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WO2014033244A2 - Substituted mesoionic imine compounds for combating animal pests - Google Patents

Substituted mesoionic imine compounds for combating animal pests Download PDF

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Publication number
WO2014033244A2
WO2014033244A2 PCT/EP2013/067962 EP2013067962W WO2014033244A2 WO 2014033244 A2 WO2014033244 A2 WO 2014033244A2 EP 2013067962 W EP2013067962 W EP 2013067962W WO 2014033244 A2 WO2014033244 A2 WO 2014033244A2
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alkyl
independently
formula
compounds
substituted
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WO2014033244A3 (en
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Arun Narine
Joachim Dickhaut
Florian Kaiser
Nina Gertrud Bandur
Karsten KÖRBER
Wolfgang Von Deyn
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BASF SE
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BASF SE
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    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D403/00—Heterocyclic compounds containing two or more hetero rings, having nitrogen atoms as the only ring hetero atoms, not provided for by group C07D401/00

Definitions

  • the invention relates to substituted mesoionic compounds and salts thereof, to methods for preparing these compounds and to compositions comprising such compounds.
  • the invention also relates to the use of the substituted mesoionic compounds, of their salts or of compositions comprising them for combating animal pests. Furthermore the invention relates to methods of applying such compounds.
  • Animal pests destroy growing and harvested crops and attack wooden dwelling and commercial structures, 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 animal pests. In particular, animal pests such as insects and acaridae are difficult to be effectively controlled.
  • WO 2012/0921 15 and WO 2012/106495 disclose pesticides having a mesoionic pyrimidine structure.
  • the known compounds are not completely satisfactory in many cases, in terms, for example, of application rate, spectrum of activity, duration of activity, tendency to form resistance or economic aspects of the preparation process.
  • R 1 , R 2 is independently hydrogen, Ci-C6-alkyl, Cs-Cs-cycloalkyl, C2-C6-alkenyl, C2-C6- alkynyl, wherein the carbon atoms of the aforementioned aliphatic and cyclo- aliphatic radicals are unsubstituted or substituted with one or more R b ; or R 1 and R 2 together with the nitrogen and carbon atom to which they are bonded, form the following substituted heterocyclic ring system:
  • k 0, 1 , 2, 3 or 4;
  • R 3 is (CR 30 R 31 )aQ 1 , Ci-C6-alkyl unsubstituted or substituted with one or more halogen or C3-C6-cycloalkyl unsubstituted or substituted with 1 to 4 substituents selected from the group consisting of halogen, Ci-C2-alkyl, 1 cyclopropyl and 1 CF3;
  • a is O or l ;
  • R A is hydrogen, Ci-C 8 -alkyl, C 3 -C 8 -cycloalkyl, C 2 -C 8 -alkenyl, C 2 -C 8 -alkynyl, C 4 -C 8 - cycloalkenyl, wherein the carbon atoms of the aforementioned aliphatic and cyclo- aliphatic radicals are unsubstituted or substituted with one or more R b ,
  • R A is OR A0 or N(R A1 ) 2 ;
  • R B is hydrogen, CrC 8 -alkyl, C 2 -C 8 -alkenyl, C 2 -C 8 -alkynyl, wherein the carbon atoms of the aforementioned aliphatic radicals are un
  • R B is N(R 9 ) 2 ;
  • each R a is independently halogen, cyano, azido, nitro, SCN, SF 5 , Ci-C 8 -alkyl, C2-C 8 - alkenyl, C2-C 8 -alkynyl, C3-C 8 -cycloalkyl, C 4 -C 8 -cycloalkenyl, wherein the carbon atoms of the aforementioned aliphatic and cyclo-aliphatic radicals are unsubstituted or substituted with one or more R b ,
  • each R c is independently hydrogen, Ci-C6-alkyl, Ci-C6-haloalkyl, C2-C6-alkenyl, C2-C6- haloalkenyl, C2-C6-alkynyl, C2-C6-haloalkynyl, Cs-Cs-cycloalkyl, Cs-Cs-halocycloalkyl,
  • each R d is independently Ci-C6-alkyl, Ci-C6-haloalkyl, C2-C6-alkenyl, C2-C6-haloalkenyl, C2-C6-alkynyl, C2-C6-haloalkynyl, Cs-Cs-cycloalkyl, Cs-Cs-halocycloalkyl, or phenyl which is unsubstituted or substituted with one or more substituents selected independently from halogen, cyano, NO2, CiC6-alkyl, Ci-C6-haloalkyl, Ci-C6-alkoxy and Ci-C6-haloalkoxy;
  • each R e is independently hydrogen, Ci-C6-alkyl, Ci-C6-haloalkyl, C2-C6-alkenyl, C2-C6- haloalkenyl, C2-C6-alkynyl, C2-C6-haloalkynyl, Cs-Cs-cycloalkyl, Cs-Cs-halocycloalkyl,
  • each R9 is independently hydrogen, Ci-C6-alkyl, Ci-C6-haloalkyl, Ci-C6-alkoxyalkyl, C2- C6-alkenyl, C2-C6-haloalkenyl, C2-C6-alkynyl, C2-C6-haloalkynyl or C1-C6- haloalkoxyalkyl;
  • each Q 3 is independently phenyl, unsubstituted or substituted with at least one
  • a 3-, 4-, 5-, 6- or 7- membered saturated, partly saturated or unsaturated aromatic heterocyclic ring comprising 1 , 2 or 3 heteroatoms or heteroatom groups selected from oxygen, nitrogen, sulfur, NO, SO and SO2 unsubstituted or substituted with up to four substituents selected independently from halogen, cyano, NO2, Ci-C6-alkyl, Ci-C6-haloalkyl, Ci-C6-alkoxy and Ci-C6-haloalkoxy; each b is independently 0 or 1 ;
  • each c is independently 0, 1 or 2;
  • substituted mesoionic compounds of formula (I), their N-oxides and their agriculturally or veterinarily acceptable salts are highly active against animal pests, especially harmful arthro- podes and nematodes, in particular against harmful insects and acaridae.
  • the invention provides substituted mesoionic compounds of formula (I), N-oxides and agriculturally or veterinarily useful salts thereof.
  • the invention provides and includes the following embodiments:
  • compositions comprising at least one compound of formula (I), N-oxide or salt thereof;
  • a method of combating animal pests which comprises contacting the animal pests, their habit, breeding ground, food supply, plant, 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 at least one compound of formula (I), N-oxide or salt thereof;
  • a method for protecting crops from attack or infestation by animal pests which comprises contacting a crop with a pesticidally effective amount of at least one compound of the formula (I), N-oxide or salt thereof;
  • a method for protecting seeds from soil insects and seedlings' roots and shoots from soil and foliar insects comprising contacting the seeds before sowing and/or after pregermina- tion with at least one compound of formula (I), N-oxide or salt thereof;
  • a method for treating 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 at least one compound of formula (I), N-oxide or veterinarily acceptable salt thereof;
  • a process for the preparation of a composition for treating or protecting animals against infestation or infection by parasites which comprises mixing a parasiticidally effective amount of at least one compound of formula (I), N-oxide or a veterinarily acceptable salt thereof with at least one veterinarily acceptable carrier;
  • the invention also provides plant propagation materials, in particular seeds, comprising at least one compound of formula (I), N-oxide or agriculturally acceptable salt thereof.
  • At least one compound of formula (I), N-oxide or salt thereof means at least one compound selected from the group consisting of compounds of formula (I), N-oxides of the compounds of formula (I), salts of the compounds of formula (I) and salts of the N-oxides of the compounds of formula (I).
  • a compound of the invention means a compound of formula (I), an N-oxide of a compound of formula (I), a salt of a compound of formula (I) or a salt of an N-oxide of a compound of formula (I).
  • the compounds of formula (I) encompass every possible stereoisomer of the compounds of formula (I), e.g. single enantiomers or diastereomers, as well as mixtures thereof.
  • the compounds of formula (I) 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 activity against certain pests.
  • the invention encompasses both amorphous and crystalline compounds of 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 formula (I) are preferably agriculturally and/or veterinarily 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 lithium, 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, C1-C4- hydroxyalkyl, Ci-C4-alkoxy, Ci-C4-alkoxy-Ci-C4-alkyl, hydroxy-Ci-C4-alkoxy-Ci-C4-alkyl, phenyl or benzyl.
  • substituted ammonium ions comprise methylammonium, isoprop- ylammonium, dimethylammonium, diisopropylammonium, trimethylammonium, tetrame- thylammonium, tetraethylammonium, tetrabutylammonium, 2-hydroxyethylammonium, 2-(2- hydroxyethoxy)ethyl-ammonium, bis(2-hydroxyethyl)ammonium, benzyltrimethylammonium 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, hydrogen carbonate, carbonate, hexafluorosilicate, hexafluorophosphate, benzoate, and the anions of C1-C4- alkanoic acids, preferably formate, acetate, propionate and butyrate. They can be formed by reacting the compounds of formula (I) with an acid of the corresponding anion, preferably of hydrochloric acid, hydrobromic acid, sulfuric acid, phosphoric acid or nitric acid.
  • organic moieties 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 means fluoro, chloro, bromo and iodo.
  • partially or fully halogenated means 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 saturated hydrocarbon group having n to m, 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-methyl
  • Ci-C4-alkyl means for example me- thyl, ethyl, propyl, 1 -methylethyl, butyl, 1 -methylpropyl, 2-methylpropyl and 1 ,1 -dimethylethyl.
  • C n -C m -haloalkyl refers to a straight-chain or branched alkyl group having n to m carbon atoms, 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, bromomethyl, dichlorome- thyl, trichloromethyl, fluoromethyl, difluoromethyl, trifluoromethyl, chlorofluoromethyl, dichloro- fluoromethyl, chlorodifluoromethyl, 1 -chloroethyl, 1 -bromoethyl, 1 -fluoroethyl, 2-fluoroethyl, 2,2- difluor
  • Ci-Cio-haloalkyl in particular comprises Ci-C2-fluoroalkyl, which is synonym with methyl or ethyl, wherein 1 , 2, 3, 4 or 5 hydrogen atoms are substituted with fluorine atoms, such as fluoromethyl, difluoromethyl, trifluoromethyl, 1 -fluoroethyl, 2-fluoroethyl, 2,2-difluoroethyl, 2,2,2-trifluoroethyl and pentafluoro- methyl.
  • 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, (as mentioned above) bonded through oxygen or sulfur linkages, respectively, at any bond in the alkyl group.
  • Examples include Ci-C4-alkoxy such as methoxy, ethoxy, propoxy, isopropoxy, butoxy, sec-butoxy, isobutoxy and tert-butoxy, futher Ci- C4-alkylthio such as methylthio, ethylthio, propylthio, isopropylthio and n-butylthio.
  • C n -C m -haloalkoxy and "C n -C m -haloalkylthio” refer to straight-chain or branched alkyl groups having n to m 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, trichloro- methoxy, fluoromethoxy, difluoromethoxy, trifluoromethoxy, chlorofluoromethoxy, dichlorofluo- romethoxy, chlorodifluoromethoxy, 1 -chloroethoxy, 1 -bromoethoxy, 1 -fluoroethoxy, 2- fluoroethoxy, 2,2-difluoro
  • Ci-C2-fluoroalkoxy and Ci-C2-fluoroalkylthio refer to Ci-C2-fluoroalkyl which is bonded to the remainder of the molecule via an oxygen atom or a sulfur atom, respectively.
  • C2-C m -alkenyl refers to a branched or unbranched unsaturated hydrocarbon group having 2 to m, e.g.
  • 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.
  • Ci-C4-alkoxy-Ci-C4-alkyl refers to alkyl having 1 to 4 carbon atoms, e.g. like the specific examples mentioned above, wherein one hydrogen atom of the alkyl radical is replaced by an Ci-C4-alkoxy group.
  • C3-C m -cycloalkyl refers to a monocyclic 3- to m-membered saturated cycloaliphatic radicals, e.g. cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, cycloheptyl, cyclooctyl and cyclodecyl.
  • aryl refers to an aromatic hydrocarbon radical such as naph- thyl or in particular phenyl.
  • 3- to 6-membered carbocyclic ring refers to cyclopropane, cyclobutane, cyclopentane and cyclohexane rings.
  • heterocyclic ring containing 1 , 2 or 3 heteroatoms or heteroatom groups selected from N, O, S, NO, SO and SO2, as ring members
  • ring members refers to monocyclic radicals, the monocyclic radicals being saturated, partially unsaturated or aromatic.
  • 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 include:
  • oxiranyl aziridinyl, azetidinyl, 2-tetrahydrofuranyl, 3-tetrahydrofuranyl, 2-tetrahydrothienyl, 3- tetrahydrothienyl, 2-pyrrolidinyl, 3-pyrrolidinyl, 3-pyrazolidinyl, 4-pyrazolidinyl, 5-pyrazolidinyl, 2- imidazolidinyl, 4-imidazolidinyl, 2-oxazolidinyl, 4-oxazolidinyl, 5-oxazolidinyl, 3-isoxazolidinyl, 4- isoxazolidinyl, 5-isoxazolidinyl, 2-thiazolidinyl, 4-thiazolidinyl, 5-thiazolidinyl, 3-isothiazolidinyl, 4- isothiazolidinyl, 5-isothiazolidinyl, 1 ,2,4-oxadiazolidin-3-yl, 1 ,2,4
  • Examples of 3-, 4-, 5-, 6- or 7-membered partially unsaturated heterocyclyl include: 2,3-dihydrofur-2-yl, 2,3-dihydrofur-3-yl, 2,4-dihydrofur-2-yl, 2,4-dihydrofur-3-yl, 2,3-dihydrothien-
  • 3-, 4-, 5-, 6- or 7-membered aromatic heterocyclyl is 5- or 6-membered aromatic heterocyclyl (hetaryl).
  • Examples 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-imidazolyl, 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.
