn-Cm-alkylsulfonyl) refers to a branched or unbranched satu- rated hydrocarbon group having n to m, e.g. 1 to 10 carbon atoms, preferably 1 to 6 carbon atoms, for example methyl, ethyl, propyl, 1-methylethyl, butyl, 1 -methylpropyl, 2-methylpropyl, 1 ,1 -dimethylethyl, pentyl, 1 -methylbutyl, 2-methylbutyl, 3-methylbutyl, 2,2-dimethylpropyl, 1 -ethylpropyl, hexyl, 1 ,1 -dimethylpropyl, 1 ,2-dimethylpropyl, 1 - methylpentyl, 2-methylpentyl, 3-methylpentyl, 4-methylpentyl, 1 ,1 -dimethylbutyl, 1 ,2- dimethylbutyl, 1 ,3-dimethylbutyl, 2,2-dimethylbutyl, 2,3-dimethylbutyl, 3,3-dimethylbutyl, 1 -ethylbutyl, 2-ethylbutyl, 1 ,1 ,2-trimethylpropyl, 1 ,2,2-trimethylpropyl, 1 -ethyl-1 - methylpropyl, 1 -ethyl-2-methylpropyl, heptyl, octyl, 2-ethylhexyl, nonyl and decyl and their isomers. Ci-C4-alkyl means for example methyl, ethyl, propyl, 1 -methylethyl, butyl,
1 - methylpropyl, 2-methylpropyl or 1 ,1 -dimethylethyl.
The term "Cn-Cm-haloalkyl" as used herein (and also in Cn-Cm-haloalkylsulfinyl and Cn- Cm-haloalkylsulfonyl) refers to a straight-chain or branched alkyl group having n to m carbon atoms, e.g. 1 to 10 in particular 1 to 6 carbon atoms (as mentioned above), where some or all of the hydrogen atoms in these groups may be replaced by halogen atoms as mentioned above, for example Ci-C4-haloalkyl, such as chloromethyl, bro- momethyl, dichloromethyl, trichloromethyl, fluoromethyl, difluoromethyl, trifluoromethyl, chlorofluoromethyl, dichlorofluoromethyl, chlorodifluoromethyl, 1 -chloroethyl, 1 - bromoethyl, 1 -fluoroethyl, 2-fluoroethyl, 2,2-difluoroethyl, 2,2,2-trifluoroethyl, 2-chloro-
2- fluoroethyl, 2-chloro-2,2-difluoroethyl, 2,2-dichloro-2-fluoroethyl, 2,2,2-trichloroethyl, pentafluoroethyl and the like. The term Ci-Cio-haloalkyl in particular comprises C1-C2- fluoroalkyl, which is synonym with methyl or ethyl, wherein 1 , 2, 3, 4 or 5 hydrogen atoms are substituted by fluorine atoms, such as fluoromethyl, difluoromethyl, trifluoromethyl, 1 -fluoroethyl, 2-fluoroethyl, 2,2-difluoroethyl, 2,2,2-trifluoroethyl and pentafluo- romethyl. Similarly, "Cn-Cm-alkoxy" and "Cn-Cm-alkylthio" (or Cn-Cm-alkylsulfenyl, respectively) refer to straight-chain or branched alkyl groups having n to m carbon atoms, e.g. 1 to 10, in particular 1 to 6 or 1 to 4 carbon atoms (as mentioned above) bonded through oxygen (or sulfur linkages, respectively) at any bond in the alkyl group. Examples in- elude Ci-C4-alkoxy such as methoxy, ethoxy, propoxy, isopropoxy, butoxy, sec-butoxy, isobutoxy and tert-butoxy, further Ci-C4-alkylthio such as methylthio, ethylthio, propylthio, isopropylthio, and n-butylthio.
Accordingly, the terms "Cn-Cm-haloalkoxy" and "Cn-Cm-haloalkylthio" (or Cn-Cm- haloalkylsulfenyl, respectively) refer to straight-chain or branched alkyl groups having n to m carbon atoms, e.g. 1 to 10, in particular 1 to 6 or 1 to 4 carbon atoms (as mentioned above) bonded through oxygen or sulfur linkages, respectively, at any bond in the alkyl group, where some or all of the hydrogen atoms in these groups may be replaced by halogen atoms as mentioned above, for example Ci-C2-haloalkoxy, such as chloromethoxy, bromomethoxy, dichloromethoxy, trichloromethoxy, fluoromethoxy, difluoromethoxy, trifluoromethoxy, chlorofluoromethoxy, dichlorofluoromethoxy, chloro- difluoromethoxy, 1 -chloroethoxy, 1 -bromoethoxy, 1 -fluoroethoxy, 2-fluoroethoxy, 2,2- difluoroethoxy, 2,2,2-trifluoroethoxy, 2-chloro-2-fluoroethoxy, 2-chloro-2,2- difluoroethoxy, 2,2-dichloro-2-fluoroethoxy, 2,2,2-trichloroethoxy and pentafluoroeth- oxy, further Ci-C2-haloalkylthio, such as chloromethylthio, bromomethylthio, dichloro- methylthio, trichloromethylthio, fluoromethylthio, difluoromethylthio, trifluoromethylthio, chlorofluoromethylthio, dichlorofluoromethylthio, chlorodifluoromethylthio, 1 - chloroethylthio, 1 -bromoethylthio, 1 -fluoroethylthio, 2-fluoroethylthio, 2,2- difluoroethylthio, 2,2,2-trifluoroethylthio, 2-chloro-2-fluoroethylthio, 2-chloro-2,2- difluoroethylthio, 2,2-dichloro-2-fluoroethylthio, 2,2,2-trichloroethylthio and pentafluoro- ethylthio and the like. Similarly the terms Ci-C2-fluoroalkoxy and Ci-C2-fluoroalkylthio refer to Ci-C2-fluoroalkyl which is bound to the remainder of the molecule via an oxygen atom or a sulfur atom, respectively.
The term "C2-Cm-alkenyl" as used herein intends a branched or unbranched unsaturated hydrocarbon group having 2 to m, e.g. 2 to 10 or 2 to 6 carbon atoms and a double bond in any position, such as ethenyl, 1 -propenyl, 2-propenyl, 1 -methyl-ethenyl, 1 - butenyl, 2-butenyl, 3-butenyl, 1 -methyl-1 -propenyl, 2-methyl-1 -propenyl, 1 -methyl-2- propenyl, 2-methyl-2-propenyl, 1 -pentenyl, 2-pentenyl, 3-pentenyl, 4-pentenyl, 1 - methyl-1 -butenyl, 2-methyl-1 -butenyl, 3-methyl-1 -butenyl, 1 -methyl-2-butenyl, 2-methyl- 2-butenyl, 3-methyl-2-butenyl, 1 -methyl-3-butenyl, 2-methyl-3-butenyl, 3-methyl-3- butenyl, 1 ,1 -dimethyl-2-propenyl, 1 ,2-dimethyl-1 -propenyl, 1 ,2-dimethyl-2-propenyl, 1 - ethyl-1 -propenyl, 1 -ethyl-2-propenyl, 1 -hexenyl, 2-hexenyl, 3-hexenyl, 4-hexenyl, 5- hexenyl, 1 -methyl-1 -pentenyl, 2-methyl-1 -pentenyl, 3-methyl-1 -pentenyl, 4-methyl-1 - pentenyl, 1 -methyl-2-pentenyl, 2-methyl-2-pentenyl, 3-methyl-2-pentenyl, 4-methyl-2- pentenyl, 1 -methyl-3-pentenyl, 2-methyl-3-pentenyl, 3-methyl-3-pentenyl, 4-methyl-3- pentenyl, 1 -methyl-4-pentenyl, 2-methyl-4-pentenyl, 3-methyl-4-pentenyl, 4-methyl-4- pentenyl, 1 ,1 -dimethyl-2-butenyl, 1 ,1 -dimethyl-3-butenyl, 1 ,2-dimethyl-1 -butenyl, 1 ,2- dimethyl-2-butenyl, 1 ,2-dimethyl-3-butenyl, 1 ,3-dimethyl-1 -butenyl, 1 ,3-dimethyl-2- butenyl, 1 ,3-dimethyl-3-butenyl, 2,2-dimethyl-3-butenyl, 2, 3-dimethyl-1 -butenyl, 2,3- dimethyl-2-butenyl, 2,3-dimethyl-3-butenyl, 3,3-dimethyl-1 -butenyl, 3,3-dimethyl-2- butenyl, 1 -ethyl-1 -butenyl, 1 -ethyl-2-butenyl, 1 -ethyl-3-butenyl, 2-ethyl-1 -butenyl, 2- ethyl-2-butenyl, 2-ethyl-3-butenyl, 1 ,1 ,2-trimethyl-2-propenyl, 1 -ethyl-1 -methyl-2- propenyl, 1 -ethyl-2-methyl-1 -propenyl and 1 -ethyl-2-methyl-2-propenyl.
The term "C2-Cm-alkynyl" as used herein refers to a branched or unbranched unsaturated hydrocarbon group having 2 to m, e.g. 2 to 10 or 2 to 6 carbon atoms and containing at least one triple bond, such as ethynyl, propynyl, 1 -butynyl, 2-butynyl, and the like.
The term "Cn-Cm-alkoxy-Cn-Cm-alkyl" as used herein refers to alkyl having n to m car- bon atoms, e.g. like specific examples mentioned above, wherein one hydrogen atom of the alkyl radical is replaced by an Cn-Cm-alkoxy group; wherein the value of n and m of the alkoxy group are independently chosen from that of the alkyl group .
The suffix " -carbonyl" in a group or " C(=0)" denotes in each case that the group is bound to the remainder of the molecule via a carbonyl C=0 group. This is the case e.g. in alkylcarbonyl, haloalkylcarbonyl, aminocarbonyl, alkylaminocarbonyl, dialkyla- minocarbonyl, alkoxycarbonyl, haloalkoxycarbonyl.
The term "aryl" as used herein refers to a mono-, bi- or tricyclic aromatic hydrocarbon radical such as phenyl or naphthyl, in particular phenyl (also referred as to C6H5 as subsitituent).
The term "ring system" denotes two or more directly connected rings.
The term "C3-Cm-cycloalkyl" as used herein refers to a monocyclic ring of 3- to m- membered saturated cycloaliphatic radicals, e.g. cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, cycloheptyl, cyclooctyl and cyclodecyl.
The term "alkylcycloalkyl" denotes as well as the term " alkyl which may be substituted by cycloalkyi" an alkyl group which is substituted by a cycloalkyi ring, wherein alkyl and cycloakyl are as herein defined.
The term "cycloalkylalkyl" denotes as well as the term " cycloalkyi which may be substituted by alkyl" a cycloalkyi ring which is substituted by an alkyl group, wherein alkyl and cycloakyl are as herein defined.
The term "a I kyl cy cl oa I ky I a I ky I" denotes as well as the term " alkylcycloalkyl which may be substituted by alkyl" an alkylcycloalkyl group which is substituted by an alkyl, wherein alkyl and alkylcycloakyl are as herein defined.
The term " C3-Cm-cycloalkenyl" as used herein refers to a monocyclic ring of 3- to m- membered partially unsaturated cycloaliphatic radicals.
The term "cycloalkylcycloalkyi" denotes as well as the term " cycloalkyi which may be substituted by cycloalkyi" a cycloalkyi substitution on another cycloalkyi ring, wherein each cycloalkyi ring independently has from 3 to 7 carbon atom ring members and the cycloalkyls are linked through one single bond or have one common carbon atom. Examples of cycloalkylcycloalkyi include cyclopropylcyclopropyl (e.g. 1 ,1 '-bicyclopropyl-2 - yl), cyclohexylcyclohexyl wherein the two rings are linked through one single common carbon atom (e.g. 1 ,1 '-bicyclohexyl-2-yl), cyclohexylcyclopentyl wherein the two rings are linked through one single bond (e.g. 4-cyclopentylcyclohexyl) and their different stereoisomers such as (1 R,2S)-1 , 1 '-bicyclopropyl-2-yl and (1 R,2R)-1 ,1 '-bicyclopropyl- 2-yl.
The term "3- to 6-membered carbocyclic ring" as used herein refers to cyclopropane, cyclobutane, cyclopentane and cyclohexane rings.
The term "3-, 4-, 5-, 6- or 7-membered saturated, partially unsaturated or aromatic heterocyclic ring which may contain 1 , 2, 3 or 4 heteroatoms" or "containing heteroatom groups", wherein those heteroatom(s) (group(s)) are selected from N (N-substituted groups), O and S (S-substituted groups) as used herein refers to monocyclic radicals, the monocyclic radicals being saturated, partially unsaturated or aromatic (completely unsaturated). The heterocyclic radical may be attached to the remainder of the molecule via a carbon ring member or via a nitrogen ring member.
Examples of 3-, 4-, 5-, 6- or 7-membered saturated heterocyclyl or heterocyclic rings include: oxiranyl, aziridinyl, azetidinyl, 2-tetrahydrofuranyl, 3-tetrahydrofuranyl, 2-tetra- hydrothienyl, 3-tetrahydrothienyl, 2-pyrrolidinyl, 3-pyrrolidinyl, 3-pyrazolidinyl, 4-pyrazo- lidinyl, 5-pyrazolidinyl, 2-imidazolidinyl, 4-imidazolidinyl, 2-oxazolidinyl, 4-oxazolidinyl, 5-oxazolidinyl, 3-isoxazolidinyl, 4-isoxazolidinyl, 5-isoxazolidinyl, 2-thiazolidinyl, 4-thia- zolidinyl, 5-thiazolidinyl, 3-isothiazolidinyl, 4-isothiazolidinyl, 5-isothiazolidinyl, 1 ,2,4- oxadiazolidin-3-yl, 1 ,2,4-oxadiazolidin 5 yl, 1 ,2,4-thiadiazolidin-3-yl, 1 ,2,4-thiadiazolidin- 5-yl, 1 ,2,4-triazolidin-3-yl,-1 ,3,4-oxadiazolidin-2-yl, 1 ,3,4-thiadiazolidin-2-yl, 1 ,3,4-triazo- lidin-2-yl, 2-tetrahydropyranyl, 4-tetrahydropyranyl, 1 ,3-dioxan-5-yl, 1 ,4-dioxan-2-yl, 2- piperidinyl, 3-piperidinyl, 4-piperidinyl, 3-hexahydropyridazinyl, 4-hexahydropyridazinyl, 2-hexahydropyrimidinyl, 4-hexahydropyrimidinyl, 5-hexahydropyrimidinyl, 2-piperazinyl, 1 ,3,5-hexahydrotriazin-2-yl and 1 ,2,4-hexahydrotriazin-3-yl, 2-morpholinyl, 3-morpho- linyl, 2-thiomorpholinyl, 3-thiomorpholinyl, 1 -oxothiomorpholin-2-yl, 1 -oxothiomorpholin- 3-yl, 1 ,1 -dioxothiomorpholin-2-yl, 1 ,1 -dioxothiomorpholin-3-yl, hexahydroazepin-1 -, -2-, -3- or -4-yl, hexahydrooxepinyl, hexahydro-1 ,3-diazepinyl, hexahydro-1 ,4-diazepinyl, hexahydro-1 ,3-oxazepinyl, hexahydro-1 ,4-oxazepinyl, hexahydro-1 ,3-dioxepinyl, hexa- hydro-1 ,4-dioxepinyl and the like.
Examples of 3-, 4-, 5-, 6- or 7-membered partially unsaturated heterocyclyl or hetero- cyclic rings include: 2,3-dihydrofur-2-yl, 2,3-dihydrofur-3-yl, 2,4-dihydrofur-2-yl, 2,4-di- hydrofur-3-yl, 2,3-dihydrothien-2-yl, 2,3-dihydrothien-3-yl, 2,4-dihydrothien-2-yl, 2,4- dihydrothien-3-yl, 2-pyrrolin-2-yl, 2-pyrrolin-3-yl, 3-pyrrolin-2-yl, 3-pyrrolin-3-yl, 2-isoxa- zolin-3-yl, 3-isoxazolin-3-yl, 4-isoxazolin 3 yl, 2-isoxazolin-4-yl, 3-isoxazolin-4-yl, 4- isoxazolin-4-yl, 2-isoxazolin-5-yl, 3-isoxazolin-5-yl, 4-isoxazolin-5-yl, 2-isothiazolin-3-yl, 3-isothiazolin-3-yl, 4-isothiazolin-3-yl, 2-isothiazolin-4-yl, 3-isothiazolin-4-yl, 4-isothia- zolin-4-yl, 2-isothiazolin-5-yl, 3-isothiazolin-5-yl, 4-isothiazolin-5-yl, 2,3 dihydropyrazol- 1 -yl, 2,3-dihydropyrazol-2-yl, 2,3-dihydropyrazol-3-yl, 2,3-dihydropyrazol-4-yl, 2,3-di- hydropyrazol-5-yl, 3,4-dihydropyrazol-1 -yl, 3,4-dihydropyrazol-3-yl, 3,4-dihydropyrazol- 4-yl, 3,4-dihydropyrazol-5-yl, 4,5-dihydropyrazol-1-yl, 4,5-dihydropyrazol-3-yl, 4,5-di- hydropyrazol-4-yl, 4,5-dihydropyrazol-5-yl, 2,3-dihydrooxazol-2-yl, 2,3-dihydrooxazol-3- yl, 2,3-dihydrooxazol-4-yl, 2,3-dihydrooxazol-5-yl, 3,4-dihydrooxazol-2-yl, 3,4-dihydro- oxazol-3-yl, 3,4-dihydrooxazol-4-yl, 3,4-dihydrooxazol-5-yl, 3,4-dihydrooxazol-2-yl, 3,4- dihydrooxazol-3-yl, 3,4-dihydrooxazol-4-yl, 2-, 3-, 4-, 5- or 6-di- or tetrahydropyridinyl, 3-di- or tetrahydropyridazinyl, 4-di- or tetrahydropyridazinyl, 2-di- or tetrahydropyrimidi- nyl, 4-di- or tetrahydropyrimidinyl, 5-di- or tetrahydropyrimidinyl, di- or tetrahydropyrazi- nyl, 1 ,3, 5-di- or tetrahydrotriazin-2-yl, 1 ,2, 4-di- or tetrahydrotriazin-3-yl, 2,3,4,5-tetra- hydro[1 H]azepin-1 -, -2-, -3-, -4-, -5-, -6- or -7-yl, 3,4,5,6-tetrahydro[2H]azepin-2-, -3-, - 4-, -5-, -6- or -7-yl, 2,3,4,7 tetrahydro[1 H]azepin-1 -, -2-, -3-, -4-, -5-, -6- or -7-yl, 2,3,6,7 tetrahydro[1 H]azepin-1 -, -2-, -3-, -4-, -5-, -6- or -7-yl, tetrahydrooxepinyl, such as 2,3,4,5-tetrahydro[1 H]oxepin-2-, -3-, -4-, -5-, -6- or -7-yl, 2,3,4,7 tetrahydro[1 H]oxepin- 2-, -3-, -4-, -5-, -6- or -7-yl, 2,3,6,7 tetrahydro[1 H]oxepin-2-, -3-, -4-, -5-, -6- or -7-yl, tetrahydro-1 ,3-diazepinyl, tetrahydro-1 ,4-diazepinyl, tetrahydro-1 ,3-oxazepinyl, tetrahy- dro-1 ,4-oxazepinyl, tetrahydro-1 ,3-dioxepinyl and tetrahydro-1 ,4-dioxepinyl.
Examples of 5- or 6-membered aromatic heterocyclic (hetaryl) or heteroaromatic rings are: 2-furyl, 3-furyl, 2-thienyl, 3-thienyl, 2-pyrrolyl, 3-pyrrolyl, 3-pyrazolyl, 4-pyrazolyl, 5- pyrazolyl, 2-oxazolyl, 4-oxazolyl, 5-oxazolyl, 2-thiazolyl, 4-thiazolyl, 5-thiazolyl, 2-imida- zolyl, 4-imidazolyl, 1 ,3,4-triazol-2-yl, 2-pyridinyl, 3-pyridinyl, 4-pyridinyl, 3-pyridazinyl, 4- pyridazinyl, 2-pyrimidinyl, 4-pyrimidinyl, 5-pyrimidinyl and 2-pyrazinyl.
A "C2-Cm-alkylene" is divalent branched or preferably unbranched saturated aliphatic chain having 2 to m, e.g. 2 to 7 carbon atoms, for example CH2CH2, -CH(CH3)-, CH2CH2CH2, CH(CH3)CH2, CH2CH(CH3), CH2CH2CH2CH2, CH2CH2CH2CH2CH2, CH2CH2CH2CH2CH2CH2, and CH2CH2CH2CH2CH2CH2CH2.
Embodiments and preferred compounds of the present invention for use in pesticidal methods and for insecticidal application purposes are outlined in the following paragraphs.
The remarks made below concerning preferred embodiments of the variables (substit- uents) of the compounds according to the invention, especially with respect to their substituents X, Y, Z, X1, X2, Y1, A, R1, Ra, Raa, Rb, Rc, Rd, Re, R2, R2a, R2aa, R3, m, n, p and Het are valid both on their own and, in particular, in every possible combination with each other and where applicable, the uses, the methods and the compositions according to the invention.
In a particular embodiment, the variables of the compounds of formula (I) have the following meanings, these meanings, both on their own and in combination with one another, being particular embodiments of the compounds of the formula (I):
In one preferred embodimentof the compounds of formula (I), X is O. These compounds correspond to the compounds of formula (1.1 ).
In a further embodiment of the compounds of the formula (I), X is S. These compounds correspond to the compounds of formula (1.2).
Figure imgf000013_0001
In another embodiment of the compounds of formula (I), Y is S. These compounds respond to the compounds of formula (I.A). In another embodiment of the compounds of formula (I), Y is O. These compounds correspond to the compounds of formula (I.B).
Figure imgf000014_0001
In another embodiment of the compounds of formula (I), Y is S and X is O. These compounds correspond to compounds of formula 1.1. A:
Figure imgf000014_0002
In another embodiment of the compounds of formula (I), Y is S and X is S. These compounds correspond to compounds of formula I.2.A.
Figure imgf000014_0003
In another embodiment of the compounds of formula (I), Y is O and X is O. These compounds correspond to compounds of formula I.1 .B.
Figure imgf000014_0004
In another embodiment of the compounds of formula (I), Y is O and X is S. These com pounds correspond to compounds of formula I.2.B.
Figure imgf000014_0005
Within these embodiments, compound of formula I.1.B are preferred.
In an embodiment of the compounds of formula (I), Z is a direct bond or C(RaRaa)0. In a further embodiment of the compounds of formula (I), Z is a direct bond.
In an embodiment of the compounds of formula (I), Z is O, S(0)m, NRb, C(=X1), C(=X1)Y1,or Y1C(=X1). In a further embodiment, Z is O, S(0)m, or NRb. In another embodiment, Z is C(=X1), C(=X1)Y1, or Y C(=X1).
In an embodiment of the compounds of formula (I), X1 is O.
In an embodiment of the compounds of formula (I), X1 is S.
In an embodiment of the compounds of formula (I), X1 is NRb. In an embodiment of the compounds of formula (I), Y1 is O.
In an embodiment of the compounds of formula (I), Y1 is S.
In an embodiment of the compounds of formula (I), Y1 is NRC. In an embodiment of the compounds of formula (I), A is CH or N, and wherein the nitrogen of the pyrimidinium ring taken together with the contiguous linking carbon atom and A as depicted in formula (I), form a five or six membered ring, wherein each remaining ring member is selected from carbon atoms and up to one heteroatoms independently selected from O, S, and N(RC)P, wherein each ring may be substituted with up to one Ra, wherein Ra has the meaning as hereunder described.
In a further embodiment of the compounds of formula (I), A is CH or N, and wherein the nitrogen of the pyrimidinium ring taken together with the contiguous linking carbon atom and A as depicted in formula (I), form a five membered ring, wherein each remaining ring member is selected from carbon atoms and up to one heteroatoms inde- pendently selected from O, S, and N(RC)P.
In a further embodiment of the compounds of formula (I), A is CH or N, and wherein the nitrogen of the pyrimidinium ring taken together with the contiguous linking carbon atom and A as depicted in formula (I), form a six membered ring, wherein each remaining ring member is selected from carbon atoms and up to one heteroatoms independently selected from O, S, and N(RC)P.
In a further embodiment, preferred are compounds of formula (I), wherein A is CH, and wherein the nitrogen of the pyrimidinium ring taken together with the contiguous linking carbon atom and A as depicted in formula (I), form a five or six membered ring result- ing in the compounds of formula (II) selected from the group of compounds of formulae 11-1 to 11-15:
Figure imgf000015_0001
Figure imgf000015_0002
Figure imgf000016_0001
In a further embodiment, compounds of formula (I) are selected from the group of compounds of formulae 11-1 , II-2, II-3, II-4, II-5, II-6, II-7 and 11-15.
In a further embodiment, compounds of formula (I) are selected from the group of compounds of formulae 11-1 , II-2, II-3, II-4, II-5, II-6 and II-7.
In a preferred embodiment, the compounds of formula (I) is a compound of formula 11-1 . In an other embodiment, the compound of formula (I) is a compound of formula 11-15. In an other embodiment, the compound of formula (I) is a compound of formula 11-16.
In an embodiment, R1 is hydrogen, d-Cs-alkyl, C2-C8-alkenyl, C2-C8-alkynyl, C1-C6- alkoxy, C3-C6-cycloalkyl, C4-Cio-cycloalkenyl or Cs-Cn-cycloalkylcycloalkyl, wherein the C-atoms of the aforementioned groups may be unsubstituted, or partially or fully substituted by Ra, wherein Ra has the meaning as hereunder described.
In another embodiment, R1 is a three- to ten-membered saturated, or partially saturated or heterocyclic ring system, which may contain 1 to 3 heteroatoms selected from N(Rc)p, O, and S, wherein S may be oxidized and which heterocyclic ring may be unsubstituted or substituted by Ra.
In a further embodiment, R1 is hydrogen, Ci-C4-alkyl, C2-Cs-alkenyl, Ci-C6-alkoxy, C3- C6-cycloalkyl or Cs-Cn-cycloalkylcycloalkyl, wherein the C-atoms of the aforementioned groups may be unsubstituted, or partially or fully substituted by halogen.
In a further embodiment R1 is Ci-C4-alkyl, C2-Cs-alkenyl, C3-C6-cycloalkyl, phenyl or benzyl, wherein the C-atoms of the aforementioned groups may be unsubstituted, or partially or fully substituted by Ra, wherein Ra has the meaning as hereunder described. In a further embodiment R1 is Ci-C4-alkyl, C3-C6-cycloalkyl or phenyl, wherein the C- atoms of the aforementioned groups may be unsubstituted, or partially or fully substituted by halogen or Ci-C4-alkyl.
In a further embodiment R1 is Ci-C4-alkyl, C2-C4-alkenyl, phenyl or benzyl, wherein the c-atoms of the aforementioned groups may be partially or fully substituted with halo- gen, preferably CI or F.
In a further embodiment R1 is Ci-C4-alkyl, C3-C6-cycloalkyl or phenyl, preferably CH3, CH2CH3, CH(CH3)2, cyclopropyl or phenyl.
In another embodiment R1 is Ci-C3-alkyl, preferably CH3, CH2CH3 or CH(CH3)2; particularly R is CH2CH3. In an embodiment, R2 is hydrogen, halogen, CN, NO2, Ci-C6-alkyl, Ci-C6-haloalkyl, Ci- C6-haloalkoxy, Ci-C6-alkoxy, C2-C6-alkenyl, C2-C6-alkynyl, C3-C6-cycloalkyl, C5-C6- cycloalkenyl, Cs-Cu-cycloalkylcycloalkyl or S(0)mRb, wherein the C-atoms of the aforementioned groups may be unsubstituted, or partially or fully substituted by R2a. In an embodiment, R2 is hydrogen, halogen, CN, Ci-C6-alkyl, Ci-C2-alkoxy-Ci-C2-alkyl or C3-C6-cycloalkyl, wherein the C-atoms of the aforementioned groups may be substituted by halogen or CN.
In an embodiment, R2 is hydrogen, halogen, CN or Ci-C4-alkyl which may be substitut- ed by halogen.
In a further embodiment R2 is CN.
In a further embodiment, R2 is hydrogen or Ci-C2-alkyl, particularly CH3.
In a further embodiment, R2 is Ci-C6-haloalkyl, preferably Ci-C2-haloalkyl, particularly halomethyl, such as CFs or CHF2.
In another embodiment, R2 is Ci-C2-alkoxy-Ci-C2-alkyl, preferably Ci-C2-alkoxy-methyl, particularly CH2OCH3.
In another embodiment, R2 is C3-C6-cycloalkyl, preferably cyclopropyl which may be substituted, preferably by halogen or cyano.
In another embodiment, R2 is C2-C6-alkyl, preferably C2-C4-alkyl, particularly CH2CH3 or C(CH3)3.
In another embodiment, R2 is Ci-C6-alkyl, preferably Ci-C2-alkyl, particularly CH3.
In another embodiment, R2 is halogen, preferably CI or F, particularly F.
In another embodiment, R2 is a five- or six- membered carbo- or heterocyclic ring, which ring may be unsubstituted, partially, or fully substituted by R2a, and wherein R2a is as hereunder defined or R2a is preferably halogen, Ci-C6-haloalkyl, Ci-C6-haloalkoxy, ORc, C(=0)ORc, C(=0)NRbRc, phenyl, or pyridyl which may be substituted by halogen, Ci-C6-haloalkyl or Ci-C6-haloalkoxy.
In a further embodiment, R2 is a six- membered carbo- or heterocyclic ring, which ring may be unsubstituted, partially, or fully substituted by R2a, and wherein R2a is halogen, d-Ce-haloalkyl, Ci-Ce-haloalkoxy, ORc, C(=0)ORc, C(=0)NRbRc, phenyl, or pyridyl which may be substituted by R2aa, wherein R2aa is as hereunder defined.
In a further embodiment, R2 is a six- membered aromatic carbocyclic ring, which ring may be unsubstituted, partially, or fully substituted by R2a, and wherein R2a is halogen, Ci-Ce-haloalkyl, Ci-Ce-haloalkoxy, ORc, C(=0)ORc, C(=0)NRbRc, phenyl, or pyridyl which may be substituted by R2aa, wherein R2aa is as hereunder defined, preferably R2aa is halogen, Ci-C6-haloalkyl or Ci-C6-haloalkoxy.
Within this embodiment, R2 is phenyl which may be substituted by halogen, C1-C6- haloalkyl or Ci-C6-haloalkoxy.
Further, within this embodiment R2 is phenyl which may be substituted with phenyl. In a further embodiment, R2 is a six-membered heterocyclic ring, which contains 1 or 2, preferably 1 , heteroatom(s) selected from N-Rc, O, and S, wherein S may be oxidised, which heterocyclic ring is unsubstituted or substituted by one or more groups R2a, wherein R2a is as hereunder defined. In an embodiment, Ra is halogen, Ci-C6-alkyl, Ci-C6-haloalkyl, Ci-C6-alkoxy, C1-C6- haloalkoxy, C3-C6-cycloalkyl, CN, ORc, NRbRc, N02, phenyl, pyridyl, thiazyl, furanyl, pyrimidinyl or thienyl, wherein the C-atoms aforementioned which groups may be un- substituted or substituted by one or more Raa, wherein Raa is as hereunder defined. In a further embodiment, Ra is halogen, Ci-C4-alkyl, Ci-C4-haloalkyl or C3-C6-cycloalkyl. In a further embodiment, Ra is halogen, Ci-C4-alkyl, Ci-C4-haloalkyl or C3-C6-cycloalkyl. In a further embodiment, Ra is halogen.
In an embodiment, Ra is halogen, CN, N02, S(0)mRb, C(0)Rc, C(0)ORc, C(0)NRbRc, C(=S)NRbRc, d-Ce-alkyl, C3-C6-cycloalkyl, C2-C6-alkenyl, C2-C6-alkynyl, Ci-C6-alkoxy, C2-C6-alkenyloxy or C2-C6-alkynyloxy, wherein the C-atoms of the aforementioned groups may be unsubstituted, partially or fully substituted by Raa, wherein is as hereunder defined.
In a further embodiment, Ra is halogen, CN, Ci-C6-alkyl, C3-C6-cycloalkyl, C2-C6- alkenyl, C2-C6-alkynyl, Ci-C6-alkoxy, C2-C6-alkenyloxy or C2-C6-alkynyloxy, which C- atoms of the aforementioned groups may be unsubstituted, partially or fully substituted by Raa, wherein Raa is as hereunder defined.
In a further embodiment, Ra is halogen, CN, Ci-C6-alkyl, C3-C6-cycloalkyl, C2-C6- alkenyl, C2-C6-alkynyl, Ci-C6-alkoxy, C2-C6-alkenyloxy or C2-C6-alkynyloxy, wherein the C-atoms of the aforementioned groups may be unsubstituted, partially or fully substituted by halogen.
In a further embodiment, Ra is halogen, Ci-C6-haloalkyl or Ci-C6-alkoxy.
In a further embodiment, Ra is halogen, CN or Ci-C2-haloalkyl.
In a further embodiment, Ra is halogen or Ci-C2-haloalkyl.
In an embodiment, Ra is halogen, preferably Br, CI or F, particularly CI.
In another embodiment, Ra is Ci-C2-haloalkyl, preferably halomethyl such as CHF2 or CF3, particularly CF3.
In an embodiment, two geminally bound groups Ra together may form a group selected from =0, =S, =CR Rc, =NRC, =NORc, and =NNRCRC;
In another embodiment, two geminally bound groups Ra together may form a group selected from =CRbRc, =NRC, =NORc, and =NNRCRC;
In another embodiment, two geminally bound groups Ra together may form a group selected from =0, =S and =N(Ci-C6-alkyl).
In another embodiment, two geminally bound groups Ra together may form a =N(Ci-C6- alkyl) group.
In an embodiment, Rb is hydrogen, Ci-C6-alkyl, Ci-C6-haloalkyl, Ci-C6-alkoxy, C1-C6- haloalkoxy, phenyl, pyridyl, thiazyl or thienyl, wherein the C-atoms of the aforementioned groups may be substituted by Raa, wherein Raa is as hereunder defined. In a further embodiment, Rb is hydrogen, Ci-C6-alkyl, Ci-C6-haloalkyl, Ci-C6-alkoxy or Ci- C6-haloalkoxy. In a further embodiment, Rb is hydrogen, Ci-C6-alkyl or Ci-C6-haloalkyl. In an embodiment, Rb is Ci-C6-alkyl or Ci-C6-haloalkyl. In an embodiment, Rb is H. In an embodiment, Rc is hydrogen, Ci-C4-alkyl, Ci-C4-haloalkyl, Ci-C4-alkylcarbonyl, C1-C6 cycloalkyl, phenyl, pyridyl, thiazyl or thienyl wherein the C-atoms of the aforementioned groups may be substituted by Raa, wherein Raa is as hereunder defined. In a further embodiment, Rc is hydrogen, Ci-C4-alkyl, Ci-C4-haloalkyl, Ci-C4-alkylcarbonyl, or Ci-C6-cycloalkyl. In an embodiment, Rc is hydrogen, Ci-C6-alkyl or Ci-C6-haloalkyl. In an embodiment, Rc is Ci-C6-alkyl or Ci-C6-haloalkyl. In an embodiment, Rc is H.
In an embodiment, two geminally bound groups RbRb, RcRb or RCRC together with the atom to which they are bound, may form a 3-, 4-, 5-, 6- or 7- membered saturated, partially unsaturated or aromatic carbo- or heterocyclic ring, which may contain 1 to 2 heteroatoms or heteroatoms groups selected from N, O, S, NO, SO and SO2 and wherein the carbo- or heterocyclic ring may be partially or fully substituted by R3.
In another embodiment, two geminally bound groups RbRb, RcRb or RCRC together with the atom to which they are bound, may form a 5- or 6- membered saturated, partially unsaturated or aromatic carbocyclic ring, which ring may be partially or fully substituted by R3, and wherein R3 is as hereunder defined.
In another embodiment, two geminally bound groups RbRb, RcRb or RCRC together with the atom to which they are bound, may form a 5- or 6- membered saturated, partially unsaturated or aromatic heterocyclic ring, which may contain 1 to 2 heteroatoms or heteroatoms groups selected from N, O, S, NO, SO and SO2, wherein the heterocyclic ring may be partially or fully substituted by R3, and wherein R3 is as hereunder defined.
In an embodiment, Rd is hydrogen, phenyl, Ci-C4-alkyl or C2-C6-alkenyl, wherein the aforementioned groups may be substituted by one or more halogen. In a further em- bodiment, Rd is Ci-C4-alkyl or phenyl, which may be substituted by halogen. In another embodiment, Rc Ci-C4-alkyl, preferably CH3.
In an embodiment, Re is Ci-C4-alkyl, Ci-C4-haloalkyl, Ci-C4-alkylcarbonyl, C1-C6 cycloalkyl, phenyl, pyridyl, thiazyl or thienyl wherein the aforementioned groups may be sub- stituted by Raa, wherein Raa is as hereunder defined. In a further embodiment, Re is Ci- C4-alkyl, Ci-C4-haloalkyl, Ci-C4-alkylcarbonyl, or Ci-C6-cycloalkyl. In a further embodiment, Re is Ci-C4-alkyl or Ci-C4-haloalkyl.
In an embodiment, Raa is halogen, Ci-C6-alkyl or Ci-C6-haloalkyl. In another embodi- ment, Raa is Ci-C6-alkoxy or Ci-C6-haloalkoxy. In an embodiment, Raa is halogen.
In an embodiment, R2a is halogen, Ci-C6-haloalkyl, Ci-C6-alkoxy, Ci-C6-haloalkoxy, ORc, C(=0)ORc, C(=0)NRbRc, or phenyl, wherein the C-atoms of the aforementioned groups may be unsubstituted or substituted by one or more R2aa, wherein R2aa is as hereunder defined, particularly R2a is halogen, Ci-C6-alkoxy, or Ci-C6-haloalkoxy.
In an embodiment, two geminally bound groups R2a together may form a group selected from =0, =S and =N(Ci-C6-alkyl). In an embodiment, R2a is halogen, Ci-C6-alkyl, Ci-C6-haloalkyl, Ci-C6-alkoxy, C1-C6- haloalkoxy, C3-C6-cycloalkyl, CN, ORc, NRbRc, N02, phenyl, pyridyl, thiazyl, furanyl, pyrimidinyl or thienyl, wherein the C-atoms of the aforementioned groups may be unsubstituted or substituted by one or more R2aa, wherein R2aa is as hereunder defined. In a further embodiment, R2a is halogen, Ci-C4-haloalkyl or C3-C6-haloalkoxy.
In a another embodiment, R2a is phenyl which may be substituted by one or more R2aa. In a another embodiment, R2a is halogen. In another embodiment, R2a is C1-C6- haloalkyl. In another embodiment, R2a is Ci-C6-haloalkoxy.
In another embodiment, R2a is halogen, CN, N02, S(0)mRb, C(=0)Rc, C(=0)ORc, C(0)NRbRc, C(=S)NRbRc, Ci-Ce-alkyl, C3-C6-cycloalkyl, C2-C6-alkenyl, C2-C6-alkynyl, Ci-C6-alkoxy, C2-C6-alkenyloxy or C2-C6-alkynyloxy, which C-atoms of the aforementioned groups may be unsubstituted, partially or fully substituted by Raa, wherein is as hereunder defined.
In further embodiment, R2a is, C(=0)ORc or C(=0)NRbRc.
In another embodiment, R2a is halogen, CN, Ci-C6-alkyl, C3-C6-cycloalkyl, C2-C6- alkenyl, C2-C6-alkynyl, Ci-C6-alkoxy, C2-C6-alkenyloxy or C2-C6-alkynyloxy, which C- atoms of the aforementioned groups may be unsubstituted, partially or fully substituted by R2aa, wherein R2aa is as hereunder defined.
In an embodiment, R2a is Br, CI or F, particularly CI.
In another embodiment, R2a is Ci-C2-haloalkyl, preferably halomethyl such as CHF2 or
CF3, particularly CF3.
In an embodiment, R2aa is halogen, Ci-C6-alkyl, Ci-C6-haloalkyl, Ci-C6-alkoxy, C1-C6- haloalkoxy, C2-C4-alkenyl, C2-C4-alkynyl, C3-C6-cycloalkyl, CN, N(Ci-C6-alkyl)( Ci-C6- alkyl), C(=0)(0)P(Ci-C6-alkyl), C(=0)N(Ci-C6-alkyl)( Ci-Ce-alkyl), S(0)m(Ci-C6-alkyl), S02N(Ci-C6-alkyl)(Ci-C6-alkyl), OS02(Ci-C6-alkyl), N(Ci-C6-alkyl)S02(Ci-C6-alkyl), or S(=0)p(=N(Ci-C6-alkyl))(Ci-C6-alkyl) or two geminally bound groups R2aa together may form a group selected from =0, =S and =N(Ci-C6-alkyl).
In an embodiment, R2aa is halogen, Ci-C6-alkyl, Ci-C6-haloalkyl, Ci-C6-alkoxy, C1-C6- haloalkoxy, C2-C4-alkenyl, C2-C4-alkynyl, C3-C6-cycloalkyl, CN, N(Ci-C6-alkyl)( Ci-Ce- alkyl), C(=0)(0)P(Ci-C6-alkyl), C(=0)N(Ci-C6-alkyl)( Ci-Ce-alkyl), S(0)m(Ci-C6-alkyl), S02N(Ci-C6-alkyl)(Ci-C6-alkyl), OS02(Ci-C6-alkyl), N(Ci-C6-alkyl)S02(Ci-C6-alkyl), or S(=0)p(=N(Ci-C6-alkyl))(Ci-C6-alkyl). In another embodiment, two geminally bound groups R2aa together may form a group selected from =0, =S and =N(Ci-C6-alkyl).
In an embodiment, R3 is halogen, Ci-C6-alkyl, Ci-C6-haloalkyl, Ci-C6-alkoxy, C1-C6- haloalkoxy, C2-C4-alkenyl, C2-C4-alkynyl, C3-C6-cycloalkyl, CN, N(Ci-C6-alkyl)( Ci-Ce- alkyl), C(=0)(0)P(Ci-C6-alkyl), C(=0)N(Ci-C6-alkyl)( Ci-Ce-alkyl), S(0)m(Ci-C6-alkyl), S02N(Ci-C6-alkyl)(Ci-C6-alkyl), OS02(Ci-C6-alkyl), N(Ci-C6-alkyl)S02(Ci-C6-alkyl), S(=0)p(=N(Ci-C6-alkyl))(Ci-C6-alkyl), or
two geminally bound groups R3 together may form a group selected from =0, =S and =N(Ci-C6-alkyl). In an embodiment, R3a is halogen, Ci-C6-alkyl, Ci-C6-haloalkyl, Ci-C6-alkoxy, C1-C6- haloalkoxy, C2-C4-alkenyl, C2-C4-alkynyl, C3-C6-cycloalkyl, CN, N(Ci-C6-alkyl)( Ci-C6- alkyl),C(=0)(0)P(Ci-C6-alkyl), C(=0)N(Ci-C6-alkyl)( Ci-C6-alkyl), S(0)m(Ci-C6-alkyl), S02N(Ci-C6-alkyl)(Ci-C6-alkyl), OS02(Ci-C6-alkyl), N(Ci-C6-alkyl)S02(Ci-C6-alkyl), or S(=0)p(=N(Ci-C6-alkyl))(Ci-C6-alkyl). In another embodiment, two geminally bound groups R3a together may form a group selected from =0, =S and =N(Ci-C6-alkyl).
In an embodiment, m is 0. In another embodiment, m is 1. In another embodiment, m is 2.
In an embodiment, n is 0. In another embodiment, n is 1. In another embodiment, n is 2.
In an embodiment, p is 0. In another embodiment, p is 1 .
In an embodiment Het is a five- or six-membered saturated, partially unsaturated or aromatic heterocyclic ring, which may contain 1 to 4 heteroatoms selected from N(RC)P, O and S, wherein the heterocyclic ring is substituted by (Ra)n and the remaining variables in the meaning of Het are as above defined.
In an embodiment Het is a five- or six-membered saturated, partially unsaturated or aromatic heterocyclic ring, which may contain 1 to 2 heteroatoms selected from N(RC)P, O and S, wherein the heterocyclic ring is substituted by (Ra)n.
In an embodiment Het is a five-membered aromatic heterocyclic ring, which contains 2 heteroatoms selected from N(RC)P, O and S, wherein the heterocyclic ring is substituted by (Ra)n.
In an embodiment Het is a five-membered saturated heterocyclic ring, which contains 1 heteroatom selected from N(RC)P, O and S, preferably O, wherein the heterocyclic ring is substituted by (Ra)n.
In an embodiment Het is a six-membered aromatic heterocyclic ring, which contains 2 heteroatoms selected from N(RC)P, O and S, preferably N(RC)P, wherein the heterocyclic ring is substituted by (Ra)n.
In an embodiment Het is a six-membered aromatic heterocyclic ring, which contains 1 heteroatom selected from N(RC)P, O and S, preferably N(RC)P, wherein the heterocyclic ring is substituted by (Ra)n.
In an embodiment Het is pyridyl which is substituted by (Ra)n.
In an embodiment Het is tetrahydrofuryl which is substituted by (Ra)n.
In another embodiment, Het is selected from any one of the following ring systems D-1 to D-56:
Figure imgf000022_0001
Figure imgf000023_0001
D-36 D-37 D-38 D-39 D-40
Figure imgf000023_0002
D-41 D-42 D-43 D-44 D-45
Figure imgf000023_0003
D-46 D-47 D-48 D-49 D-50
Figure imgf000023_0004
D-51 D-52 D-53 D-54 D-55 D-56 Wherever used in a structure, the following: # denotes the bond to A in formula (I)
In a further embodiment Het is selected from any one of the following ring systems:
Figure imgf000023_0005
D-1 D-2 D-3 D-5 D-6 D-7
Figure imgf000023_0006
D-25 D-26 D-27 D-28 D-29
Figure imgf000023_0007
D-30 D-35 D-36 D-54 D-55 D-56 In a further embodiment, Het is selected from the following rings systems D-2, D-9, D- 22, D-25, D-28, D-29 and D-54:
Figure imgf000024_0001
D-2 D-9 D-22 D-25 D-28 D-29
Figure imgf000024_0002
wherein Ra is halogen, Ci-C4-haloalkyl, CiC4-alkoxy or Ci-C4-alkylthio or phenyl; pref- erably Ra is halogen or halomethyl.
In a further embodiment, Het is selected from the following rings systems D-2, D-9 and D-25:
Figure imgf000024_0003
D-2 D-9 D-25 D-56 wherein Ra is halogen, Ci-C4-haloalkyl, CiC4-alkoxy or Ci-C4-alkylthio or phenyl, pref- erably halogen or Ci-C4-haloalkyl; more preferably Ra is CI, Br, F or CF3, most preferably Ra is CI or CF3.
In a further embodiment Het is selected from the following rings systems D-2, D-25 or D-54:
Figure imgf000024_0004
D-2 D-25 D-54
wherein Ra is halogen or Ci-C4-haloalkyl; preferably Ra is CI, Br, F or CF3, most preferably Ra is CI or CF3.
In another embodiment Het is selected from the following rings systems D-2a, D-2b, D- 2c, D-25a and D-54a:
Figure imgf000025_0001
D-2b D-2c D-25a
Figure imgf000025_0002
D-54a D-56
wherein Ra are independently from each other selected from CI, Br, F and CF3.
In another embodiment Het is D-2, preferably D-2b or D-2c, particularly D-2b, wherein Ra is CI or CF3.
In a further embodiment Het is D-2a.
In another embodiment, Het is D-25, preferably D-25a substituted by CI.
In another embodiment, Het is D-9, preferably D-9a or D9b.
In another embodiment, Het is D-56, preferably D-56a. In particular, with a view to their use, preference is given to the compounds of the formula (I) compiled in the tables below, which compounds correspond to the compounds of formulae I.1 .B (i.e. wherein X and Y are O) and to the preferred compounds of formula 11-1 , II-2, 11—3 , II-4, II-5, II-6, II-7, and 11-15. Each of the groups mentioned for the substituents in the tables are furthermore per se, independently of the combination in which they are mentioned, a particularly preferred aspect of the substituent in question. Further, each individual meaning of a substituent in the tables constitutes a particularly preferred embodiment of the substituents in question.
Table 1 : Compounds of the formula (111-1 ) corresponding to the compounds of the formula 11-1 , in which X and Y are O, Het is D-2b wherein Ra is CI, and the combination of R1, ZR2 for a compound corresponds in each case to one line of Table A:
Figure imgf000025_0003
Table 2 : Compounds of the formula (III-2) corresponding to the compounds of the formula II-2, in which X and Y are O, Het is D-2b wherein Ra is CI, and the combination of R1, ZR2 for a compound corresponds in each case to one line of Table A:
Figure imgf000026_0001
Table 3 : Compounds of the formula (III-3) corresponding to the compounds of the formula 11—3 , in which X and Y are O, Het is D-2b wherein Ra is CI, and the combination of R1, ZR2 for a compound corresponds in each case to one line of Table A.
Figure imgf000026_0002
Table 4 : Compounds of the formula (III-4) corresponding to the compounds of the formula II-4, in which X and Y are O, Het is D-2b wherein Ra is CI, and the combination of R1, ZR2 for a compound corresponds in each case to one line of Table A.
Figure imgf000026_0003
Table 5 : Compounds of the formula (III-5) corresponding to the compounds of the formula II-5, in which X and Y are O, Het is D-2b wherein Ra is CI, and the combination of R1, ZR2 for a compound cor line of Table A.
Figure imgf000026_0004
Table 6 : Compounds of the formula (III-6) corresponding to the compounds of the formula II-6, in which X and Y are O, Het is D-2b wherein Ra is CI, and the combination of R1, ZR2 for a compound corresponds in each case to one line of Table A.
Figure imgf000027_0001
Table 7 Compounds of the formula (III-7) corresponding to the compounds of the formula II-7, in which X and Y are O, Het is D-2b wherein Ra is CI, and the combination of R1, ZR2 for a compound corresponds in each case to one line of Table A.
Figure imgf000027_0002
Table 8 : Compounds of the formula (III-8) corresponding to the compounds of the formula 11-15, in which X and Y are O, Het is D-2b wherein Ra is CI, and the combination of R1, ZR2 for a compound to one line of Table A.
Figure imgf000027_0003
Table 9 : Compounds of the formula (III-9) corresponding to the compounds of the formula 11-1 , in which X and Y are O, Het is D-25a wherein Ra is CI, and the combination of R1, ZR2 for a compound o one line of Table A:
Figure imgf000027_0004
Table 10 : Compounds of the formula (111-10) corresponding to the compounds of the formula II-2, in which X and Y are O, Het is D-25a wherein Ra is CI, and the combination of R1, ZR2 for a compound corresponds in each case to one line of Table A.
Figure imgf000028_0001
Table 1 1 : Compounds of the formula (111-1 1 ) corresponding to the compounds of the formula 11—3 , in which X and Y are O, Het is D-25a wherein Ra is CI, and the combination of R1, ZR2 for a compound corresponds in each case to one line of Table A.
Figure imgf000028_0002
Table 12 : Compounds of the formula (111-12) corresponding to the compounds of the formula II-4, in which X and Y are O, Het is D-25a wherein Ra is CI, and the combination of R1, ZR2 for a compound corresponds in each case to one line of Table A.
Figure imgf000028_0003
Table 13 : Compounds of the formula (111-13) corresponding to the compounds of the formula II-5, in which X and Y are O, Het is D-25a wherein Ra is CI, and the combination of R1, ZR2 for a compound one line of Table A..
Figure imgf000028_0004
Table 14 : Compounds of the formula (111-14) corresponding to the compounds of the formula II-6, in which X and Y are O, Het is D-25a wherein Ra is CI, and the combination of R1, ZR2 for a compound corresponds in each case to one line of Table A.
Figure imgf000029_0001
Table 15 Compounds of the formula (111-15) corresponding to the compounds of the formula II-7, in which X and Y are O, Het is D-25a wherein Ra is CI, and the combination of R1, ZR2 for a compoun one line of Table A.
Figure imgf000029_0002
Table 16 : Compounds of the formula (111-16) corresponding to the compounds of the formula 11-15, in which X and Y are O, Het is D-25a wherein Ra is CI, and the combination of R1, ZR2 for a compoun to one line of Table A.
Figure imgf000029_0003
Table 17 : Compounds of the formula (111-17) corresponding to the compounds of the formula 11-1 , in which X and Y are O, Het is D-2b wherein Ra is CI, and the combination of R1, ZR2 for a compound corre ne line of Table A:
Figure imgf000029_0004
Table 18 : Compounds of the formula (111-18) corresponding to the compounds of the formula II-2, in which X and Y are O, Het is D-9b, and the combination of R1, ZR2 for a compound corresponds in each case to one line of Table A:
Figure imgf000030_0001
Table 19 : Compounds of the formula (111-19) corresponding to the compounds of the formula 11—3 , in which X and Y are O, Het is D-9b, and the combination of R1, ZR2 for a compound corresponds in each case to one line of Table A.
Figure imgf000030_0002
Table 20 : Compounds of the formula (III-20) corresponding to the compounds of the formula II-4, in which X and Y are O, Het is D-9b, and the combination of R1, ZR2 for a compound corresponds in each .
Figure imgf000030_0003
Table 21 : Compounds of the formula (111-21 ) corresponding to the compounds of the formula II-5, in which X and Y are O, Het is D-9b, and the combination of R1, ZR2 for a compound corresponds in eac .
Figure imgf000030_0004
Table 22 : Compounds of the formula (III-22) corresponding to the compounds of the formula II-6, in which X and Y are O, Het is D-9b, and the combination of R1, ZR2 for a compound corresponds in each case to one line of Table A.
Figure imgf000031_0001
Table 23 Compounds of the formula (111-23) corresponding to the compounds of the formula 11-7, in which X and Y are O, Het is D-9b, and the combination of R1, ZR2 for a compound corresponds in each case to one line of Table A.
Figure imgf000031_0002
Table 24 : Compounds of the formula (III-24) corresponding to the compounds of the formula 11-15, in which X and Y are O, Het is D-9b, and the combination of R1, ZR2 for a compound corresponds in each case to one line of Table A.
Figure imgf000031_0003
Table 25 : Compounds of the formula (III-25) corresponding to the compounds of the formula 11-1 , in which X and Y are O, Het is D-25a wherein Ra is S-CH3, and the combination of R1, ZR2 for a compound corresponds in each case to one line of Table A:
Figure imgf000031_0004
Table 26 : Compounds of the formula (III-26) corresponding to the compounds of the formula II-2, in which X and Y are O, Het is D-25a wherein Ra is S-CH3, and the combination of R1, ZR2 for a compound corresponds in each case to one line of Table A.
Figure imgf000032_0001
Table 27 : Compounds of the formula (III-27) corresponding to the compounds of the formula 11—3 , in which X and Y are O, Het is D-25a wherein Ra is S-CH3, and the combination of R1, ZR2 for a compound corresponds in each case to one line of Table A.
Figure imgf000032_0002
Table 28 : Compounds of the formula (III-28) corresponding to the compounds of the formula II-4, in which X and Y are O, Het is D-25a wherein Ra is S-CH3, and the combination of R1, ZR2 for a compound corresponds in each case to one line of Table A.
Figure imgf000032_0003
Table 29 : Compounds of the formula (III-29) corresponding to the compounds of the formula II-5, in which X and Y are O, Het is D-25a wherein Ra is S-CH3, and the combination of R1, ZR2 for a comp o one line of Table A..
Figure imgf000032_0004
Table 30 : Compounds of the formula (III-30) corresponding to the compounds of the formula II-6, in which X and Y are O, Het is D-25a wherein Ra is S-CH3, and the combination of R1, ZR2 for a compound corresponds in each case to one line of Table A.
Figure imgf000033_0001
Table 31 Compounds of the formula (111-31 ) corresponding to the compounds of the formula II-7, in which X and Y are O, Het is D-25a wherein Ra is S-CH3, and the combination of R1, ZR2 for a compound corresponds in each case to one line of Table A.
Figure imgf000033_0002
Table 32 : Compounds of the formula (III-32) corresponding to the compounds of the formula 11-15, in which X and Y are O, Het is D-25a wherein Ra is S-CH3, and the combination of R1, ZR2 for a compound corresponds in each case to one line of Table A.
Figure imgf000033_0003
Table 33 : Compounds of the formula (III-33) corresponding to the compounds of the formula 11-1 , in which X and Y are O, Het is D-2c wherein Ra is CI and Phenyl, and the combination of R1, ZR2 for a compound corresponds in each case to one line of Table A:
Figure imgf000033_0004
Table 34 : Compounds of the formula (III-34) corresponding to the compounds of the formula II-2, in which X and Y are O, Het is D-2c wherein Ra is CI and Phenyl, and the combination of R1, ZR2 for a compound corresponds in each case to one line of Table A:
Figure imgf000034_0001
Table 35 : Compounds of the formula (111-35) corresponding to the compounds of the formula 11-3, in which X and Y are O, Het is D-2c wherein Ra is CI and phenyl, and the combination of R1, ZR2 for a compound corresponds in each case to one line of Table A.
Figure imgf000034_0002
Table 36 : Compounds of the formula (III-36) corresponding to the compounds of the formula II-4, in which X and Y are O, Het is D-2c wherein Ra is CI and phenyl, and the combination of R1, ZR2 for a compound corresponds in each case to one line of Table A.
Figure imgf000034_0003
Table 37 : Compounds of the formula (III-37) corresponding to the compounds of the formula II-5, in which X and Y are O, Het is D-2c wherein Ra is CI and phenyl, and the combination of R1, ZR2 for a compound corresponds in each case to one line of Table A.
Figure imgf000034_0004
Table 38 : Compounds of the formula (III-38) corresponding to the compounds of the formula II-6, in which X and Y are O, Het is D-2c wherein Ra is CI and phenyl, and the combination of R1, ZR2 for a compound corresponds in each case to one line of Table A.
Figure imgf000035_0001
Table 39 Compounds of the formula (III-39) corresponding to the compounds of the formula II-7, in which X and Y are O, Het is D-2c wherein Ra is CI and phenyl, and the combination of R1, ZR2 for a compound corresponds in each case to one line of Table A.
Figure imgf000035_0002
Table 40 : Compounds of the formula (III-40) corresponding to the compounds of the formula 11-15, in which X and Y are O, Het is D-2c wherein Ra is CI and phenyl, and the combination of R1, ZR2 for a compound corresponds in each case to one line of Table A.
Figure imgf000035_0003
Table 41 : Compounds of the formula (111-41 ) corresponding to the compounds of the formula 11-1 , in which X and Y are O, Het is D-56a wherein Ra is O-Me, and the combination of R1, ZR2 for a to one line of Table A:
Figure imgf000035_0004
Table 42 : Compounds of the formula (III-42) corresponding to the compounds of the formula II-2, in which X and Y are O, Het is D-56a wherein Ra is O-Me, and the combination of R1, ZR2 for a one line of Table A.
Figure imgf000036_0001
Table 43 : Compounds of the formula (III-43) corresponding to the compounds of the formula 11—3 , in which X and Y are O, Het is D-56a wherein Ra is O-Me, and the combination of R1, ZR2 for a compound corresponds in each case to one line of Table A.
Figure imgf000036_0002
Table 44 : Compounds of the formula (111-12) corresponding to the compounds of the formula II-4, in which X and Y are O, Het is D-56a wherein Ra is O-Me, and the combination of R1, ZR2 for a compound corresponds in each case to one line of Table A.
Figure imgf000036_0003
Table 45 : Compounds of the formula (III-45) corresponding to the compounds of the formula II-5, in which X and Y are O, Het is D-56a wherein Ra is O-Me, and the combination of R1, ZR2 for a compound corresponds in each case to one line of Table A..
Figure imgf000036_0004
Table 46 : Compounds of the formula (III-46) corresponding to the compounds of the formula II-6, in which X and Y are O, Het is D-56a wherein Ra is O-Me, and the combination of R1, ZR2 for a compound corresponds in each case to one line of Table A.
Figure imgf000037_0001
Table 47 Compounds of the formula (111-47) corresponding to the compounds of the formula 11-7, in which X and Y are O, Het is D-56a wherein Ra is O-Me, and the combination of R1, ZR2 for a compound corresponds in each case to one line of Table A.
Figure imgf000037_0002
Table 48 : Compounds of the formula (III-48) corresponding to the compounds of the formula 11-15, in which X and Y are O, Het is D-56a wherein Ra is O-Me, and the combination of R1, ZR2 for a compound corresponds in each case to one line of Table A.
Figure imgf000037_0003
Table 49 : Compounds of the formula (III-49) corresponding to the compounds of the formula 11-16, in which X and Y are O, Het is D-2b wherein Ra is CI, and the combination of R1, ZR2 for a co e of Table A:
Figure imgf000037_0004
Table 50 : Compounds of the formula (III-50) corresponding to the compounds of the formula 11-16, in which X and Y are O, Het is D-25a wherein Ra is CI, and the combination of R1, ZR2 for a compound corresponds in each case to one line of Table A:
Figure imgf000038_0001
Table 51 : Compounds of the formula (111-51 ) corresponding to the compounds of the formula 11-16, in which X and Y are O, Het is D-2c wherein Ra is CI and Phenyl, and the combination of R1, ZR2 for a compound corresponds in each case to one line of Table A:
Figure imgf000038_0002
Table 52 : Compounds of the formula (III-52) corresponding to the compounds of the formula 11-16, in which X and Y are O, Het is D-25a wherein Ra is S-Me, and the combination of R1, ZR2 for a line of Table A:
Figure imgf000038_0003
Table 53 : Compounds of the formula (III-53) corresponding to the compounds of the formula 11-16, in which X and Y are O, Het is D-9b, and the combination of R1, ZR2 for a compound corresponds in each case to one line of Table A:
Figure imgf000038_0004
Table 54 : Compounds of the formula (III-54) corresponding to the compounds of the formula 11-16, in which X and Y are O, Het is D-56a wherein Ra is O-Me, and the combination of R1, ZR2 for a compound corresponds in each case to one line of Table A:
Figure imgf000038_0005
able A:
Figure imgf000039_0001
Figure imgf000040_0001
Figure imgf000041_0001
Figure imgf000042_0001
Figure imgf000043_0001
The compound of formula (I) according to the present invention can be prepared according to the following syntheses routes, e.g. according to the preparation methods and preparation schemes as described below.
The compound of formula (I) according to the present invention can be prepared, according to the e.g. preparation methods and preparation schemes as described below. The compounds used as starting materials for the syntheses of the compounds according to the present invention can generally be prepared by standard methods of organic chemistry. If not otherwise specified, the definitions of the variables such as X, Y, Het, R1 and R2 of the structures given in the schemes have the same meaning as defined above.
Compounds of the formula (I) can for example be prepared by reacting the appropriately substituted compounds P-1 with the a malonate derivative P-2 analogous to the methods described by Holyoke et al. in WO 2009/099929 (Scheme 1 ):
Scheme 1
Figure imgf000043_0002
Compounds like P-1 can be prepared from the corresponding compounds P-3, by re- acting it with an amine nucleophile like P-4 as described by, for example, Michel
Langlois et al, Journal of Heterocyclic Chemistry, 19(1 ), 193-200; 1982, wherein LG denotes a leaving group such as halogen (e.g. chlorine or bromine), OR' , or SR' , with R' being Ci-C6-alkyl, preferably chlorine methoxy ethoxy, methylthio or ethylthio (Scheme 2):
Scheme 2
Figure imgf000043_0003
Compounds like P-3 are available from the corresponding lactams P-5 by standard procedures known to a person skilled in the art. For example see Allen, Jennifer Re- becca et ai in WO 2004/094382 or Lang, Kai et ai, Journal of Organic Chemistry, 75(19), 6424-6435; 2010 (Scheme 3):
Scheme 3
Figure imgf000044_0001
P-5 P-3
Lactams are widespread in organic chemistry and methods to produce them are well known. For example see: Smith, M. B, in Science of Synthesis, (2005) 21 , 653.
If individual compounds cannot be prepared via the above described routes, they can be prepared by derivatization of other compounds of formula (I) or by customary modifications of the synthesis routes described.
For example, in individual cases, certain compounds of formula (I) can advantageously be prepared from other compounds of formula (I) by derivatization, e.g. by ester hydrolysis, amidation, esterification, ether cleavage, olefination, reduction, oxidation and the like, or by customary modifications of the synthesis routes described.
The reaction mixtures are worked up in the customary manner, for example by mixing with water, separating the phases, and, if appropriate, purifying the crude products by chromatography, for example on alumina or silica gel. The term "invertebrate pest" as used herein encompasses animal populations, such as arthropod pests, including insects and arachnids, as well as nematodes, which may attack plants thereby causing substantial damage to the plants attacked, as well as ectoparasites which may infest animals, in particular warm blooded animals such as e.g. mammals or birds, or other higher animals such as reptiles, amphibians or fish, thereby causing substantial damage to the animals infested.
The compounds of formula (I) according to the present invention are in particular suitable for efficiently controlling arthropod pests such as arachnids, myriapedes and insects as well as nematodes.
The compounds of the formula (I) are especially suitable for efficiently combating the following pests:
Insects from the order of the lepidopterans (Lepidoptera), for example Agrotis ypsilon, Agrotis segetum, Alabama argillacea, Anticarsia gemmatalis, Argyresthia conjugella, Autographa gamma, Bupalus piniarius, Cacoecia murinana, Capua reticulana, Chei- matobia brumata, Choristoneura fumiferana, Choristoneura occidentalis, Cirphis unipuncta, Cydia pomonella, Dendrolimus pini, Diaphania nitidalis, Diatraea grandiosel- la, Earias insulana, Elasmopalpus lignosellus, Eupoecilia ambiguella, Evetria bouliana, Feltia subterranea, Galleria mellonella, Grapholitha funebrana, Grapholitha molesta, Heliothis armigera, Heliothis virescens, Heliothis zea, Hellula undalis, Hibernia defoliar- ia, Hyphantria cunea, Hyponomeuta malinellus, Keiferia lycopersicella, Lambdina fis- cellaria, Laphygma exigua, Leucoptera coffeella, Leucoptera scitella, Lithocolletis blan- cardella, Lobesia botrana, Loxostege sticticalis, Lymantria dispar, Lymantria monacha, Lyonetia clerkella, Malacosoma neustria, Mamestra brassicae, Orgyia pseudotsugata, Ostrinia nubilalis, Panolis flammea, Pectinophora gossypiella, Peridroma saucia, Phalera bucephala, Phthorimaea operculella, Phyllocnistis citrella, Pieris brassicae, Plathypena scabra, Plutella xylostella, Pseudoplusia includens, Rhyacionia frustrana, Scrobipalpula absoluta, Sitotroga cerealella, Sparganothis pilleriana, Spodoptera frugi- perda, Spodoptera littoralis, Spodoptera litura, Thaumatopoea pityocampa, Tortrix viri- dana, Trichoplusia ni and Zeiraphera canadensis; beetles (Coleoptera), for example Agrilus sinuatus, Agriotes lineatus, Agriotes obscur- us, Amphimallus solstitialis, Anisandrus dispar, Anthonomus grandis, Anthonomus po- morum, Aphthona euphoridae, Athous haemorrhoidalis, Atomaria linearis, Blastopha- gus piniperda, Blitophaga undata, Bruchus rufimanus, Bruchus pisorum, Bruchus len- tis, Byctiscus betulae, Cassida nebulosa, Cerotoma trifurcata, Cetonia aurata, Ceuthor- rhynchus assimilis, Ceuthorrhynchus napi, Chaetocnema tibialis, Conoderus vesperti- nus, Crioceris asparagi, Ctenicera ssp., Diabrotica longicornis, Diabrotica semipunc- tata, Diabrotica 12-punctata Diabrotica speciosa, Diabrotica virgifera, Epilachna varivestis, Epitrix hirtipennis, Eutinobothrus brasiliensis, Hylobius abietis, Hypera brun- neipennis, Hypera postica, Ips typographus, Lema bilineata, Lema melanopus, Leptino- tarsa decemlineata, Limonius californicus, Lissorhoptrus oryzophilus, Melanotus communis, Meligethes aeneus, Melolontha hippocastani, Melolontha melolontha, Oulema oryzae, Otiorrhynchus sulcatus, Otiorrhynchus ovatus, Phaedon cochleariae, Phyllobi- us pyri, Phyllotreta chrysocephala, Phyllophaga sp., Phyllopertha horticola, Phyllotreta nemorum, Phyllotreta striolata, Popillia japonica, Sitona lineatus and Sitophilus grana- ria;
flies, mosquitoes (Diptera), e.g. Aedes aegypti, Aedes albopictus, Aedes vexans, Anas- trepha ludens, Anopheles maculipennis, Anopheles crucians, Anopheles albimanus, Anopheles gambiae, Anopheles freeborni, Anopheles leucosphyrus, Anopheles minimus, Anopheles quadrimaculatus, Calliphora vicina, Ceratitis capitata, Chrysomya bezziana, Chrysomya hominivorax, Chrysomya macellaria, Chrysops discalis, Chrys- ops silacea, Chrysops atlanticus, Cochliomyia hominivorax, Contarinia sorghicola Cordylobia anthropophaga, Culicoides furens, Culex pipiens, Culex nigripalpus, Culex quinquefasciatus, Culex tarsalis, Culiseta inornata, Culiseta melanura, Dacus cucurbi- tae, Dacus oleae, Dasineura brassicae, Delia antique, Delia coarctata, Delia platura, Delia radicum, Dermatobia hominis, Fannia canicularis, Geomyza Tripunctata, Gaster- ophilus intestinalis, Glossina morsitans, Glossina palpalis, Glossina fuscipes, Glossina tachinoides, Haematobia irritans, Haplodiplosis equestris, Hippelates spp., Hylemyia platura, Hypoderma lineata, Leptoconops torrens, Liriomyza sativae, Liriomyza trifolii, Lucilia caprina, Lucilia cuprina, Lucilia sericata, Lycoria pectoralis, Mansonia titillanus, Mayetiola destructor, Musca autumnalis, Musca domestica, Muscina stabulans, Oestrus ovis, Opomyza florum, Oscinella frit, Pegomya hysocyami, Phorbia antiqua, Phor- bia brassicae, Phorbia coarctata, Phlebotomus argentipes, Psorophora columbiae, Psila rosae, Psorophora discolor, Prosimulium mixtum, Rhagoletis cerasi, Rhagoletis pomonella, Sarcophaga haemorrhoidalis, Sarcophaga spp., Simulium vittatum, Stomoxys calcitrans, Tabanus bovinus, Tabanus atratus, Tabanus lineola, Tabanus similis, Tipula oleracea, and Tipula paludosa;
thrips (Thysanoptera), e.g. Dichromothrips corbetti, Dichromothrips ssp., Frankliniella fusca, Frankliniella occidentalis, Frankliniella tritici, Scirtothrips citri, Thrips oryzae, Thrips palmi and Thrips tabaci, termites (Isoptera), e.g. Calotermes flavicollis, Leucotermes flavipes, Heterotermes aureus, Reticulitermes flavipes, Reticulitermes virginicus, Reticulitermes lucifugus, Re- ticulitermes santonensis, Reticulitermes grassei, Termes natalensis, and Coptotermes formosanus;
cockroaches (Blattaria - Blattodea), e.g. Blattella germanica, Blattella asahinae, Peri- planeta americana, Periplaneta japonica, Periplaneta brunnea, Periplaneta fuligginosa, Periplaneta australasiae, and Blatta orientalis;