  • C2-C7-alkylene is divalent branched or preferably unbranched saturated aliphatic chain having 2 to 7 carbon atoms, for example CH 2 CH 2 , -CH(CH 3 )-, CH2CH2CH2, CH(CH 3 )CH 2 , CH 2 CH(CH 3 ), CH2CH2CH2, CH2CH2CH2CH2CH2, CH2CH2CH2CH2CH2, and
  • the substituted mesoionic compound of formula (I) is a compound of formula (1-1 ):
  • the substituted mesoionic compound of formula (I) is a compound of formula (I-2):
  • the substituted mesoionic compound of formula (I) is a compound of formula (I-3);
  • the substituted mesoionic compound of formula (I) is a com- pound of formula (1 -4):
  • the substituted mesoionic compound of formula (I) is a compound of formula (I-5):
  • the substituted mesoionic compound of formula (I) is a compound of formula (I-6):
  • the substitutet mesoionic compound of formula (i) is a compound of formula (1 -7):
  • the substituted mesoionic compound of formula (I) is a compound of formula (I-8):
  • the substituted mesoionic compound of formula (I) is a compound of formula (I-9):
  • each A 1 , A 2 , A 3 , A 4 ist independently N or C-R a' ,
  • each R a' is independently H or R a .
  • X is preferably O or S.
  • Y is preferably O or S.
  • A, A 0 is preferably independently phenyl, naphthyl or a 5- or 6-membered heteroaromatic ring system, or a 8-10-membered heteroaromatic bicyclic ring system, each unsubstituted or substituted with up to 6 substituents R a .
  • R 1 , R 2 is preferably independently hydrogen, Ci-C6-alkyl, Cs-Cs-cycloalkyl, C2-C6-alkenyl,
  • R 1 and R 2 together with the nitrogen and carbon atom to which they are bonded, form the fol- lowing substituted heterocyclic ring system:
  • k is preferably 0, 1 or 2.
  • R 3 is preferably (CR 30 R 31 ) a Q 1 .
  • a is preferably 1 .
  • Each R 30 and R 31 is preferably independently hydrogen or halogen, and one of R 30 , R 31 is hydrogen, halogen, cyano, or methyl.
  • Q 1 is preferably a heterocyclic ring system:
  • R A is preferably hydrogen, Ci-C3-alkyl, C3-C6-cycloalkyl, C2-C4-alkenyl, C2-C4-alkynyl,
  • R A is OR A0 or N(R A ) 2 .
  • R B is preferably hydrogen, CrC 3 -alkyl, C 2 -C 4 -alkenyl, C 2 -C 4 -alkynyl, wherein the carbon atoms of the aforementioned aliphatic radicals are unsubstituted or substituted with one or more R b ,
  • Each R a is preferably independently halogen, cyano, Ci-C3-alkyl, C2-C4-alkenyl, C2-C4- alkynyl, C3-C6-cycloalkyl, C4-C6-cycloalkenyl, wherein the carbon atoms of the aforementioned aliphatic and cyclo-aliphatic radicals are unsubstituted or substituted with one or more R b .
  • Each R b is preferably independently halogen, cyano, nitro, Ci-C3-alkoxy, C1-C3- haloalkoxy, Ci-C3-alkylthio, Ci-C3-alkylsulfinyl, Ci-C3-alkylsulfonyl, C1-C3- haloalkylthio, C3-C6-cycloalkyl, C3-C6-halocycloalkyl, C2-C4-alkenyl, C2-C4- haloalkenyl, C2-C4-alkynyl or C2-C4-haloalkynyl.
  • Each R c is preferably independently hydrogen, Ci-C6-alkyl, Ci-C6-haloalkyl, C2-C6- alkenyl, C2-C6-haloalkenyl, C2-C6-alkynyl, C2-C6-haloalkynyl, Cs-Cs-cycloalkyl, C3-C8- halocycloalkyl, Ci-C6-alkoxyalkyl, Ci-C6-haloalkoxyalkyl or phenyl which is unsubstituted or substituted with one or more substituents selected independently from halo- gen, cyano, NO2, Ci-C6-alkyl, Ci-C6-haloalkyl, Ci-C6-alkoxy and Ci-C6-haloalkoxy.
  • Each R d is preferably independently Ci-C6-alkyl, Ci-C6-haloalkyl, C2-C6-alkenyl, C2-C6- haloalkenyl, C2-C6-alkynyl, C2-C6-haloalkynyl, Cs-Cs-cycloalkyl, Cs-Cs-halocycloalkyl, or phenyl which is unsubstituted or substituted with one or more substituents selected independently from halogen, cyano, NO2, CiC6-alkyl, Ci-C6-haloalkyl, Ci- C6-alkoxy and Ci-C6-haloalkoxy.
  • Each R e is preferably independently hydrogen, Ci-C6-alkyl, Ci-C6-haloalkyl, C2-C6- alkenyl, C2-C6-haloalkenyl, C2-C6-alkynyl, C2-C6-haloalkynyl, Cs-Cs-cycloalkyl, Cs-Cs- halocycloalkyl, Ci-C6-alkoxyalkyl, Ci-C6-haloalkoxyalkyl or phenyl which is unsubstituted or substituted with one or more substituents selected independently from halo- gen, cyano, NO2, Ci-C6-alkyl, Ci-C6-haloalkyl, Ci-C6-alkoxy and Ci-C6-haloalkoxy.
  • Each R f is preferably independently hydrogen, halogen, cyano, nitro, OH , SH , SCN , SF 5 , Ci-C6-alkoxy, Ci-C6-haloalkoxy, Ci-C6-alkylthio, Ci-C6-alkylsulfinyl, C1-C6- alkylsulfonyl, Ci-C6-haloalkylthio, trimethylsilyl, triethylsilyl, tert-butyldimethylsilyl, Ci-
  • Each R9 is preferably independently hydrogen, Ci-C6-alkyl, Ci-C6-haloalkyl, C2-C6- alkenyl, C2-C6-haloalkenyl, C2-C6-alkynyl, C2-C6-haloalkynyl, Ci-C6-alkoxyalkyl or Ci- C6-haloalkoxyalkyl.
  • Each Q 3 is preferably independently phenyl, unsubstituted or substituted with at least one substituent selected from halogen, cyano, nitro, Ci-C6-alkyl, Ci-C6-haloalkyl, Ci- C6-alkoxy and Ci-C6-haloalkoxy,
  • a 3-, 4-, 5-, 6- or 7- membered saturated, partly saturated or unsaturated aromatic heterocyclic ring comprising 1 , 2 or 3 heteroatoms or heteroatom groups selected from oxygen, nitrogen, sulfur, NO, SO and SO2 unsubstituted or substituted with up to four substituents selected independently from halogen, cyano, NO2, Ci-C6-alkyl,
  • Ci-C6-haloalkyl Ci-C6-alkoxy and Ci-C6-haloalkoxy.
  • Each b is preferably independently 0 or 1 .
  • Each c is preferably independently 0, 1 or 2.
  • each of the symbols in formula (I) has the preferred meanings.
  • X is more preferred O.
  • Y is more preferred O.
  • A is more preferred phenyl with up to 3 substituents R a .
  • a 0 is more preferred phenyl with up to 3 substituents R a or pyridyl, with up to 2 substituents R a .
  • R 1 , R 2 is more preferred independently hydrogen, Ci-C6-alkyl, Cs-Cs-cycloalkyl, C2-C6- alkenyl, C2-C6-alkynyl, wherein the carbon atoms of the aforementioned aliphatic and cyclo-aliphatic radicals are unsubstituted or substituted with one or more R b ; or
  • R 1 and R 2 together with the nitrogen and carbon atom to which they are bonded, more preferred form the following substituted heterocyclic ring system:
  • k is more preferred 0, 1 or 2.
  • R 3 is more preferred (CR 30 R 31 ) a Q 1 .
  • a is more preferred 1 .
  • Each R 30 and R 31 is more preferred hydrogen and one of R 30 , R 31 , hydrogen or methyl.
  • Q 1 is more preferred a heterocyclic ring system:
  • R A is more preferred Ci-C3-alkyl, C3-C6-cycloalkyl, wherein the carbon atoms of the aforementioned aliphatic and cyclo-aliphatic radicals are unsubstituted or substituted with one or more R b ,
  • R A is OR A0 or N(R A ) 2
  • R B is more preferred hydrogen, Ci-C3-alkyl, wherein the carbon atoms of the aforementioned aliphatic radicals are unsubstituted or substituted with one or more R b ,
  • R B is N(R 9 ) 2 .
  • Each R a is more preferred independently halogen, cyano, OCH3, CF3, OCF3, SCF3 or
  • Each R b is more preferred independently halogen, cyano, Ci-C3-alkoxy, Ci-C3-haloalkoxy, Ci-C3-alkylthio, Ci-C3-alkylsulfinyl, Ci-C3-alkylsulfonyl or Ci-C3-haloalkylthio.
  • Each R c is more preferred independently hydrogen, Ci-C6-alkyl, Ci-C6-haloalkyl, C 2 -C6- alkenyl, C 2 -C6-haloalkenyl, C 2 -C6-alkynyl, C 2 -C6-haloalkynyl, Cs-Cs-cycloalkyl, C3-C8- halocycloalkyl, Ci-C6-alkoxyalkyl or Ci-C6-haloalkoxyalkyl.
  • Each R d is more preferred independently Ci-C6-alkyl, Ci-C6-haloalkyl, C 2 -C6-alkenyl, C 2 -C6- haloalkenyl, C 2 -C6-alkynyl, C 2 -C6-haloalkynyl, Cs-Cs-cycloalkyl or Cs-Cs-halocycloalkyl.
  • Each R e is more preferred independently hydrogen, Ci-C6-alkyl, Ci-C6-haloalkyl, C 2 -C6- alkenyl, C 2 -C6-haloalkenyl, C 2 -C6-alkynyl, C 2 -C6-haloalkynyl, Cs-Cs-cycloalkyl, Cs-Cs- halocycloalkyl, Ci-C6-alkoxyalkyl or Ci-C6-haloalkoxyalkyl.
  • Each R9 is more preferred independently hydrogen, Ci-C6-alkyl, Ci-C6-haloalkyl, C2-C6- alkenyl, C2-C6-haloalkenyl, C2-C6-alkynyl, C2-C6-haloalkynyl, Ci-C6-alkoxyalkyl or C1-C6- haloalkoxyalkyl.
  • Each Q 3 is more preferred independently phenyl, unsubstituted or substituted with at least one substituent selected from halogen, cyano, nitro, Ci-C6-alkyl, Ci-C6-haloalkyl, C1-C6- alkoxy and Ci-C6-haloalkoxy,
  • a 3-, 4-, 5-, 6- or 7- membered saturated, partly saturated or unsaturated aromatic heterocyclic ring comprising 1 , 2 or 3 heteroatoms or heteroatom groups selected from oxygen, nitrogen, sulfur, NO, SO and SO2 unsubstituted or substituted with up to four substituents selected independently from halogen, cyano, NO2, Ci-C6-alkyl, Ci-C6-haloalkyl, C1-C6- alkoxy and Ci-C6-haloalkoxy.
  • Each b is more preferred independently 0 or 1 .
  • Each c is more preferred independently 0, 1 or 2.
  • each of the symbols in formula (I) has the more preferred meanings.
  • X is especially preferred O.
  • Y is especially preferred O.
  • A is especially preferred phenyl with up to 3 substituents R a .
  • a 0 is especially preferred phenyl with up to 3 substituents R a or pyridyl, with up to 2 substituents R a .
  • R 1 and R 2 together with the nitrogen and carbon atom to which they are bonded, form especially preferred the following substituted heterocyclic ring system:
  • k is especially preferred 0, 1 or 2.
  • R 3 is especially preferred CH 2 Q 1 or CH(CH 3 )Q 1 .
  • Q 1 is especially preferred a heterocyclic ring system:
  • R A is especially preferred Ci-C3-alkyl, C3-C6-cycloalkyl, wherein the carbon atoms of the aforementioned aliphatic and cyclo-aliphatic radicals are unsubstituted or substituted with one or more R b ,
  • R A is OR A0 or N(R A ) 2 .
  • R B is especially preferred hydrogen, Ci-C3-alkyl, wherein the carbon atoms of the aforementioned aliphatic radicals are unsubstituted or substituted with one or more R b ,
  • R B is N(R 9 ) 2 .
  • Each R c is especially preferred independently hydrogen, Ci-C6-alkyl, Ci-C6-haloalkyl, C 2 -C6- alkenyl, C 2 -C6-haloalkenyl, C 2 -C6-alkynyl, C 2 -C6-haloalkynyl, Cs-Cs-cycloalkyl, C3-C8- halocycloalkyl, Ci-C6-alkoxyalkyl or Ci-C6-haloalkoxyalkyl.
  • Each R d is especially preferred independently Ci-C6-alkyl, Ci-C6-haloalkyl, C 2 -C6-alkenyl, C 2 - C6-haloalkenyl, C 2 -C6-alkynyl, C 2 -C6-haloalkynyl, Cs-Cs-cycloalkyl or Cs-Cs-halocycloalkyl.
  • Each R e is especially preferred independently hydrogen, Ci-C6-alkyl, Ci-C6-haloalkyl, C 2 -C6- alkenyl, C 2 -C6-haloalkenyl, C 2 -C6-alkynyl, C 2 -C6-haloalkynyl, Cs-Cs-cycloalkyl, Cs-Cs- halocycloalkyl, Ci-C6-alkoxyalkyl or Ci-C6-haloalkoxyalkyl.
  • Each Rs is especially preferred independently hydrogen, Ci-C6-alkyl, Ci-C6-haloalkyl, C 2 -C6- alkenyl, C 2 -C6-haloalkenyl, C 2 -C6-alkynyl, C 2 -C6-haloalkynyl, Ci-C6-alkoxyalkyl or C1-C6- haloalkoxyalkyl.