bugs, aphids, leafhoppers, whiteflies, scale insects, cicadas (Hemiptera), e.g. Acrosternum hilare, Blissus leucopterus, Cyrtopeltis notatus, Dysdercus cingulatus, Dysdercus intermedius, Eurygaster integriceps, Euschistus impictiventris, Leptoglossus phyllopus, Lygus lineolaris, Lygus pratensis, Nezara viridula, Piesma quadrata, Solu- bea insularis , Thyanta perditor, Acyrthosiphon onobrychis, Adelges laricis, Aphidula nasturtii, Aphis fabae, Aphis forbesi, Aphis pomi, Aphis gossypii, Aphis grossulariae, Aphis schneideri, Aphis spiraecola, Aphis sambuci, Acyrthosiphon pisum, Aulacorthum solani, Bemisia argentifolii, Brachycaudus cardui, Brachycaudus helichrysi, Brachycau- dus persicae, Brachycaudus prunicola, Brevicoryne brassicae, Capitophorus horni, Cerosipha gossypii, Chaetosiphon fragaefolii, Cryptomyzus ribis, Dreyfusia nordmanni- anae, Dreyfusia piceae, Dysaphis radicola, Dysaulacorthum pseudosolani, Dysaphis plantaginea, Dysaphis pyri, Empoasca fabae, Hyalopterus pruni, Hyperomyzus lac- tucae, Macrosiphum avenae, Macrosiphum euphorbiae, Macrosiphon rosae, Megoura viciae, Melanaphis pyrarius, Metopolophium dirhodum, Myzus persicae, Myzus ascalo- nicus, Myzus cerasi, Myzus varians, Nasonovia ribis-nigri, Nilaparvata lugens, Pemphi- gus bursarius, Perkinsiella saccharicida, Phorodon humuli, Psylla mali, Psylla piri, Rhopalomyzus ascalonicus, Rhopalosiphum maidis, Rhopalosiphum padi, Rhopalosiphum insertum, Sappaphis mala, Sappaphis mali, Schizaphis graminum, Schizoneura lanuginosa, Sitobion avenae, Trialeurodes vaporariorum, Toxoptera au- rantiiand, Viteus vitifolii, Cimex lectularius, Cimex hemipterus, Reduvius senilis, Tria- toma spp., and Arilus critatus;
ants, bees, wasps, sawflies (Hymenoptera), e.g. Athalia rosae, Atta cephalotes, Atta capiguara, Atta cephalotes, Atta laevigata, Atta robusta, Atta sexdens, Atta texana, Crematogaster spp., Hoplocampa minuta, Hoplocampa testudinea, Lasius niger, Mon- omorium pharaonis, Solenopsis geminata, Solenopsis invicta, Solenopsis richteri, So- lenopsis xyloni, Pogonomyrmex barbatus, Pogonomyrmex californicus, Pheidole meg- acephala, Dasymutilla occidentalis, Bombus spp., Vespula squamosa, Paravespula vulgaris, Paravespula pennsylvanica, Paravespula germanica, Dolichovespula macula- ta, Vespa crabro, Polistes rubiginosa, Camponotus floridanus, and Linepithema humile;
crickets, grasshoppers, locusts (Orthoptera), e.g. Acheta domestica, Gryllotalpa gryllo- talpa, Locusta migratoria, Melanoplus bivittatus, Melanoplus femurrubrum, Melanoplus mexicanus, Melanoplus sanguinipes, Melanoplus spretus, Nomadacris septemfasciata, Schistocerca americana, Schistocerca gregaria, Dociostaurus maroccanus, Tachycines asynamorus, Oedaleus senegalensis, Zonozerus variegatus, Hieroglyphus daganensis, Kraussaria angulifera, Calliptamus italicus, Chortoicetes terminifera, and Locustana pardalina;
arachnoidea, such as arachnids (Acarina), e.g. of the families Argasidae, Ixodidae and Sarcoptidae, such as Amblyomma americanum, Amblyomma variegatum, Ambryomma maculatum, Argas persicus, Boophilus annulatus, Boophilus decoloratus, Boophilus microplus, Dermacentor silvarum, Dermacentor andersoni, Dermacentor variabilis, Hy- alomma truncatum, Ixodes ricinus, Ixodes rubicundus, Ixodes scapularis, Ixodes holo- cyclus, Ixodes pacificus, Ornithodorus moubata, Ornithodorus hermsi, Ornithodorus turicata, Ornithonyssus bacoti, Otobius megnini, Dermanyssus gallinae, Psoroptes ovis, Rhipicephalus sanguineus, Rhipicephalus appendiculatus, Rhipicephalus evertsi, Sarcoptes scabiei, and Eriophyidae spp. such as Aculus schlechtendali, Phyllocoptrata oleivora and Eriophyes sheldoni; Tarsonemidae spp. such as Phytonemus pallidus and Polyphagotarsonemus latus; Tenuipalpidae spp. such as Brevipalpus phoenicis; Tetranychidae spp. such as Tetranychus cinnabarinus, Tetranychus kanzawai, Tetranychus pacificus, Tetranychus telarius and Tetranychus urticae, Panonychus ul- mi, Panonychus citri, and Oligonychus pratensis; Araneida, e.g. Latrodectus mactans, and Loxosceles reclusa;
fleas (Siphonaptera), e.g. Ctenocephalides felis, Ctenocephalides canis, Xenopsylla cheopis, Pulex irritans, Tunga penetrans, and Nosopsyllus fasciatus,
silverfish, firebrat (Thysanura), e.g. Lepisma saccharina and Thermobia domestica, centipedes (Chilopoda), e.g. Scutigera coleoptrata,
millipedes (Diplopoda), e.g. Narceus spp.,
Earwigs (Dermaptera), e.g. forficula auricularia,
lice (Phthiraptera), e.g. Pediculus humanus capitis, Pediculus humanus corporis,
Pthirus pubis, Haematopinus eurysternus, Haematopinus suis, Linognathus vituli, Bo- vicola bovis, Menopon gallinae, Menacanthus stramineus and Solenopotes capillatus.
Collembola (springtails), e.g. Onychiurus ssp..
The compounds of formula (I) are also suitable for controlling Nematodes: plant para- sitic nematodes such as root knot nematodes, Meloidogyne hapla, Meloidogyne incognita, Meloidogyne javanica, 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 spe- cies; Sting nematodes, Belonolaimus longicaudatus and other Belonolaimus species; Pine nematodes, Bursaphelenchus xylophilus and other Bursaphelenchus species; Ring nematodes, Criconema species, Criconemella species, Criconemoides species, Mesocriconema species; Stem and bulb nematodes, Ditylenchus destructor, Ditylen- chus dipsaci and other Ditylenchus species; Awl nematodes, Dolichodorus species; Spiral nematodes, Heliocotylenchus multicinctus and other Helicotylenchus species; Sheath and sheathoid nematodes, Hemicycliophora species and Hemicriconemoides species; Hirshmanniella species; Lance nematodes, Hoploaimus species; false root- knot nematodes, Nacobbus species; Needle nematodes, Longidorus elongatus and other Longidorus 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 and other Rotylenchus species; Scutello- nema species; Stubby root nematodes, Trichodorus primitivus and other Trichodorus species, Paratrichodorus species; Stunt nematodes, Tylenchorhynchus claytoni, Tylenchorhynchus dubius and other Tylenchorhynchus species; Citrus nematodes, Tylen- chulus species; Dagger nematodes, Xiphinema species; and other plant parasitic nematode species.
The compounds of formula (I) are particularly useful for controlling, or combating, or treating, or preventing or protecting each of the individual group of target pests as above listed as well as each combination thereof.
Each of the groups or subgroup of the above listed pests constitute per se, independently of every possible combination a particular preferred target pests for which the compounds of the present invention are useful and therefore particular embodiment. Useful in this context is to be understood as:
use for combating such pest(s) or,
use for controlling such pest(s) or,
use for protecting from attack by such pest(s) or,
use for treating against infestation or infection by such pest(s) or,
use for controlling against infestation or infection by such pest(s) or,
use for preventing against infestation or infection by such pest(s) or,
use for protecting against infestation or infection by such pest(s).
The Compounds of the formula (I) are particularly useful for controlling insects, prefer- ably piercing-sucking insects such as insects from the genera Thysanoptera, Diptera and Hemiptera.
Compounds of the formula (I) are particularly useful for controlling insects of the orders Hemiptera and Thysanoptera. For use in a method according to the present invention, the compounds of formula (I) can be converted into the customary formulations, e.g. solutions, emulsions, suspensions, dusts, powders, pastes, granules and directly sprayable solutions. The use form depends on the particular purpose and application method. Formulations and application methods are chosen to ensure in each case a fine and uniform distribution of the compound of formula (I) according to the invention.
An agrochemical composition according to the present invention comprises a pesti- cidally effective amount of a compound of formula (I) according to the present invention. The term "effective amount" denotes an amount of the composition or of the com- pounds of formula (I), which is sufficient for controlling animal pests on a locus, such as crops, cultivated plants or in the protection of materials and which does not result in a substantial damage to the treated plants. Such an amount can vary in a broad range and is dependent on various factors, such as the animal pest species to be controlled, the treated cultivated plant or material, the climatic conditions and the specific compound of formula (I) used.
The compounds of formula (I) according to the invention can be converted into customary types of agrochemical compositions, e. g. solutions, emulsions, suspensions, dusts, powders, pastes, granules, pressings, capsules, and mixtures thereof. Examples for composition types are suspensions (e.g. SC, OD, FS), emulsifiable concentrates (e.g. EC), emulsions (e.g. EW, EO, ES, ME), capsules (e.g. CS, ZC), pastes, pastilles, wettable powders or dusts (e.g. WP, SP, WS, DP, DS), pressings (e.g. BR, TB, DT), granules (e.g. WG, SG, GR, FG, GG, MG), insecticidal articles (e.g. LN), as well as gel formulations for the treatment of plant propagation materials such as seeds (e.g. GF). These and further compositions types are defined in the " Catalogue of pesticide formulation types and international coding system" , Technical Monograph No. 2, 6th Ed. May 2008, CropLife International.
The compositions are prepared in a known manner, such as described by Mollet and Grubemann, Formulation technology, Wiley VCH, Weinheim, 2001 ; or Knowles, New developments in crop protection product formulation, Agrow Reports DS243, T&F In- forma, London, 2005.
Examples for suitable auxiliaries for the formulations and or the agrochemicals compositions according to the inventions are solvents, liquid carriers, solid carriers or fillers, surfactants, dispersants, emulsifiers, wetters, adjuvants, solubilizers, penetration en- hancers, protective colloids, adhesion agents, thickeners, humectants, repellents, at- tractants, feeding stimulants, compatibilizers, bactericides, antifreezing agents, anti- foaming agents, colorants, tackifiers and binders.
Suitable solvents and liquid carriers are water and organic solvents, such as mineral oil fractions of medium to high boiling point, e.g. kerosene, diesel oil; oils of vegetable or animal origin; aliphatic, cyclic and aromatic hydrocarbons, e. g. toluene, paraffin, tetra- hydronaphthalene, alkylated naphthalenes; alcohols, e.g. ethanol, propanol, butanol, benzylalcohol, cyclohexanol; glycols; DMSO; ketones, e.g. cyclohexanone; esters, e.g. lactates, carbonates, fatty acid esters, gammabutyrolactone; fatty acids; phosphonates; amines; amides, e.g. N-methylpyrrolidone, fatty acid dimethylamides; and mixtures thereof.
Suitable solid carriers or fillers are mineral earths, e.g. silicates, silica gels, talc, kaolins, lime-stone, lime, chalk, clays, dolomite, diatomaceous earth, bentonite, calcium sulfate, magnesium sulfate, magnesium oxide; polysaccharide powders, e.g. cellulose, starch; fertilizers, e.g. ammonium sulfate, ammonium phosphate, ammonium nitrate, ureas; products of vegetable origin, e.g. cereal meal, tree bark meal, wood meal, nutshell meal, and mixtures thereof.
Suitable surfactants are surface active compounds, such as anionic, cationic, nonionic and amphoteric surfactants, block polymers, polyelectrolytes, and mixtures thereof. Such surfactants can be used as emulsifier, dispersant, solubilizer, wetter, penetration enhancer, protective colloid, or adjuvant. Examples of surfactants are listed in
McCutcheon' s, Vol.1 : Emulsifiers & Detergents, McCutcheon' s Directories, Glen Rock, USA, 2008 (International Ed. or North American Ed.).
Suitable anionic surfactants are alkali, alkaline earth or ammonium salts of sulfonates, sulfates, phosphates, carboxylates, and mixtures thereof. Examples of sulfonates are alkylarylsulfonates, diphenylsulfonates, alpha-olefin sulfonates, lignine sulfonates, sulfonates of fatty acids and oils, sulfonates of ethoxylated alkylphenols, sulfonates of alkoxylated arylphenols, sulfonates of condensed naphthalenes, sulfonates of dodecyl- and tridecylbenzenes, sulfonates of naphthalenes and alkylnaphthalenes, sulfosuccin- ates or sulfosuccinamates. Examples of sulfates are sulfates of fatty acids and oils, of ethoxylated alkylphenols, of alcohols, of ethoxylated alcohols, or of fatty acid esters. Examples of phosphates are phosphate esters. Examples of carboxylates are alkyl carboxylates, and carboxylated alcohol or alkylphenol ethoxylates.
Suitable nonionic surfactants are alkoxylates, N-substituted fatty acid amides, amine oxides, esters, sugar based surfactants, polymeric surfactants, and mixtures thereof. Examples of alkoxylates are compounds such as alcohols, alkylphenols, amines, amides, arylphenols, fatty acids or fatty acid esters which have been alkoxylated with 1 to 50 equivalents. Ethylene oxide and/or propylene oxide may be employed for the alkoxylation, preferably ethylene oxide. Examples of N-substituted fatty acid amides are fatty acid glucamides or fatty acid alkanolamides. Examples of esters are fatty acid esters, glycerol esters or monoglycerides. Examples of sugar-based surfactants are sorbitans, ethoxylated sorbitans, sucrose and glucose esters or alkylpolyglucosides. Examples of polymeric surfactants are homo- or copolymers of vinylpyrrolidone, vinyl- alcohols, or vinylacetate.
Suitable cationic surfactants are quaternary surfactants, for example quaternary ammonium compounds with one or two hydrophobic groups, or salts of long chain primary amines. Suitable amphoteric surfactants are alkylbetains and imidazolines. Suitable block polymers are block polymers of the A-B or A-B-A type comprising blocks of poly- ethylene oxide and polypropylene oxide, or of the A-B-C type comprising alkanol, polyethylene oxide and polypropylene oxide. Suitable polyelectrolytes are polyacids or pol- ybases. Examples of polyacids are alkali salts of polyacrylic acid or polyacid comb polymers. Examples of polybases are polyvinylamines or polyethyleneamines.
Suitable adjuvants are compounds, which have a neglectable or even no pesticidal activity themselves, and which improve the biological performance of the compound of formula (I) on the target. Examples are surfactants, mineral or vegetable oils, and other auxiliaries. Further examples are listed by Knowles, Adjuvants and additives, Agrow Reports DS256, T&F Informa UK, 2006, chapter 5.
Suitable thickeners are polysaccharides (e.g. xanthan gum, carboxymethylcellulose), anorganic clays (organically modified or unmodified), polycarboxylates, and silicates. Suitable bactericides are bronopol and isothiazolinone derivatives such as alkylisothia- zolinones and benzisothiazolinones.
Suitable antifreezing agents are ethylene glycol, propylene glycol, urea and glycerine. Suitable antifoaming agents are silicones, long chain alcohols, and salts of fatty acids. Suitable colorants (e.g. in red, blue, or green) are pigments of low water solubility and water-soluble dyes. Examples are inorganic colorants (e.g. iron oxide, titan oxide, iron hexacyanoferrate) and organic colorants (e.g. alizarin-, azo- and phthalocyanine color- ants).
Suitable tackifiers or binders are polyvinylpyrrolidons, polyvinylacetates, polyvinyl alcohols, polyacrylates, biological or synthetic waxes, and cellulose ethers.
Examples for composition types and their preparation are:
i) Water soluble concentrates (SL, LS)
10-60 wt% of a compound of formula (I) according to the invention and 5-15 wt% wetting agent (e.g. alcohol alkoxylates) are dissolved in water and/or in a water- soluble solvent (e.g. alcohols) up to 100 wt%. The active substance dissolves upon dilution with water.
ii) Dispersible concentrates (DC)
5-25 wt% of a compound of formula (I) according to the invention and 1 -10 wt% dispersant (e. g. polyvinylpyrrolidone) are dissolved in up to 100 wt% organic solvent (e.g. cyclohexanone). Dilution with water gives a dispersion.
iii) Emulsifiable concentrates (EC)
15-70 wt% of a compound of formula (I) according to the invention and 5-10 wt% emulsifiers (e.g. calcium dodecylbenzenesulfonate and castor oil ethoxylate) are dissolved in up to 100 wt% water insoluble organic solvent (e.g. aromatic hydrocarbon). Dilution with water gives an emulsion.
iv) Emulsions (EW, EO, ES)
5-40 wt% of a compound of formula (I) according to the invention and 1 -10 wt% emulsifiers (e.g. calcium dodecylbenzenesulfonate and castor oil ethoxylate) are dissolved in 20-40 wt% water insoluble organic solvent (e.g. aromatic hydrocarbon). This mixture is introduced into up to 100 wt% water by means of an emulsifying machine and made into a homogeneous emulsion. Dilution with water gives an emulsion.
v) Suspensions (SC, OD, FS)
In an agitated ball mill, 20-60 wt% of a compound of formula (I) according to the invention are comminuted with addition of 2-10 wt% dispersants and wetting agents (e.g. sodium lignosulfonate and alcohol ethoxylate), 0,1 -2 wt% thickener (e.g. xanthan gum) and up to 100 wt% water to give a fine active substance suspension. Dilution with water gives a stable suspension of the active substance. For FS type composition up to 40 wt% binder (e.g. polyvinylalcohol) is added. vi) Water dispersible granules and water soluble granules (WG, SG)
50-80 wt% of a compound of formula (I) according to the invention are ground finely with addition of up to 100 wt% dispersants and wetting agents (e.g. sodium lignosulfonate and alcohol ethoxylate) and prepared as water dispersible or water soluble granules by means of technical appliances (e. g. extrusion, spray tower, fluidized bed). Dilution with water gives a stable dispersion or solution of the active substance.
vii) Water dispersible powders and water-soluble powders (WP, SP, WS)
50-80 wt% of a compound of formula (I) according to the invention are ground in a rotor stator mill with addition of 1 -5 wt% dispersants (e.g. sodium ligno- sufonate), 1 -3 wt% wetting agents (e.g. alcohol ethoxylate) and up to 100 wt% solid carrier, e.g. silica gel. Dilution with water gives a stable dispersion or solution of the active substance.
viii) Gel (GW, GF)
In an agitated ball mill, 5-25 wt% of a compound of formula (I) according to the invention are comminuted with addition of 3-10 wt% dispersants (e.g. sodium lig- nosulfonate), 1 -5 wt% thickener (e.g. carboxymethylcellulose) and up to 100 wt% water to give a fine suspension of the active substance. Dilution with water gives a stable suspension of the active substance.
iv) Microemulsion (ME)
5-20 wt% of a compound of formula (I) according to the invention are added to 5- 30 wt% organic solvent blend (e.g. fatty acid dimethylamide and cyclohexanone), 10-25 wt% surfactant blend (e.g. alkohol ethoxylate and arylphenol ethoxylate), and water up to 100 %. This mixture is stirred for 1 h to produce spontaneously a thermodynamically stable microemulsion.
iv) Microcapsules (CS)
An oil phase comprising 5-50 wt% of a compound of formula (I) according to the invention, 0-40 wt% water insoluble organic solvent (e.g. aromatic hydrocarbon), 2-15 wt% acrylic monomers (e.g. methylmethacrylate, methacrylic acid and a di- or triacrylate) are dispersed into an aqueous solution of a protective colloid (e.g. polyvinyl alcohol). Radical polymerization initiated by a radical initiator results in the formation of poly(meth)acrylate microcapsules. Alternatively, an oil phase comprising 5-50 wt% of a compound I according to the invention, 0-40 wt% water insoluble organic solvent (e.g. aromatic hydrocarbon), and an isocyanate mono- mer (e.g. diphenylmethene-4,4' -diisocyanatae) are dispersed into an aqueous solution of a protective colloid (e.g. polyvinyl alcohol). The addition of a polyam- ine (e.g. hexamethylenediamine) results in the formation of a polyurea microcapsules. The monomers amount to 1 -10 wt%. The wt% relate to the total CS composition.
ix) Dunstable powders (DP, DS)
1 -10 wt% of a compound of formula (I) according to the invention are ground finely and mixed intimately with up to 100 wt% solid carrier, e.g. finely divided kaolin. x) Granules (GR, FG)
0.5-30 wt% of a compound of formula (I) according to the invention is ground finely and associated with up to 100 wt% solid carrier (e.g. silicate). Granulation is achieved by extrusion, spray drying or the fluidized bed.
xi) Ultra-low volume liquids (UL) 1 -50 wt% of a compound of formula (I) according to the invention are dissolved in up to 100 wt% organic solvent, e.g. aromatic hydrocarbon.
The compositions types i) to xi) may optionally comprise further auxiliaries, such as 0,1 -1 wt% bactericides, 5-15 wt% antifreezing agents, 0,1 -1 wt% antifoaming agents, and 0,1 -1 wt% colorants.
The agrochemical compositions generally comprise between 0.01 and 95%, preferably between 0.1 and 90%, and most preferably between 0.5 and 75%, by weight of active substance i.e. the compounds of formula (I) according to the invention. The active substances are generally employed in a purity of from 90% to 100%, preferably from 95% to 100% (according to NMR spectrum).
Water soluble concentrates (LS), Suspoemulsions (SE), flowable concentrates (FS), powders for dry treatment (DS), water dispersible powders for slurry treatment (WS), water soluble powders (SS), emulsions (ES), emulsifiable concentrates (EC) and gels (GF) are usually employed for the purposes of treatment of plant propagation materials, particularly seeds.
The compositions according to the invention in question give, after two-to-tenfold dilution, concentrations of active substance of from 0.01 to 60% by weight, preferably from 0.1 to 40% by weight, in the ready-to-use preparations.
Application can be carried out before or during sowing. Methods for applying or treating compound of formula (I) and compositions thereof, respectively, on to plant propagation material, especially seeds include dressing, coating, pelleting, dusting, soaking and in furrow application methods of the propagation material. Preferably, compound of formula (I) or the compositions thereof, respectively, are applied on to the plant propa- gation material by a method such that germination is not induced, e.g. by seed dressing, pelleting, coating and dusting.
When employed in plant protection, the amounts of active substances applied are, depending on the kind of effect desired, from 0.001 to 2 kg per ha, preferably from 0.005 to 2 kg per ha, more preferably from 0.05 to 0.9 kg per ha, in particular from 0.1 to 0.75 kg per ha.
In treatment of plant propagation materials such as seeds, e. g. by dusting, coating or drenching seed, amounts of active substance of from 0.1 to 1000 g, preferably from 1 to 1000 g, more preferably from 1 to 100 g and most preferably from 5 to 100 g, per 100 kilogram of plant propagation material (preferably seed) are generally required. When used in the protection of materials or stored products, the amount of active substance applied depends on the kind of application area and on the desired effect.
Amounts customarily applied in the protection of materials are 0.001 g to 2 kg, preferably 0.005 g to 1 kg, of active substance per cubic meter of treated material.
Various types of oils, wetters, adjuvants, fertilizer, or micronutrients, and other pesti- cides (e.g. herbicides, insecticides, fungicides, growth regulators, safeners) may be added to the active substances or the compositions comprising them as premix or, if appropriate not until immediately prior to use (tank mix). These agents can be admixed with the compositions according to the invention in a weight ratio of 1 :100 to 100:1 , preferably 1 :10 to 10:1.
The user applies the composition according to the invention usually from a predosage device, a knapsack sprayer, a spray tank, a spray plane, or an irrigation system. Usual- ly, the agrochemical composition is made up with water, buffer, and/or further auxiliaries to the desired application concentration and the ready-to-use spray liquor or the agrochemical composition according to the invention is thus obtained. Usually, 20 to 2000 liters, preferably 50 to 400 liters, of the ready-to-use spray liquor are applied per hectare of agricultural useful area.
According to one embodiment of the present invention, individual components of the composition according to the invention such as parts of a kit or parts of a binary or ternary mixture may be mixed by the user himself in a spray tank and further auxiliaries may be added, if appropriate.
In a further embodiment, either individual components of the composition according to the invention or partially premixed components, e. g. components comprising compounds of formula (I) and/or additional active substances from the groups M.1 ) to M.26, including M-X or F.I to F.XII, may be mixed by the user in a spray tank and further auxiliaries and additives may be added, if appropriate.
In a further embodiment, either individual components of the composition according to the invention or partially premixed components, e. g. components comprising compounds of formula (I) and/or active substances from the groups M.1 to M.26, including M-X or F.I to F.XII, can be applied jointly (e.g. after tank mix) or consecutively.
Mixtures
The following list M of pesticides, grouped and numbered according the Mode of Action Classification of the Insecticide Resistance Action Committee (IRAC), together with which the compounds according to the invention can be used and with which potential synergistic effects might be produced, is intended to illustrate the possible combina- tions, but not to impose any limitation:
M.1 Acetylcholine esterase (AChE) inhibitors from the class of
M.1A carbamates, for example aldicarb, alanycarb, bendiocarb, benfuracarb, butocar- boxim, butoxycarboxim, carbaryl, carbofuran, carbosulfan, ethiofencarb, fenobucarb, formetanate, furathiocarb, isoprocarb, methiocarb, methomyl, metolcarb, oxamyl, pi- rimicarb, propoxur, thiodicarb, thiofanox, trimethacarb, XMC, xylylcarb and triazamate; or from the class of
M.1 B organophosphates, for example acephate, azamethiphos, azinphos-ethyl, az- inphosmethyl, cadusafos, chlorethoxyfos, chlorfenvinphos, chlormephos, chlorpyrifos, chlorpyrifos-methyl, coumaphos, cyanophos, demeton-S-methyl, diazinon, dichlorvos/ DDVP, dicrotophos, dimethoate, dimethylvinphos, disulfoton, EPN, ethion, ethopro- phos, famphur, fenamiphos, fenitrothion, fenthion, fosthiazate, heptenophos, imicyafos, isofenphos, isopropyl O- (methoxyaminothio-phosphoryl) salicylate, isoxathion, mala- thion, mecarbam, methamidophos, methidathion, mevinphos, monocrotophos, naled, omethoate, oxydemeton-methyl, parathion, parathion-methyl, phenthoate, phorate, phosalone, phosmet, phosphamidon, phoxim, pirimiphos- methyl, profenofos, prope- tamphos, prothiofos, pyraclofos, pyridaphenthion, quinalphos, sulfotep, tebupirimfos, temephos, terbufos, tetrachlorvinphos, thiometon, triazophos, trichlorfon and vami- dothion;
M.2. GABA-gated chloride channel antagonists such as:
M.2A cyclodiene organochlorine compounds, as for example endosulfan or chlordane; or
M.2B fiproles (phenylpyrazoles), as for example ethiprole, fipronil, flufiprole, pyra- fluprole and pyriprole;
M.3 Sodium channel modulators from the class of
M.3A pyrethroids, for example acrinathrin, allethrin, d-cis-trans allethrin, d-trans alle- thrin, bifenthrin, bioallethrin, bioallethrin S-cylclopentenyl, bioresmethrin, cycloprothrin, cyfluthrin, beta-cyfluthrin, cyhalothrin, lambda-cyhalothrin, gamma-cyhalothrin, cyper- methrin, alpha-cypermethrin, beta-cypermethrin, theta-cypermethrin, zeta- cypermethrin, cyphenothrin, deltamethrin, empenthrin, esfenvalerate, etofenprox, fenpropathrin, fenvalerate, flucythrinate, flumethrin, tau-fluvalinate, halfenprox, hep- tafluthrin, imiprothrin, meperfluthrin,metofluthrin, momfluorothrin, permethrin, phe- nothrin, prallethrin, profluthrin, pyrethrin (pyrethrum), resmethrin, silafluofen, tefluthrin, tetramethylfluthrin, tetramethrin, tralomethrin and transfluthrin; or
M.3B sodium channel modulators such as DDT or methoxychlor;
M.4 Nicotinic acetylcholine receptor agonists (nAChR) from the class of
M.4A neonicotinoids, for example acteamiprid, chlothianidin, cycloxaprid, dinotefuran, imidacloprid, nitenpyram, thiacloprid and thiamethoxam; or the compounds
M.4A.2: (2E-)-1 -[(6-Chloropyridin-3-yl)methyl]-N'-nitro-2- pentylidenehydrazinecarboximidamide; or
M4.A.3: 1 -[(6-Chloropyridin-3-yl)methyl]-7-methyl-8-nitro-5-propoxy-1 ,2,3,5,6,7- hexahydroimidazo[1 ,2-a]pyridine;
or from the class M.4B nicotine; M.5 Nicotinic acetylcholine receptor allosteric activators from the class of spinosyns, for example spinosad or spinetoram;
M.6 Chloride channel activators from the class of avermectins and milbemycins, for example abamectin, emamectin benzoate, ivermectin, lepimectin or milbemectin;
M.7 Juvenile hormone mimics, such as
M.7A juvenile hormone analogues as hydroprene, kinoprene and methoprene; or others as M.7B fenoxycarb or M.7C pyriproxyfen; M.8 miscellaneous non-specific (multi-site) inhibitors, for example
M.8A alkyl halides as methyl bromide and other alkyl halides, or
M.8B chloropicrin, or M.8C sulfuryl fluoride, or M.8D borax, or M.8E tartar emetic;
M.9 Selective homopteran feeding blockers, for example
M.9B pymetrozine, or M.9C flonicamid;
M.10 Mite growth inhibitors, for example
M.10A clofentezine, hexythiazox and diflovidazin, or M.10B etoxazole;
M.1 1 Microbial disruptors of insect midgut membranes, for example bacillus thuringiensis or bacillus sphaericus and the insecticdal proteins they produce such as bacillus thuringiensis subsp. israelensis, bacillus sphaericus, bacillus thuringiensis subsp. aizawai, bacillus thuringiensis subsp. kurstaki and bacillus thuringiensis subsp. tenebri- onis, or the Bt crop proteins: CrylAb, CrylAc, Cryl Fa, Cry2Ab, mCry3A, Cry3Ab, Cry3Bb and Cry34/35Ab1 ;
M.12 Inhibitors of mitochondrial ATP synthase, for example
M.12A diafenthiuron, or
M.12B organotin miticides such as azocyclotin, cyhexatin or fenbutatin oxide, or M.12C propargite, or M.12D tetradifon;
M.13 Uncouplers of oxidative phosphorylation via disruption of the proton gradient, for example chlorfenapyr, DNOC or sulfluramid;
M.14 Nicotinic acetylcholine receptor (nAChR) channel blockers, for example nereis- toxin analogues as bensultap, cartap hydrochloride, thiocyclam or thiosultap sodium; M.15 Inhibitors of the chitin biosynthesis type 0, such as benzoylureas as for example bistrifluron, chlorfluazuron, diflubenzuron, flucycloxuron, flufenoxuron, hexaflumuron, lufenuron, novaluron, noviflumuron, teflubenzuron or triflumuron;
M.16 Inhibitors of the chitin biosynthesis type 1 , as for example buprofezin;
M.17 Moulting disruptors, Dipteran, as for example cyromazine;
M.18 Ecdyson receptor agonists such as diacylhydrazines, for example methoxyfeno- zide, tebufenozide, halofenozide, fufenozide or chromafenozide;
M.19 Octopamin receptor agonists, as for example amitraz;
M.20 Mitochondrial complex III electron transport inhibitors, for example M.20A hydramethylnon, or M.20B acequinocyl, or M.20C fluacrypyrim;
M.21 Mitochondrial complex I electron transport inhibitors, for example
M.21A METI acaricides and insecticides such as fenazaquin, fenpyroximate, pyrimidif- en, pyridaben, tebufenpyrad or tolfenpyrad, or M.21 B rotenone;
M.22 Voltage-dependent sodium channel blockers, for example
M.22A indoxacarb, or M.22B metaflumizone, or M.22B.1 : 2-[2-(4-Cyanophenyl)-1 -[3- (trifluoromethyl)phenyl]ethylidene]-N-[4-(difluoromethoxy)phenyl]- hydrazinecarboxamide or M.22B.2: N-(3-Chloro-2-methylphenyl)-2-[(4-chlorophenyl)[4- [methyl(methylsulfonyl)amino]phenyl]methylene]-hydrazinecarboxamide;
M.23 Inhibitors of the of acetyl CoA carboxylase, such as Tetronic and Tetramic acid derivatives, for example spirodiclofen, spiromesifen or spirotetramat;
M.24 Mitochondrial complex IV electron transport inhibitors, for example
M.24A phosphine such as aluminium phosphide, calcium phosphide, phosphine or zinc phosphide, or M.24B cyanide; M.25 Mitochondrial complex II electron transport inhibitors, such as beta-ketonitrile derivatives, for example cyenopyrafen or cyflumetofen;
M.28 Ryanodine receptor-modulators from the class of diamides, as for example flubendiamide, chlorantraniliprole (rynaxypyr®), cyantraniliprole (cyazypyr®), or the phthalamide compounds
M.28.1 : (R)-3-Chlor-N1 -{2-methyl-4-[1 , 2,2,2 - tetrafluor-1 -(trifluormethyl)ethyl]phenyl}- N2-(1 -methyl-2-methylsulfonylethyl)phthalamid and
M.28.2: (S)-3-Chlor-N1 -{2-methyl-4-[1 ,2,2,2 - tetrafluor-1 -(trifluormethyl)ethyl]phenyl}- N2-(1 -methyl-2-methylsulfonylethyl)phthalamid, or the compound
M.28.3: 3-bromo-N-{2-bromo-4-chloro-6-[(1 -cyclopropylethyl)carbamoyl]phenyl}-1 -(3- chlorpyridin-2-yl)-1 H-pyrazole-5-carboxamide (proposed ISO name: cyclaniliprole), or the compound
M.28.4: methyl-2-[3,5-dibromo-2-({[3-bromo-1 -(3-chlorpyridin-2-yl)-1 H-pyrazol-5- yl]carbonyl}amino)benzoyl]-1 ,2-dimethylhydrazinecarboxylate; or a compound selected from M.28.5a) to M.28.5I):
M.28.5a) N-[4,6-dichloro-2-[(diethyl-lambda-4-sulfanylidene)carbamoyl]-phenyl]-2-(3- chloro-2-pyridyl)-5-(trifluoromethyl)pyrazole-3-carboxamide;
M.28.5b) N-[4-chloro-2-[(diethyl-lambda-4-sulfanylidene)carbamoyl]-6-methyl-phenyl]- 2-(3-chloro-2-pyridyl)-5-(trifluoromethyl)pyrazole-3-carboxamide;
M.28.5c) N-[4-chloro-2-[(di-2-propyl-lambda-4-sulfanylidene)carbamoyl]-6-methyl- phenyl]-2-(3-chloro-2-pyridyl)-5-(trifluoromethyl)pyrazole-3-carboxamide;
M.28.5d) N-[4,6-dichloro-2-[(di-2-propyl-lambda-4-sulfanylidene)carbamoyl]-phenyl]-2- (3-chloro-2-pyridyl)-5-(trifluoromethyl)pyrazole-3-carboxamide; M.28.5e) N-[4,6-dichloro-2-[(diethyl-lambda-4-sulfanylidene)carbamoyl]-phenyl]-2-(3- chloro-2-pyridyl)-5-(difluoromethyl)pyrazole-3-carboxamide;
M.28.5f) N-[4,6-dibromo-2-[(di-2-propyl-lambda-4-sulfanylidene)carbamoyl]-phenyl]-2- (3-chloro-2-pyridyl)-5-(trifluoromethyl)pyrazole-3-carboxamide;
M.28.5g) N-[4-chloro-2-[(di-2-propyl-lambda-4-sulfanylidene)carbamoyl]-6-cyano- phenyl]-2-(3-chloro-2-pyridyl)-5-(trifluoromethyl)pyrazole-3-carboxamide;
M.28.5h) N-[4,6-dibromo-2-[(diethyl-lambda-4-sulfanylidene)carbamoyl]-phenyl]-2-(3- chloro-2-pyridyl)-5-(trifluoromethyl)pyrazole-3-carboxamide;
Μ.28.5Ϊ) N-[2-(5-Amino-1 ,3,4-thiadiazol-2-yl)-4-chloro-6-methylphenyl]-3-bromo-1 -(3- chloro-2-pyridinyl)-1 H-pyrazole-5-carboxamide;
M.28.5j) 3-Chloro-1 -(3-chloro-2-pyridinyl)-N-[2,4-dichloro-6-[[(1 -cyano-1 - methylethyl)amino]carbonyl]phenyl]-1 H-pyrazole-5-carboxamide;
M.28.5k) 3-Bromo-N-[2,4-dichloro-6-(methylcarbamoyl)phenyl]-1 -(3,5-dichloro-2- pyridyl)-1 H-pyrazole-5-carboxamide;
M.28.5I) N-[4-Chloro-2-[[(1 ,1 -dimethylethyl)amino]carbonyl]-6-methylphenyl]-1 -(3- chloro-2-pyridinyl)-3-(fluoromethoxy)-1 H-pyrazole-5-carboxamide;
or a compound selected from
M.28.6: N-(2-cyanopropan-2-yl)-N-(2,4-dimethylphenyl)-3-iodobenzene-1 ,2- dicarboxamide; or
M.28.7: 3-Chloro-N-(2-cyanopropan-2-yl)-N-(2,4-dimethylphenyl)-benzene-1 ,2- dicarboxamide;
M.28.8a) 1 -(3-Chloro-2-pyridinyl)-N-[4-cyano-2-methyl-6-
[(methylamino)carbonyl]phenyl]-3-[[5-(trifluoromethyl)-2H-tetrazol-2-yl]methyl]-1 H- pyrazole-5-carboxamide; or
M.28.8b) 1 -(3-Chloro-2-pyridinyl)-N-[4-cyano-2-methyl-6-
[(methylamino)carbonyl]phenyl]-3-[[5-(trifluoromethyl)-1 H-tetrazol-1 -yl]methyl]-1 H- pyrazole-5-carboxamide;
M.UN. insecticidal active compounds of unknown or uncertain mode of action, as for example afidopyropen, afoxolaner, azadirachtin, amidoflumet, benzoximate, bifena- zate, bromopropylate, chinomethionat, cryolite, dicofol, flufenerim, flometoquin, fluen- sulfone, fluopyram, flupyradifurone, fluralaner, metoxadiazone, piperonyl butoxide, pyflubumide, pyridalyl, pyrifluquinazon, sulfoxaflor, tioxazafen, triflumezopyrim, or the compounds
M.UN.3: 1 1 -(4-chloro-2,6-dimethylphenyl)-12-hydroxy-1 ,4-dioxa-9-azadispiro[4.2.4.2]- tetradec-1 1 -en-10-one, or the compound
M.UN.4: 3-(4' -fluoro-2,4-dimethylbiphenyl-3-yl)-4-hydroxy-8-oxa-1 -azaspiro[4.5]dec- 3-en-2-one, or the compound
M.UN.5: 1 -[2-fluoro-4-methyl-5-[(2,2,2-trifluoroethyl)sulfinyl]phenyl]-3-(trifluoromethyl)- 1 H-1 ,2,4-triazole-5-amine, or actives on basis of bacillus firmus (Votivo, 1-1582); or a compound selected from the group of M.UN.6, wherein the compound is selected from M.UN.6a) to M.UN.6k): M.UN.6a) (E/Z)-N-[1 -[(6-chloro-3-pyridyl)methyl]-2-pyridylidene]-2,2,2-trifluoro- acetamide;
M.UN.6b) (E/Z)-N-[1 -[(6-chloro-5-fluoro-3-pyridyl)methyl]-2-pyridylidene]-2,2,2-trifluoro- acetamide;
M.UN.6c) (E/Z)-2,2,2-trifluoro-N-[1 -[(6-fluoro-3-pyridyl)methyl]-2- pyridylidene]acetamide;
M.UN.6d) (E/Z)-N-[1 -[(6-bromo-3-pyridyl)methyl]-2-pyridylidene]-2,2,2-trifluoro- acetamide;
M.UN.6e) (E/Z)-N-[1 -[1 -(6-chloro-3-pyridyl)ethyl]-2-pyridylidene]-2,2,2-trifluoro- acetamide;
M.UN.6f) (E/Z)-N-[1 -[(6-chloro-3-pyndyl)methyl]-2-pyridylidene]-2,2-difluoro-acetamide; M.UN.6g) (E/Z)-2-chloro-N-[1 -[(6-chloro-3-pyridyl)methyl]-2-pyridylidene]-2,2-difluoro- acetamide;
M.UN.6h) (E/Z)-N-[1 -[(2-chloropyrimidin-5-yl)methyl]-2-pyridylidene]-2,2,2-trifluoro- acetamide;
M.UN.6i) (E/Z)-N-[1 -[(6-chloro-3-pyridyl)methyl]-2-pyridylidene]-2,2,3,3,3-pentafluoro- propanamide.);
M.UN.6j) N-[1 -[(6-chloro-3-pyndyl)methyl]-2-pyndylidene]-2,2,2-trifluoro-thioacetamide or of the compound
M.UN.6k) N-[1 -[(6-chloro-3-pyridyl)methyl]-2-pyridylidene]-2,2,2-trifluoro-N'-isopropyl- acetamidine
or the compounds
M.UN.8: 8-chloro-N-[2-chloro-5-methoxyphenyl)sulfonyl]-6-trifluoromethyl)-imidazo[1 ,2- a]pyridine-2-carboxamide; or
M.UN.9: 4-[5-(3,5-dichlorophenyl)-5-(trifluoromethyl)-4H-isoxazol-3-yl]-2-methyl-N-(1 - oxothietan-3-yl)benzamide; or
M.UN.10: 5-[3-[2,6-dichloro-4-(3,3-dichloroallyloxy)phenoxy]propoxy]-1 H-pyrazole; or a compound selected from the group of M.UN.1 1 , wherein the compound is selected from M. UN.1 1 a) to M.UN.1 1 p):
M.UN.1 1. a) 3-[benzoyl(methyl)amino]-N-[2-bromo-4-[1 ,2,2,2-tetrafluoro-1 -
(trifluoromethyl)ethyl]-6-(trifluoromethyl)phenyl]-2-fluoro-benzamide;
M.UN.1 1.b) 3-(benzoylmethylamino)-N-[2-bromo-4-[1 ,2,2,3,3,3-hexafluoro-1 -
(trifluoromethyl)propyl]-6-(trifluoromethyl)phenyl]-2-fluoro-benzamide;
M.UN.1 1.c) 3-(benzoylmethylamino)-2-fluoro-N-[2-iodo-4-[1 ,2,2,2-tetrafluoro-1 - (trifluoromethyl)ethyl]-6-(trifluoromethyl)phenyl]-benzamide;
M.UN.1 1.d) N-[3-[[[2-iodo-4-[1 ,2,2,2-tetrafluoro-1 -(trifluoromethyl)ethyl]-6-
(trifluoromethyl)phenyl]amino]carbonyl]phenyl]-N-methyl-benzamide;
M.UN.1 1.e) N-[3-[[[2-bromo-4-[1 ,2,2,2-tetrafluoro-1 -(trifluoromethyl)ethyl]-6-
(trifluoromethyl)phenyl]amino]carbonyl]-2-fluorophenyl]-4-fluoro-N-methyl-benzamide; M.UN.1 1.f) 4-fluoro-N-[2-fluoro-3-[[[2-iodo-4-[1 ,2,2,2-tetrafluoro-1 -
(trifluoromethyl)ethyl]-6-(trifluoromethyl)phenyl]amino]carbonyl]phenyl]-N-methyl- benzamide; M.UN.H .g) 3-fluoro-N-[2-fluoro-3-[[[2-iodo-4-[1 ,2,2,2-tetrafluoro-1 -
(trifluoromethyl)ethyl]-6-(trifluoromethyl)phenyl]amino]carbonyl]pheny^
benzamide;
M.UN.H .h) 2-chloro-N-[3-[[[2-iodo-4-[1 ,2,2,2-tetrafluoro-1 -(trifluoromethyl)ethyl]-6- (trifluoromethyl)phenyl]amino]carbonyl]phenyl]- 3-pyridinecarboxamide;
M.UN.H .i) 4-cyano-N-[2-cyano-5-[[2,6-dibromo-4-[1 ,2,2,3,3,3-hexafluoro-1 - (trifluoromethyl)propyl]phenyl]carbamoyl]phenyl]-2-methyl-benzamide;
M.UN.1 1 .j) 4-cyano-3-[(4-cyano-2-methyl-benzoyl)amino]-N-[2,6-dichloro-4- [1 ,2,2,3,3,3-hexafluoro-1 -(trifluoromethyl)propyl]phenyl]-2-fluoro-benzamide;
M.UN.1 1.k) N-[5-[[2-chloro-6-cyano-4-[1 ,2,2,3,3,3-hexafluoro-1 -
(trifluoromethyl)propyl]phenyl]carbamoyl]-2-cyano-phenyl]-4-cyano-2-methyl- benzamide;
M.UN.1 1 .1) N-[5-[[2-bromo-6-chloro-4-[2,2,2-trifluoro-1 -hydroxy-1 - (trifluoromethyl)ethyl]phenyl]carbamoyl]-2-cyano-phenyl]-4-cyano-2-methyl-ben M.UN.1 1 .m) N-[5-[[2-bromo-6-chloro-4-[1 ,2,2,3,3,3-hexafluoro-1 -
(trifluoromethyl)propyl]phenyl]carbamoyl]-2-cyano-phenyl]-4-cyano-2-methyl- benzamide;
M.UN.1 1.n) 4-cyano-N-[2-cyano-5-[[2,6-dichloro-4-[1 ,2,2,3,3,3-hexafluoro-1 - (trifluoromethyl)propyl]phenyl]carbamoyl]phenyl]-2-methyl-benzamide;
M.UN.1 1.o) 4-cyano-N-[2-cyano-5-[[2,6-dichloro-4-[1 ,2,2,2-tetrafluoro-1 - (trifluoromethyl)ethyl]phenyl]carbamoyl]phenyl]-2-methyl-benzamide;
M.UN.1 1.p) N-[5-[[2-bromo-6-chloro-4-[1 ,2,2,2-tetrafluoro-1 - (trifluoromethyl)ethyl]phenyl]carbamoyl]-2-cyano-phenyl]-4-cyano-2-methyl-ben or a compound selected from the group of M.UN.12, wherein the compound is selected from M. UN.12a) to M. UN.12m):
M.UN.12.a) 2-(1 ,3-Dioxan-2-yl)-6-[2-(3-pyridinyl)-5-thiazolyl]-pyridine;
M.UN.12.b) 2-[6-[2-(5-Fluoro-3-pyridinyl)-5-thiazolyl]-2-pyridinyl]-pyrimidine;
M.UN.12.C) 2-[6-[2-(3-Pyridinyl)-5-thiazolyl]-2-pyridinyl]-pyrimidine;
M.UN.12.d) N-Methylsulfonyl-6-[2-(3-pyridyl)thiazol-5-yl]pyridine-2-carboxamide M.UN.12.e) N-Methylsulfonyl-6-[2-(3-pyridyl)thiazol-5-yl]pyridine-2-carboxamide M.UN.12.†) N-Ethyl-N-[4-methyl-2-(3-pyridyl)thiazol-5-yl]-3-methylthio-propanamide M.UN.12.g) N-Methyl-N-[4-methyl-2-(3-pyridyl)thiazol-5-yl]-3-methylthio-propanamide M.UN.12.h) N,2-Dimethyl-N-[4-methyl-2-(3-pyridyl)thiazol-5-yl]-3-methylthio- propanamide
M.UN.12.1) N-Ethyl-2-methyl-N-[4-methyl-2-(3-pyridyl)thiazol-5-yl]-3-methylthio- propanamide
M.UN.12J) N-[4-Chloro-2-(3-pyridyl)thiazol-5-yl]-N-ethyl-2-methyl-3-methylthio- propanamide
M.UN.12.k) N-[4-Chloro-2-(3-pyridyl)thiazol-5-yl]-N,2-dimethyl-3-methylthio- propanamide
M.UN.12.1) N-[4-Chloro-2-(3-pyridyl)thiazol-5-yl]-N-methyl-3-methylthio-propanamide M.UN.12.m) N-[4-Chloro-2-(3-pyridyl)thiazol-5-yl]-N-ethyl-3-methylthio-propanamide; or the compound M.UN.13: 2-(4-methoxyiminocyclohexyl)-2-(3,3,3-trifluoropropylsulfonyl)acetonitrile; or the compounds
M. UN.14a) 1 -[(6-Chloro-3-pyridinyl)methyl]-1 ,2,3,5,6,7-hexahydro-5-methoxy-7-methyl- 8-nitro-imidazo[1 ,2-a]pyridine; or
M. UN.14b) 1 -[(6-Chloropyridin-3-yl)methyl]-7-methyl-8-nitro-1 , 2,3,5,6,7- hexahydroimidazo[1 ,2-a]pyridin-5-ol; or the compound
M.UN.15: 1 -[(2-Chloro-1 ,3-thiazol-5-yl)methyl]-3-(3,5-dichlorophenyl)-9-methyl-4-oxo- 4H-pyrido[1 ,2-a]pyrimidin-1 -ium-2-olate.
The commercially available compounds of the group M listed above may be found in The Pesticide Manual, 15th Edition, C. D. S. Tomlin, British Crop Protection Council (201 1 ) among other publications. The neonicotinoid cycloxaprid is known from WO20120/069266 and WO201 1/06946, and the neonicotinoid compound M.4A.2, sometimes also to be named as Guadipyr, is known from WO2013/003977, and the neonicotinoid compound M.4A.3. (approved as paichongding in China) is known from WO2010/069266. The Metaflumizone analogue M.22B.1 is described in CN 10171577 and the analogue M.22B.2 in CN102126994. The phthalamides M.28.1 and M.28.2 are both known from WO 2007/101540. The an- thranilamide M.28.3 has been described in WO2005/077934. The hydrazide compound M.28.4 has been described in WO 2007/043677. The anthranilamides M.28.5a) to M.28.5h) can be prepared as described in WO 2007/006670, WO2013/024009 and WO2013/024010, the anthranilamide compound Μ.28.5Ϊ) is described in
WO201 1/085575, the compound M.28.5j) in WO2008/134969, the compound M.28.5k) in US201 1/046186 and the compound M.28.5I) in WO2012/034403. The diamide compounds M.28.6 and M.28.7 can be found in CN102613183. The anthranilamide compounds M.28.8a) and M.28.8b) are known from WO2010/069502. The quinoline derivative flometoquin is shown in WO2006/013896. The aminofuranone compounds flupyradifurone is known from WO 2007/1 15644. The sulfoximine compound sulfoxaflor is known from WO2007/149134. From the pyrethroids group mom- fluorothrin is known from US6908945 and heptafluthrin from W010133098. The oxadiazolone compound metoxadiazone can be found in JP13/166707. The pyrazole acaricide pyflubumide is known from WO2007/020986. The isoxazoline compounds have been described in following publications: fluralaner in WO2005/085216, afoxolan- er in WO2009/002809 and in WO201 1/149749 and the isoxazoline compound M.UN.9 in WO2013/050317. The pyripyropene derivative afidopyropen has been described in WO 2006/129714. The nematicide tioxazafen has been disclosed in WO09023721 and nematicide fluopyram in WO2008126922, nematicidal mixtures comprising flupyram in WO2010108616. The triflumezopyrim compound was described in WO2012/0921 15. The spiroketal-substituted cyclic ketoenol derivative M.UN.3 is known from
WO2006/089633 and the biphenyl-substituted spirocyclic ketoenol derivative M.UN.4 from WO2008/06791 1. The triazoylphenylsulfide M.UN.5 has been described in WO2006/043635, and biological control agents on basis of bacillus firmus in
WO2009/124707.
The compounds M.UN.6a) to M.UN.6i) listed under M.UN.6 have been described in WO2012/029672 and compounds M.UN.6j) and M.UN.6k) in WO2013129688. The nematicide compound M.UN.8 in WO2013/055584 and the Pyridalyl-type analogue M.UN.10 in WO2010/060379. The carboxamide compounds M. UN.1 1 . a) to M.UN.H .h) can be prepared as described in WO 2010/018714 and the carboxamide M.UN.1 1 i) to M.UN.1 1.p) are described WO2010/127926. The pyridylthiazoles M.UN.12.a) to M.UN.12.C) are known from WO2010/006713, M.UN.12.C) and M.UN.12.d)
WO2012000896 and M.UN.12.f) to M.UN.12.m) in WO2010129497. The malononitrile compound M.UN.13 was described in WO2009/0051 10. The compounds M. UN.14a) and M. UN.14b) are known from WO2007/101369. The compound M.UN.15 can be found in WO 2013/192035.
The following list F of active fungicidal substances, in conjunction with which the compounds according to the invention can be used, is intended to illustrate the possible combinations but does not limit them:
F.I) Respiration Inhibitors
F.1-1 ) Inhibitors of complex III at Qo site:
strobilurins: azoxystrobin, coumethoxystrobin, coumoxystrobin, dimoxystrobin, ene- stroburin, fluoxastrobin, kresoxim-methyl, metominostrobin, orysastrobin, picoxystrobin, pyraclostrobin, pyrametostrobin, pyraoxystrobin, pyribencarb, triclopy- ricarb/chlorodincarb, trifloxystrobin, 2-[2-(2,5-dimethyl-phenoxymethyl)-phenyl]-3- methoxy-acrylic acid methyl ester and 2 (2-(3-(2,6-dichlorophenyl)-1 -methyl- allylideneaminooxymethyl)-phenyl)-2-methoxyimino-N methyl-acetamide;
oxazolidinediones and imidazolinones: famoxadone, fenamidone;
F.I-2) Inhibitors of complex II (e.g. carboxamides):
carboxanilides: benodanil, benzovindiflupyr, bixafen, boscalid, carboxin, fenfuram, fenhexamid, fluopyram, flutolanil, furametpyr, isopyrazam, isotianil, mepronil, oxycar- boxin, penflufen, penthiopyrad, sedaxane, tecloftalam, thifluzamide, tiadinil, 2-amino-4 methyl-thiazole-5-carboxanilide, N-(3',4',5' trifluorobiphenyl-2 yl)-3-difluoromethyl-1 - methyl-1 H-pyrazole-4 carboxamide (fluxapyroxad), N-(4'-trifluoromethylthiobiphenyl-2- yl)-3 difluoromethyl-1 -methyl-1 H pyrazole-4-carboxamide, N-(2-(1 ,3,3-trimethyl-butyl)- phenyl)-1 ,3-dimethyl-5 fluoro-1 H-pyrazole-4 carboxamide, 3-(difluoromethyl)-1 -methyl- N-(1 ,1 ,3-trimethylindan-4-yl)pyrazole-4-carboxamide, 3-(trifluoromethyl)-1 -methyl-N- (1 ,1 ,3-trimethylindan-4-yl)pyrazole-4-carboxamide, 1 ,3-dimethyl-N-(1 ,1 ,3-trimethyl- indan-4-yl)pyrazole-4-carboxamide, 3-(trifluoromethyl)-1 ,5-dimethyl-N-(1 ,1 ,3-trimethyl- indan-4-yl)pyrazole-4-carboxamide, 3-(difluoromethyl)-1 ,5-dimethyl-N-(1 ,1 ,3-trimethyl- indan-4-yl)pyrazole-4-carboxamide, 1 ,3,5-trimethyl-N-(1 ,1 ,3-trimethylindan-4-yl)pyra- zole-4-carboxamide, , 3-(difluoromethyl)-1 -methyl-N-(1 ,1 ,3-trimethylindan-4-yl)pyra- zole-4-carboxamide, 3-(trifluoromethyl)-1 -methyl-N-(1 ,1 ,3-trimethylindan-4-yl)pyrazole- 4-carboxamide, 1 ,3-dimethyl-N-(1 ,1 ,3-trimethylindan-4-yl)pyrazole-4-carboxamide, 3- (trifluoromethyl)-l ,5-dimethyl-N-(1 ,1 ,3-trimethylindan-4-yl)pyrazole-4-carboxamide, 3- (difluoromethyl)-l ,5-dimethyl-N-(1 ,1 ,3-trimethylindan-4-yl)pyrazole-4-carboxamide, 1 ,3,5-trimethyl-N-(1 ,1 ,3-trimethylindan-4-yl)pyrazole-4-carboxamide;
F.I-3) Inhibitors of complex III at Qi site: cyazofamid, amisulbrom, [(3S,6S,7R,8R)-8- benzyl-3-[(3-acetoxy-4-methoxy-pyridine-2-carbonyl)amino]-6-methyl-4,9-dioxo-1 ,5-di- oxonan-7-yl] 2-methylpropanoate, [(3S,6S,7R,8R)-8-benzyl-3-[[3-(acetoxymethoxy)-4- methoxy-pyridine-2-carbonyl]amino]-6-methyl-4,9-dioxo-1 ,5-dioxonan-7-yl]
2-methylpropanoate, [(3S,6S,7R,8R)-8-benzyl-3-[(3-isobutoxycarbonyloxy-4-methoxy- pyridine-2-carbonyl)amino]-6-methyl-4,9-dioxo-1 ,5-dioxonan-7-yl] 2-methylpropanoate, [(3S,6S,7R,8R)-8-benzyl-3-[[3-(1 ,3-benzodioxol-5-ylmethoxy)-4-methoxy-pyridine-2- carbonyl]amino]-6-methyl-4,9-dioxo-1 ,5-dioxonan-7-yl] 2-methylpropanoate,
3S,6S,7R,8R)-3-[[(3-hydroxy-4-methoxy-2-pyridinyl)carbonyl]amino]-6-methyl-4,9- dioxo-8-(phenylmethyl)-1 ,5-dioxonan-7-yl 2-methylpropanoate;
F.I-4) Other respiration inhibitors (complex I, uncouplers) diflumetorim; (5,8-difluoro- quinazolin-4-yl)-{2-[2-fluoro-4-(4-trifluoromethylpyridin-2-yloxy)-phenyl]-ethyl}-amine; tecnazen; ferimzone; ametoctradin; silthiofam; nitrophenyl derivates: binapacryl, dino- buton, dinocap, fluazinam, nitrthal-isopropyl, and
including organometal compounds: fentin salts, such as fentin-acetate, fentin chloride or fentin hydroxide;
F.ll) Sterol biosynthesis inhibitors (SBI fungicides)
F.II-1 ) C14 demethylase inhibitors (DMI fungicides, e.g. triazoles, imidazoles) triazoles: azaconazole, bitertanol, bromuconazole, cyproconazole, difenoconazole, diniconazole, diniconazole-M, epoxiconazole, fenbuconazole, fluquinconazole, flusi- lazole, flutriafol, hexaconazole, imibenconazole, ipconazole, metconazole, myclobu- tanil, paclobutrazole, penconazole, propiconazole, prothioconazole, simeconazole, tebuconazole, tetraconazole, triadimefon, triadimenol, triticonazole, uniconazole, , 1 - [re/-(2S;3R)-3-(2-chlorophenyl)-2-(2,4-difluorophenyl)-oxiranylmethyl]-5-thiocyanato- 1 H-[1 ,2,4]triazole, 2-[re/-(2S;3R)-3-(2-chlorophenyl)-2-(2,4-difluorophenyl)-oxiranyl- methyl]-2H-[1 ,2,4]triazole-3-thiol;
imidazoles: imazalil, pefurazoate, oxpoconazole, prochloraz, triflumizole;
pyrimidines, pyridines and piperazines: fenarimol, nuarimol, pyrifenox, triforine, 1 -[rel- (2S;3R)-3-(2-chlorophenyl)-2-(2,4-difluorophenyl)-oxiranylmethyl]-5-thiocyanato-1 H- [1 ,2,4]triazole, 2-[rel-(2S;3R)-3-(2-chlorophenyl)-2-(2,4-difluorophenyl)-oxiranylmethyl]- 2H-[1 ,2,4]triazole-3-thiol;
F.II-2) Delta14-reductase inhitors (Amines, e.g. morpholines, piperidines)
morpholines: aldimorph, dodemorph, dodemorph-acetate, fenpropimorph, tridemorph; piperidines: fenpropidin, piperalin; spiroketalamines: spiroxamine;
F.II-3) Inhibitors of 3-keto reductase: hydroxyanilides: fenhexamid;
F.lll) Nucleic acid synthesis inhibitors
F.III-1 ) RNA, DNA synthesis
phenylamides or acyl amino acid fungicides: benalaxyl, benalaxyl-M, kiralaxyl, met- alaxyl, metalaxyl-M (mefenoxam), ofurace, oxadixyl;
isoxazoles and iosothiazolones: hymexazole, octhilinone; R.111-2) DNA topisomerase inhibitors: oxolinic acid;
R.111-3) Nucleotide metabolism (e.g. adenosin-deaminase), hydroxy (2-amino)- pyrimidines: bupirimate;
F.IV) Inhibitors of cell division and or cytoskeleton
F.IV-1 ) Tubulin inhibitors: benzimidazoles and thiophanates: benomyl, carbendazim, fuberidazole, thiabendazole, thiophanate-methyl;
triazolopyrimidines: 5-chloro-7 (4-methylpiperidin-1 -yl)-6-(2,4,6-trifluorophenyl)- [1 ,2,4]triazolo[1 ,5 a]pyrimidine;
F.IV-2) Other cell division inhibitors
benzamides and phenyl acetamides: diethofencarb, ethaboxam, pencycuron, fluopico- lide, zoxamide;
F.IV-3) Actin inhibitors: benzophenones: metrafenone, pyriofenone;
F.V) Inhibitors of amino acid and protein synthesis
F.V-1 ) Methionine synthesis inhibitors (anilino-pyrimidines)
anilino-pyrimidines: cyprodinil, mepanipyrim, nitrapyrin, pyrimethanil;
F.V-2) Protein synthesis inhibitors (anilino-pyrimidines)
antibiotics: blasticidin-S, kasugamycin, kasugamycin hydrochloride-hydrate, mildiomy- cin, streptomycin, oxytetracyclin, polyoxine, validamycin A;
F.VI) Signal transduction inhibitors
F.VI-1 ) MAP / Histidine kinase inhibitors (e.g. anilino-pyrimidines)
dicarboximides: fluoroimid, iprodione, procymidone, vinclozolin;
phenylpyrroles: fenpiclonil, fludioxonil;
F.VI-2) G protein inhibitors: quinolines: quinoxyfen;
F.VI I) Lipid and membrane synthesis inhibitors
F.VI 1-1 ) Phospholipid biosynthesis inhibitors
organophosphorus compounds: edifenphos, iprobenfos, pyrazophos;
dithiolanes: isoprothiolane;
F.VII-2) Lipid peroxidation: aromatic hydrocarbons: dicloran, quintozene, tecnazene, tolclofos-methyl, biphenyl, chloroneb, etridiazole;
F.VII-3) Carboxyl acid amides (CAA fungicides)
cinnamic or mandelic acid amides: dimethomorph, flumorph, mandiproamid, pyrimorph; valinamide carbamates: benthiavalicarb, iprovalicarb, pyribencarb, valifenalate and N-
(1 -(1 -(4-cyano-phenyl)ethanesulfonyl)-but-2-yl) carbamic acid-(4-fluorophenyl) ester;
F.VII-4) Compounds affecting cell membrane permeability and fatty acids:
1 -[4-[4-[5-(2,6-difluorophenyl)-4,5-dihydro-3-isoxazolyl]-2-thiazolyl]-1 -piperidinyl]-2-[5- methyl-3-(trifluoromethyl)-1 H-pyrazol-1 -yl]ethanone, carbamates: propamocarb, pro- pamocarb-hydrochlorid;
F.VII-5) fatty acid amide hydrolase inhibitors: 1 -[4-[4-[5-(2,6-difluorophenyl)-4,5- dihydro-3-isoxazolyl]-2-thiazolyl]-1 -piperidinyl]-2-[5-methyl-3-(trifluoromethyl)-1 H- pyrazol-1 -yl]ethanone;
F.VI II) Inhibitors with Multi Site Action
F.VI 11-1 ) Inorganic active substances: Bordeaux mixture, copper acetate, copper hydroxide, copper oxychloride, basic copper sulfate, sulfur; F.VIII-2) Thio- and dithiocarbamates: ferbam, mancozeb, maneb, metam,
methasulphocarb, metiram, propineb, thiram, zineb, ziram;
F.VIII-3) Organochlorine compounds (e.g. phthalimides, sulfamides, chloronitriles): anilazine, chlorothalonil, captafol, captan, folpet, dichlofluanid, dichlorophen, flusulfa- mide, hexachlorobenzene, pentachlorphenole and its salts, phthalide, tolylfluanid, N-(4- chloro-2-nitro-phenyl)-N-ethyl-4-methyl-benzenesulfonamide;
F.VIII-4) Guanidines and other: guanidine, dodine, dodine free base, guazatine, guaza- tine-acetate, iminoctadine, iminoctadine-triacetate, iminoctadine-tris(albesilate), 2,6- dimethyl-1 H,5H-[1 ,4]dithiino[2,3-c:5,6-c']dipyrrole-1 ,3,5,7(2H,6H)-tetraone;
F.VIII-5) Ahtraquinones: dithianon;
F.IX) Cell wall synthesis inhibitors
F.IX-1 ) Inhibitors of glucan synthesis: validamycin, polyoxin B;
F.IX-2) Melanin synthesis inhibitors: pyroquilon, tricyclazole, carpropamide, dicyclomet, fenoxanil;
F.X) Plant defence inducers
F.X-1 ) Salicylic acid pathway: acibenzolar-S-methyl;
F.X-2) Others: probenazole, isotianil, tiadinil, prohexadione-calcium;
phosphonates: fosetyl, fosetyl-aluminum, phosphorous acid and its salts;
F.XI) Unknown mode of action:bronopol, chinomethionat, cyflufenamid, cymoxanil, dazomet, debacarb, diclomezine, difenzoquat, difenzoquat-methylsulfate, diphenyla- min, fenpyrazamine, flumetover, flusulfamide, flutianil, methasulfocarb, nitrapyrin, ni- trothal-isopropyl, oxathiapiprolin, oxin-copper, proquinazid, tebufloquin, tecloftalam, triazoxide, 2-butoxy-6-iodo-3-propylchromen-4-one, N-(cyclopropylmethoxyimino-(6- difluoro-methoxy-2,3-difluoro-phenyl)-methyl)-2-phenyl acetamide, N'-(4-(4-chloro-3- trifluoromethyl-phenoxy)-2,5-dimethyl-phenyl)-N-ethyl-N methyl formamidine, N' (4-(4- fluoro-3-trifluoromethyl-phenoxy)-2,5-dimethyl-phenyl)-N-ethyl-N-methyl formamidine, N'-(2-methyl-5-trifluoromethyl-4-(3-trimethylsilanyl-propoxy)-phenyl)-N-ethyl-N-methyl formamidine, N'-(5-difluoromethyl-2 methyl-4-(3-trimethylsilanyl-propoxy)-phenyl)-N- ethyl-N-methyl formamidine, 2-{1 -[2-(5-methyl-3-trifluoromethyl-pyrazole-1 -yl)-acetyl]- piperidin-4-yl}-thiazole-4-carboxylic acid methyl-(1 ,2,3,4-tetrahydro-naphthalen-1 -yl)- amide, 2-{1 -[2-(5-methyl-3-trifluoromethyl-pyrazole-1 -yl)-acetyl]-piperidin-4-yl}-thiazole- 4-carboxylic acid methyl-(R)-1 ,2,3,4-tetrahydro-naphthalen-1 -yl-amide, methoxy-acetic acid 6-tert-butyl-8-fluoro-2,3-dimethyl-quinolin-4-yl ester and N-Methyl-2-{1 -[(5-methyl- 3-trifluoromethyl-1 H-pyrazol-1 -yl)-acetyl]-piperidin-4-yl}-N-[(1 R)-1 ,2,3,4- tetrahydronaphthalen-1 -yl]-4-thiazolecarboxamide, 3-[5-(4-chloro-phenyl)-2,3-dimethyl- isoxazolidin-3 yl]-pyridine, pyrisoxazole, 5-amino-2-isopropyl-3-oxo-4-ortho-tolyl-2,3- dihydro-pyrazole-1 carbothioic acid S-allyl ester, N-(6-methoxy-pyridin-3-yl) cyclopro- panecarboxylic acid amide, 5-chloro-1 (4,6-dimethoxy-pyrimidin-2-yl)-2-methyl-1 H- benzoimidazole, 2-(4-chloro-phenyl)-N-[4-(3,4-dimethoxy-phenyl)-isoxazol-5-yl]-2-prop- 2-ynyloxy-acetamide,.
F.XI) Growth regulators: abscisic acid, amidochlor, ancymidol, 6-benzylaminopurine, brassinolide, butralin, chlormequat (chlormequat chloride), choline chloride, cyclanilide, daminozide, dikegulac, dimethipin, 2,6-dimethylpuridine, ethephon, flumetralin, flur- primidol, fluthiacet, forchlorfenuron, gibberellic acid, inabenfide, indole-3-acetic acid, maleic hydrazide, mefluidide, mepiquat (mepiquat chloride), naphthaleneacetic acid, N 6-benzyladenine, paclobutrazol, prohexadione (prohexadione-calcium), prohydro- jasmon, thidiazuron, triapenthenol, tributyl phosphorotrithioate, 2,3,5 tri iodobenzoic acid, trinexapac-ethyl and uniconazole;
F.XII) Biological control agents
Ampelomyces quisqualis (e.g. AQ 10® from Intrachem Bio GmbH & Co. KG, Germany), Aspergillus flavus (e.g. AFLAGUARD® from Syngenta, CH), Aureobasidium pullulans (e.g. BOTECTOR® from bio-ferm GmbH, Germany), Bacillus pumilus (e.g. NRRL Ac- cession No. B-30087 in SONATA® and BALLAD® Plus from AgraQuest Inc., USA), Bacillus subtilis (e.g. isolate NRRL-Nr. B-21661 in RHAPSODY®, SERENADE® MAX and SERENADE® ASO from AgraQuest Inc., USA), Bacillus subtilis var. amyloliquefaciens FZB24 (e.g. TAEGRO® from Novozyme Biologicals, Inc., USA), Candida oleophila I-82 (e.g. ASPIRE® from Ecogen Inc., USA), Candida saitoana (e.g. BIOCURE® (in mixture with lysozyme) and BIOCOAT® from Micro Flo Company, USA (BASF SE) and Arysta), Chitosan (e.g. ARMOUR-ZEN from BotriZen Ltd., NZ), Clonostachys rosea f. catenula- ta, also named Gliocladium catenulatum (e.g. isolate J 1446: PRESTOP® from Verdera, Finland), Coniothyrium minitans (e.g. CONTANS® from Prophyta, Germany),
Cryphonectria parasitica (e.g. Endothia parasitica from CNICM, France), Cryptococcus albidus (e.g. YIELD PLUS® from Anchor Bio-Technologies, South Africa), Fusarium oxysporum (e.g. BIOFOX® from S.I.A.P.A., Italy, FUSACLEAN® from Natural Plant Protection, France), Metschnikowia fructicola (e.g. SHEMER® from Agrogreen, Israel), Microdochium dimerum (e.g. ANTIBOT® from Agrauxine, France), Phlebiopsis gigantea (e.g. ROTSOP® from Verdera, Finland), Pseudozyma flocculosa (e.g. SPORODEX® from Plant Products Co. Ltd., Canada), Pythium oligandrum DV74 (e.g. POLYVER- SUM® from Remeslo SSRO, Biopreparaty, Czech Rep.), Reynoutria sachlinensis (e.g. REGALIA® from Marrone Biolnnovations, USA), Talaromyces f/avus VH 7b (e.g. PRO- TUS® from Prophyta, Germany), Trichoderma asperellum SKT-1 (e.g. ECO-HOPE® from Kumiai Chemical Industry Co., Ltd., Japan), T. atroviride LC52 (e.g. SENTINEL® from Agrimm Technologies Ltd, NZ), T. harzianum T-22 (e.g. PLANTSHIELD® der Fir- ma BioWorks Inc., USA), T. harzianum JH 35 (e.g. ROOT PRO® from Mycontrol Ltd., Israel), T. harzianum T-39 (e.g. TRICHODEX® and TRICHODERMA 2000® from Mycontrol Ltd., Israel and Makhteshim Ltd., Israel), T. harzianum and T. viride (e.g. TRI- CHOPEL from Agrimm Technologies Ltd, NZ), T. harzianum ICC012 and T. viride ICC080 (e.g. REMEDIER® WP from Isagro Ricerca, Italy), T. polysporum and T. harzianum (e.g. BINAB® from BINAB Bio-Innovation AB, Sweden), T. stromaticum (e.g. TRICOVAB® from C.E.P.L.A.C., Brazil), T. virens GL-21 (e.g. SOILGARD® from Certis LLC, USA), T. viride {e.g. TRIECO® from Ecosense Labs. (India) Pvt. Ltd., Indien, BIOCURE® F from T. Stanes & Co. Ltd., Indien), T. viride TV1 (e.g. T. viride TV1 from Ag- ribiotec srl, Italy), Ulocladium oudemansii HRU3 (e.g. BOTRY-ZEN® from Botry-Zen Ltd, NZ).. The animal pest, i.e. the insects, arachnids and nematodes, the plant, soil or water in which the plant is growing can be contacted with the present compounds of formula (I) or composition(s) containing them by any application method known in the art. As such, "contacting" includes both direct contact (applying the compounds/compositions direct- ly on the animal pest or plant, typically to the foliage, stem or roots of the plant) and indirect contact (applying the compounds/compositions to the locus of the animal pest or plant).