  • Each Q 3 is especially preferred independently phenyl, unsubstituted or substituted with at least one substituent selected from halogen, cyano, nitro, Ci-C6-alkyl, Ci-C6-haloalkyl, Ci- C6-alkoxy and Ci-C6-haloalkoxy, a 3-, 4-, 5-, 6- or 7- membered saturated, partly saturated or unsaturated aromatic heterocyclic ring comprising 1 , 2 or 3 heteroatoms or heteroatom groups selected from oxygen, nitrogen, sulfur, NO, SO and SO2 unsubstituted or substituted with up to four substituents selected independently from halogen, cyano, NO2, Ci-C6-alkyl, Ci-C6-haloalkyl, C1-C6- alkoxy and Ci-C6-haloalkoxy.
  • Each b is especially preferred independently 0 or 1 .
  • Each c is especially preferred independently 0, 1 or 2.
  • X is particularly preferred O.
  • Y is particularly preferred O.
  • A, A 0 is particularly preferred independently phenyl, unsubstituted or substituted with up to
  • R 1 and R 2 together with the nitrogen and carbon atom to which they are bonded, particularly preferred form the following substituted heterocyclic ring system:
  • CH2Q 1 is particularly preferred.
  • R A is particularly preferred Ci-C3-alkyl, C3-C6-cycloalkyl, Ci-C3-haloalkyl or C3-C6- halocycloalkyl;
  • R A is OR A0 or N(R A ) 2 .
  • R B is particularly preferred hydrogen, Ci-C3-alkyl, Ci-C3-haloalkyl or C3-C6-halocycloalkyl.
  • Each R c is particularly preferred independently hydrogen, Ci-C6-alkyl, Ci-C6-haloalkyl, C2-C6- alkenyl, C2-C6-haloalkenyl, C2-C6-alkynyl, C2-C6-haloalkynyl, Cs-Cs-cycloalkyl, C3-C8- halocycloalkyl, Ci-C6-alkoxyalkyl or Ci-C6-haloalkoxyalkyl.
  • Each R d is particularly preferred independently Ci-C6-alkyl, Ci-C6-haloalkyl, C2-C6-alkenyl, C2-C6-haloalkenyl, C2-C6-alkynyl, C2-C6-haloalkynyl, Cs-Cs-cycloalkyl, C3-C8- halocycloalkyl.
  • Each R e is particularly preferred independently hydrogen, Ci-C6-alkyl, Ci-C6-haloalkyl, C2-C6- alkenyl, C2-C6-haloalkenyl, C2-C6-alkynyl, C2-C6-haloalkynyl, Cs-Cs-cycloalkyl, C3-C8- halocycloalkyl, Ci-C6-alkoxyalkyl or Ci-C6-haloalkoxyalkyl.
  • Each R f is particularly preferred independently hydrogen, halogen, cyano, nitro, C1-C6- alkoxy, Ci-C6-haloalkoxy, Ci-C6-alkylthio, Ci-C6-alkylsulfinyl, Ci-C6-alkylsulfonyl, C1-C6- haloalkylthio, Ci-C6-alkyl, C2-C6-alkenyl, C2-C6-alkynyl, Cs-Cs-cycloalkyl, wherein the four last mentioned aliphatic and cyclo-aliphatic radicals are unsubstituted, partially or fully halogenated.
  • Each Q 3 is particularly preferred independently phenyl, unsubstituted or substituted with at least one substituent selected from halogen, cyano, nitro, Ci-C6-alkyl, Ci-C6-haloalkyl, Ci- C6-alkoxy and Ci-C6-haloalkoxy,
  • a 3-, 4-, 5-, 6- or 7- membered saturated, partly saturated or unsaturated aromatic heterocyclic ring comprising 1 , 2 or 3 heteroatoms or heteroatom groups selected from oxygen, nitrogen, sulfur, NO, SO and SO2 unsubstituted or substituted with up to four substituents selected independently from halogen, cyano, NO2, Ci-C6-alkyl, Ci-C6-haloalkyl, C1-C6- alkoxy and Ci-C6-haloalkoxy.
  • Each b is particularly preferred independently 0 or 1 .
  • Each c is particularly preferred independently 0, 1 or 2.
  • each of the symbols in formula (I) has the particularly preferred meanings.
  • R a' , R a" each independently are hydrogen or R a , and
  • R a' , R 30 , Q 1 , R A , R B have the meanings given in formula (I)
  • Me is CHs
  • Et is C 2 H 5
  • i-Pr isCH(CH 3 ) 2
  • c-Pr is cyclopropyl.

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Description

Substituted mesoionic imine compounds for combating animal pests
The invention relates to substituted mesoionic compounds and salts thereof, to methods for preparing these compounds and to compositions comprising such compounds. The invention also relates to the use of the substituted mesoionic compounds, of their salts or of compositions comprising them for combating animal pests. Furthermore the invention relates to methods of applying such compounds.
Animal pests destroy growing and harvested crops and attack wooden dwelling and commercial structures, 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 animal pests. In particular, animal pests such as insects and acaridae are difficult to be effectively controlled.
WO 2009/099929, WO 201 1/017334, WO 201 1/017347, WO 201 1/017342, WO
201 1/017351 , WO 2012/0921 15 and WO 2012/106495 disclose pesticides having a mesoionic pyrimidine structure. However, the known compounds are not completely satisfactory in many cases, in terms, for example, of application rate, spectrum of activity, duration of activity, tendency to form resistance or economic aspects of the preparation process.
It is therefore a continuing objective to provide further pesticidal mesoionic pyrimidine compounds which, at least in some aspects, offer advantages over the known compounds.
It has been found that particular mesoionic pyrimidine compounds carrying substituted pyrimidine group are particularly suitable for controlling pests.
Accordingly, in one aspect of the invention there is provided a substituted mesoionic compound of formula (I),
Figure imgf000002_0001
wherein
is O or S;
is O or S;
is independently phenyl, naphthyl or a 5- or 6-membered heteroaromatic ring system, or a 8-10 -membered heteroaromatic bicyclic ring system, each un- substituted or substituted with up to 6 substituents Ra;
R1, R2 is independently hydrogen, Ci-C6-alkyl, Cs-Cs-cycloalkyl, C2-C6-alkenyl, C2-C6- alkynyl, wherein the carbon atoms of the aforementioned aliphatic and cyclo- aliphatic radicals are unsubstituted or substituted with one or more Rb; or R1 and R2 together with the nitrogen and carbon atom to which they are bonded, form the following substituted heterocyclic ring system:
Figure imgf000003_0001
k is 0, 1 , 2, 3 or 4;
R3 is (CR30R31)aQ1 , Ci-C6-alkyl unsubstituted or substituted with one or more halogen or C3-C6-cycloalkyl unsubstituted or substituted with 1 to 4 substituents selected from the group consisting of halogen, Ci-C2-alkyl, 1 cyclopropyl and 1 CF3;
a is O or l ;
each R30 and R31 is independently hydrogen or halogen, and one of R30, R31 is hydrogen, halogen or cyano, hydroxy, amino, nitro, OCN, SCN, CHO, C(=0)OH, C(=0)NH2, C(=S)NH2 or SO2NH2,
or d-Ce-alkyl, C2-Ce-alkenyl, C2-Ce-alkynyl, C3-C8-cycloalkyl, C4-
Cs-alkylcycloalkyl, C4-C8-cycloalkylalkyl, Ci-C6-alkoxy, C3-C6- cycloalkoxy, C4-C8-cycloalkylalkoxy, C2-C6-alkenyloxy or C2-C6- alkynyloxy, each unsubstituted or substituted with at least one halogen;
Q1 is a three to eleven-membered heterocyclic ring system, which contains from 1 to 6 heteroatoms selected from N(R)eb, O and S(0)c, , and wherein 1 , 2 or 3 carbon-atoms of the heterocyclic ring are optionally selected from C(=0), C(=NRe) and (C=S), wherein the heterocyclic ring is unsubstituted or substituted with one or more radicals Ra;
RA is hydrogen, Ci-C8-alkyl, C3-C8-cycloalkyl, C2-C8-alkenyl, C2-C8-alkynyl, C4-C8- cycloalkenyl, wherein the carbon atoms of the aforementioned aliphatic and cyclo- aliphatic radicals are unsubstituted or substituted with one or more Rb,
or
RA is ORA0 or N(RA1)2;
RA0, RA1 is hydrogen, C C8-alkyl, C3-C8-cycloalkyl, C2-C8-alkenyl, C2-C8-alkynyl, C4-C8- cycloalkenyl, wherein the carbon atoms of the aforementioned aliphatic and cyclo-aliphatic radicals are unsubstituted or substituted with one or more Rb or is C(=0)N(Re)2, C(=S)N(Re)2, C(=0)Re, C(=0)ORe, C(=S)Re or C(=S)ORe; RB is hydrogen, CrC8-alkyl, C2-C8-alkenyl, C2-C8-alkynyl, wherein the carbon atoms of the aforementioned aliphatic radicals are unsubstituted or substituted with one or more Rb,
or
RB is N(R9)2;
each Ra is independently halogen, cyano, azido, nitro, SCN, SF5, Ci-C8-alkyl, C2-C8- alkenyl, C2-C8-alkynyl, C3-C8-cycloalkyl, C4-C8-cycloalkenyl, wherein the carbon atoms of the aforementioned aliphatic and cyclo-aliphatic radicals are unsubstituted or substituted with one or more Rb,
Si(Rc)3, ORe, OS(0)cRd, S(0)cRd, S(0)cN(Re)2, N(Re)2, C(=0)Re, C(=0)ORe,
C(=NRe)Rd, C(=0)N(Re)2, C(=S)N(Re)2 or Q2; or
two Ra together on one ring atom are =0, =C(Re)2, =NRe, =NORd or =NN(Rd)2;
each Rb is independently halogen, cyano, azido, nitro, -SCN, SF5, Ci-C6-alkoxy, C1-C6- haloalkoxy, Ci-C6-alkylthio, Ci-C6-alkylsulfinyl, Ci-C6-alkylsulfonyl, C1-C6- haloalkylthio, Cs-Cs-cycloalkyl, Cs-Cs-halocycloalkyl, C2-C6-alkenyl, C2-C6- haloalkenyl, C2-C6-alkynyl, C2-C6-haloalkynyl, Si(Rc)3, ORe, OS02Rd, S(0)cRd, S(0)cN(Re)2, N(Re)2, C(=0)N(Re)2, C(=S)N(Re)2, C(=0)ORe or Q2;
each Rc is independently hydrogen, Ci-C6-alkyl, Ci-C6-haloalkyl, C2-C6-alkenyl, C2-C6- haloalkenyl, C2-C6-alkynyl, C2-C6-haloalkynyl, Cs-Cs-cycloalkyl, Cs-Cs-halocycloalkyl,
Ci-C6-alkoxyalkyl, Ci-C6-haloalkoxyalkyl or phenyl which is unsubstituted or substituted with one or more substituents selected independently from halogen, cyano, NO2, Ci-C6-alkyl, Ci-C6-haloalkyl, Ci-C6-alkoxy and Ci-C6-haloalkoxy;
each Rd is independently Ci-C6-alkyl, Ci-C6-haloalkyl, C2-C6-alkenyl, C2-C6-haloalkenyl, C2-C6-alkynyl, C2-C6-haloalkynyl, Cs-Cs-cycloalkyl, Cs-Cs-halocycloalkyl, or phenyl which is unsubstituted or substituted with one or more substituents selected independently from halogen, cyano, NO2, CiC6-alkyl, Ci-C6-haloalkyl, Ci-C6-alkoxy and Ci-C6-haloalkoxy;
each Re is independently hydrogen, Ci-C6-alkyl, Ci-C6-haloalkyl, C2-C6-alkenyl, C2-C6- haloalkenyl, C2-C6-alkynyl, C2-C6-haloalkynyl, Cs-Cs-cycloalkyl, Cs-Cs-halocycloalkyl,
Ci-C6-alkoxyalkyl, Ci-C6-haloalkoxyalkyl or phenyl which is unsubstituted or substituted with one or more substituents selected independently from halogen, cyano, NO2, Ci-C6-alkyl, Ci-C6-haloalkyl, Ci-C6-alkoxy and Ci-C6-haloalkoxy;
each Q2 is independently a 3- to 10-membered ring or a 7- to 1 1 -membered ring sys- tern, each ring or ring system containing ring members 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, 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)c, each ring or ring system unsubstituted or substituted with up to 5 substitu- ents Rf;
each Rf is independently hydrogen, halogen, cyano, nitro, OH, SH , SCN, SF5, C1-C6- alkoxy, Ci-C6-haloalkoxy, Ci-C6-alkylthio, Ci-C6-alkylsulfinyl, Ci-C6-alkylsulfonyl, Ci- C6-haloalkylthio, trimethylsilyl, triethylsilyl, tert-butyldimethylsilyl, Ci-C6-alkyl, C2-C6- alkenyl, C2-C6-alkynyl or Cs-Cs-cycloalkyl, wherein the four last mentioned aliphatic and cyclo-aliphatic radicals are unsubstituted, partially or fully halogenated and/or substituted with (=0) and/or carry 1 or 2 radicals selected from Ci-C4-alkoxy; Q3; or two Rf present on the same carbon atom are together =CH(Ci-C4), =C(Ci-C4-alkyl)2,
=N(Ci-C6-alkyl) or =NO(Ci-C6-alkyl);
each R9 is independently hydrogen, Ci-C6-alkyl, Ci-C6-haloalkyl, Ci-C6-alkoxyalkyl, C2- C6-alkenyl, C2-C6-haloalkenyl, C2-C6-alkynyl, C2-C6-haloalkynyl or C1-C6- haloalkoxyalkyl;
each Q3 is independently phenyl, unsubstituted or substituted with at least one
substituent selected from halogen, cyano, nitro, Ci-C6-alkyl, Ci-C6-haloalkyl, C1-C6- alkoxy and Ci-C6-haloalkoxy,
a 3-, 4-, 5-, 6- or 7- membered saturated, partly saturated or unsaturated aromatic heterocyclic ring comprising 1 , 2 or 3 heteroatoms or heteroatom groups selected from oxygen, nitrogen, sulfur, NO, SO and SO2 unsubstituted or substituted with up to four substituents selected independently from halogen, cyano, NO2, Ci-C6-alkyl, Ci-C6-haloalkyl, Ci-C6-alkoxy and Ci-C6-haloalkoxy; each b is independently 0 or 1 ;
each c is independently 0, 1 or 2;
and N-oxides and salts thereof.