The compounds of formula (I) or the pesticidal compositions comprising them may be used to protect growing plants and crops from attack or infestation by animal pests, especially insects, acaridae or arachnids by contacting the plant/crop with a pesticidally effective amount of compounds of formula (I). The term "crop" refers both to growing and harvested crops. The compounds of the present invention and the compositions comprising them are particularly important in the control of a multitude of insects on various cultivated plants, such as cereal, root crops, oil crops, vegetables, spices, ornamentals, for example seed of durum and other wheat, barley, oats, rye, maize (fodder maize and sugar maize / sweet and field corn), soybeans, oil crops, crucifers, cotton, sunflowers, ba- nanas, rice, oilseed rape, turnip rape, sugar beet, fodder beet, eggplants, potatoes, grass, lawn, turf, fodder grass, tomatoes, leeks, pumpkin/squash, cabbage, iceberg lettuce, pepper, cucumbers, melons, Brassica species, melons, beans, peas, garlic, onions, carrots, tuberous plants such as potatoes, sugar cane, tobacco, grapes, petunias, geranium/pelargoniums, pansies and impatiens.
The compounds of the present invention are employed as such or in form of compositions by treating the insects or the plants, plant propagation materials, such as seeds, soil, surfaces, materials or rooms to be protected from insecticidal attack with an insec- ticidally effective amount of the compound of formula (I). The application can be carried out both before and after the infection of the plants, plant propagation materials, such as seeds, soil, surfaces, materials or rooms by the insects.
The present invention also includes a method of combating animal pests which comprises contacting the animal pests, their habit, breeding ground, food supply, cultivated plants, seed, soil, area, material or environment in which the animal pests are growing or may grow, or the materials, plants, seeds, soils, surfaces or spaces to be protected from animal attack or infestation with a pesticidally effective amount of a mixture of at least one compound of formula (I).
Moreover, animal pests may be controlled by contacting the target pest, its food supply, habitat, breeding ground or its locus with a pesticidally effective amount of compounds of formula (I). As such, the application may be carried out before or after the infection of the locus, growing crops, or harvested crops by the pest.
The compounds of the invention can also be applied preventively to places at which occurrence of the pests is expected.
The compounds of formula (I) may be also used to protect growing plants from attack or infestation by pests by contacting the plant with a pesticidally effective amount of compounds of formula (I). As such, "contacting" includes both direct contact (applying the compounds/compositions directly on the pest and/or plant - typically to the foliage, stem or roots of the plant) and indirect contact (applying the compounds/compositions to the locus of the pest and/or plant).
"Locus" means a habitat, breeding ground, plant, seed, soil, area, material or environment in which a pest or parasite is growing or may grow.
The term "plant propagation material" is to be understood to denote all the generative parts of the plant such as seeds and vegetative plant material such as cuttings and tubers (e. g. potatoes), which can be used for the multiplication of the plant. This includes seeds, roots, fruits, tubers, bulbs, rhizomes, shoots, sprouts and other parts of plants. Seedlings and young plants, which are to be transplanted after germination or after emergence from soil, may also be included. These plant propagation materials may be treated prophylactically with a plant protection compound either at or before planting or transplanting.
The term "cultivated plants" is to be understood as including plants which have been modified by breeding, mutagenesis or genetic engineering. Genetically modified plants are plants, which genetic material has been so modified by the use of recombinant DNA techniques that under natural circumstances cannot readily be obtained by cross breeding, mutations or natural recombination. Typically, one or more genes have been integrated into the genetic material of a genetically modified plant in order to improve certain properties of the plant. Such genetic modifications also include but are not lim- ited to targeted post-transtional modification of protein(s) (oligo- or polypeptides) poly for example by glycosylation or polymer additions such as prenylated, acetylated or farnesylated moieties or PEG moieties(e.g. as disclosed in Biotechnol Prog. 2001 Jul- Aug;17(4):720-8., Protein Eng Des Sel. 2004 Jan;17(1 ):57-66, Nat Protoc.
2007;2(5):1225-35., Curr Opin Chem Biol. 2006 Oct;10(5):487-91. Epub 2006 Aug 28., Biomaterials. 2001 Mar;22(5):405-17, Bioconjug Chem. 2005 Jan-Feb;16(1 ):1 13-21 ). The term "cultivated plants" is to be understood also including plants that have been rendered tolerant to applications of specific classes of herbicides, such as hy- droxy-phenylpyruvate dioxygenase (HPPD) inhibitors; acetolactate synthase (ALS) inhibitors, such as sulfonyl ureas (see e. g. US 6,222,100, WO 01/82685, WO
00/26390, WO 97/41218, WO 98/02526, WO 98/02527, WO 04/106529, WO 05/20673, WO 03/14357, WO 03/13225, WO 03/14356, WO 04/16073) or imidazolinones (see e. g. US 6,222,100, WO 01/82685, WO 00/26390, WO 97/41218, WO 98/02526, WO 98/02527, WO 04/106529, WO 05/20673, WO 03/14357, WO 03/13225, WO 03/14356, WO 04/16073); enolpyruvylshikimate-3-phosphate synthase (EPSPS) inhibitors, such as glyphosate (see e. g. WO 92/00377); glutamine synthetase (GS) inhibitors, such as glufosinate (see e. g. EP-A-0242236, EP-A-242246) or oxynil herbicides (see e. g. US 5,559,024) as a result of conventional methods of breeding or genetic engineering. Several cultivated plants have been rendered tolerant to herbicides by conventional methods of breeding (mutagenesis), for example Clearfield® summer rape (Canola) being tolerant to imidazolinones, e. g. imazamox. Genetic engineering methods have been used to render cultivated plants, such as soybean, cotton, corn, beets and rape, tolerant to herbicides, such as glyphosate and glufosinate, some of which are commer- cially available under the trade names RoundupReady® (glyphosate) and LibertyLink® (glufosinate).
The term "cultivated plants" is to be understood also including plants that are by the use of recombinant DNA techniques capable to synthesize one or more insecticidal proteins, especially those known from the bacterial genus Bacillus, particularly from Bacillus thuringiensis, such as a-endotoxins, e. g. CrylA(b), CrylA(c), CrylF, CrylF(a2), CryllA(b), CrylllA, CrylllB(bl ) or Cry9c; vegetative insecticidal proteins (VIP), e. g. VIP1 , VIP2, VIP3 or VIP3A; insecticidal proteins of bacteria colonizing nematodes, for example Photorhabdus spp. or Xenorhabdus spp.; toxins produced by animals, such as scorpion toxins, arachnid toxins, wasp toxins, or other insect-specific neurotoxins; toxins produced by fungi, such Streptomycetes toxins, plant lectins, such as pea or barley lectins; agglutinins; proteinase inhibitors, such as trypsin inhibitors, serine protease inhibitors, patatin, cystatin or papain inhibitors; ribosome-inactivating proteins (RIP), such as ricin, maize-RIP, abrin, luffin, saporin or bryodin; steroid metabolism enzymes, such as 3-hydroxysteroid oxidase, ecdysteroid-IDP-glycosyl-transferase, cholesterol oxidases, ecdysone inhibitors or HMG-CoA-reductase; ion channel blockers, such as blockers of sodium or calcium channels; juvenile hormone esterase; diuretic hormone receptors (helicokinin receptors); stilben synthase, bibenzyl synthase, chitinases or glucanases. In the context of the present invention these insecticidal proteins or toxins are to be understood expressly also as pre-toxins, hybrid proteins, trun- cated or otherwise modified proteins. Hybrid proteins are characterized by a new combination of protein domains, (see, for example WO 02/015701 ). Further examples of such toxins or genetically-modified plants capable of synthesizing such toxins are dis-closed, for example, in EP-A 374 753, WO 93/007278, WO 95/34656, EP-A 427 529, EP-A 451 878, WO 03/018810 und WO 03/052073. The methods for producing such genetically modified plants are generally known to the person skilled in the art and are described, for example, in the publications mentioned above. These insecticidal proteins contained in the genetically modified plants impart to the plants producing these proteins protection from harmful pests from certain taxonomic groups of arthropods, particularly to beetles (Coleoptera), flies (Diptera), and butterflies and moths (Lepidoptera) and to plant parasitic nematodes (Nematoda).
The term "cultivated plants" is to be understood also including plants that are by the use of recombinant DNA techniques capable to synthesize one or more proteins to increase the resistance or tolerance of those plants to bacterial, viral or fungal pathogens. Examples of such proteins are the so-called " pathogenesis-related proteins" (PR proteins, see, for example EP-A 0 392 225), plant disease resistance genes (for example potato cultivars, which express resistance genes acting against Phytophthora infestans derived from the mexican wild potato Solanum bulbocastanum) or T4- lyso-zym (e. g. potato cultivars capable of synthesizing these proteins with increased resistance against bacteria such as Erwinia amylvora). The methods for producing such genetically modified plants are generally known to the person skilled in the art and are described, for example, in the publications mentioned above.
The term "cultivated plants" is to be understood also including plants that are by the use of recombinant DNA techniques capable to synthesize one or more proteins to increase the productivity (e. g. bio mass production, grain yield, starch content, oil content or protein content), tolerance to drought, salinity or other growth-limiting envi- ron-mental factors or tolerance to pests and fungal, bacterial or viral pathogens of those plants.
The term "cultivated plants" is to be understood also including plants that contain by the use of recombinant DNA techniques a modified amount of substances of content or new substances of content, specifically to improve human or animal nutrition, for ex-ample oil crops that produce health-promoting long-chain omega-3 fatty acids or unsaturated omega-9 fatty acids (e. g. Nexera® rape).
The term "cultivated plants" is to be understood also including plants that contain by the use of recombinant DNA techniques a modified amount of substances of content or new substances of content, specifically to improve raw material production, for example potatoes that produce increased amounts of amylopectin (e. g. Amflora® potato). In general, "pesticidally effective amount" means the amount of active ingredient (here of compound of formula (I)) needed to achieve an observable effect on growth, including the effects of necrosis, death, retardation, prevention, and removal, destruction, or otherwise diminishing the occurrence and activity of the target organism. The pesticidally effective amount can vary for the various compounds/compositions used in the invention. A pesticidally effective amount of the compositions will also vary according to the prevailing conditions such as desired pesticidal effect and duration, weather, target species, locus, mode of application, and the like.
In the case of soil treatment or of application to the pests dwelling place or nest, the quantity of active ingredient ranges from 0.0001 to 500 g per 100 m2, preferably from 0.001 to 20 g per 100 m2.
Customary application rates in the protection of materials are, for example, from 0.01 g to 1000 g of active ingredient per m2 treated material, desirably from 0.1 g to 50 g per m2.
Insecticidal compositions for use in the impregnation of materials typically contain from 0.001 to 95 weight %, preferably from 0.1 to 45 weight %, and more preferably from 1 to 25 weight % of at least one repellent and/or insecticide.
For use in treating crop plants, the rate of application of the active ingredients of this invention may be in the range of 0.1 g to 4000 g per hectare, desirably from 25 g to 600 g per hectare, more desirably from 50 g to 500 g per hectare.
The compounds of formula (I) are effective through both contact (via soil, glass, wall, bed net, carpet, plant parts or animal parts), and ingestion (bait, or plant part). The compounds of the invention may also be applied against non-crop insect pests, such as ants, termites, wasps, flies, mosquitos, crickets, or cockroaches. For use against said non-crop pests, compounds of formula (I) are preferably used in a bait composition.
The bait can be a liquid, a solid or a semisolid preparation (e.g. a gel). Solid baits can be formed into various shapes and forms suitable to the respective application e.g. granules, blocks, sticks, disks. Liquid baits can be filled into various devices to ensure proper application, e.g. open containers, spray devices, droplet sources, or evaporation sources. Gels can be based on aqueous or oily matrices and can be formulated to par- ticular necessities in terms of stickiness, moisture retention or aging characteristics. The bait employed in the composition is a product, which is sufficiently attractive to incite insects such as ants, termites, wasps, flies, mosquitos, crickets etc. or cockroaches to eat it. The attractiveness can be manipulated by using feeding stimulants or sex pheromones. Food stimulants are chosen, for example, but not exclusively, from animal and/or plant proteins (meat-, fish- or blood meal, insect parts, egg yolk), from fats and oils of animal and/or plant origin, or mono-, oligo- or polyorganosaccharides, especially from sucrose, lactose, fructose, dextrose, glucose, starch, pectin or even molasses or honey. Fresh or decaying parts of fruits, crops, plants, animals, insects or specific parts thereof can also serve as a feeding stimulant. Sex pheromones are known to be more insect specific. Specific pheromones are described in the literature and are known to those skilled in the art.
For use in bait compositions, the typical content of active ingredient is from 0.001 weight % to 15 weight %, desirably from 0.001 weight % to 5% weight % of active ingredient.
Formulations of compounds of formula (I) as aerosols (e.g. in spray cans), oil sprays or pump sprays are highly suitable for the non-professional user for controlling pests such as flies, fleas, ticks, mosquitos or cockroaches. Aerosol recipes are preferably composed of the active ingredient, solvents such as lower alcohols (e.g. methanol, ethanol, propanol, butanol), ketones (e.g. acetone, methyl ethyl ketone), paraffin hydrocarbons (e.g. kerosenes) having boiling ranges of approximately 50 to 250 °C, dimethylforma- mide, N-methylpyrrolidone, dimethyl sulfoxide, aromatic hydrocarbons such as toluene, xylene, water, furthermore auxiliaries such as emulsifiers such as sorbitol monooleate, oleyl ethoxylate having 3-7 mol of ethylene oxide, fatty alcohol ethoxylate, perfume oils such as ethereal oils, esters of medium fatty acids with lower alcohols, aromatic car- bonyl compounds, if appropriate stabilizers such as sodium benzoate, amphoteric surfactants, lower epoxides, triethyl orthoformate and, if required, propellants such as propane, butane, nitrogen, compressed air, dimethyl ether, carbon dioxide, nitrous oxide, or mixtures of these gases.
The oil spray formulations differ from the aerosol recipes in that no propellants are used.
For use in spray compositions, the content of active ingredient is from 0.001 to 80 weights %, preferably from 0.01 to 50 weight % and most preferably from 0.01 to 15 weight %. The compound of formula (I) and its respective compositions can also be used in mosquito and fumigating coils, smoke cartridges, vaporizer plates or long-term vaporizers and also in moth papers, moth pads or other heat-independent vaporizer systems. Methods to control infectious diseases transmitted by insects (e.g. malaria, dengue and yellow fever, lymphatic filariasis, and leishmaniasis) with compounds of formula (I) and its respective compositions also comprise treating surfaces of huts and houses, air spraying and impregnation of curtains, tents, clothing items, bed nets, tsetse-fly trap or the like. Insecticidal compositions for application to fibers, fabric, knitgoods, nonwovens, netting material or foils and tarpaulins preferably comprise a mixture in- eluding the insecticide, optionally a repellent and at least one binder. Suitable repellents for example are Ν,Ν-Diethyl-meta-toluamide (DEET), N,N-diethylphenylacetamide (DEPA), 1 -(3-cyclohexan-1 -yl-carbonyl)-2-methylpiperine, (2-hydroxymethylcyclohexyl) acetic acid lactone, 2-ethyl-1 ,3-hexandiol, indalone, Methylneodecanamide (MNDA), a pyrethroid not used for insect control such as {(+/-)-3-allyl-2-methyl-4-oxocyclopent-2- (+)-enyl-(+)-trans-chrysantemate (Esbiothrin), a repellent derived from or identical with plant extracts like limonene, eugenol, (+)-Eucamalol (1 ), (-)-l -epi-eucamalol or crude plant extracts from plants like Eucalyptus maculata, Vitex rotundifolia, Cymbopogan martinii, Cymbopogan citratus (lemon grass), Cymopogan nartdus (citronella). Suitable binders are selected for example from polymers and copolymers of vinyl esters of ali- phatic acids (such as such as vinyl acetate and vinyl versatate), acrylic and methacrylic esters of alcohols, such as butyl acrylate, 2-ethylhexylacrylate, and methyl acrylate, mono- and di-ethylenically unsaturated hydrocarbons, such as styrene, and aliphatic diens, such as butadiene.
The impregnation of curtains and bednets is done in general by dipping the textile ma- terial into emulsions or dispersions of the insecticide or spraying them onto the nets.
The compound of formula (I) and its compositions can be used for protecting wooden materials such as trees, board fences, sleepers, etc. and buildings such as houses, outhouses, factories, but also construction materials, furniture, leathers, fibers, vinyl articles, electric wires and cables etc. from ants and/or termites, and for controlling ants and termites from doing harm to crops or human being (e.g. when the pests invade into houses and public facilities). The compounds of formula (I) are applied not only to the surrounding soil surface or into the under-floor soil in order to protect wooden materials but it can also be applied to lumbered articles such as surfaces of the under-floor con- crete, alcove posts, beams, plywoods, furniture, etc., wooden articles such as particle boards, half boards, etc. and vinyl articles such as coated electric wires, vinyl sheets, heat insulating material such as styrene foams, etc. In case of application against ants doing harm to crops or human beings, the ant controller of the present invention is applied to the crops or the surrounding soil, or is directly applied to the nest of ants or the like. The compounds of formula (I) are also suitable for the treatment of seeds in order to protect the seed from insect pest, in particular from soil-living insect pests and the resulting plant' s roots and shoots against soil pests and foliar insects.
The compounds of formula (I) are particularly useful for the protection of the seed from soil pests and the resulting plant's roots and shoots against soil pests and foliar insects. The protection of the resulting plant's roots and shoots is preferred. More preferred is the protection of resulting plant's shoots from piercing and sucking insects, wherein the protection from aphids is most preferred.
The present invention therefore comprises a method for the protection of seeds from insects, in particular from soil insects and of the seedling's roots and shoots from insects, in particular from soil and foliar insects, said method comprising contacting the seeds before sowing and/or after pregermination with a compound of the general formula (I) or a salt thereof. Particularly preferred is a method, wherein the plant's roots and shoots are protected, more preferably a method, wherein the plants shoots are protected from piercing and sucking insects, most preferably a method, wherein the plants shoots are protected from aphids.
The term seed embraces seeds and plant propagules of all kinds including but not limited to true seeds, seed pieces, suckers, corms, bulbs, fruit, tubers, grains, cuttings, cut shoots and the like and means in a preferred embodiment true seeds.
The term 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 present invention also comprises seeds coated with or containing the compound of formula (I). The term "coated with and/or containing" generally signifies that the active ingredient is for the most part on the surface of the propagation product at the time of application, although a greater or lesser part of the ingredient may penetrate into the propagation product, depending on the method of application. When the said propagation product is (re)planted, it may absorb the active ingredient.
Suitable seed is seed of cereals, root crops, oil crops, vegetables, spices, ornamentals, for example seed of durum and other wheat, barley, oats, rye, maize (fodder maize and sugar maize / sweet and field corn), soybeans, oil crops, crucifers, cotton, sunflowers, bananas, rice, oilseed rape, turnip rape, sugar beet, fodder beet, eggplants, potatoes, grass, lawn, turf, fodder grass, tomatoes, leeks, pumpkin/squash, cabbage, iceberg lettuce, pepper, cucumbers, melons, Brassica species, melons, beans, peas, garlic, onions, carrots, tuberous plants such as potatoes, sugar cane, tobacco, grapes, petunias, geranium/pelargoniums, pansies and impatiens.
In addition, the compound of formula (I) may also be used for the treatment seeds from plants, which tolerate the action of herbicides or fungicides or insecticides owing to breeding, including genetic engineering methods.
For example, the compound of formula (I) can be employed in treatment of seeds from plants, which are resistant to herbicides from the group consisting of the sulfonylureas, imidazolinones, glufosinate-ammonium or glyphosate-isopropylammonium and analogous active substances (see for example, EP-A-0242236, EP-A-242246) (WO
92/00377) (EP-A-0257993, U.S. Pat. No. 5,013,659) or in transgenic crop plants, for example cotton, with the capability of producing Bacillus thuringiensis toxins (Bt toxins) which make the plants resistant to certain pests (EP-A-0142924, EP-A-0193259), Furthermore, the compound of formula (I) can be used also for the treatment of seeds from plants, which have modified characteristics in comparison with existing plants consist, which can be generated for example by traditional breeding methods and/or the generation of mutants, or by recombinant procedures). For example, a number of cases have been described of recombinant modifications of crop plants for the purpose of modifying the starch synthesized in the plants (e.g. WO 92/1 1376, WO 92/14827, WO 91/19806) or of transgenic crop plants having a modified fatty acid composition (WO 91/13972). The seed treatment application of the compound of formula (I) is carried out by spraying or by dusting the seeds before sowing of the plants and before emergence of the plants.
Compositions which are especially useful for seed treatment are e.g.:
A Soluble concentrates (SL, LS)
D Emulsions (EW, EO, ES)
E Suspensions (SC, OD, FS)
F Water-dispersible granules and water-soluble granules (WG, SG)
G Water-dispersible powders and water-soluble powders (WP, SP, WS)
H Gel-Formulations (GF)
I Dustable powders (DP, DS)
Conventional seed treatment formulations include for example flowable concentrates FS, solutions LS, powders for dry treatment DS, water dispersible powders for slurry treatment WS, water-soluble powders SS and emulsion ES and EC and gel formulation GF. These formulations can be applied to the seed diluted or undiluted. Application to the seeds is carried out before sowing, either directly on the seeds or after having pregerminated the latter
In a preferred embodiment a FS formulation is used for seed treatment. Typically, a FS formulation may comprise 1 -800 g/l of active ingredient, 1 -200 g/l Surfactant, 0 to 200 g/l antifreezing agent, 0 to 400 g/l of binder, 0 to 200 g/l of a pigment and up to 1 liter of a solvent, preferably water.
Especially preferred FS formulations of compounds of formula (I) for seed treatment usually comprise from 0.1 to 80% by weight (1 to 800 g/l) of the active ingredient, from 0.1 to 20 % by weight (1 to 200 g/l) of at least one surfactant, e.g. 0.05 to 5 % by weight of a wetter and from 0.5 to 15 % by weight of a dispersing agent, up to 20 % by weight, e.g. from 5 to 20 % of an anti-freeze agent, from 0 to 15 % by weight, e.g. 1 to 15 % by weight of a pigment and/or a dye, from 0 to 40 % by weight, e.g. 1 to 40 % by weight of a binder (sticker /adhesion agent), optionally up to 5 % by weight, e.g. from 0.1 to 5 % by weight of a thickener, optionally from 0.1 to 2 % of an anti-foam agent, and optionally a preservative such as a biocide, antioxidant or the like, e.g. in an amount from 0.01 to 1 % by weight and a filler/vehicle up to 100 % by weight.
Seed Treatment formulations may additionally also comprise binders and optionally colorants.
Binders can be added to improve the adhesion of the active materials on the seeds after treatment. Suitable binders are homo- and copolymers from alkylene oxides like ethylene oxide or propylene oxide, polyvinylacetate, polyvinylalcohols, polyvinylpyrrolidones, and copolymers thereof, ethylene-vinyl acetate copolymers, acrylic homo- and copolymers, polyethyleneamines, polyethyleneamides and polyethyleneimines, polysaccharides like celluloses, tylose and starch, polyolefin homo- and copolymers like olefin/maleic anhydride copolymers, polyurethanes, polyesters, polystyrene homo and copolymers
Optionally, also colorants can be included in the formulation. Suitable colorants or dyes for seed treatment formulations are Rhodamin B, C.I. Pigment Red 1 12, C.I. Solvent Red 1 , pigment blue 15:4, pigment blue 15:3, pigment blue 15:2, pigment blue 15:1 , pigment blue 80, pigment yellow 1 , pigment yellow 13, pigment red 1 12, pigment red 48:2, pigment red 48:1 , pigment red 57:1 , pigment red 53:1 , pigment orange 43, pigment orange 34, pigment orange 5, pigment green 36, pigment green 7, pigment white 6, pigment brown 25, basic violet 10, basic violet 49, acid red 51 , acid red 52, acid red 14, acid blue 9, acid yellow 23, basic red 10, basic red 108.
Examples of a gelling agent is carrageen (Satiagel®)
In the treatment of seed, the application rates of the compounds I are generally from 0.1 g to 10 kg per 100 kg of seed, preferably from 1 g to 5 kg per 100 kg of seed, more preferably from 1 g to 1000 g per 100 kg of seed and in particular from 1 g to 200 g per 100 kg of seed.
The invention therefore also relates to seed comprising a compound of the formula (I), or an agriculturally useful salt of I, as defined herein. The amount of the compound I or the agriculturally useful salt thereof will in general vary from 0.1 g to 10 kg per 100 kg of seed, preferably from 1 g to 5 kg per 100 kg of seed, in particular from 1 g to 1000 g per 100 kg of seed. For specific crops such as lettuce the rate can be higher.
The compounds of formula (I) or the enantiomers or veterinary acceptable salts thereof are in particular also suitable for being used for combating parasites in and on animals. An object of the present invention is therefore also to provide new methods to control parasites in and on animals. Another object of the invention is to provide safer pesticides for animals. Another object of the invention is further to provide pesticides for animals that may be used in lower doses than existing pesticides. And another object of the invention is to provide pesticides for animals, which provide a long residual con- trol of the parasites. The invention also relates to compositions containing a parasiticidally effective amount of compounds of formula (I) or the enantiomers or veterinarily acceptable salts thereof and an acceptable carrier, for combating parasites in and on animals.
The present invention also provides a method for treating, controlling, preventing and protecting animals against infestation and infection by parasites, which comprises orally, topically or parenterally administering or applying to the animals a parasiticidally effective amount of a compound of formula (I) or the enantiomers or veterinarily acceptable salts thereof or a composition comprising it.
The invention also provides a process for the preparation of a composition for treating, controlling, preventing or protecting animals against infestation or infection by parasites which comprises a parasiticidally effective amount of a compound of formula (I) or the enantiomers or veterinarily acceptable salts thereof or a composition comprising it. Activity of compounds against agricultural pests does not suggest their suitability for control of endo- and ectoparasites in and on animals which requires, for example, low, non-emetic dosages in the case of oral application, metabolic compatibility with the animal, low toxicity, and a safe handling.
Surprisingly it has now been found that compounds of formula (I) are suitable for combating endo- and ectoparasites in and on animals.
Compounds of formula (I) or the enantiomers or veterinarily acceptable salts thereof and compositions comprising them are preferably used for controlling and preventing infestations and infections animals including warm-blooded animals (including humans) and fish. They are for example suitable for controlling and preventing infestations and infections in mammals such as cattle, sheep, swine, camels, deer, horses, pigs, poultry, rabbits, goats, dogs and cats, water buffalo, donkeys, fallow deer and reindeer, and also in fur-bearing animals such as mink, chinchilla and raccoon, birds such as hens, geese, turkeys and ducks and fish such as fresh- and salt-water fish such as trout, carp and eels.
Compounds of formula (I) or the enantiomers or veterinarily acceptable salts thereof and compositions comprising them are preferably used for controlling and preventing infestations and infections in domestic animals, such as dogs or cats.