The substituted mesoionic compounds of formula (I), their N-oxides and their agriculturally or veterinarily acceptable salts are highly active against animal pests, especially harmful arthro- podes and nematodes, in particular against harmful insects and acaridae.
Accordingly, the invention provides substituted mesoionic compounds of formula (I), N-oxides and agriculturally or veterinarily useful salts thereof.
Moreover, the invention provides and includes the following embodiments:
- agricultural and veterinary compositions comprising at least one compound of formula (I), N-oxide or salt thereof;
the use of at least one compound of formula (I), N-oxide or salt thereof for combating animal pests;
a method of combating animal pests which comprises contacting the animal pests, their habit, breeding ground, food supply, plant, 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 at least one compound of formula (I), N-oxide or salt thereof;
a method for protecting crops from attack or infestation by animal pests, which comprises contacting a crop with a pesticidally effective amount of at least one compound of the formula (I), N-oxide or salt thereof;
a method for protecting seeds from soil insects and seedlings' roots and shoots from soil and foliar insects comprising contacting the seeds before sowing and/or after pregermina- tion with at least one compound of formula (I), N-oxide or salt thereof;
- seeds comprising at least one compound of formula (I), N-oxide or salt thereof;
the use of at least one compound of formula (I), N-oxide or veterinarily acceptable salt thereof for combating parasites in and on animals.
a method for treating 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 at least one compound of formula (I), N-oxide or veterinarily acceptable salt thereof;
a process for the preparation of a composition for treating or protecting animals against infestation or infection by parasites which comprises mixing a parasiticidally effective amount of at least one compound of formula (I), N-oxide or a veterinarily acceptable salt thereof with at least one veterinarily acceptable carrier;
the use of at least one compound of formula (I), N-oxide or veterinarily acceptable salt thereof for the preparation of a medicament for treating, controlling, preventing or protecting animals against infestation or infection by parasites;
a compound of formula (I), N-oxide or salt thereof as a medicament, in particular for use in a method for treating animals against infestation or infection by parasites.
The invention also provides plant propagation materials, in particular seeds, comprising at least one compound of formula (I), N-oxide or agriculturally acceptable salt thereof.
The term "at least one compound of formula (I), N-oxide or salt thereof" means at least one compound selected from the group consisting of compounds of formula (I), N-oxides of the compounds of formula (I), salts of the compounds of formula (I) and salts of the N-oxides of the compounds of formula (I). Likewise "a compound of the invention" means a compound of formula (I), an N-oxide of a compound of formula (I), a salt of a compound of formula (I) or a salt of an N-oxide of a compound of formula (I).
The compounds of formula (I) encompass every possible stereoisomer of the compounds of formula (I), e.g. single enantiomers or diastereomers, as well as mixtures thereof.
The compounds of formula (I) 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 activity against certain pests. The invention encompasses both amorphous and crystalline compounds of 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 formula (I) are preferably agriculturally and/or veterinarily 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 lithium, 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, C1-C4- hydroxyalkyl, Ci-C4-alkoxy, Ci-C4-alkoxy-Ci-C4-alkyl, hydroxy-Ci-C4-alkoxy-Ci-C4-alkyl, phenyl or benzyl. Examples of substituted ammonium ions comprise methylammonium, isoprop- ylammonium, dimethylammonium, diisopropylammonium, trimethylammonium, tetrame- thylammonium, tetraethylammonium, tetrabutylammonium, 2-hydroxyethylammonium, 2-(2- hydroxyethoxy)ethyl-ammonium, bis(2-hydroxyethyl)ammonium, benzyltrimethylammonium 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, hydrogen carbonate, carbonate, hexafluorosilicate, hexafluorophosphate, benzoate, and the anions of C1-C4- alkanoic acids, preferably formate, acetate, propionate and butyrate. They can be formed by reacting the compounds of formula (I) with an acid of the corresponding anion, preferably of hydrochloric acid, hydrobromic acid, sulfuric acid, phosphoric acid or nitric acid.
The organic moieties 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" means fluoro, chloro, bromo and iodo.
The term "partially or fully halogenated" means 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-alkylthio, Cn-Cm-alkylsulfinyl and Cn-Cm-alkylsulfonyl) refers to a branched or unbranched saturated hydrocarbon group having n to m, 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, hep- tyl, octyl, 2-ethylhexyl, nonyl and decyl and their isomers. Ci-C4-alkyl means for example me- thyl, ethyl, propyl, 1 -methylethyl, butyl, 1 -methylpropyl, 2-methylpropyl and 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, 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, bromomethyl, dichlorome- thyl, trichloromethyl, fluoromethyl, difluoromethyl, trifluoromethyl, chlorofluoromethyl, dichloro- fluoromethyl, 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 Ci-C2-fluoroalkyl, which is synonym with methyl or ethyl, wherein 1 , 2, 3, 4 or 5 hydrogen atoms are substituted with fluorine atoms, such as fluoromethyl, difluoromethyl, trifluoromethyl, 1 -fluoroethyl, 2-fluoroethyl, 2,2-difluoroethyl, 2,2,2-trifluoroethyl and pentafluoro- methyl.
Similarly, "Cn-Cm-alkoxy" and "Cn-Cm-alkylthio" refer to straight-chain or branched alkyl groups having n to m carbon atoms, (as mentioned above) bonded through oxygen or sulfur linkages, respectively, at any bond in the alkyl group. Examples include Ci-C4-alkoxy such as methoxy, ethoxy, propoxy, isopropoxy, butoxy, sec-butoxy, isobutoxy and tert-butoxy, futher Ci- C4-alkylthio such as methylthio, ethylthio, propylthio, isopropylthio and n-butylthio.
Accordingly, the terms "Cn-Cm-haloalkoxy" and "Cn-Cm-haloalkylthio" refer to straight-chain or branched alkyl groups having n to m 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, trichloro- methoxy, fluoromethoxy, difluoromethoxy, trifluoromethoxy, chlorofluoromethoxy, dichlorofluo- romethoxy, chlorodifluoromethoxy, 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 pentafluoroethoxy, further Ci-C2-haloalkylthio, such as chloromethylthio, bromomethylthio, dichloromethylthio, trichlorome- thylthio, fluoromethylthio, difluoromethylthio, trifluoromethylthio, chlorofluoromethylthio, dichloro- fluoromethylthio, 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 pentafluo- roethylthio and the like. Similarly the terms Ci-C2-fluoroalkoxy and Ci-C2-fluoroalkylthio refer to Ci-C2-fluoroalkyl which is bonded to the remainder of the molecule via an oxygen atom or a sulfur atom, respectively. The term "C2-Cm-alkenyl" 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 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 "Ci-C4-alkoxy-Ci-C4-alkyl" as used herein refers to alkyl having 1 to 4 carbon atoms, e.g. like the specific examples mentioned above, wherein one hydrogen atom of the alkyl radical is replaced by an Ci-C4-alkoxy group.
The term "C3-Cm-cycloalkyl" as used herein refers to a monocyclic 3- to m-membered saturated cycloaliphatic radicals, e.g. cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, cycloheptyl, cyclooctyl and cyclodecyl.
The term "aryl" as used herein refers to an aromatic hydrocarbon radical such as naph- thyl or in particular phenyl.
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 containing 1 , 2 or 3 heteroatoms or heteroatom groups selected from N, O, S, NO, SO and SO2, as ring members" as used herein refers to monocyclic radicals, the monocyclic radicals being saturated, partially unsaturated or aromatic. 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 include:
oxiranyl, aziridinyl, azetidinyl, 2-tetrahydrofuranyl, 3-tetrahydrofuranyl, 2-tetrahydrothienyl, 3- tetrahydrothienyl, 2-pyrrolidinyl, 3-pyrrolidinyl, 3-pyrazolidinyl, 4-pyrazolidinyl, 5-pyrazolidinyl, 2- imidazolidinyl, 4-imidazolidinyl, 2-oxazolidinyl, 4-oxazolidinyl, 5-oxazolidinyl, 3-isoxazolidinyl, 4- isoxazolidinyl, 5-isoxazolidinyl, 2-thiazolidinyl, 4-thiazolidinyl, 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-triazolidin-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- morpholinyl, 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 and hexahydro-1 ,4-dioxepinyl.
Examples of 3-, 4-, 5-, 6- or 7-membered partially unsaturated heterocyclyl include: 2,3-dihydrofur-2-yl, 2,3-dihydrofur-3-yl, 2,4-dihydrofur-2-yl, 2,4-dihydrofur-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-isoxazolin-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-isothiazolin-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-dihydropyrazol-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-dihydropyrazol-
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-dihydrooxazol-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 tetrahydro- pyridazinyl, 2-di- or tetrahydropyrimidinyl, 4-di- or tetrahydropyrimidinyl, 5-di- or tetrahydropyrimidinyl, di- or tetrahydropyrazinyl, 1 ,3, 5-di- or tetrahydrotriazin-2-yl, 1 ,2, 4-di- or tetrahydrotriazin- 3-yl, 2,3,4,5-tetrahydro[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, tetrahydro-1 ,4-oxazepinyl, tetrahydro-1 ,3- dioxepinyl and tetrahydro-1 ,4-dioxepinyl.
3-, 4-, 5-, 6- or 7-membered aromatic heterocyclyl is 5- or 6-membered aromatic heterocyclyl (hetaryl). Examples 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-imidazolyl, 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.
C2-C7-alkylene is divalent branched or preferably unbranched saturated aliphatic chain having 2 to 7 carbon atoms, for example CH2CH2, -CH(CH3)-, CH2CH2CH2, CH(CH3)CH2, CH2CH(CH3), CH2CH2CH2CH2, CH2CH2CH2CH2CH2, CH2CH2CH2CH2CH2CH2, and
CH2CH2CH2CH2CH2CH2CH2.
If not otherwise specified, all symbols and indices have the meaning given in formula (I). In the following listing of preferred embodiments, if not otherwise stated, a reference to a compound of formula (I) shall include N-oxides and salts thereof. The preferred, more preferred, especially preferred and particularly preferred embodiments of the invention mentioned herein below have to be understood as being preferred either independently from each other or in combination with one another.
In one preferred embodiment, the substituted mesoionic compound of formula (I) is a compound of formula (1-1 ):
Figure imgf000010_0001
In another preferred embodiment, the substituted mesoionic compound of formula (I) is a compound of formula (I-2):
Figure imgf000010_0002
In another preferred embodiment, the substituted mesoionic compound of formula (I) is a compound of formula (I-3);
Figure imgf000010_0003
In another preferred embodiment, the substituted mesoionic compound of formula (I) is a com- pound of formula (1 -4):
Figure imgf000010_0004
In another preferred embodiment, the substituted mesoionic compound of formula (I) is a compound of formula (I-5):
Figure imgf000011_0001
In another preferred embodiment, the substituted mesoionic compound of formula (I) is a compound of formula (I-6):
Figure imgf000011_0002
In another preferred embodiment, the substitutet mesoionic compound of formula (i) is a compound of formula (1 -7):
Figure imgf000011_0003
In another preferred embodiment, the substituted mesoionic compound of formula (I) is a compound of formula (I-8):
Figure imgf000011_0004
In another preferred embodiment, the substituted mesoionic compound of formula (I) is a compound of formula (I-9):
Figure imgf000012_0001
In each of formulae (1-1 ) to (I-9)
Z is the group C(=NRA)RB,
each A1, A2, A3, A4 ist independently N or C-Ra',
with the proviso that no more than two of A1, A2, A3 and A4 are N, and
each Ra' is independently H or Ra.
In preferred embodiments of the invention the symbols in formula (I), each independently, have the following meanings:
X is preferably O or S.
Y is preferably O or S.
A, A0 is preferably independently phenyl, naphthyl or a 5- or 6-membered heteroaromatic ring system, or a 8-10-membered heteroaromatic bicyclic ring system, each unsubstituted or substituted with up to 6 substituents Ra.
R1, R2 is preferably independently hydrogen, Ci-C6-alkyl, Cs-Cs-cycloalkyl, C2-C6-alkenyl,
C2-C6-alkynyl, wherein the carbon atoms of the aforementioned aliphatic and cyclo- aliphatic radicals are unsubstituted or substituted with one or more Rb; or
R1 and R2 together with the nitrogen and carbon atom to which they are bonded, form the fol- lowing substituted heterocyclic ring system:
Figure imgf000012_0002
k is preferably 0, 1 or 2.
R3 is preferably (CR30R31)aQ1.
a is preferably 1 .
Each R30 and R31 is preferably independently hydrogen or halogen, and one of R30, R31 is hydrogen, halogen, cyano, or methyl.
Q1 is preferably a heterocyclic ring system:
Figure imgf000013_0001
Figure imgf000014_0001
D-36 D-37 D-38 D-39 D-40
Figure imgf000014_0002
D-41 D-42 D-43 D-44 D-45
Figure imgf000014_0003
D-46 D-47 D-48 D-49 D-50
Figure imgf000014_0004
D-51 D-52 D-53 D-54 D-55 RA is preferably hydrogen, Ci-C3-alkyl, C3-C6-cycloalkyl, C2-C4-alkenyl, C2-C4-alkynyl,
C4-C6-cycloalkenyl, wherein the carbon atoms of the aforementioned aliphatic and cyclo-aliphatic radicals are unsubstituted or substituted with one or more Rb, or
RA is ORA0 or N(RA )2.
RA0, RA1 is preferably hydrogen, Ci-C3-alkyl, C3-C6-cycloalkyl, C2-C4-alkenyl, C2-C4- alkynyl, C4-C6-cycloalkenyl, wherein the carbon atoms of the aforementioned aliphatic and cyclo-aliphatic radicals are unsubstituted or substituted with one or more Rb, or is C(=0)N(Re)2, C(=S)N(Re)2, C(=0)Re, C(=0)ORe, C(=S)Re or C(=S)ORe. RB is preferably hydrogen, CrC3-alkyl, C2-C4-alkenyl, C2-C4-alkynyl, wherein the carbon atoms of the aforementioned aliphatic radicals are unsubstituted or substituted with one or more Rb,
or
Figure imgf000014_0005
Each Ra is preferably independently halogen, cyano, Ci-C3-alkyl, C2-C4-alkenyl, C2-C4- alkynyl, C3-C6-cycloalkyl, C4-C6-cycloalkenyl, wherein the carbon atoms of the aforementioned aliphatic and cyclo-aliphatic radicals are unsubstituted or substituted with one or more Rb.
Each Rb is preferably independently halogen, cyano, nitro, Ci-C3-alkoxy, C1-C3- haloalkoxy, Ci-C3-alkylthio, Ci-C3-alkylsulfinyl, Ci-C3-alkylsulfonyl, C1-C3- haloalkylthio, C3-C6-cycloalkyl, C3-C6-halocycloalkyl, C2-C4-alkenyl, C2-C4- haloalkenyl, C2-C4-alkynyl or C2-C4-haloalkynyl. Each Rc is preferably independently hydrogen, Ci-C6-alkyl, Ci-C6-haloalkyl, C2-C6- alkenyl, C2-C6-haloalkenyl, C2-C6-alkynyl, C2-C6-haloalkynyl, Cs-Cs-cycloalkyl, C3-C8- halocycloalkyl, Ci-C6-alkoxyalkyl, Ci-C6-haloalkoxyalkyl or phenyl which is unsubstituted or substituted with one or more substituents selected independently from halo- gen, cyano, NO2, Ci-C6-alkyl, Ci-C6-haloalkyl, Ci-C6-alkoxy and Ci-C6-haloalkoxy.
Each Rd is preferably independently Ci-C6-alkyl, Ci-C6-haloalkyl, C2-C6-alkenyl, C2-C6- haloalkenyl, C2-C6-alkynyl, C2-C6-haloalkynyl, Cs-Cs-cycloalkyl, Cs-Cs-halocycloalkyl, or phenyl which is unsubstituted or substituted with one or more substituents selected independently from halogen, cyano, NO2, CiC6-alkyl, Ci-C6-haloalkyl, Ci- C6-alkoxy and Ci-C6-haloalkoxy.
Each Re is preferably independently hydrogen, Ci-C6-alkyl, Ci-C6-haloalkyl, C2-C6- alkenyl, C2-C6-haloalkenyl, C2-C6-alkynyl, C2-C6-haloalkynyl, Cs-Cs-cycloalkyl, Cs-Cs- halocycloalkyl, Ci-C6-alkoxyalkyl, Ci-C6-haloalkoxyalkyl or phenyl which is unsubstituted or substituted with one or more substituents selected independently from halo- gen, cyano, NO2, Ci-C6-alkyl, Ci-C6-haloalkyl, Ci-C6-alkoxy and Ci-C6-haloalkoxy.
Each Q2 is preferably independently a 3- to 10-membered ring or a 7- to 1 1 -membered ring system, each ring or ring system containing ring members 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, wherein up to 3 carbon atom ring members are independently select- ed from C(=0) and C(=S) and the sulfur atom ring members are independently selected from S(=0)c, each ring or ring system unsubstituted or substituted with up to 5 substituents Rf.
Each Rf is preferably independently hydrogen, halogen, cyano, nitro, OH , SH , SCN , SF5, Ci-C6-alkoxy, Ci-C6-haloalkoxy, Ci-C6-alkylthio, Ci-C6-alkylsulfinyl, C1-C6- alkylsulfonyl, Ci-C6-haloalkylthio, trimethylsilyl, triethylsilyl, tert-butyldimethylsilyl, Ci-
C6-alkyl, C2-C6-alkenyl, C2-C6-alkynyl or Cs-Cs-cycloalkyl, wherein the four last mentioned aliphatic and cyclo-aliphatic radicals are unsubstituted, partially or fully halo- genated and/or substituted with (=0) and/or carry 1 or 2 radicals selected from Ci- C4-alkoxy; Q3; or
two Rf present on the same carbon atom are together =CH(Ci-C4), =C(Ci-C4-alkyl)2,
=N(Ci-C6-alkyl) or =NO(Ci-C6-alkyl).
Each R9 is preferably independently hydrogen, Ci-C6-alkyl, Ci-C6-haloalkyl, C2-C6- alkenyl, C2-C6-haloalkenyl, C2-C6-alkynyl, C2-C6-haloalkynyl, Ci-C6-alkoxyalkyl or Ci- C6-haloalkoxyalkyl.
Each Q3 is preferably independently phenyl, unsubstituted or substituted with at least one substituent selected from halogen, cyano, nitro, Ci-C6-alkyl, Ci-C6-haloalkyl, Ci- C6-alkoxy and Ci-C6-haloalkoxy,
a 3-, 4-, 5-, 6- or 7- membered saturated, partly saturated or unsaturated aromatic heterocyclic ring comprising 1 , 2 or 3 heteroatoms or heteroatom groups selected from oxygen, nitrogen, sulfur, NO, SO and SO2 unsubstituted or substituted with up to four substituents selected independently from halogen, cyano, NO2, Ci-C6-alkyl,
Ci-C6-haloalkyl, Ci-C6-alkoxy and Ci-C6-haloalkoxy.
Each b is preferably independently 0 or 1 .
Each c is preferably independently 0, 1 or 2. In a preferred embodiment of the invention each of the symbols in formula (I) has the preferred meanings.
In more preferred embodiments of the invention the symbols in formula (I), each independently, have the following meanings:
X is more preferred O.
Y is more preferred O.
A is more preferred phenyl with up to 3 substituents Ra.
A0 is more preferred phenyl with up to 3 substituents Ra or pyridyl, with up to 2 substituents Ra.
R1, R2 is more preferred independently hydrogen, Ci-C6-alkyl, Cs-Cs-cycloalkyl, C2-C6- alkenyl, C2-C6-alkynyl, wherein the carbon atoms of the aforementioned aliphatic and cyclo-aliphatic radicals are unsubstituted or substituted with one or more Rb; or
R1 and R2 together with the nitrogen and carbon atom to which they are bonded, more preferred form the following substituted heterocyclic ring system:
Figure imgf000016_0001
k is more preferred 0, 1 or 2.
R3 is more preferred (CR30R31)aQ1.
a is more preferred 1 .
Each R30 and R31 is more preferred hydrogen and one of R30, R31, hydrogen or methyl. Q1 is more preferred a heterocyclic ring system:
Figure imgf000016_0002
D-1 D-2 D-3 D-5
Figure imgf000016_0003
D-16 D-17 D-20 D-22
Figure imgf000016_0004
Figure imgf000017_0001
D-26 D-27 D-28 D-29 D-30
Figure imgf000017_0002
D-35
Figure imgf000017_0003
D-36 D-54 D-55
RA is more preferred Ci-C3-alkyl, C3-C6-cycloalkyl, wherein the carbon atoms of the aforementioned aliphatic and cyclo-aliphatic radicals are unsubstituted or substituted with one or more Rb,
or
RA is ORA0 or N(RA )2
RA0, RA1 is more preferred Ci-C3-alkyl, C3-C6-cycloalkyl, wherein the carbon atoms of the aforementioned aliphatic and cyclo-aliphatic radicals are unsubstituted or substituted with one or more Rb or is C(=0)N(Re)2, C(=S)N(Re)2 or C(=0)Re.
RB is more preferred hydrogen, Ci-C3-alkyl, wherein the carbon atoms of the aforementioned aliphatic radicals are unsubstituted or substituted with one or more Rb,
or
RB is N(R9)2.
Each Ra is more preferred independently halogen, cyano, OCH3, CF3, OCF3, SCF3 or
OCF2H.
Each Rb is more preferred independently halogen, cyano, Ci-C3-alkoxy, Ci-C3-haloalkoxy, Ci-C3-alkylthio, Ci-C3-alkylsulfinyl, Ci-C3-alkylsulfonyl or Ci-C3-haloalkylthio.
Each Rc is more preferred independently hydrogen, Ci-C6-alkyl, Ci-C6-haloalkyl, C2-C6- alkenyl, C2-C6-haloalkenyl, C2-C6-alkynyl, C2-C6-haloalkynyl, Cs-Cs-cycloalkyl, C3-C8- halocycloalkyl, Ci-C6-alkoxyalkyl or Ci-C6-haloalkoxyalkyl.
Each Rd is more preferred independently Ci-C6-alkyl, Ci-C6-haloalkyl, C2-C6-alkenyl, C2-C6- haloalkenyl, C2-C6-alkynyl, C2-C6-haloalkynyl, Cs-Cs-cycloalkyl or Cs-Cs-halocycloalkyl. Each Re is more preferred independently hydrogen, Ci-C6-alkyl, Ci-C6-haloalkyl, C2-C6- alkenyl, C2-C6-haloalkenyl, C2-C6-alkynyl, C2-C6-haloalkynyl, Cs-Cs-cycloalkyl, Cs-Cs- halocycloalkyl, Ci-C6-alkoxyalkyl or Ci-C6-haloalkoxyalkyl.
Each Q2 is more preferred independently a 3- to 10-membered ring or a 7- to 1 1 -membered ring system, each ring or ring system containing ring members 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, 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)c, each ring or ring system unsubstituted or substituted with up to 5 substituents Rf.
Each Rf is more preferred independently hydrogen, halogen, cyano, nitro, OH, SH, SCN, SF5, Ci-C6-alkoxy, Ci-C6-haloalkoxy, Ci-C6-alkylthio, Ci-C6-alkylsulfinyl, C1-C6- alkylsulfonyl, Ci-C6-haloalkylthio, trimethylsilyl, triethylsilyl, tert-butyldimethylsilyl, C1-C6- alkyl, C2-C6-alkenyl, C2-C6-alkyl, Cs-Cs-cycloalkyl, wherein the four last mentioned aliphatic and cyclo-aliphatic radicals are unsubstituted, partially or fully halogenated and/or substituted with (=0) and/or carry 1 or 2 radicals selected from Ci-C4-alkoxy; Q3.
Each R9 is more preferred independently hydrogen, Ci-C6-alkyl, Ci-C6-haloalkyl, C2-C6- alkenyl, C2-C6-haloalkenyl, C2-C6-alkynyl, C2-C6-haloalkynyl, Ci-C6-alkoxyalkyl or C1-C6- haloalkoxyalkyl.
Each Q3 is more preferred independently phenyl, unsubstituted or substituted with at least one substituent selected from halogen, cyano, nitro, Ci-C6-alkyl, Ci-C6-haloalkyl, C1-C6- alkoxy and Ci-C6-haloalkoxy,
a 3-, 4-, 5-, 6- or 7- membered saturated, partly saturated or unsaturated aromatic heterocyclic ring comprising 1 , 2 or 3 heteroatoms or heteroatom groups selected from oxygen, nitrogen, sulfur, NO, SO and SO2 unsubstituted or substituted with up to four substituents selected independently from halogen, cyano, NO2, Ci-C6-alkyl, Ci-C6-haloalkyl, C1-C6- alkoxy and Ci-C6-haloalkoxy.
Each b is more preferred independently 0 or 1 .
Each c is more preferred independently 0, 1 or 2.
In a more preferred embodiment of the invention each of the symbols in formula (I) has the more preferred meanings.
In especially preferred embodiments of the invention the symbols in formula (I), each independently, have the following meanings:
X is especially preferred O.
Y is especially preferred O.
A is especially preferred phenyl with up to 3 substituents Ra.
A0 is especially preferred phenyl with up to 3 substituents Ra or pyridyl, with up to 2 substituents Ra.
R1 and R2 together with the nitrogen and carbon atom to which they are bonded, form especially preferred the following substituted heterocyclic ring system:
Figure imgf000018_0001
k is especially preferred 0, 1 or 2.
R3 is especially preferred CH2Q1 or CH(CH3)Q1.
Q1 is especially preferred a heterocyclic ring system:
Figure imgf000019_0001
D-2 D-25 D-54
RA is especially preferred Ci-C3-alkyl, C3-C6-cycloalkyl, wherein the carbon atoms of the aforementioned aliphatic and cyclo-aliphatic radicals are unsubstituted or substituted with one or more Rb,
or
RA is ORA0 or N(RA )2.
RA0, RA1 is especially preferred Ci-C3-alkyl, C3-C6-cycloalkyl, wherein the carbon atoms of the aforementioned aliphatic and cyclo-aliphatic radicals are unsubstituted or substituted with one or more Rb or is C(=0)N(Re)2, C(=S)N(Re)2, C(=0)Re.
RB is especially preferred hydrogen, Ci-C3-alkyl, wherein the carbon atoms of the aforementioned aliphatic radicals are unsubstituted or substituted with one or more Rb,
or
RB is N(R9)2.
Each Rc is especially preferred independently hydrogen, Ci-C6-alkyl, Ci-C6-haloalkyl, C2-C6- alkenyl, C2-C6-haloalkenyl, C2-C6-alkynyl, C2-C6-haloalkynyl, Cs-Cs-cycloalkyl, C3-C8- halocycloalkyl, Ci-C6-alkoxyalkyl or Ci-C6-haloalkoxyalkyl.