Infestations in warm-blooded animals and fish include, but are not limited to, lice, biting lice, ticks, nasal bots, keds, biting flies, muscoid flies, flies, myiasitic fly larvae, chig- gers, gnats, mosquitoes and fleas.
The compounds of formula (I) or the enantiomers or veterinarily acceptable salts thereof and compositions comprising them are suitable for systemic and/or non- systemic control of ecto- and/or endoparasites. They are active against all or some stages of development.
The compounds of formula (I) are especially useful for combating ectoparasites. The compounds of formula (I) are especially useful for combating parasites of the following orders and species (e.g. as above previously listed in the target pests if not explicitly listed hereunder), respectively:
fleas (Siphonaptera);
cockroaches (Blattaria - Blattodea);
flies, mosquitoes (Diptera);
lice (Phthiraptera);
ticks and parasitic mites (Parasitiformes) from arachnoidea;
Actinedida (Prostigmata) und Acaridida (Astigmata);
Bugs (Heteropterida);
Anoplurida, e.g. Haematopinus spp., Linognathus spp., Pediculus spp., Phtirus spp., and Solenopotes spp; Mallophagida (suborders Arnblycerina and Ischnocerina), e.g.
Trimenopon spp., Menopon spp., Trinoton spp., Bovicola spp., Werneckiella spp.,
Lepikentron spp., Trichodectes spp., and Felicola spp;
Roundworms Nematoda, e.g. Wipeworms and Trichinosis (Trichosyringida), e.g.
Trichinellidae (Trichinella spp.), (Trichuridae) Trichuris spp., Capillaria spp; Rhabditida, e.g. Rhabditis spp, Strongyloides spp., Helicephalobus spp,
Strongylida, e.g. Strongylus spp., Ancylostoma spp., Necator americanus, Bunosto- mum spp. (Hookworm), Trichostrongylus spp., Haemonchus contortus., Ostertagia spp., Cooperia spp., Nematodirus spp., Dictyocaulus spp., Cyathostoma spp., Oe- sophagostomum spp., Stephanurus dentatus, Ollulanus spp., Chabertia spp., Stepha- nurus dentatus , Syngamus trachea, Ancylostoma spp., Uncinaria spp., Globocephalus spp., Necator spp., Metastrongylus spp., Muellerius capillaris, Protostrongylus spp., Angiostrongylus spp., Parelaphostrongylus spp. Aleurostrongylus abstrusus, and Dioc- tophyma renale;
Intestinal roundworms (Ascaridida), e.g. Ascaris lumbricoides, Ascaris suum, Ascaridia galli, Parascaris equorum, Enterobius vermicularis (Threadworm), Toxocara canis, Toxascaris leonine, Skrjabinema spp., and Oxyuris equi,
Camallanida, e.g. Dracunculus medinensis (guinea worm)
Spirurida, e.g. Thelazia spp. Wuchereria spp., Brugia spp., Onchocerca spp., Dirofilari spp. a, Dipetalonema spp., Setaria spp., Elaeophora spp., Spirocerca lupi, and Habro- nema spp;
Thorny headed worms (Acanthocephala), e.g. Acanthocephalus spp.,
Macracanthorhynchus hirudinaceus and Oncicola spp,
Planarians (Plathelminthes):
Flukes (Trematoda), e.g. Faciola spp., Fascioloides magna, Paragonimus spp., Dicro- coelium spp., Fasciolopsis buski, Clonorchis sinensis, Schistosoma spp., Trichobilhar- zia spp., Alaria alata, Paragonimus spp., and Nanocyetes spp,
Cercomeromorpha, in particular Cestoda (Tapeworms), e.g. Diphyllobothrium spp., Tenia spp., Echinococcus spp., Dipylidium caninum, Multiceps spp., Hymenolepis spp.,
Mesocestoides spp., Vampirolepis spp., Moniezia spp., Anoplocephala spp., Sirometra spp., Anoplocephala spp., and Hymenolepis spp. The compounds of formula (I) and compositions containing them are particularly useful for the control of pests from the orders Diptera, Siphonaptera and Ixodida.
Moreover, the use of the compounds of formula (l)formula (I) and compositions containing them for combating mosquitoes is especially preferred.
The use of the compounds of formula I and compositions containing them for combating flies is a further preferred embodiment of the present invention.
Furthermore, the use of the compounds of formula (I) and compositions containing them for combating fleas is especially preferred.
The use of the compounds of formula (I) and compositions containing them for combat- ing ticks is a further preferred embodiment of the present invention.
The compounds of formula (I) also are especially useful for combating endoparasites (roundworms nematoda, thorny headed worms and planarians).
Administration can be carried out both prophylactically and therapeutically. Administra- tion of the active component(s) is carried out directly or in the form of suitable preparations, orally, topically/dermally or parenterally. The term active component(s) as used above mean comprising at least one compound of formula (I) and eventually further active compound(s).
For oral administration to warm-blooded animals, the compounds of formula (I) may be formulated as animal feeds, animal feed premixes, animal feed concentrates, pills, solutions, pastes, suspensions, drenches, gels, tablets, boluses and capsules. In addition, the compounds of formula (I) may be administered to the animals in their drinking water. For oral administration, the dosage form chosen should provide the animal with 0.01 mg/kg to 100 mg/kg of animal body weight per day of the formula (I) compound, preferably with 0.5 mg/kg to 100 mg/kg of animal body weight per day.
Alternatively, the compounds of formula (I) may be administered to animals parenterally, for example, by intraruminal, intramuscular, intravenous or subcutaneous injection. The compounds of formula (I) may be dispersed or dissolved in a physiologically acceptable carrier for subcutaneous injection. Alternatively, the compounds of formula (I) may be formulated into an implant for subcutaneous administration. In addition the compound of formula (I) may be transdermally administered to animals. For parenteral administration, the dosage form chosen should provide the animal with 0.01 mg/kg to 100 mg/kg of animal body weight per day of the compound of formula (I).
The compounds of formula (I) may also be applied topically to the animals in the form of dips, dusts, powders, collars, medallions, sprays, shampoos, spot-on and pour-on formulations and in ointments or oil-in-water or water-in-oil emulsions. For topical application, dips and sprays usually contain 0.5 ppm to 5,000 ppm and preferably 1 ppm to 3,000 ppm of the compound of formula (I). In addition, the compounds of formula (I) may be formulated as ear tags for animals, particularly quadrupeds such as cattle and sheep. Suitable preparations are:
- Solutions such as oral solutions, concentrates for oral administration after dilution, solutions for use on the skin or in body cavities, pouring-on formulations, gels; - Emulsions and suspensions for oral or dermal administration; semi-solid preparations;
- Formulations in which the active component is processed in an ointment base or in an oil-in-water or water-in-oil emulsion base;
- Solid preparations such as powders, premixes or concentrates, granules, pellets, tab- lets, boluses, capsules; aerosols and inhalants, and active component containing shaped articles.
Compositions suitable for injection are prepared by dissolving the active ingredient in a suitable solvent and optionally adding further ingredients such as acids, bases, buffer salts, preservatives, and solubilizers. The solutions are filtered and filled sterile.
Suitable solvents are physiologically tolerable solvents such as water, alkanols such as ethanol, butanol, benzyl alcohol, glycerol, propylene glycol, polyethylene glycols, N- methyl-pyrrolidone, 2-pyrrolidone, and mixtures thereof.
The active component(s) can optionally be dissolved in physiologically tolerable vege- table or synthetic oils which are suitable for injection.
Suitable solubilizers are solvents which promote the dissolution of the active component in the main solvent or prevent its precipitation. Examples are polyvinylpyrrolidone, polyvinyl alcohol, polyoxyethylated castor oil, and polyoxyethylated sorbitan ester. Suitable preservatives are benzyl alcohol, trichlorobutanol, p-hydroxybenzoic acid es- ters, and n-butanol.
Oral solutions are administered directly. Concentrates are administered orally after prior dilution to the use concentration. Oral solutions and concentrates are prepared according to the state of the art and as described above for injection solutions, sterile procedures not being necessary.
Solutions for use on the skin are trickled on, spread on, rubbed in, sprinkled on or sprayed on.
Solutions for use on the skin are prepared according to the state of the art and according to what is described above for injection solutions, sterile procedures not being necessary.
In general, "parasiticidally effective amount" means the amount of active ingredient needed to achieve an observable effect on growth, including the effects of necrosis, death, retardation, prevention, and removal, destruction, or otherwise diminishing the occurrence and activity of the target organism. The parasiticidally effective amount can vary for the various compounds/compositions used in the invention. A parasiticidally effective amount of the compositions will also vary according to the prevailing conditions such as desired parasiticidal effect and duration, target species, mode of application, and the like.
The compositions which can be used in the invention can comprise generally from about 0.001 to 95% of the compound of formula (I).
Generally it is favorable to apply the compounds of formula (I) in total amounts of 0.5 mg/kg to 100 mg/kg per day, preferably 1 mg/kg to 50 mg/kg per day. Ready-to-use preparations contain the compounds acting against parasites, preferably ectoparasites, in concentrations of 10 ppm to 80 per cent by weight, preferably from 0.1 to 65 per cent by weight, more preferably from 1 to 50 per cent by weight, most preferably from 5 to 40 per cent by weight.
Preparations which are diluted before use contain the compounds acting against ectoparasites in concentrations of 0.5 to 90 per cent by weight, preferably of 1 to 50 per cent by weight.
Furthermore, the preparations comprise the compounds of formula (I) against endo- parasites in concentrations of 10 ppm to 2 per cent by weight, preferably of 0.05 to 0.9 per cent by weight, very particularly preferably of 0.005 to 0.25 per cent by weight.
In a preferred embodiment of the present invention, the compositions comprising the compounds of formula (I) are applied dermally / topically.
In a further preferred embodiment, the topical application is conducted in the form of compound-containing shaped articles such as collars, medallions, ear tags, bands for fixing at body parts, and adhesive strips and foils.
Generally it is favorable to apply solid formulations which release compounds of formula (I) in total amounts of 10 mg/kg to 300 mg/kg, preferably 20 mg/kg to 200 mg/kg, most preferably 25 mg/kg to 160 mg/kg body weight of the treated animal in the course of three weeks.
For the preparation of the shaped articles, thermoplastic and flexible plastics as well as elastomers and thermoplastic elastomers are used. Suitable plastics and elastomers are polyvinyl resins, polyurethane, polyacrylate, epoxy resins, cellulose, cellulose de- rivatives, polyamides and polyester which are sufficiently compatible with the compounds of formula (I). A detailed list of plastics and elastomers as well as preparation procedures for the shaped articles is given e.g. in WO 03/086075.
The present invention is now illustrated in further details by the following examples, without imposing any limitation thereto.
S. Synthesis Examples
Example.1 : Synthesis S1 :
Synthesis of Example numbered C-3: 6-(6-chloro-3-pyridyl)-1 -isopropyl-3-methyl-4- oxo-7,8-dihydro-6H-pyrrolo[1 ,2-a]pyrimidin-1 -ium-2-olate
Figure imgf000080_0001
C-3 Step 1 .1 : 6-chloro-3-pyridyl) methanol
To a solution of LiAIH4 (25 g, 0.65 mol) in THF (1500 ml) was added a solution of 6- chloropyridine-3-carboxylic acid (50 g, 0.323 mol) in THF drop-wise at 0°C, and the mixture was stirred for 3h at 0°C. THF and Na2S04 x 5H2O was added slowly. After stirring for 20 min, the mixture was filtered and the filtrate was concentrated to give crude product (26 g, yield: 57.1 %).
Step 1 .2: 6-chloropyridine-3-carbaldehyde
To a solution of PCC (58 g, 0.27 mol) in DCM (1500 ml) was added the product of the proceeding step (26 g, 0.184mol) as a solution in DCM drop wise at 0°C. The mixture was then stirred for 2h at 20°C. It was filtered through diatomaceous earth and the filter contents were washed with DCM. The organic phase was concentrated to give the crude product, which was purified by column chromatography to give the product (15 g, yield: 60.1 %).
1H NMR (400 MHz, CDCI3): δ 10.067 (s, 1 H), 8.874 (s, 1 H, J=3Hz), 8.158-8.138 (d, 1 H, J=8Hz), 7.534-7.513 (d, 1 H, J=8Hz)
Step 1 .3: Methyl 4-(6-chloro-3-pyridyl)-4-oxo-butanoate
To a solution of 6-chloropyridine-3-carbaldehyde (10 g, 70 mmol) in DMF (40 ml) was added NaCN (0.7 g, 14 mmol). The mixture was stirred for 1 h followed by dropwise addition of methyl acrylate (5.2 g, 60 mmol). Stirring was continued for 3h at room temperature, the solution was poured into water, and extracted with EtOAc. The organic phase was dried, filtered and concentrated to give methyl 4-(6-chloro-3-pyridyl)- 4-oxo-butanoate (6.8 g, yield: 42.5%).
1H NMR (400 MHz, CDCI3): δ 8.971 -8.968 (m, 1 H), 8.219-8.198 (d, 1 H, J=8.4Hz), 7.462-7.441 (d, 1 H, J=8.4Hz), 3.710 (s, 3H), 3.306-3.274 (m, 1 H) 2.812-2.760 (m, 2H).
Step 1 .4: 5-(6-chloro-3-pyridyl) pyrrolidin-2-one
To a solution of methyl 4-(6-chloro-3-pyridyl)-4-oxo-butanoate (6.7 g, 29.5 mmol) in MeOH (100 ml) was added NH4OAc (6.8 g, 88.3 mmol) and NaBH3CN (5.6 g, 88.3 mmol), and the mixture was refluxed overnight. The solvent was removed in vacuo, the residue dissolved in DCM, washed with brine, dried, and concentrated to give the crude product. Purification by column chromatography gave the product (3 g, yield: 51 .9%). 1H NMR (400 MHz, CDCI3): δ 8.336-8.330 (d, 1 H, J=2.4Hz), 7.642-7.616 (m, 1 H), 7.361 -7.340 (d, 1 H, J=8.4Hz), 6.987 (s, 1 H), 4.819-4.782 (m, 1 H), 2.634-2.482 (m, 1 H), 2.474-2.432 (m, 2H), 1 .967-1.935 (m, 1 H).
Step 1 .5: 5-(6-chloro-3-pyridyl) pyrrolidine-2-thione
To a solution of the compound from the preceding step (2.4 g, 12.24 mmol) in dioxane (150 ml) was added P2S5 (3.3 g, 14.7 mmol) at RT. The mixture was heated to 1 10°C and stirred for 2.0 h. After filtration of the hot mixture, the filtrate was concentrated to give the crude material. Purification by column chromatography yielded the pure product (1 .56 g, yield: 60.2%).
Step 1 .6: 2-chloro-5-(5-methylsulfanyl-3,4-dihydro-2H-pyrrol-2-yl)pyridine
To a solution of 5-(6-chloro-3-pyridyl) pyrrolidine-2-thione (2 g, 9.4 mmol) in acetone (100 ml) was added K2CO3. After stirring at RT for 30 min, iodomethane was added and stirred for additional 3h at room temperature. After filtration, the filtrate was concentrated to give the crude material. Purification by column chromatography yielded the pure product (2.1 g, yield: 97.6%).
1H NMR (400 MHz, CDCI3): δ 8.320 (s, 1 H), 7.564-7.544 (d, 1 H, J=8.0Hz),
7.298-7.278 (d, 1 H, J=8.0Hz), 5.105-5.068 (m, 1 H), 2.856-2.792 (m, 2H),
2.634-2.513 (m, 2H), 2.179 (s, 3H), 1 .820-1.255 (m, 1 H).
Step 1 .7: 2-(6-chloro-3-pyridyl)-N-isopropyl-3,4-dihydro-2H-pyrrol-5-amine
To the product from step 6 (0.25g, 1.03 mmol) in THF (30 ml) was added isopropyl amine (580 mg, 10.3mmol) and the mixture was heated in a sealed tube at 130°C overnight. Cooled to 20°C the solvent was removed in vacuo. The residue was dissolved in EtOAc (60 mL), washed with water (30 mL), brine, and concentrated to give the product (230 mg, yield: 88.1 %).
Step 1 .8: 3-(6-chloro-3-pyridyl)-8-(dimethylamino)-5-oxo-6-phenyl-1 ,2,3,8- tetrahydroindolizin-4-ium-7-olate.
The product from step 7 (0.23 g, 0.96 mmol) and bis(2,4,6-trichlorophenyl) 2- phenylpropanedioate (0.62 g, 1.2 mmol) was taken up in toluene (5 ml) with a few drops of DMF. The reaction mixture was heated in a microwave oven at 150°C for 90 min. After cooling to RT, it was poured into water (10ml), and extracted with EtOAc (45mL). The organic phase was dried with Na2S04, and concentrated to give the crude material. Purification by column chromatography yielded the pure product (0.155 g, yield: 57.8%).
1H NMR (400 MHz, CDCI3): δ 8.400-8.394 (d, 1 H, J=2.4Hz), 7.8818-7.791 (m, 1 H), 7.470-7.395 (m, 3H), 7.285-7.142 (m, 3H), 5.841 -5.807 (m, 1 H), 3.771 -3.608 (m, 2H), 2.982-2.869 (m, 2H), 2.249-2.192 (m, 1 H), 1 .722-1.671 (m, 6H).
Example 2: Synthesis S2:
Synthesis of Example numbered C-8: 6-(6-chloro-3-pyridyl)-1 -methyl-4-oxo-3-phenyl-
6,7,8,9-tetrahydropyrido[1 ,2-a]pyrimidin-5-ium-2-olate
Figure imgf000082_0001
Step2.1 : Methyl 5-(6-chloro-3-pyridyl)-5-oxo-pentanoate
To a mixture of Zn metal (21.7 g, 0.339 mol) and DMI (38.6 g, 0.339 mol) in MeCN (300 mL) was added under an argon atmosphere 0.2 ml of TMSCI at 60°C stirred for 5 min, followed by addition of methyl 4-iodo butanoate (58 g, 0.254 mol). The mixture was stirred for 2 hours at this temperature, and then cooled to room temperature. This solution was used directly.
To a mixture of 6-chloropyridine-3-carbonyl chloride (14.8 g, 0.085 mol) and Pd(OAc)2 (0.57 g, 0.00254 mol) in MeCN (300 mL) was added under an argon atmosphere the alkyl zinc reagent and stirred at room temperature. After 2 hours, sat.NhUCI solution was added to the reaction mixture and it was extracted with EtOAc. The organic phases were combined, washed with brine, dried, filtered and concentrated to give the crude product. Purification by column chromatography yielded the pure product (9.5 g). H NMR (400 MHz, CDCI3): δ d 8.88-8.89 (d, 1 H, J=2Hz), 8.13-8.19 (m, 1 H),
7.36-7.40 (d, 1 H, J=16Hz), 4.03-4.01 (q, 2H), 2.98-3.02 (t, 2H, J=6.8Hz) 2.37-2.407 (t, 2H, J=7.2Hz), 1.98-2.05 (m, 2H), 1.15-1.22 (t, 2H, J=13Hz).
Step2.2: 6-(6-chloro-3-pyridyl) piperidin-2-one
To a solution of methyl 5-(6-chloro-3-pyridyl)-5-oxo-pentanoate (9.5g, 39.4 mmol) in MeOH (150 ml) was added NH4OAc (6.1 g, 78.8mmol) and NaBH3CN (5 g, 78.8 mmol), and the mixture refluxed for overnight. Cooled to RT, the solvent was removed in vacuo, the residue dissolved in DCM, washed with brine dried concentrated to give the crude product. Purification by column chromatography yielded the pure product (5g, yield: 61 %). Step 2.3: 6-(6-chloro-3-pyridyl)piperidine-2-thione
To a solution of 6-(6-chloro-3-pyridyl)piperidin-2-one (2.2 g, 10.4 mmol) in dioxane (150 ml) was added P2S5 (2.8 g, 12.6 mmol) at 20°C The mixture was stirred for 2.5 h at 120°C. After filtration of the hot mixture, the filtrate was concentrated to give the crude material. Purification by column chromatography yielded the pure product (1 .5 g, yield: 63.5%).
Step 2.4: 2-chloro-5-(6-methylsulfanyl-2,3,4,5-tetrahydropyridin-2-yl)pyridine
To a solution of 6-(6-chloro-3-pyridyl)piperidine-2-thione (1.5 g, 6.64 mmol) in acetone (120 ml) was added K2CO3 and stirred for 30 min, then iodo methane (1.42 g, 9.96 mmol) was added and stirred for overnight at 20°C. After filtration, the filtrate was concentrated to give the crude material. Purification by column chromatography yielded the pure product (1.2 g, yield: 75.3%).
Step 2.5: 2-(6-chloro-3-pyridyl)-N-methyl-2,3,4,5-tetrahydropyridin-6-amine
2-chloro-5-(6-methylsulfanyl-2,3,4,5-tetrahydropyridin-2-yl)pyridine (0.6 g, 2.5 mmol) was taken up in methyl amine (20 mL, 40 mmol), and the mixture was heated in a sealed tube at 80°C for overnight. Cooled to 20°C the solvent was removed in vacuo, the residue was dissolved in EtOAc (60 mL) and washed with water (30 mL), and brine. The organic phase was concentrated to give the product (480 mg, crude).
Step 2.6: 6-(6-chloro-3-pyridyl)-1 -methyl-4-oxo-3-phenyl-6,7,8,9-tetrahydropyrido[1 ,2- a]pyrimidin-5-ium-2-olate
The product from the preceding step (0.48 g, crude) and bis(2,4,6-trichlorophenyl) 2- phenylpropanedioate (1 .4 g, 2.4 mmol) was taken up in toluene (5 ml) with a few drops of DMF. The reaction mixture was heated in a microwave oven at 150°C for 90 min. After cooling to RT, it was poured into water (10ml), and extracted with EtOAc (45mL). The organic phase was dried with Na2S04, and concentrated to give the crude material. Purification by column chromatography yielded the pure product (0.4 g, yield:
50.7%).
H N MR (400 MHz, CDCI3): δ d 8.381 -8.375 (d, 1 H, J=2.4Hz), 7.818-7.791 (m, 1 H), 7.552-7.485 (m, 3H), 7.207-7.048 (m, 3H), 5.941 -5.933 (s, 1 H), 3.495 (s, 3H), 3.236-3.174 (m, 2H), 2.179-2.132 (m, 2H), 1 .822-1.426 (m, 2H).
Example 3, Synthesis S3:
Synthesis of Example numbered C-6: 6 -(2-chlorothiazol-5-yl)-1 -methyl-4-oxo-3-phenyl- 3,6,7,8-tetrahydro-2H-pyrrolo[1 ,2-a]pyrimidin-5-ium-2-olate
Figure imgf000084_0001
C-6
A mixture of 2-(2-chlorothiazol-5-yl)-N-methyl-3,4-dihydro-2H-pyrrol-5-amine
(230 mg, 1.07 mmol) and bis(2,4,6-trichlorophenyl) 2-phenylpropanedioate (632 mg, 1 .17 mmol) in toluene (10 ml) in sealed tube was heated at 150°C for 90 min under microwave irradiation. Cooled to RT, the resulting mixture was concentrated, and the residue was purified by preparative TLC to give 6-(2-chlorothiazol-5-yl)-1 -methyl-4-oxo- 3-phenyl-3,6,7,8-tetrahydro-2H-pyrrolo[1 ,2-a]pyrimidin-5-ium-2-olate (90 mg, yield: 23%) as a yellow solid.
1H NMR (400 MHz, CDCI3): δ d 7.87 (s, 1 H), 7.60 (d, 2H, J=7.2 Hz), 7.23 (t, 2H, J=7.6 Hz), 7.08 (t, 1 H, J=7.6 Hz), 5.98-5.95 (m, 1 H), 3.67-3.59 (m, 1 H), 3.51 -3.44 (m, 1 H), 3.37 (s, 3H), 2.69-2.67 (m, 1 H), 2.60-2.54 (m, 1 H).
Compounds can in general be characterized e.g. by coupled High Performance Liquid Chromatography / mass spectrometry (HPLC/MS), by 1H-NMR and/or by their melting points.
Conditions: Analytical HPLC column 1 : RP-18 column Chromolith Speed ROD from Merck KgaA, Germany). Elution: acetonitrile + 0.1 % trifluoroacetic acid (TFA) / water + 0.1 % tri- fluoroacetic acid (TFA) in a ratio from 5:95 to 95:5 in 5 minutes at 40 °C.
r.t. = HPLC retention time (RT) in minutes; m/z of the [M+H]+, [M+Na]+ or [M+K]+ peaks.
Analytical HPLC column 2: Phenomenex Kinetex 1 ,7μηι XB-C18 100A; 50 x 2,1 mm Elution: A: acetonitrile + 0.1 % trifluoroacetic acid (TFA) / water + 0.1 % trifluoroacetic acid (TFA) in a ratio of from 5:95 to 95:5 in 1.5 minutes at 50 °C.
MS-method: ESI positive.
1H-NMR, respectively 13C-NMR: The signals are characterized by chemical shift δ
(ppm) vs. tetramethylsilane, respectively CDC for 13C-NMR, by their multiplicity and by their integral (relative number of hydrogen atoms given). The following abbreviations are used to characterize the multiplicity of the signals: m = multiplett, q = quartett, t = triplett, d = doublet and s = singulett. The coupling constant (J) is expressed in Hertz (Hz).
Further compounds examples of the present invention were prepared by analogy to the above described synthetic methods and the hereunder table illustrates, without imposing any limitation thereto, compounds examples of formula (I) including their corre- sponding characterization data:
Figure imgf000085_0001
Figure imgf000086_0001
Figure imgf000087_0001
Figure imgf000088_0001
Figure imgf000089_0001
Figure imgf000090_0001
Figure imgf000091_0001
Figure imgf000092_0001
Figure imgf000093_0001
The biological activity of the compounds of formula (I) of the present invention can be evaluated in biological tests as described in the following. General conditions: If not otherwise specified, most test solutions are to be prepared as follows:
The active compound is dissolved at the desired concentration in a mixture of 1 :1 (vohvol) distilled water : acetone. The test solution is prepared at the day of use.
Test solutions are prepared in general at concentrations of 2500 ppm, 1000 ppm, 500 ppm, 300 ppm, 100 ppm and 30 ppm (wt/vol).
Boll weevil (Anthonomus grandis)
For evaluating control of boll weevil (Anthonomus grandis) the test unit consisted of 96- well-microtiter plates containing an insect diet and 5-10 A. grandis eggs.
The compounds were formulated using a solution containing 75% v/v water and 25% v/v DMSO. Different concentrations of formulated compounds were sprayed onto the insect diet at 5 μΙ, using a custom built micro atomizer, at two replications.
After application, microtiter plates were incubated at about 25 + 1 °C and about 75 + 5 % relative humidity for 5 days. Egg and larval mortality was then visually assessed.
In this test, compounds C-3, C-47, C-29, C-40 and C-44 at 2500 ppm showed over 75
% mortality in comparison with untreated controls.
Green Peach Aphid (Myzus persicae)
For evaluating control of green peach aphid (Myzus persicae) through systemic means the test unit consisted of 96-well-microtiter plates containing liquid artificial diet under an artificial membrane.
The compounds were formulated using a solution containing 75% v/v water and 25% v/v DMSO. Different concentrations of formulated compounds were pipetted into the aphid diet, using a custom built pipetter, at two replications. After application, 5 - 8 adult aphids were placed on the artificial membrane inside the microtiter plate wells. The aphids were then allowed to suck on the treated aphid diet and incubated at about 23 + 1 °C and about 50 + 5 % relative humidity for 3 days. Aphid mortality and fecundity was then visually assessed.
In this test, compounds C-1 , C-2, C-3, C-6, C-8, C-9 , C-12, C-13, C-21 , C-34, C-45, C- 23, C-22, C-24, C-27, C-49, C-47, C-48, C-50, C-29, C-40, C-32, C-43, C-44, C-38, C- 17, C-41 and C-31 at 2500 ppm showed over 75% mortality in comparison with untreated controls. Orchid thrips (dichromothrips corbetti)
Dichromothrips corbetti adults used for bioassay were obtained from a colony maintained continuously under laboratory conditions. For testing purposes, the test compound is diluted in a 1 :1 mixture of acetone:water (vohvol), plus 0.01 % vol/vol Al- kamuls® EL 620 surfactant.
Thrips potency of each compound was evaluated by using a floral-immersion technique. Plastic petri dishes were used as test arenas. All petals of individual, intact orchid flowers were dipped into treatment solution and allowed to dry. Treated flowers were placed into individual petri dishes along with about 20 adult thrips. The petri dishes were then covered with lids. All test arenas were held under continuous light and a temperature of about 28°C for duration of the assay. After 3 days, the numbers of live thrips were counted on each flower, and along inner walls of each petri dish. The percent mortality was recorded 72 hours after treatment.
In this test, compounds C-1 , C-2, C-3, C-6, C-8, C-34, C-45, C-22, C-24, C-27, C-49, C-47, C-28, C-48, C-50, C-29, C-42, C-35 and C-38 at 500 ppm showed over 75 % mortality in comparison with untreated controls.
Rice green leafhopper (Nephotettix virescens)
Rice seedlings were cleaned and washed 24 hours before spraying. The active compounds were formulated in 50:50 acetone:water (vohvol), and 0.1 % vol/vol surfactant (EL 620) was added. Potted rice seedlings were sprayed with 5 ml test solution, air dried, placed in cages and inoculated with 10 adults. Treated rice plants were kept at about 28-29°C and relative humidity of about 50-60%. Percent mortality was recorded after 72 hours.
In this test, compounds C-1 , C-2, C-6, C-8, C-22, C-24, C-47, C-28, C-42 and C-38 at 500 ppm showed over 75 % mortality in comparison with untreated controls.
Rice brown plant hopper (Nilaparvata lugens)
Rice seedlings were cleaned and washed 24 hours before spraying. The active compounds were formulated in 50:50 acetone:water (vohvol) and 0.1 % vol/vol surfactant (EL 620) was added. Potted rice seedlings were sprayed with 5 ml test solution, air dried, placed in cages and inoculated with 10 adults. Treated rice plants were kept at about 28-29°C and relative humidity of about 50-60%. Percent mortality was recorded after 72 hours. In this test, compounds C-1 , C-6, C-24, C-28, C-29, C-42 and C-38 at 500 ppm showed over 75 % mortality in comparison with untreated controls.
Spider Mite (Tetranychus spp.)
The active compound is dissolved at the desired concentration in a mixture of 1 :1 (vohvol) distilled water : acetone. The test solution is prepared at the day of use.
Potted cotton plants at two weeks of age were cleaned, air dried and inoculated with approximately 50 mites of various stages. The potted plants are sprayed after the pest population has been recorded. Percent mortality is recorded 72 hours after treatment. In this test, compounds C-9 and C-42 at 500 ppm showed over 75 % mortality in comparison with untreated controls.
Tobacco budworm (Heliothis virescens)
For evaluating control of tobacco budworm (Heliothis virescens) the test unit consisted of 96-well-microtiter plates containing an insect diet and 15-25 H. virescens eggs.
The compounds were formulated using a solution containing 75% v/v water and 25% v/v DMSO. Different concentrations of formulated compounds were sprayed onto the insect diet at 10 μΙ, using a custom built micro atomizer, at two replications.
After application, microtiter plates were incubated at about 28 + 1 °C and about 80 + 5 % relative humidity for 5 days. Egg and larval mortality was then visually assessed.
In this test, compounds C-1 , C-45, C-44 and C-38 at 2500 ppm showed over 75 % mortality in comparison with untreated controls.
Vetch aphid (Megoura viciae)
For evaluating control of vetch aphid (Megoura viciae) through contact or systemic means the test unit consisted of 24-well-microtiter plates containing broad bean leaf disks.
The compounds were formulated using a solution containing 75% v/v water and 25% v/v DMSO. Different concentrations of formulated compounds were sprayed onto the leaf disks at 2.5 μΙ, using a custom built micro atomizer, at two replications.
After application, the leaf disks were air-dried and 5 - 8 adult aphids placed on the leaf disks inside the microtiter plate wells. The aphids were then allowed to suck on the treated leaf disks and incubated at about 23 + 1 °C and about 50 + 5 % relative humidity for 5 days. Aphid mortality and fecundity was then visually assessed.
In this test, compounds C-1 , C-2, C-3, C-6, C-8, C-9,C-13, C-34, C-45, C-22, C-24, C- 27, C-49, C-47, C-48, C-50, C-29, C-40, C-44, C-38, C-19 and C-31 at 2500 ppm showed over 75 % mortality in comparison with untreated controls.