Each Rd is especially preferred independently Ci-C6-alkyl, Ci-C6-haloalkyl, C2-C6-alkenyl, C2- C6-haloalkenyl, C2-C6-alkynyl, C2-C6-haloalkynyl, Cs-Cs-cycloalkyl or Cs-Cs-halocycloalkyl. Each Re is especially preferred independently hydrogen, Ci-C6-alkyl, Ci-C6-haloalkyl, C2-C6- alkenyl, C2-C6-haloalkenyl, C2-C6-alkynyl, C2-C6-haloalkynyl, Cs-Cs-cycloalkyl, Cs-Cs- halocycloalkyl, Ci-C6-alkoxyalkyl or Ci-C6-haloalkoxyalkyl.
Each Q2 is especially preferred independently a 3- to 10-membered ring or a 7- to 11- membered ring system, each ring or ring system containing ring members 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, 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)c, each ring or ring system unsubstituted or substituted with up to 5 substituents Rf. Each Rf is especially preferred independently hydrogen, halogen, cyano, nitro, OH, SH, SCN, SF5, d-Ce-alkoxy, Ci-C6-haloalkoxy, Ci-C6-alkylthio, Ci-C6-alkylsulfinyl, Ci-C6- alkylsulfonyl, Ci-C6-haloalkylthio, trimethylsilyl, triethylsilyl, tert-butyldimethylsilyl, C1-C6- alkyl, C2-C6-alkenyl, C2-C6-alkyl, Cs-Cs-cycloalkyl, wherein the four last mentioned aliphatic and cyclo-aliphatic radicals are unsubstituted, partially or fully halogenated and/or substituted with (=0) and/or carry 1 or 2 radicals selected from Ci-C4-alkoxy; OA
Each Rs is especially preferred independently hydrogen, Ci-C6-alkyl, Ci-C6-haloalkyl, C2-C6- alkenyl, C2-C6-haloalkenyl, C2-C6-alkynyl, C2-C6-haloalkynyl, Ci-C6-alkoxyalkyl or C1-C6- haloalkoxyalkyl.
Each Q3 is especially preferred independently phenyl, unsubstituted or substituted with at least one substituent selected from halogen, cyano, nitro, Ci-C6-alkyl, Ci-C6-haloalkyl, Ci- C6-alkoxy and Ci-C6-haloalkoxy, a 3-, 4-, 5-, 6- or 7- membered saturated, partly saturated or unsaturated aromatic heterocyclic ring comprising 1 , 2 or 3 heteroatoms or heteroatom groups selected from oxygen, nitrogen, sulfur, NO, SO and SO2 unsubstituted or substituted with up to four substituents selected independently from halogen, cyano, NO2, Ci-C6-alkyl, Ci-C6-haloalkyl, C1-C6- alkoxy and Ci-C6-haloalkoxy.
Each b is especially preferred independently 0 or 1 .
Each c is especially preferred independently 0, 1 or 2.
In an especially preferred embodiment of the invention each of the symbols in formula (I) has the preferred meanings.
In particularly preferred embodiments of the invention the symbols in formula (I), each independently, have the following meanings:
X is particularly preferred O.
Y is particularly preferred O.
A, A0 is particularly preferred independently phenyl, unsubstituted or substituted with up to
4 substituents Ra.
R1 and R2 together with the nitrogen and carbon atom to which they are bonded, particularly preferred form the following substituted heterocyclic ring system:
Figure imgf000020_0001
is particularly preferred 0, 1 or 2.
is particularly preferred CH2Q1.
is particularly preferred 1 .
is particularly preferred a heterocyclic ring system
Figure imgf000020_0002
D-2 D-25 D-54
RA is particularly preferred Ci-C3-alkyl, C3-C6-cycloalkyl, Ci-C3-haloalkyl or C3-C6- halocycloalkyl;
or
RA is ORA0 or N(RA )2.
RA0, RA1 is particularly preferred Ci-C3-alkyl, C3-C6-cycloalkyl, wherein the carbon atoms of the aforementioned aliphatic and cyclo-aliphatic radicals are unsubstituted or substituted with one or more Rb or is C(=0)N(Re)2, C(=S)N(Re)2, C(=0)Re.
RB is particularly preferred hydrogen, Ci-C3-alkyl, Ci-C3-haloalkyl or C3-C6-halocycloalkyl. Each Rc is particularly preferred independently hydrogen, Ci-C6-alkyl, Ci-C6-haloalkyl, C2-C6- alkenyl, C2-C6-haloalkenyl, C2-C6-alkynyl, C2-C6-haloalkynyl, Cs-Cs-cycloalkyl, C3-C8- halocycloalkyl, Ci-C6-alkoxyalkyl or Ci-C6-haloalkoxyalkyl. Each Rd is particularly preferred independently Ci-C6-alkyl, Ci-C6-haloalkyl, C2-C6-alkenyl, C2-C6-haloalkenyl, C2-C6-alkynyl, C2-C6-haloalkynyl, Cs-Cs-cycloalkyl, C3-C8- halocycloalkyl.
Each Re is particularly preferred independently hydrogen, Ci-C6-alkyl, Ci-C6-haloalkyl, C2-C6- alkenyl, C2-C6-haloalkenyl, C2-C6-alkynyl, C2-C6-haloalkynyl, Cs-Cs-cycloalkyl, C3-C8- halocycloalkyl, Ci-C6-alkoxyalkyl or Ci-C6-haloalkoxyalkyl.
Each Q2 is particularly preferred independently a 3- to 6-membered ring, each ring or ring system containing ring members 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, wherein up to 3 carbon at- om ring members are independently selected from C(=0) and C(=S) and the sulfur atom ring members are independently selected from S(=0)c, each ring or ring system unsubstituted or substituted with up to 5 substituents Rf.
Each Rf is particularly preferred independently hydrogen, halogen, cyano, nitro, C1-C6- alkoxy, Ci-C6-haloalkoxy, Ci-C6-alkylthio, Ci-C6-alkylsulfinyl, Ci-C6-alkylsulfonyl, C1-C6- haloalkylthio, Ci-C6-alkyl, C2-C6-alkenyl, C2-C6-alkynyl, Cs-Cs-cycloalkyl, wherein the four last mentioned aliphatic and cyclo-aliphatic radicals are unsubstituted, partially or fully halogenated.
Each Q3 is particularly preferred independently phenyl, unsubstituted or substituted with at least one substituent selected from halogen, cyano, nitro, Ci-C6-alkyl, Ci-C6-haloalkyl, Ci- C6-alkoxy and Ci-C6-haloalkoxy,
a 3-, 4-, 5-, 6- or 7- membered saturated, partly saturated or unsaturated aromatic heterocyclic ring comprising 1 , 2 or 3 heteroatoms or heteroatom groups selected from oxygen, nitrogen, sulfur, NO, SO and SO2 unsubstituted or substituted with up to four substituents selected independently from halogen, cyano, NO2, Ci-C6-alkyl, Ci-C6-haloalkyl, C1-C6- alkoxy and Ci-C6-haloalkoxy.
Each b is particularly preferred independently 0 or 1 .
Each c is particularly preferred independently 0, 1 or 2.
In a particularly preferred embodiment of the invention each of the symbols in formula (I) has the particularly preferred meanings.
Further especially preferred are the following groups of compounds of formulae (1-1 -1 ) to (1-1 1 - 8):
Figure imgf000022_0001
(I-2-9) (1-2-10)
Figure imgf000023_0001
Figure imgf000024_0001
(I-5-8)
Figure imgf000024_0002
(1-5-12)
Figure imgf000024_0003
(1-5-14)
Figure imgf000025_0001
(1-5-17) (1-5-18)
Figure imgf000025_0002
(1-5-19) (I-5-20)
Figure imgf000025_0003
Figure imgf000026_0001
Figure imgf000026_0002
Figure imgf000027_0001
Figure imgf000027_0002
Figure imgf000027_0003
In formulae (1-1 -1 ) to (1-8-15) the symbols have the following meanings:
A is
Figure imgf000027_0004
Ra', Ra" each independently are hydrogen or Ra, and
Ra', R30, Q1, RA, RB have the meanings given in formula (I)
In a further preferred embodiment the symbols in formulae (1-1 -1 ) to (1-8-15) have the meanings given in Table A1 to A608. In Table A1 toA252
Figure imgf000028_0001
Me is CHs,
Et is C2H5, i-Pr isCH(CH3)2, c-Pr is cyclopropyl.
Table A
Figure imgf000028_0002
Figure imgf000029_0001
62 Qio H NHC(=0)OMe Me
63 Qio H NHC(=0)OMe Et
64 Qio H NHC(=0)OMe i-Pr
65 Qio H NHC(=0)OMe CH2CF3
66 Qio H NHC(=0)NHMe H
67 Qio H NHC(=0)NHMe Me
68 Qio H NHC(=0)NHMe Et
69 Qio H NHC(=0)NHMe i-Pr
70 Qio H NHC(=0)NHMe CH2CF3
71 Qio H NHC(=0)NHCH2CF3 H
72 Qio H NHC(=0)NHCH2CF3 Me
73 Qio H NHC(=0)NHCH2CF3 Et
74 Qio H NHC(=0)NHCH2CF3 i-Pr
75 Qio H NHC(=0)NHCH2CF3 CH2CF3
76 Qio H N(Me)C(=0)Me H
77 Qio H N(Me)C(=0)Me Me
78 Qio H N(Me)C(=0)Me Et
79 Qio H N(Me)C(=0)Me i-Pr
80 Qio H N(Me)C(=0)Me CH2CF3
81 Qio H N(Me)C(=0)OMe H
82 Qio H N(Me)C(=0)OMe Me
83 Qio H N(Me)C(=0)OMe Et
84 Qio H N(Me)C(=0)OMe i-Pr
85 Qio H N(Me)C(=0)OMe CH2CF3
86 Qio H N(Me)C(=0)NHMe H
87 Qio H N(Me)C(=0)NHMe Me
88 Qio H N(Me)C(=0)NHMe Et
89 Qio H N(Me)C(=0)NHMe i-Pr
90 Qio H N(Me)C(=0)NHMe CH2CF3
91 Qio H N(Me)C(=0)NHCH2CF3 H
92 Qio H N(Me)C(=0)NHCH2CF3 Me
93 Qio H N(Me)C(=0)NHCH2CF3 Et
94 Qio H N(Me)C(=0)NHCH2CF3 i-Pr
95 Qio H N(Me)C(=0)NHCH2CF3 CH2CF3
96 Qio H N(Me)2 H
97 Qio H N(Me)2 Me 98 Qio H N(Me)2 Et
99 Qio H N(Me)2 i-Pr
100 Qio H N(Me)2 CH2CF3
101 Qio H N(Me)(Et) H
102 Qio H N(Me)(Et) Me
103 Qio H N(Me)(Et) Et
104 Qio H N(Me)(Et) i-Pr
105 Qio H N(Me)(Et) CH2CF3
106 Qio H N(Et)2 NH2
107 Qio H N(Et)2 NHMe
108 Qio H N(Et)2 NHEt
109 Qio H N(Et)2 NH-i-Pr
1 10 Qio H N(Et)2 CH2CF3
1 1 1 Qio H OH NH2
1 12 Qio H OH NHMe
1 13 Qio H OH NH-i-Pr
1 14 Qio H OH NHCH2CF3
1 15 Qio H OH N(Me)2
1 16 Qio H OH N(Me)(Et)
1 17 Qio H OH N(Et)2
1 18 Qio H OMe NH2
1 19 Qio H OMe NHMe
120 Qio H OMe NH-i-Pr
121 Qio H OMe NHCH2CF3
122 Qio H OMe N(Me)2
123 Qio H OMe N(Me)(Et)
124 Qio H OMe N(Et)2
125 Qio H OEt NH2
126 Qio H OEt NHMe
127 Qio H OEt NH-i-Pr
128 Qio H OEt NHCH2CF3
129 Qio H OEt N(Me)2
130 Qio H OEt N(Me)(Et)
131 Qio H OEt N(Et)2
132 Qio H O-c-Pr NH2
133 Qio H O-c-Pr NHMe
Figure imgf000032_0001
Figure imgf000033_0001
Figure imgf000034_0001
242 Qio Me N(Me)C(=0)NHMe CH2CF3
243 Qio Me N(Me)C(=0)NHCH2CF3 H
244 Qio Me N(Me)C(=0)NHCH2CF3 Me
245 Qio Me N(Me)C(=0)NHCH2CF3 Et
246 Qio Me N(Me)C(=0)NHCH2CF3 i-Pr
247 Qio Me N(Me)C(=0)NHCH2CF3 CH2CF3
248 Qio Me N(Me)2 H
249 Qio Me N(Me)2 Me
250 Qio Me N(Me)2 Et
251 Qio Me N(Me)2 i-Pr
252 Qio Me N(Me)2 CH2CF3
253 Qio Me N(Me)(Et) H
254 Qio Me N(Me)(Et) Me
255 Qio Me N(Me)(Et) Et
256 Qio Me N(Me)(Et) i-Pr
257 Qio Me N(Me)(Et) CH2CF3
258 Qio Me N(Et)2 NH2
259 Qio Me N(Et)2 NHMe
260 Qio Me N(Et)2 NHEt
261 Qio Me N(Et)2 NH-i-Pr
262 Qio Me N(Et)2 CH2CF3
263 Qio Me OH NH2
264 Qio Me OH NHMe
265 Qio Me OH NH-i-Pr
266 Qio Me OH NHCH2CF3
267 Qio Me OH N(Me)2
268 Qio Me OH N(Me)(Et)
269 Qio Me OH N(Et)2
270 Qio Me OMe NH2
271 Qio Me OMe NHMe
272 Qio Me OMe NH-i-Pr
273 Qio Me OMe NHCH2CF3
274 Qio Me OMe N(Me)2
275 Qio Me OMe N(Me)(Et)
276 Qio Me OMe N(Et)2
277 Qio Me OEt NH2
Figure imgf000036_0001
Figure imgf000037_0001
Figure imgf000038_0001
Figure imgf000039_0001
Figure imgf000040_0001
Figure imgf000041_0001
Figure imgf000042_0001
Figure imgf000043_0001
Figure imgf000044_0001
Figure imgf000045_0001
Further preferred are compounds of formulae (1-2-1 ) to (1-8-15) where Ra' has the meanings given in Table B1 to B9.
Figure imgf000045_0002
With respect to their use, particular preference is given to the compounds of formulae (1-2-1 ) to (1-8-15) compiled in the tables C1 to C262 below. Moreover, the groups mentioned for a substit- uent in the tables are on their own, independently of the combination in which they are men- tioned, a particularly preferred embodiment of the substituent in question.
Table C1
Compounds of formula (1-2-1 ) wherein Ra' denotes B1 and Q1, Ra", RA and RB in each case correspond to a row of Table A.
Table C2
Compounds of formula (1-2-1 ) wherein Ra' denotes B2 and Q1, Ra", RA and RB in each case correspond to a row of Table A.
Table C3
Compounds of formula (1-2-1 ) wherein Ra' denotes B3 and Q1, Ra", RA and RB in each case correspond to a row of Table A.
Table C4
Compounds of formula (1-2-1 ) wherein Ra' denotes B4 and Q1, Ra", RA and RB in each case correspond to a row of Table A.
Table C5 Compounds of formula (1-2-1 ) wherein Ra' denotes B5 and Q1, Ra", RA and RB in each case correspond to a row of Table A.
Table C6
Compounds of formula (1-2-1 ) wherein Ra' denotes B6 and Q1,Ra", RA and RB in each case cor- respond to a row of Table A.
Table C7
Compounds of formula (1-2-1 ) wherein Ra' denotes B7 and Q1, Ra", RA and RB in each case correspond to a row of Table A.
Table C8
Compounds of formula (1-2-1 ) wherein Ra' denotes B8 and Q1, Ra", RA and RB in each case correspond to a row of Table A.
Table C9
Compounds of formula (1-2-1 ) wherein Ra' denotes B9 and Q1, Ra", RA and RB in each case correspond to a row of Table A.
Table C10
Compounds of formula (I-2-2) wherein Ra' denotes B2 and Q1, Ra", RA and RB in each case correspond to a row of Table A.
Table C1 1
Compounds of formula (I-2-2 wherein Ra' denotes B3 and Q1, Ra", RA and RB in each case cor- respond to a row of Table A.
Table C12
Compounds of formula (I-2-2) wherein Ra' denotes B4 and Q1, Ra", RA and RB in each case correspond to a row of Table A.
Table C13
Compounds of formula (I-2-2) wherein Ra' denotes B5 and Q1, Ra", RA and RB in each case correspond to a row of Table A.
Table C14
Compounds of formula (I-2-2) wherein Ra' denotes B6 and Q1, Ra", RA and RB in each case correspond to a row of Table A.
Table C15
Compounds of formula (I-2-2) wherein Ra' denotes B7 and Q1, Ra", RA and RB in each case correspond to a row of Table A.
Table C16
Compounds of formula (I-2-2) wherein Ra' denotes B8 and Q1, Ra", RA and RB in each case correspond to a row of Table A.
Table C17
Compounds of formula (I-2-2) wherein Ra' denotes B9 and Q1, Ra", RA and RB in each case correspond to a row of Table A.
Table C18
Compounds of formula (I-2-3) wherein Ra' denotes B2 and Q1, Ra", RA and RB in each case correspond to a row of Table A.
Table C19
Compounds of formula (I-2-3) wherein Ra' denotes B3 and Q1, Ra", RA and RB in each case correspond to a row of Table A. Table C20
Compounds of formula (1-2-3) wherein Ra' denotes B4 and Q1, Ra", RA and RB in each case correspond to a row of Table A.
Table C21
Compounds of formula (I-2-3) wherein Ra' denotes B5 and Q1, Ra", RA and RB in each case correspond to a row of Table A.
Table C22
Compounds of formula (I-2-3) wherein Ra' denotes B6 and Q1, Ra", RA and RB in each case correspond to a row of Table A.
Table C23
Compounds of formula (I-2-3) wherein Ra' denotes B7 and Q1, Ra", RA and RB in each case correspond to a row of Table A.
Table C24
Compounds of formula (I-2-3) wherein Ra' denotes B8 and Q , Ra", RA and RB in each case correspond to a row of Table A.
Table C25
Compounds of formula (I-2-3) wherein Ra' denotes B9 and Q1, Ra", RA and RB in each case correspond to a row of Table A.
Table C26
Compounds of formula (I-2-4) wherein Ra' denotes B2 and Q1, Ra", RA and RB in each case correspond to a row of Table A.
Table C27
Compounds of formula (I-2-4) wherein Ra' denotes B3 and Q1, Ra", RA and RB in each case correspond to a row of Table A.
Table C28
Compounds of formula (I-2-4) wherein Ra' denotes B4 and Q1, Ra", RA and RB in each case correspond to a row of Table A.
Table C29
Compounds of formula (I-2-4) wherein Ra' denotes B5 and Q1, Ra", RA and RB in each case correspond to a row of Table A.
Table C30
Compounds of formula (I-2-4) wherein Ra' denotes B6 and Q1, Ra", RA and RB in each case correspond to a row of Table A.
Table C31
Compounds of formula (I-2-4) wherein Ra' denotes B7 and Q1, Ra", RA and RB in each case correspond to a row of Table A.
Table C32
Compounds of formula (I-2-4) wherein Ra' denotes B8 and Q1, Ra", RA and RB in each case correspond to a row of Table A.
Table C33
Compounds of formula (I-2-4) wherein Ra' denotes B9 and Q1, Ra", RA and RB in each case correspond to a row of Table A.
Table C34 Compounds of formula (1-2-5) wherein Ra' denotes B1 and Q1, Ra", RA and RB in each case correspond to a row of Table A.
Table C35
Compounds of formula (I-2-5) wherein Ra' denotes B2 and Q1, Ra", RA and RB in each case correspond to a row of Table A.
Table C36
Compounds of formula (I-2-5) wherein Ra' denotes B3 and Q1, Ra", RA and RB in each case correspond to a row of Table A.
Table C37
Compounds of formula (I-2-5) wherein Ra' denotes B4 and Q1, Ra", RA and RB in each case correspond to a row of Table A.
Table C38
Compounds of formula (I-2-5) wherein Ra' denotes B5 and Q1, Ra", RA and RB in each case correspond to a row of Table A.
Table C39
Compounds of formula (I-2-5) wherein Ra' denotes B6 and Q1, Ra", RA and RB in each case correspond to a row of Table A.
Table C40
Compounds of formula (I-2-5) wherein Ra' denotes B7 and Q1, Ra", RA and RB in each case correspond to a row of Table A.
Table C41
Compounds of formula (I-2-5) wherein Ra' denotes B8 and Q1, Ra", RA and RB in each case correspond to a row of Table A.
Table C42
Compounds of formula (I-2-5) wherein Ra' denotes B9 and Q1, Ra", RA and RB in each case correspond to a row of Table A.
Table C43
Compounds of formula (I-2-6) wherein Ra' denotes B2 and Q1, Ra", RA and RB in each case correspond to a row of Table A.
Table C44
Compounds of formula (I-2-6) wherein Ra' denotes B3 and Q1, Ra", RA and RB in each case correspond to a row of Table A.
Table C45
Compounds of formula (I-2-6) wherein Ra' denotes B4 and Q1, Ra", RA and RB in each case correspond to a row of Table A.
Table C46
Compounds of formula (I-2-6) wherein Ra' denotes B5 and Q1, Ra", RA and RB in each case correspond to a row of Table A.
Table C47
Compounds of formula (I-2-6) wherein Ra' denotes B6 and Q1, Ra", RA and RB in each case correspond to a row of Table A.
Table C48
Compounds of formula (I-2-6) wherein Ra' denotes B7 and Q\ Ra", RA and RB in each case correspond to a row of Table A. Table C49
Compounds of formula (1-2-6) wherein Ra' denotes B8 and Q1, Ra", RA and RB in each case correspond to a row of Table A.
Table C50
Compounds of formula (I-2-6) wherein Ra' denotes B9 and Q1, Ra", RA and RB in each case correspond to a row of Table A.
Table C51
Compounds of formula (I-2-7) wherein Ra' denotes B1 and Q1, Ra", RA and RB in each case correspond to a row of Table A.
Table C52
Compounds of formula (I-2-7) wherein Ra' denotes B2 and Q1, Ra", RA and RB in each case correspond to a row of Table A.
Table C53
Compounds of formula (I-2-7) wherein Ra' denotes B3 and Q1, Ra", RA and RB in each case correspond to a row of Table A.
Table C54
Compounds of formula (I-2-7) wherein Ra' denotes B4 and Q1, Ra", RA and RB in each case correspond to a row of Table A.
Table C55
Compounds of formula (I-2-7) wherein Ra' denotes B5 and Q1, Ra", RA and RB in each case correspond to a row of Table A.
Table C56
Compounds of formula (I-2-7) wherein Ra' denotes B6 and Q1,Ra", RA and RB in each case correspond to a row of Table A.
Table C57
Compounds of formula (I-2-7) wherein Ra' denotes B7 and Q1, Ra", RA and RB in each case correspond to a row of Table A.
Table C58
Compounds of formula (I-2-7) wherein Ra' denotes B8 and Q1, Ra", RA and RB in each case correspond to a row of Table A.
Table C59
Compounds of formula (I-2-7) wherein Ra' denotes B9 and Q1, Ra", RA and RB in each case correspond to a row of Table A.
Table C60
Compounds of formula (I-2-8) wherein Ra' denotes B2 and Q1, Ra", RA and RB in each case correspond to a row of Table A.
Table C61
Compounds of formula (I-2-8) wherein Ra' denotes B3 and Q1, Ra", RA and RB in each case correspond to a row of Table A.
Table C62
Compounds of formula (I-2-8) wherein Ra' denotes B4 and Q1, Ra", RA and RB in each case correspond to a row of Table A.
Table C63 Compounds of formula (1-2-8) wherein Ra' denotes B5 and Q1, Ra", RA and RB in each case correspond to a row of Table A.
Table C64
Compounds of formula (I-2-8) wherein Ra' denotes B6 and Q1, Ra", RA and RB in each case correspond to a row of Table A.
Table C65
Compounds of formula (I-2-8) wherein Ra' denotes B7 and Q1, Ra", RA and RB in each case correspond to a row of Table A.
Table C66
Compounds of formula (I-2-8) wherein Ra' denotes B8 and Q1, Ra", RA and RB in each case correspond to a row of Table A.
Table C67
Compounds of formula (I-2-8) wherein Ra' denotes B9 and Q1, Ra", RA and RB in each case correspond to a row of Table A.
Table C68
Compounds of formula (I-2-9) wherein Ra' denotes B2 and Q1, Ra", RA and RB in each case correspond to a row of Table A.
Table C69
Compounds of formula (I-2-9) wherein Ra' denotes B3 and Q1, Ra", RA and RB in each case correspond to a row of Table A.
Table C70
Compounds of formula (I-2-9) wherein Ra' denotes B4 and Q1, Ra", RA and RB in each case correspond to a row of Table A.
Table C71
Compounds of formula (I-2-9) wherein Ra' denotes B5 and Q1, Ra", RA and RB in each case correspond to a row of Table A.
Table C72
Compounds of formula (I-2-9) wherein Ra' denotes B6 and Q1, Ra", RA and RB in each case correspond to a row of Table A.
Table C73
Compounds of formula (I-2-9) wherein Ra' denotes B7 and Q1, Ra", RA and RB in each case correspond to a row of Table A.
Table C74
Compounds of formula (I-2-9) wherein Ra' denotes B8 and Q1, Ra", RA and RB in each case correspond to a row of Table A.
Table C75
Compounds of formula (I-2-9) wherein Ra' denotes B9 and Q1, Ra", RA and RB in each case correspond to a row of Table A.
Compounds of formula (1-2-10) wherein Ra' denotes B2 and Q1, Ra", RA and RB in each case correspond to a row of Table A.
Table C76
Compounds of formula (1-2-10) wherein Ra' denotes B3 and Q1, Ra", RA and RB in each case correspond to a row of Table A.
Table C77 Compounds of formula (1-2-10) wherein Ra' denotes B4 and Q1, Ra", RA and RB in each case correspond to a row of Table A.
Table C78
Compounds of formula (1-2-10) wherein Ra' denotes B5 and Q1, Ra", RA and RB in each case correspond to a row of Table A.
Table C79
Compounds of formula (1-2-10) wherein Ra' denotes B6 and Q1, Ra", RA and RB in each case correspond to a row of Table A.
Table C80
Compounds of formula (1-2-10) wherein Ra' denotes B7 and Q1, Ra", RA and RB in each case correspond to a row of Table A.
Table C81
Compounds of formula (1-2-10) wherein Ra' denotes B8 and Q1, Ra", RA and RB in each case correspond to a row of Table A.
Table C82
Compounds of formula (1-2-10) wherein Ra' denotes B9 and Q1, Ra", RA and RB in each case correspond to a row of Table A.
Table C83
Compounds of formula (1-2-1 1 ) wherein Ra' denotes B1 and Q1, Ra", RA and RB in each case correspond to a row of Table A.
Table C84
Compounds of formula (1-2-1 1 ) wherein Ra' denotes B2 and Q1, Ra", RA and RB in each case correspond to a row of Table A.
Table C85
Compounds of formula (1-2-1 1 ) wherein Ra' denotes B3 and Q1, Ra", RA and RB in each case correspond to a row of Table A.
Table C86
Compounds of formula (1-2-1 1 ) wherein Ra' denotes B4 and Q1, Ra", RA and RB in each case correspond to a row of Table A.