Claims

Substituted pyrimidinium compounds of formula (I)
Figure imgf000096_0001
wherein
are each independently O or S;
is a direct bond, O, S(0)m, NRb, C(RaRaa)0, C(=X1), C(=X1)Y1,or Y C(=X1);
X1 is O, S, or NRb;
Y1 is O, S, or NRC;
is CH or N and, wherein the nitrogen of the pyrimidinium ring taken together with the contiguous linking carbon atom and A as depicted in formula (I), form a four- to sev- en-membered ring, wherein each remaining ring member is selected from carbon atoms and up to 3 heteroatoms independently selected from up to 2 O, up to 2 S, and up to 3 N(RC)P, wherein up to 2 carbon atom ring members are independently selected from C(=0) and C(=S), and the sulfur atom ring members are independently selected from S(=0)m, wherein each ring may be substituted with up to 3 Ra;
Het is a three- to ten-membered heterocyclic ring or a seven- to eleven-membered heterocyclic ring system, each ring or ring system member selected from carbon atoms and up to 4 heteroatoms independently selected from up to 2 O, up to 2 S, and up to 4 N(Rc)p, wherein up to 3 carbon atom ring members are independently selected from C(=0) and C(=S) and the sulfur atom ring members are independently selected from
Figure imgf000096_0002
each ring or ring system optionally substituted with up to 5 Ra; o, q are each independently 0, 1 or 2, provided that the sum (o + q) is 0, 1 or 2 for each ring;
R is hydrogen, Ci-Cs-alkyl, C2-C8-alkenyl, C2-C8-alkynyl, C3-Cio-cycloalkyl, C4-Cio- cycloalkenyl, Cs-C-u-cycloalkylcycloalkyl or R1 may form a three- to eleven- membered saturated, or partially unsaturated or aromatic carbo-or heterocyclic ring or ring system, which may contain 1 to 4 heteroatoms selected from N(RC)P, O, and S, wherein S may be oxidized, and wherein the aforementioned groups and the car- bo- or heterocyclic rings system may be unsubstituted, partially or fully substituted by Ra; or
R1 is C(=0)Rb, C(=0)ORe, NRbRc, C(=0)NR Rc, C(=S)NR Rc, S02NR Rc,
OC(=0)Rc, OC(=0)ORe, OC(=0)NR Re, N(Rc)C(=0)Rc, N(Rc)C(=0)ORe,
N(Rc)C(=0)NR Rc, NRcS02R , NRcS02NR Rc, Si(Rd)3, C(=NRC)RC, C(=NORc)Rc , C(=NNR Rc)Rc, C(=NN(C(=0)R )Rc)Rc C(=N N(C=0)ORc)(Rc)2, S(=0)0(=NR )qRc or N=CRbRc;
Ra is each independently halogen, Ci-C6-alkyl, Ci-C6-haloalkyl, Ci-C6-alkoxy, Ci- Ce-haloalkoxy, C2-C4-alkenyl, C2-C4-alkynyl, C3-C6-cycloalkyl, CN, ORc, NRbRc, N02, C(=0)(0)PRc, OC(=0)(0)PRe, C(=0)NR Rc, OC(=0)NR Re,
NRbC(=0)(0)PRe , NRbC(=0)NRbRc, C(=S)NR Rc, S(0)mR , S02NR Rc, OS02Rc, OS02NR Rc, NR S02Rc, NRbS02NRbRc, N=S(=0)PRcRc,
Figure imgf000097_0001
SF5, OCN, SCN, Si(Rd)3 or a three- to six-membered saturated, or partially unsaturated or aromatic carbo- or heterocyclic ring, which may contain 1 to 3 heteroatoms selected from N-(RC)P, O, and S which may be oxidized, and wherein the aforementioned groups and the carbo- or heterocyclic ring may be partially or fully substituted by Raa, or
two geminally bound groups Ra together may form a group selected from =0, =S, =CR Rc, =NRC, =NORc, and =NNRCRC;
Raa is each independently halogen, Ci-C6-alkyl, Ci-C6-haloalkyl, Ci- C6-alkoxy or Ci-C6-haloalkoxy;
Rb is each independently hydrogen, Ci-C6-alkyl, Ci-C6-haloalkyl, Ci-C6-alkoxy, Ci-C6-haloalkoxy or a three- to six-membered saturated, or partially unsaturated or aromatic carbo- or heterocyclic ring, which may contain 1 to 3 heteroatoms selected from N(RC)P, O, and S, wherein S may be oxidized and which carbo- or heterocyclic ring may be partially or fully substituted by Raa;
Rc is each independently hydrogen, Ci-C4-alkyl, Ci-C4-haloalkyl, C1-C4- alkylcarbonyl, CrC6 cycloalkyi, or a three- to six-membered saturated, partially unsaturated or aromatic carbo- or heterocyclic ring, which may contain 1 to 3 heteroatoms selected from N(Raa)p, O and S, wherein S may be oxidized and wherein the carbo- or heterocyclic ring may be partially or fully substituted by Raa;
wherein two geminally bound groups RbRb, RcRb or RCRC together with the atom to which they are bound, may form a 3-, 4-, 5-, 6- or 7- membered saturated, partially unsaturated or aromatic carbo- or heterocyclic ring, which may contain 1 to 2 heteroatoms or heteroatoms groups selected from N, O, S, NO, SO and S02 and wherein the carbo- or heterocyclic ring may be partially or fully substituted by R3;
Rd is each independently hydrogen, phenyl, Ci-C6-alkyl, C2-C6-alkenyl, C2-C6- alkynyl, Cs-Cs-cycloalkyl, or Ci-C6-alkoxyalkyl, wherein the above mentioned groups may be substituted by one or more halogen;
Re is each independently, Ci-C4-alkyl, Ci-C4-haloalkyl, Ci-C4-alkylcarbonyl, CrC6 cycloalkyi, or a three- to six-membered saturated, partially unsaturated or aromatic carbo- or heterocyclic ring, which may contain 1 to 3 heteroatoms selected from N(Raa)p, O and S, wherein S may be oxidized and wherein the carbo- or heterocyclic ring may be partially or fully substituted by Raa;
n is 0, 1 or 2;
m is 0, 1 , or 2;
p is O or l ; is H , halogen, CN , Ci-Cs alkyl, C2-Cs alkenyl, C2-Cs alkynyl, C3-C10 cycloalkyi, C4-C10 alkylcycloalkyl, C4-C10 cycloalkylalkyl, C6-C14 cycloalkylcycloalkyl, C5-C10 alkylcyclo- alkylalkyi, or C3-C6 cycloalkenyl, wherein the aforementioned groups may be unsub- stituted, partially, or fully substituted with R2a, or R2 may form a carbo-or heterocyclic three- to ten-membered ring or a seven- to eleven-membered rings system, which ring or ring system may be saturated, partially unsaturated, or aromatic, and which ring or ring system may contain 1 to 4 heteroatoms selected from N(RC)P, O, and S, wherein S may be oxidized, and wherein the carbo- or heterocyclic ring or rings system may be unsubstituted, partially, or fully substituted by R2a;
with the proviso that if R2 is halogen or CN, then Z is a direct bond;
R2a is each independently halogen, Ci-C6-alkyl, Ci-C6-haloalkyl, Ci-C6-alkoxy, Ci- Ce-haloalkoxy, C2-C4-alkenyl, C2-C4-alkynyl, C3-C6-cycloalkyl, CN, ORc, NRbRc N02, C(=0)(0)PRc, OC(=0)(0)PRe, C(=0)NR Rc, OC(=0)NR Re,
NRbC(=0)(0)PRe , NRbC(=0)NRbRc, C(=S)NR Rc, S(0)mR , S02NR Rc, OS02Rc, OS02NR Rc, NR S02Rc, NRbS02NRbRc, SF5, OCN, SCN, Si(Rd)3, C(=N(0)PR ) R , C(=NNRbRc)Rb, C(=NN(C(=0)0PRc)Rc)R , ON=CR Rc, ONRbRc,
Figure imgf000098_0001
OP(=X2)(ORc)2, N=CRbRc, NRbN=CRbRc, NRbNRbRc, NRbC(=S)NRbRc , NRbC(=NRb)NRbRc, N RbN RbC(=X2) N RbRc, N RbN RbS02N RbRc, N=S(=0)PRcRc, or a three- to six-membered saturated, or partially unsaturated or aromatic carbo- or heterocyclic ring, which may contain 1 to 3 heteroatoms selected from N-(Rc)p, O, and S, wherein S may be oxidized, and wherein the aforementioned groups and the carbo- or heterocyclic ring may be partially or fully substituted by R2aa or
two geminally bound groups R2a together may form a group selected from =0, =S, =CR Rc, =NRC, =NORc, and =NNRCRC;
R2aa is each independently halogen, Ci-C6-alkyl, Ci-C6-haloalkyl, C1-C6- alkoxy, Ci-C6-haloalkoxy, C2-C4-alkenyl, C2-C4-alkynyl, C3-C6-cycloalkyl, CN, ORc, NRbRc, N02, C(=0)(0)PRc, OC(=0)(0)PRe, C(=0)NR Rc, OC(=0)NR Re, NR C(=0)(0)PRe , NRbC(=0)NRbRc, C(=S)NR Rc, S(0)mR , S02NR Rc, OS02Rc, OS02NR Rc, NR S02Rc, NRbS02NRbRc, SF5, OCN, SCN, Si(Rd)3, C(=N(0)PR )R , C(=NNRbRc)Rb,
C(=NN(C(=0)0PRc)R )R , ON=CR Rc, ONRbRc, S(=0)0(=NR )qRc, S02NR (=0)NR Rc, P(=X2)R Rc, OP(=X2)(0PRc)R , OP(=X2)(ORc)2, N=CRbRc, NRbN=CRbRc, NRbNRbRc, NRbC(=S)NRbRc ,
NRbC(=NRb)NRbRc, N RbN RbC(=X2) N RbRc, N RbN RbS02N RbRc, or N=S(=0)PRcRc or
two geminally bound groups R2aa together may form a group selected from =0 =S,=CR Rc, =NRC, =NORc, and =NNRCRC;
X2 is independently O or S;
R3 is each independently halogen, Ci-C6-alkyl, Ci-C6-haloalkyl, Ci-C6-alkoxy, Ci- Ce-haloalkoxy, C2-C4-alkenyl, C2-C4-alkynyl, C3-C6-cycloalkyl, CN, ORc, NRbRc N02, C(=0)(0)PRc, OC(=0)(0)PRe, C(=0)NR Rc, OC(=0)NR Re,
NR C(=0)(0)PRe , NRbC(=0)NRbRc, C(=S)NR Rc, S(0)mR , S02NR Rc, OS02Rc, OS02NR Rc, NR S02Rc, NRbS02NRbRc, SF5, OCN, SCN, Si(Rd)3, C(=N(0)PRb)Rb, C(=NNRbRc)Rb, C(=NN(C(=0)0PRc)R )R , ON=CR Rc, ONRbRc,
Figure imgf000099_0001
OP(=X2)(ORc)2, N=CRbRc, NRbN=CRbRc, NRbNRbRc, NRbC(=S)NRbRc , NRbC(=NRb)NRbRc, N RbN RbC(=X2) N RbRc, NR NR S02NR Rc, or N=S(=0)PRcRc or
two geminally bound groups R3 together may form a group selected from =0,
=S, =CR Rc, =NRC, =NORc, and =NNRCRC;
and/or stereoisomers or agriculturally or veterinary acceptable salts or tautomers or N- oxides thereof.
The compounds of formula (I) and/or stereoisomers or agriculturally or veterinary acceptable salts or tautomers or N-oxides thereof according to claim 1 , wherein Het is a five- or six-membered saturated, partially unsaturated or aromatic heterocyclic ring, which may contain 1 to 2 heteroatoms selected from N(RC)P, O and S, which heterocyclic ring may be substituted with up to 2 Ra.
The compounds of formula (I) and/or stereoisomers or agriculturally or veterinary acceptable salts or tautomers or N-oxides thereof according to claim 1 or 2, wherein Het is selected from structures D-2, D-9, D-22, D25, D28, D-29 and D-54:
Figure imgf000099_0002
wherein
Ra is halogen, Ci-C4-haloalkyl, CiC4-alkoxy or Ci-C4-alkylthio or phenyl,
n is 0, 1 or 2, and wherever used in a structure, the following:
# denotes the bond to A in formula (I).
4. The compounds of formula (I) and/or stereoisomers or agriculturally or veterinary acceptable salts or tautomers or N-oxides thereof according to any one of preceding claims, wherein A is CH or N, wherein the nitrogen of the pyrimidinium ring taken together with the contiguous linking carbon atom and A as depicted in formula (I), form a five or six membered ring, wherein each remaining ring member is selected from carbon atoms and up to one heteroatom selected from O, S and N(RC)P, which ring may be substituted by Ra.
5. The compounds of formula (I) and/or stereoisomers or agriculturally or veterinary acceptable salts or tautomers or N-oxides thereof according to any one of the preceding claims, wherein X and Y are O. 6. The compounds of formula (I) and/or stereoisomers or agriculturally or veterinary acceptable salts or tautomers or N-oxides thereof according to any one of the preceding claims, wherein
Z is a direct bond, and
R2 is a six membered carbo- or heterocyclic ring, which ring may be unsubstituted, par- tially, or fully substituted by R2a, and wherein R2a is halogen, Ci-C6-haloalkyl, C1-C6- haloalkoxy, ORc, C(=0)ORc, C(=0)NRbRc, phenyl, or pyridyl, which may be substituted by halogen, Ci-C6-haloalkyl or Ci-C6-haloalkoxy.
7. The compounds of formula (I) and/or stereoisomers or agriculturally or veterinary ac- ceptable salts or tautomers or N-oxides thereof according to any one of the preceding claims, wherein
R1 is Ci-C4-alkyl, C3-C6-cycloalkyl, C2-C4-alkenyl, benzyl or phenyl, which groups may be partially or fully substituted by halogen or Ci-C4-alkyl. 8. The compounds of formula (I) and/or stereoisomers or agriculturally or veterinary acceptable salts or tautomers or N-oxides thereof according to claim 3, wherein
X, Y are each O;
A is CH and the nitrogen of the pyrimidinium ring taken together with the contiguous linking carbon atom and A as depicted in formula (I), form a five or six membered ring, wherein each remaining ring member is selected from 2 and 3 carbon atoms;
R1 is CH3, CH2CH3, isopropyl, cyclopropyl, CH2CF3, phenyl, allyl or benzyl;
R2 is phenyl which may be substituted by halogen, Ci-C6-haloalkyl, Ci-C6-haloalkoxy or phenyl;
Z is a direct bond and
Het is D-2, D-9, D-25 or D-56 and Ra is CI, Br, F, SCH3, CF3, OCH3 or phenyl.
9. A composition comprising at least one compound of formula (I), as defined in any one of claims 1 to 8, and at least one inert liquid and/or solid carrier. 10. An agricultural composition for combating animal pests comprising at least one compound of formula (I) and/or stereoisomers or agriculturally or veterinary acceptable salts or tautomers or N-oxides thereof, as defined in any one of claims 1 to 8, and at least one inert liquid and/or solid acceptable carrier and, if desired, at least one surfactant. 1 1 . A method for protecting crops, plants, plant propagation material and/or growing plants from attack or infestation by invertebrate pests comprising contacting or treating the crops, plants, plant propagation material and growing plants, or soil, material, surface, space, area or water in which the crops, plants, plant propagation material is stored or the plant is growing with a pesticidally effective amount of at least one compound of formula (I) and/or stereoisomers or agriculturally or veterinary acceptable salts or tautomers or N-oxides thereof as defined in any one of the claims 1 to 8 or with a composition as defined in any one of the claims 9 to 10.
12. A method for combating, controlling, preventing or protecting against infestation or infection by invertebrates pest, which method comprises contacting said pest or its food supply, habitat or breeding grounds with a pesticidally effective amount of at least one compound of formula (I) and/or stereoisomers or agriculturally or veterinary acceptable salts or tautomers or N-oxides thereof as defined in any one of the claims 1 to 8, or a composition as defined in any of claims 9 to 10.
A non-therapeutic method for treating animals infested or infected by parasites or preventing animals of getting infected or infested by parasites or protecting animals against infestation or infection by parasites which comprises orally, topically or parenterally administering or applying to the animals a parasiticidally effective amount of a compound of formula (I) and/or stereoisomers or agriculturally or veterinary acceptable salts or tautomers or N-oxides thereof as defined in any of claims 1 to 8.
Seed comprising a compound of formula (I) and/or stereoisomers or agriculturally or veterinary acceptable salts or tautomers or N-oxides thereof as defined in any one of the claims 1 to 8 in an amount of from 0.1 g to 10 kg per 100 kg of seed.
The use of the compounds of formula (I) and/or stereoisomers or agriculturally or veterinary acceptable salts or tautomers or N-oxides thereof as defined in any one of the claims 1 to 8 for protecting growing plants or plant propagation material from attack or infestation by invertebrate pests.
The use of a compound of formula (I) and/or stereoisomer or agriculturally or veterinary acceptable salt or tautomer or N-oxide thereof as defined in any one of the claims 1 to 8 for the preparation of a veterinary composition for treating animals infested or infected by parasites, for preventing animals of getting infected or infested by parasites or protecting animals against infestation or infection by parasites.
PCT/EP2014/057344 2013-04-11 2014-04-11 Substituted pyrimidinium compounds and derivatives for combating animal pests WO2014167084A1 (en)

Priority Applications (14)

Application Number Priority Date Filing Date Title
UAA201510934A UA115904C2 (en) 2013-04-11 2014-04-11 Substituted pyrimidinium compounds and derivatives for combating animal pests
CN201480020609.3A CN105121441B (en) 2013-04-11 2014-04-11 For preventing and kill off the substituted pyrimidines compound and derivative of animal pest
BR112015021863-6A BR112015021863B1 (en) 2013-04-11 2014-04-11 SUBSTITUTED COMPOUNDS OF PYRIMIDINIUM, COMPOSITION, AGRICULTURAL COMPOSITION, METHOD FOR THE PROTECTION OF CROPS, VEGETABLES, VEGETABLE PROPAGATION MATERIAL, METHOD FOR COMBATING, CONTROL, PREVENTING OR PROTECTING AND USING COMPOUNDS
EP14716829.8A EP2984089B1 (en) 2013-04-11 2014-04-11 Substituted pyrimidinium compounds and derivatives for combating animal pests
JP2016506980A JP6449850B2 (en) 2013-04-11 2014-04-11 Substituted pyrimidinium compounds and derivatives for controlling animal pests
AU2014253086A AU2014253086B2 (en) 2013-04-11 2014-04-11 Substituted pyrimidinium compounds and derivatives for combating animal pests
CA2901559A CA2901559C (en) 2013-04-11 2014-04-11 Substituted pyrimidinium compounds and derivatives for combating animal pests
KR1020157032205A KR102223216B1 (en) 2013-04-11 2014-04-11 Substituted pyrimidinium compounds and derivatives for combating animal pests
KR1020217005894A KR20210024256A (en) 2013-04-11 2014-04-11 Substituted pyrimidinium compounds and derivatives for combating animal pests
US14/783,600 US9730451B2 (en) 2013-04-11 2014-04-11 Substituted pyrimidinium compounds and derivatives for combating animal pests
ES14716829T ES2913139T3 (en) 2013-04-11 2014-04-11 Substituted pyrimidinium compounds and derivatives for combating animal pests
MX2015014204A MX2015014204A (en) 2013-04-11 2014-04-11 Substituted pyrimidinium compounds and derivatives for combating animal pests.
CR20150610A CR20150610A (en) 2013-04-11 2015-11-10 PIRIMIDINE COMPOUNDS REPLACED AND DERIVATIVES TO COMBAT ANIMAL PESTS
US15/656,293 US11019820B2 (en) 2013-04-11 2017-07-21 Substituted pyrimidinium compounds and derivatives for combating animal pests

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
US201361810746P 2013-04-11 2013-04-11
US61/810,746 2013-04-11

Related Child Applications (2)

Application Number Title Priority Date Filing Date
US14/783,600 A-371-Of-International US9730451B2 (en) 2013-04-11 2014-04-11 Substituted pyrimidinium compounds and derivatives for combating animal pests
US15/656,293 Continuation US11019820B2 (en) 2013-04-11 2017-07-21 Substituted pyrimidinium compounds and derivatives for combating animal pests

Publications (1)

Publication Number Publication Date
WO2014167084A1 true WO2014167084A1 (en) 2014-10-16

Family

ID=50478847

Family Applications (1)

Application Number Title Priority Date Filing Date
PCT/EP2014/057344 WO2014167084A1 (en) 2013-04-11 2014-04-11 Substituted pyrimidinium compounds and derivatives for combating animal pests

Country Status (16)

Country Link
US (2) US9730451B2 (en)
EP (1) EP2984089B1 (en)
JP (2) JP6449850B2 (en)
KR (2) KR102223216B1 (en)
CN (1) CN105121441B (en)
AR (1) AR096022A1 (en)
AU (1) AU2014253086B2 (en)
BR (1) BR112015021863B1 (en)
CA (1) CA2901559C (en)
CL (1) CL2015003001A1 (en)
CR (1) CR20150610A (en)
ES (1) ES2913139T3 (en)
MX (1) MX2015014204A (en)
PT (1) PT2984089T (en)
UA (1) UA115904C2 (en)
WO (1) WO2014167084A1 (en)

Cited By (36)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2018033455A1 (en) 2016-08-15 2018-02-22 Bayer Cropscience Aktiengesellschaft Condensed bicyclic heterocycle derivatives as pest control agents
US9975895B2 (en) 2013-06-17 2018-05-22 Basf Se Substituted pyrimidinium compounds and derivatives for combating animal pests
WO2018139560A1 (en) 2017-01-26 2018-08-02 三井化学アグロ株式会社 Pyridone compound and bactericide for agricultural and horticultural use, which uses said compound as active ingredient
WO2018177970A1 (en) 2017-03-31 2018-10-04 Basf Se Process for preparing chiral 2,3-dihydrothiazolo[3,2-a]pyrimidin-4-ium compounds
WO2018190350A1 (en) 2017-04-10 2018-10-18 三井化学アグロ株式会社 Pyridone compound, and agricultural and horticultural fungicide having this as active component
WO2018190352A1 (en) 2017-04-11 2018-10-18 三井化学アグロ株式会社 Pyridone compound, and agricultural and horticultural fungicide having this as active component
WO2018190351A1 (en) 2017-04-10 2018-10-18 三井化学アグロ株式会社 Pyridone compound, and agricultural and horticultural fungicide having this as active component
WO2018197541A1 (en) 2017-04-27 2018-11-01 Basf Se Process for preparing optically active 2,3-dihydrothiazolo[3,2-a]pyrimidin-4-ium compounds
WO2018202654A1 (en) 2017-05-03 2018-11-08 Basf Se Process for preparing chiral 2,3-dihydrothiazolo[3,2-a]pyrimidin-4-ium compounds
WO2018225829A1 (en) 2017-06-08 2018-12-13 三井化学アグロ株式会社 Pyridone compound and agricultural and horticultural fungicide
WO2018229202A1 (en) 2017-06-16 2018-12-20 Basf Se Mesoionic imidazolium compounds and derivatives for combating animal pests
WO2018234202A1 (en) 2017-06-19 2018-12-27 Basf Se Substituted pyrimidinium compounds and derivatives for combating animal pests
WO2019042932A1 (en) 2017-08-31 2019-03-07 Basf Se Method of controlling rice pests in rice
WO2019072906A1 (en) 2017-10-13 2019-04-18 Basf Se Imidazolidine pyrimidinium compounds for combating animal pests
US10266531B2 (en) 2016-10-21 2019-04-23 Novartis Ag Naphthyridinone derivatives and their use in the treatment of arrhythmia
WO2019086474A1 (en) 2017-10-31 2019-05-09 Syngenta Participations Ag Pesticidally active mesoionics heterocyclic compounds
JP2019515890A (en) * 2016-04-01 2019-06-13 ビーエーエスエフ ソシエタス・ヨーロピアＢａｓｆ Ｓｅ Bicyclic compound
WO2019115404A1 (en) 2017-12-13 2019-06-20 Syngenta Participations Ag Pesticidally active mesoionic heterocyclic compounds
WO2020022412A1 (en) 2018-07-25 2020-01-30 三井化学アグロ株式会社 Pyridone compound and agricultural and horticultural fungicide having this as active component
WO2020058010A1 (en) 2018-09-19 2020-03-26 Basf Se Pesticidal mixtures comprising a mesoionic compound
EP3628157A1 (en) 2018-09-28 2020-04-01 Basf Se Method of controlling insecticide resistant insects and virus transmission to plants
EP3628158A1 (en) 2018-09-28 2020-04-01 Basf Se Pesticidal mixture comprising a mesoionic compound and a biopesticide
EP3628156A1 (en) 2018-09-28 2020-04-01 Basf Se Method for controlling pests of sugarcane, citrus, rapeseed, and potato plants
WO2020064492A1 (en) 2018-09-28 2020-04-02 Basf Se Method of controlling pests by seed treatment application of a mesoionic compound or mixture thereof
WO2020126591A1 (en) 2018-12-18 2020-06-25 Basf Se Substituted pyrimidinium compounds for combating animal pests
WO2020239517A1 (en) 2019-05-29 2020-12-03 Basf Se Mesoionic imidazolium compounds and derivatives for combating animal pests
EP3769623A1 (en) 2019-07-22 2021-01-27 Basf Se Mesoionic imidazolium compounds and derivatives for combating animal pests
US11046658B2 (en) 2018-07-02 2021-06-29 Incyte Corporation Aminopyrazine derivatives as PI3K-γ inhibitors
EP4032886A1 (en) 2021-01-22 2022-07-27 Basf Se Method for preparing an enantiomerically enriched form of 2-[2-(2-chlorothiazol-5-yl)-2-hydroxy-ethyl]sulfanyl-6-hydroxy-3-methyl-5-phenyl-pyrimidin-4-one
EP4032894A1 (en) 2021-01-22 2022-07-27 Basf Se Method for preparing an enantiomerically enriched form of 3-(2-chlorothiazol-5-yl)-8-methyl-7-oxo-6-phenyl-2,3-dihydrothiazolo[3,2-a]pyrimidin-4-ium-5-olate
EP4032878A1 (en) 2021-01-22 2022-07-27 Basf Se Method for preparing 2-[2-(2-chlorothiazol-5-yl)-2-oxo-ethyl]sulfanyl-6-hydroxy-3-methyl-5-phenyl-pyrimidin-4-one
EP4032893A1 (en) 2021-01-22 2022-07-27 Basf Se Method for preparing an enantiomerically enriched form of 3-(2-chlorothiazol-5-yl)-8-methyl-7-oxo-6-phenyl-2,3-dihydrothiazolo[3,2-a]pyrimidin-4-ium-5-olate
EP4063362A1 (en) 2021-03-25 2022-09-28 Basf Se Method for preparing enantiomerically enriched 2-[2-(2-chlorothiazol-5-yl)-2-hydroxy-ethyl]sulfanyl-6-hydroxy-3-methyl-5-phenyl-pyrimidin-4-one by hydrogenation of the 2-oxo derivative in the presence of a chiral transition metal catalyst
TWI804514B (en) * 2018-09-28 2023-06-11 德商巴地斯顏料化工廠 Pyrimidinium compounds and their mixtures for combating animal pests
RU2809600C2 (en) * 2018-09-28 2023-12-13 Басф Се Method of combating pests of potato plants
US11926616B2 (en) 2018-03-08 2024-03-12 Incyte Corporation Aminopyrazine diol compounds as PI3K-γ inhibitors

Families Citing this family (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
AR096022A1 (en) * 2013-04-11 2015-12-02 Basf Se SUBSTITUTED PYRIMIDINUM COMPOUNDS, USEFUL TO COMBAT ANIMAL PESTS
HUE056909T2 (en) * 2016-04-06 2022-04-28 Boehringer Ingelheim Animal Health Usa Inc Process for the preparation of enantiomerically enriched isoxazoline compounds - crystalline toluene solvate of (s)-afoxolaner
CN110317200B (en) * 2018-03-28 2020-09-11 东莞市东阳光农药研发有限公司 Pyrimidinium compounds and uses thereof
CN110452238B (en) * 2018-04-18 2020-08-11 东莞市东阳光农药研发有限公司 Pyrimidinium compounds and uses thereof
TWI780230B (en) * 2018-09-28 2022-10-11 德商巴地斯顏料化工廠 Process for preparing s-containing pyrimidinium compounds
CN111620867A (en) * 2019-02-28 2020-09-04 东莞市东阳光农药研发有限公司 Mesoionic insecticides

Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2009099929A1 (en) * 2008-02-06 2009-08-13 E. I. Du Pont De Nemours And Company Mesoionic pesticides
WO2011017347A2 (en) * 2009-08-05 2011-02-10 E. I. Du Pont De Nemours And Company Mesoionic pesticides
WO2011017351A2 (en) * 2009-08-05 2011-02-10 E. I. Du Pont De Nemours And Company Mixtures of mesoionic pesticides
WO2012092115A1 (en) * 2010-12-29 2012-07-05 E. I. Du Pont De Nemours And Company Mesoionic pyrido [1,2 -a] pyrimidine pesticides
WO2012136724A1 (en) * 2011-04-06 2012-10-11 Basf Se Substituted pyrimidinium compounds for combating animal pests

Family Cites Families (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE3821711A1 (en) * 1988-06-28 1990-02-08 Bayer Ag THIAZOLOPYRIMIDINE DERIVATIVES, METHOD FOR THE PRODUCTION THEREOF AND THEIR USE AS A SCHAEDLINGSBEKAEMPFUNGSMITTEL
UA110924C2 (en) * 2009-08-05 2016-03-10 Е. І. Дю Пон Де Немур Енд Компані Mesoionic pesticides
AR096022A1 (en) * 2013-04-11 2015-12-02 Basf Se SUBSTITUTED PYRIMIDINUM COMPOUNDS, USEFUL TO COMBAT ANIMAL PESTS
MX2015017637A (en) 2013-06-17 2016-08-08 Basf Se Substituted pyrimidinium compounds and derivatives for combating animal pests.

Patent Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2009099929A1 (en) * 2008-02-06 2009-08-13 E. I. Du Pont De Nemours And Company Mesoionic pesticides
WO2011017347A2 (en) * 2009-08-05 2011-02-10 E. I. Du Pont De Nemours And Company Mesoionic pesticides
WO2011017351A2 (en) * 2009-08-05 2011-02-10 E. I. Du Pont De Nemours And Company Mixtures of mesoionic pesticides
WO2012092115A1 (en) * 2010-12-29 2012-07-05 E. I. Du Pont De Nemours And Company Mesoionic pyrido [1,2 -a] pyrimidine pesticides
WO2012136724A1 (en) * 2011-04-06 2012-10-11 Basf Se Substituted pyrimidinium compounds for combating animal pests

Cited By (71)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US9975895B2 (en) 2013-06-17 2018-05-22 Basf Se Substituted pyrimidinium compounds and derivatives for combating animal pests
JP2019515890A (en) * 2016-04-01 2019-06-13 ビーエーエスエフ ソシエタス・ヨーロピアＢａｓｆ Ｓｅ Bicyclic compound
JP7027329B2 (en) 2016-04-01 2022-03-01 ビーエーエスエフ ソシエタス・ヨーロピア Bicyclic compound
WO2018033455A1 (en) 2016-08-15 2018-02-22 Bayer Cropscience Aktiengesellschaft Condensed bicyclic heterocycle derivatives as pest control agents
US10844055B2 (en) 2016-10-21 2020-11-24 Novartis Ag Naphthyridinone derivatives and their use in the treatment of arrhythmia
US11530213B2 (en) 2016-10-21 2022-12-20 Novartis Ag Naphthyridinone derivatives and their use in the treatment of arrhythmia
US10266531B2 (en) 2016-10-21 2019-04-23 Novartis Ag Naphthyridinone derivatives and their use in the treatment of arrhythmia
WO2018139560A1 (en) 2017-01-26 2018-08-02 三井化学アグロ株式会社 Pyridone compound and bactericide for agricultural and horticultural use, which uses said compound as active ingredient
IL268866B (en) * 2017-03-31 2022-07-01 Basf Se Pyrimidinium compounds and their mixtures for combating animal pests
RU2765370C2 (en) * 2017-03-31 2022-01-28 Басф Се Pyrimidinium compounds and mixtures thereof for suppressing vermin
WO2018177970A1 (en) 2017-03-31 2018-10-04 Basf Se Process for preparing chiral 2,3-dihydrothiazolo[3,2-a]pyrimidin-4-ium compounds
US11578083B2 (en) * 2017-03-31 2023-02-14 Basf Se Pyrimidinium compounds and their mixtures for combating animal pests
AU2018241628B2 (en) * 2017-03-31 2022-03-17 Basf Se Pyrimidinium compounds and their mixtures for combating animal pests
EP3978504A1 (en) 2017-03-31 2022-04-06 Basf Se Chiral 2,3-dihydrothiazolo[3,2-a]pyrimidine derivatives for combating animal pests
WO2018190350A1 (en) 2017-04-10 2018-10-18 三井化学アグロ株式会社 Pyridone compound, and agricultural and horticultural fungicide having this as active component
WO2018190351A1 (en) 2017-04-10 2018-10-18 三井化学アグロ株式会社 Pyridone compound, and agricultural and horticultural fungicide having this as active component
WO2018190352A1 (en) 2017-04-11 2018-10-18 三井化学アグロ株式会社 Pyridone compound, and agricultural and horticultural fungicide having this as active component
WO2018197541A1 (en) 2017-04-27 2018-11-01 Basf Se Process for preparing optically active 2,3-dihydrothiazolo[3,2-a]pyrimidin-4-ium compounds
CN110546153A (en) * 2017-04-27 2019-12-06 巴斯夫欧洲公司 process for preparing optically active 2, 3-dihydrothiazolo [3,2-A ] pyrimidin-4-ium compounds
KR20190141711A (en) * 2017-04-27 2019-12-24 바스프 에스이 Method for preparing optically active 2,3-dihydrothiazolo [3,2-A] pyrimidin-4-ium compound
CN110546153B (en) * 2017-04-27 2022-09-06 巴斯夫欧洲公司 Process for preparing optically active 2, 3-dihydrothiazolo [3,2-A ] pyrimidin-4-ium compounds
KR102591738B1 (en) 2017-04-27 2023-10-19 바스프 에스이 Method for producing optically active 2,3-dihydrothiazolo[3,2-A]pyrimidin-4-ium compound
CN110621677B (en) * 2017-05-03 2022-06-07 巴斯夫欧洲公司 Process for preparing chiral 2, 3-dihydrothiazolo [3,2-A ] pyrimidin-4-ium compounds
CN110621677A (en) * 2017-05-03 2019-12-27 巴斯夫欧洲公司 Process for preparing chiral 2, 3-dihydrothiazolo [3,2-A ] pyrimidin-4-ium compounds
WO2018202654A1 (en) 2017-05-03 2018-11-08 Basf Se Process for preparing chiral 2,3-dihydrothiazolo[3,2-a]pyrimidin-4-ium compounds
WO2018225829A1 (en) 2017-06-08 2018-12-13 三井化学アグロ株式会社 Pyridone compound and agricultural and horticultural fungicide
WO2018229202A1 (en) 2017-06-16 2018-12-20 Basf Se Mesoionic imidazolium compounds and derivatives for combating animal pests
US11542280B2 (en) 2017-06-19 2023-01-03 Basf Se Substituted pyrimidinium compounds and derivatives for combating animal pests
CN110678469B (en) * 2017-06-19 2023-03-03 巴斯夫欧洲公司 Substituted pyrimidinium compounds and derivatives for combating animal pests
CN110678469A (en) * 2017-06-19 2020-01-10 巴斯夫欧洲公司 Substituted pyrimidinium compounds and derivatives for combating animal pests
WO2018234202A1 (en) 2017-06-19 2018-12-27 Basf Se Substituted pyrimidinium compounds and derivatives for combating animal pests
KR102659381B1 (en) 2017-08-31 2024-04-19 바스프 에스이 How to Control Rice Pests in Rice
WO2019043183A1 (en) 2017-08-31 2019-03-07 Basf Se Method of controlling rice pests in rice
WO2019042932A1 (en) 2017-08-31 2019-03-07 Basf Se Method of controlling rice pests in rice
CN111031798A (en) * 2017-08-31 2020-04-17 巴斯夫欧洲公司 Method for controlling rice pests in rice
KR20200041892A (en) * 2017-08-31 2020-04-22 바스프 에스이 How to control rice pests from rice
US11399543B2 (en) 2017-10-13 2022-08-02 Basf Se Substituted 1,2,3,5-tetrahydroimidazo[1,2-a]pyrimidiniumolates for combating animal pests
WO2019072906A1 (en) 2017-10-13 2019-04-18 Basf Se Imidazolidine pyrimidinium compounds for combating animal pests
WO2019086474A1 (en) 2017-10-31 2019-05-09 Syngenta Participations Ag Pesticidally active mesoionics heterocyclic compounds
WO2019115404A1 (en) 2017-12-13 2019-06-20 Syngenta Participations Ag Pesticidally active mesoionic heterocyclic compounds
US11926616B2 (en) 2018-03-08 2024-03-12 Incyte Corporation Aminopyrazine diol compounds as PI3K-γ inhibitors
US11046658B2 (en) 2018-07-02 2021-06-29 Incyte Corporation Aminopyrazine derivatives as PI3K-γ inhibitors
WO2020022412A1 (en) 2018-07-25 2020-01-30 三井化学アグロ株式会社 Pyridone compound and agricultural and horticultural fungicide having this as active component
WO2020058010A1 (en) 2018-09-19 2020-03-26 Basf Se Pesticidal mixtures comprising a mesoionic compound
TWI804514B (en) * 2018-09-28 2023-06-11 德商巴地斯顏料化工廠 Pyrimidinium compounds and their mixtures for combating animal pests
RU2809600C2 (en) * 2018-09-28 2023-12-13 Басф Се Method of combating pests of potato plants
WO2020064480A1 (en) 2018-09-28 2020-04-02 Basf Se Pesticidal mixture comprising a mesoionic compound and a biopesticide
RU2827556C9 (en) * 2018-09-28 2024-10-11 Басф Се Method of rape plant pest control
IL281813B1 (en) * 2018-09-28 2024-10-01 Basf Se Method for controlling pests of citrus plants
RU2827556C2 (en) * 2018-09-28 2024-09-30 Басф Се Method of rape plant pest control
EP3628158A1 (en) 2018-09-28 2020-04-01 Basf Se Pesticidal mixture comprising a mesoionic compound and a biopesticide
WO2020064511A1 (en) 2018-09-28 2020-04-02 Basf Se Method for controlling pests of potato plants
EP3628156A1 (en) 2018-09-28 2020-04-01 Basf Se Method for controlling pests of sugarcane, citrus, rapeseed, and potato plants
EP3628157A1 (en) 2018-09-28 2020-04-01 Basf Se Method of controlling insecticide resistant insects and virus transmission to plants
WO2020064503A1 (en) 2018-09-28 2020-04-02 Basf Se Method for controlling pests of rapeseed plants
WO2020064408A1 (en) 2018-09-28 2020-04-02 Basf Se Method of controlling insecticide resistant insects and virus transmission to plants
WO2020064492A1 (en) 2018-09-28 2020-04-02 Basf Se Method of controlling pests by seed treatment application of a mesoionic compound or mixture thereof
WO2020064501A1 (en) 2018-09-28 2020-04-02 Basf Se Method for controlling pests of citrus plants
WO2020126591A1 (en) 2018-12-18 2020-06-25 Basf Se Substituted pyrimidinium compounds for combating animal pests
WO2020239517A1 (en) 2019-05-29 2020-12-03 Basf Se Mesoionic imidazolium compounds and derivatives for combating animal pests
EP3769623A1 (en) 2019-07-22 2021-01-27 Basf Se Mesoionic imidazolium compounds and derivatives for combating animal pests
WO2022157324A1 (en) 2021-01-22 2022-07-28 Basf Se Method for preparing 2-[2-(2-chlorothiazol-5-yl)-2-oxo-ethyl]sulfanyl-6-hydroxy-3-methyl-5-phenyl-pyrimidin-4-one
WO2022157323A1 (en) 2021-01-22 2022-07-28 Basf Se Method for preparing an enantiomerically enriched form of 3-(2-chlorothiazol-5-yl)-8-methyl-7-oxo-6-phenyl-2,3-dihydrothiazolo[3,2-a]pyrimidin-4-ium-5-olate
WO2022157316A1 (en) 2021-01-22 2022-07-28 Basf Se Method for preparing an enantiomerically enriched form of 2-[2-(2-chlorothiazol-5-yl)-2-hydroxy-ethyl]sulfanyl-6-hydroxy-3-methyl-5-phenyl-pyrimidin-4-one
WO2022157321A1 (en) 2021-01-22 2022-07-28 Basf Se Method for preparing an enantiomerically enriched form of 3-(2-chlorothiazol-5-yl)-8-methyl-7-oxo-6-phenyl-2,3-dihydrothiazolo[3,2-a]pyrimidin-4-ium-5-olate
EP4032893A1 (en) 2021-01-22 2022-07-27 Basf Se Method for preparing an enantiomerically enriched form of 3-(2-chlorothiazol-5-yl)-8-methyl-7-oxo-6-phenyl-2,3-dihydrothiazolo[3,2-a]pyrimidin-4-ium-5-olate
EP4032878A1 (en) 2021-01-22 2022-07-27 Basf Se Method for preparing 2-[2-(2-chlorothiazol-5-yl)-2-oxo-ethyl]sulfanyl-6-hydroxy-3-methyl-5-phenyl-pyrimidin-4-one
EP4032894A1 (en) 2021-01-22 2022-07-27 Basf Se Method for preparing an enantiomerically enriched form of 3-(2-chlorothiazol-5-yl)-8-methyl-7-oxo-6-phenyl-2,3-dihydrothiazolo[3,2-a]pyrimidin-4-ium-5-olate
EP4032886A1 (en) 2021-01-22 2022-07-27 Basf Se Method for preparing an enantiomerically enriched form of 2-[2-(2-chlorothiazol-5-yl)-2-hydroxy-ethyl]sulfanyl-6-hydroxy-3-methyl-5-phenyl-pyrimidin-4-one
WO2022200594A1 (en) 2021-03-25 2022-09-29 Basf Se Method for preparing enantiomerically enriched 2-[2-(2-chlorothiazol-5-yl)-2-hydroxy-ethyl]sulfanyl-6-hydroxy-3-methyl-5-phenyl-pyrimidin-4-one by hydrogenation of the 2-oxo derivative in the presence of a chiral transition metal catalyst
EP4063362A1 (en) 2021-03-25 2022-09-28 Basf Se Method for preparing enantiomerically enriched 2-[2-(2-chlorothiazol-5-yl)-2-hydroxy-ethyl]sulfanyl-6-hydroxy-3-methyl-5-phenyl-pyrimidin-4-one by hydrogenation of the 2-oxo derivative in the presence of a chiral transition metal catalyst

Also Published As

Publication number Publication date
CN105121441B (en) 2018-04-20
AU2014253086B2 (en) 2018-01-18
KR20150142025A (en) 2015-12-21
KR102223216B1 (en) 2021-03-04
US9730451B2 (en) 2017-08-15
US11019820B2 (en) 2021-06-01
BR112015021863A8 (en) 2019-11-26
MX2015014204A (en) 2015-12-11
JP6449850B2 (en) 2019-01-09
US20160058009A1 (en) 2016-03-03
US20180007905A1 (en) 2018-01-11
KR20210024256A (en) 2021-03-04
CR20150610A (en) 2016-04-12
EP2984089B1 (en) 2022-03-09
BR112015021863B1 (en) 2020-08-18
CA2901559A1 (en) 2014-10-16
CN105121441A (en) 2015-12-02
AR096022A1 (en) 2015-12-02
JP2016521264A (en) 2016-07-21
BR112015021863A2 (en) 2017-07-18
CL2015003001A1 (en) 2016-04-22
ES2913139T3 (en) 2022-05-31
EP2984089A1 (en) 2016-02-17
PT2984089T (en) 2022-03-31
AU2014253086A1 (en) 2015-10-22
UA115904C2 (en) 2018-01-10
CA2901559C (en) 2021-11-02
JP2019059759A (en) 2019-04-18

Similar Documents

Publication Publication Date Title
US11019820B2 (en) Substituted pyrimidinium compounds and derivatives for combating animal pests
US9334238B2 (en) N-substituted pyridinylidenes for combating animal pests
EP2831076B1 (en) N-substituted hetero-bicyclic compounds and derivatives for combating animal pests ii
WO2013010947A2 (en) Pesticidal methods using substituted 3-pyridyl thiazole compounds and derivatives for combating animal pests ii
EP2694507A1 (en) N-substituted hetero-bicyclic compounds and derivatives for combating animal pests
EP2834228A1 (en) N- substituted hetero - bicyclic furanone derivatives for combating animal
WO2013144223A1 (en) N-substituted pyrimidinylidene compounds and derivatives for combating animal pests
WO2013150115A1 (en) N- substituted hetero - bicyclic compounds and derivatives for combating animal pests
EP3010921B1 (en) Substituted pyrimidinium compounds and derivatives for combating animal pests
WO2013144228A1 (en) Pesticidal methods using heterocyclic compounds and derivatives for combating animal pests
EP2863738A2 (en) Pesticidal methods using substituted 3-pyridyl thiazole compounds and derivatives for combating animal pests
EP2941127A1 (en) Cycloclavine and derivatives thereof for controlling invertebrate pests

Legal Events

Date Code Title Description
121 Ep: the epo has been informed by wipo that ep was designated in this application

Ref document number: 14716829

Country of ref document: EP

Kind code of ref document: A1

DPE1 Request for preliminary examination filed after expiration of 19th month from priority date (pct application filed from 20040101)
WWE Wipo information: entry into national phase

Ref document number: 2014716829

Country of ref document: EP

ENP Entry into the national phase

Ref document number: 2901559

Country of ref document: CA

WWE Wipo information: entry into national phase

Ref document number: IDP00201505028

Country of ref document: ID

WWE Wipo information: entry into national phase

Ref document number: MX/A/2015/014204

Country of ref document: MX

ENP Entry into the national phase

Ref document number: 2016506980

Country of ref document: JP

Kind code of ref document: A

WWE Wipo information: entry into national phase

Ref document number: 14783600

Country of ref document: US

NENP Non-entry into the national phase

Ref country code: DE

ENP Entry into the national phase

Ref document number: 2014253086

Country of ref document: AU

Date of ref document: 20140411

Kind code of ref document: A

WWE Wipo information: entry into national phase

Ref document number: 15253590

Country of ref document: CO

ENP Entry into the national phase

Ref document number: 20157032205

Country of ref document: KR

Kind code of ref document: A

WWE Wipo information: entry into national phase

Ref document number: A201510934

Country of ref document: UA

Ref document number: CR2015-000610

Country of ref document: CR

REG Reference to national code

Ref country code: BR

Ref legal event code: B01A

Ref document number: 112015021863

Country of ref document: BR

ENP Entry into the national phase

Ref document number: 112015021863

Country of ref document: BR

Kind code of ref document: A2

Effective date: 20150908