Table C87
Compounds of formula (1-2-1 1 ) wherein Ra' denotes B5 and Q1, Ra", RA and RB in each case correspond to a row of Table A.
Table C88
Compounds of formula (1-2-1 1 ) wherein Ra' denotes B6 and Q1, Ra", RA and RB in each case correspond to a row of Table A.
Table C89
Compounds of formula (1-2-1 1 ) wherein Ra' denotes B7 and Q1, Ra", RA and RB in each case correspond to a row of Table A.
Table C90
Compounds of formula (1-2-1 1 ) wherein Ra' denotes B8 and Q1, Ra", RA and RB in each case correspond to a row of Table A.
Table C91
Compounds of formula (1-2-11 ) wherein Ra' denotes B9 and Q\ Ra", RA and RB in each case correspond to a row of Table A. Table C92
Compounds of formula (1-2-12) wherein Ra' denotes B2 and Q1, Ra", RA and RB in each case correspond to a row of Table A.
Table C93
Compounds of formula (1-2-12) wherein Ra' denotes B3 and Q1, Ra", RA and RB in each case correspond to a row of Table A.
Table C94
Compounds of formula (1-2-12) wherein Ra' denotes B4 and Q1, Ra", RA and RB in each case correspond to a row of Table A.
Table C95
Compounds of formula (1-2-12) wherein Ra' denotes B5 and Q1, Ra", RA and RB in each case correspond to a row of Table A.
Table C96
Compounds of formula (1-2-12) wherein Ra' denotes B6 and Q1, Ra", RA and RB in each case correspond to a row of Table A.
Table C97
Compounds of formula (1-2-12) wherein Ra' denotes B7 and Q1, Ra", RA and RB in each case correspond to a row of Table A.
Table C98
Compounds of formula (1-2-12) wherein Ra' denotes B8 and Q1, Ra", RA and RB in each case correspond to a row of Table A.
Table C99
Compounds of formula (1-2-12) wherein Ra' denotes B9 and Q1, Ra", RA and RB in each case correspond to a row of Table A.
Table C100
Compounds of formula (1-2-13) wherein Ra' denotes B2 and Q1, Ra", RA and RB in each case correspond to a row of Table A.
Table C101
Compounds of formula (1-2-13) wherein Ra' denotes B3 and Q1, Ra", RA and RB in each case correspond to a row of Table A.
Table d 02
Compounds of formula (1-2-13) wherein Ra' denotes B4 and Q1, Ra", RA and RB in each case correspond to a row of Table A.
Table C103
Compounds of formula (1-2-13) wherein Ra' denotes B5 and Q1, Ra", RA and RB in each case correspond to a row of Table A.
Table C104
Compounds of formula (1-2-13) wherein Ra' denotes B6 and Q1, Ra", RA and RB in each case correspond to a row of Table A.
Table C105
Compounds of formula (1-2-13) wherein Ra' denotes B7 and Q , Ra", RA and RB in each case correspond to a row of Table A.
Table C106 Compounds of formula (1-2-13) wherein Ra' denotes B8 and Q1, Ra", RA and RB in each case correspond to a row of Table A.
Table C107
Compounds of formula (1-2-13) wherein Ra' denotes B9 and Q1, Ra", RA and RB in each case correspond to a row of Table A.
Table C108
Compounds of formula (1-5-1 ) wherein Ra' denotes B1 and Q1, Ra", RA and RB in each case correspond to a row of Table A.
Table C109
Compounds of formula (1-5-1 ) wherein Ra' denotes B2 and Q1, Ra", RA and RB in each case correspond to a row of Table A.
Table d 10
Compounds of formula (1-5-1 ) wherein Ra' denotes B3 and Q1, Ra", RA and RB in each case correspond to a row of Table A.
Table d 1 1
Compounds of formula (1-5-1 ) wherein Ra' denotes B4 and Q1, Ra", RA and RB in each case correspond to a row of Table A.
Table d 12
Compounds of formula (1-5-1 ) wherein Ra' denotes B5 and Q1, Ra", RA and RB in each case correspond to a row of Table A.
Table d 13
Compounds of formula (1-5-1 ) wherein Ra' denotes B6 and Q1, Ra", RA and RB in each case correspond to a row of Table A.
Table d 14
Compounds of formula (1-5-1 ) wherein Ra' denotes B7 and Q1, Ra", RA and RB in each case correspond to a row of Table A.
Table d 15
Compounds of formula (1-5-1 ) wherein Ra' denotes B8 and Q1, Ra", RA and RB in each case correspond to a row of Table A.
Table d 16
Compounds of formula (1-5-1 ) wherein Ra' denotes B9 and Q1, Ra", RA and RB in each case correspond to a row of Table A.
Table d 17
Compounds of formula (I-5-2) wherein Ra' denotes B2 and Q1, Ra", RA and RB in each case correspond to a row of Table A.
Table d 18
Compounds of formula (I-5-2) wherein Ra' denotes B3 and Q1, Ra", RA and RB in each case correspond to a row of Table A.
Table d 19
Compounds of formula (I-5-2) wherein Ra' denotes B4 and Q1, Ra", RA and RB in each case correspond to a row of Table A.
Table C120 Compounds of formula (1-5-2) wherein Ra' denotes B5 and Q1, Ra", RA and RB in each case correspond to a row of Table A.
Table C121
Compounds of formula (I-5-2) wherein Ra' denotes B6 and Q1, Ra", RA and RB in each case correspond to a row of Table A.
Table C122
Compounds of formula (I-5-2) wherein Ra' denotes B7 and Q1, Ra", RA and RB in each case correspond to a row of Table A.
Table C123
Compounds of formula (I-5-2) wherein Ra' denotes B8 and Q1, Ra", RA and RB in each case correspond to a row of Table A.
Table C124
Compounds of formula (I-5-2) wherein Ra' denotes B9 and Q1, Ra", RA and RB in each case correspond to a row of Table A.
Table C125
Compounds of formula (I-5-3) wherein Ra' denotes B2 and Q , Ra", RA and RB in each case correspond to a row of Table A.
Table C126
Compounds of formula (I-5-3) wherein Ra' denotes B3 and Q1, Ra", RA and RB in each case correspond to a row of Table A.
Table C127
Compounds of formula (I-5-3) wherein Ra' denotes B4 and Q1, Ra", RA and RB in each case correspond to a row of Table A.
Table C128
Compounds of formula (I-5-3) wherein Ra' denotes B5 and Q1, Ra", RA and RB in each case correspond to a row of Table A.
Table C129
Compounds of formula (I-5-3) wherein Ra' denotes B6 and Q1, Ra", RA and RB in each case correspond to a row of Table A.
Table d 30
Compounds of formula (I-5-3) wherein Ra' denotes B7 and Q1, Ra", RA and RB in each case correspond to a row of Table A.
Table C131
Compounds of formula (I-5-3) wherein Ra' denotes B8 and Q1, Ra", RA and RB in each case correspond to a row of Table A.
Table C132
Compounds of formula (I-5-3) wherein Ra' denotes B9 and Q1, Ra", RA and RB in each case correspond to a row of Table A.
Table C133
Compounds of formula (I-5-4) wherein Ra' denotes B2 and Q1, Ra", RA and RB in each case correspond to a row of Table A.
Table C134
Compounds of formula (I-5-4) wherein Ra' denotes B3 and Q1, Ra", RA and RB in each case correspond to a row of Table A. Table C135
Compounds of formula (I-5-4) wherein Ra' denotes B4 and Q , Ra", RA and RB in each case correspond to a row of Table A.
Table C136
Compounds of formula (I-5-4) wherein Ra' denotes B5 and Q1, Ra", RA and RB in each case correspond to a row of Table A.
Table C137
Compounds of formula (I-5-4) wherein Ra' denotes B6 and Q1, Ra", RA and RB in each case correspond to a row of Table A.
Table d 38
Compounds of formula (I-5-4) wherein Ra' denotes B7 and Q1, Ra", RA and RB in each case correspond to a row of Table A.
Table C139
Compounds of formula (I-5-4) wherein Ra' denotes B8 and Q1, Ra", RA and RB in each case correspond to a row of Table A.
Table C140
Compounds of formula (I-5-4) wherein Ra' denotes B9 and Q1, Ra", RA and RB in each case correspond to a row of Table A.
Table C141
Compounds of formula (I-5-5) wherein Ra' denotes B2 and Q1, Ra", RA and RB in each case correspond to a row of Table A.
Table C142
Compounds of formula (I-5-5) wherein Ra' denotes B3 and Q1, Ra", RA and RB in each case correspond to a row of Table A.
Table C143
Compounds of formula (I -5-5) wherein Ra' denotes B4 and Q1, Ra", RA and RB in each case correspond to a row of Table A.
Table C144
Compounds of formula (I-5-5) wherein Ra' denotes B5 and Q1, Ra", RA and RB in each case correspond to a row of Table A.
Table C145
Compounds of formula (I-5-5) wherein Ra' denotes B6 and Q1, Ra", RA and RB in each case correspond to a row of Table A.
Table C146
Compounds of formula (I-5-5) wherein Ra' denotes B7 and Q1, Ra", RA and RB in each case correspond to a row of Table A.
Table C147
Compounds of formula (I-5-5) wherein Ra' denotes B8 and Q1, Ra", RA and RB in each case correspond to a row of Table A.
Table C148
Compounds of formula (I-5-5) wherein Ra' denotes B9 and Q1, Ra", RA and RB in each case correspond to a row of Table A.
Table C149 Compounds of formula (1-5-6) wherein Ra' denotes B2 and Q1, Ra", RA and RB in each case correspond to a row of Table A.
Table C150
Compounds of formula (I-5-6) wherein Ra' denotes B3 and Q1, Ra", RA and RB in each case correspond to a row of Table A.
Table C151
Compounds of formula (I-5-6) wherein Ra' denotes B4 and Q1, Ra", RA and RB in each case correspond to a row of Table A.
Table C152
Compounds of formula (I-5-6) wherein Ra' denotes B5 and Q1, Ra", RA and RB in each case correspond to a row of Table A.
Table C153
Compounds of formula (I-5-6) wherein Ra' denotes B6 and Q1, Ra", RA and RB in each case correspond to a row of Table A.
Table d 54
Compounds of formula (I-5-6) wherein Ra' denotes B7 and Q1, Ra", RA and RB in each case correspond to a row of Table A.
Table C155
Compounds of formula (I-5-6) wherein Ra' denotes B8 and Q1, Ra", RA and RB in each case correspond to a row of Table A.
Table C156
Compounds of formula (I-5-6) wherein Ra' denotes B9 and Q1, Ra", RA and RB in each case correspond to a row of Table A.
Table d 57
Compounds of formula (I-5-7) wherein Ra' denotes B2 and Q1, Ra", RA and RB in each case correspond to a row of Table A.
Table 58
Compounds of formula (I-5-7) wherein Ra' denotes B3 and Q1, Ra", RA and RB in each case correspond to a row of Table A.
Table d 59
Compounds of formula (I-5-7) wherein Ra' denotes B4 and Q1, Ra", RA and RB in each case correspond to a row of Table A.
Table d 60
Compounds of formula (I-5-7) wherein Ra' denotes B5 and Q1, Ra", RA and RB in each case correspond to a row of Table A.
Table C161
Compounds of formula (I-5-7) wherein Ra' denotes B6 and Q1, Ra", RA and RB in each case correspond to a row of Table A.
Table d 62
Compounds of formula (I-5-7) wherein Ra' denotes B7 and Q1, Ra", RA and RB in each case correspond to a row of Table A. Table d 63
Compounds of formula (1-5-7) wherein Ra' denotes B8 and Q1, Ra", RA and RB in each case correspond to a row of Table A.
Table d 64
Compounds of formula (I-5-7) wherein Ra' denotes B9 and Q1, Ra", RA and RB in each case correspond to a row of Table A.
Table d 65
Compounds of formula (I-5-8) wherein Ra' denotes B2 and Q1, Ra", RA and RB in each case correspond to a row of Table A.
Table d 66
Compounds of formula (I-5-8) wherein Ra' denotes B3 and Q1, Ra", RA and RB in each case correspond to a row of Table A.
Table d 67
Compounds of formula (I-5-8) wherein Ra' denotes B4 and Q1, Ra", RA and RB in each case correspond to a row of Table A.
Table d 68
Compounds of formula (I-5-8) wherein Ra' denotes B5 and Q1, Ra", RA and RB in each case correspond to a row of Table A.
Table d 69
Compounds of formula (I-5-8) wherein Ra' denotes B6 and Q1, Ra", RA and RB in each case correspond to a row of Table A.
Table d 70
Compounds of formula (I-5-8) wherein Ra' denotes B7 and Q1, Ra", RA and RB in each case correspond to a row of Table A.
Table C171
Compounds of formula (I-5-8) wherein Ra' denotes B8 and Q1, Ra", RA and RB in each case correspond to a row of Table A.
Table C172
Compounds of formula (I-5-8) wherein Ra' denotes B9 and Q1, Ra", RA and RB in each case correspond to a row of Table A.
Table C173
Compounds of formula (I-5-3) wherein Ra' denotes B2 and Q1, Ra", RA and RB in each case correspond to a row of Table A.
Table C174
Compounds of formula (I-5-9) wherein Ra' denotes B3 and Q1, Ra", RA and RB in each case correspond to a row of Table A.
Table C175
Compounds of formula (I-5-9) wherein Ra' denotes B4 and Q1, Ra", RA and RB in each case correspond to a row of Table A.
Table d 76
Compounds of formula (I-5-9) wherein Ra' denotes B5 and Q1, Ra", RA and RB in each case correspond to a row of Table A.
Table C177 Compounds of formula (1-5-9) wherein Ra' denotes B6 and Q1, Ra", RA and RB in each case correspond to a row of Table A.
Table C178
Compounds of formula (I-5-9) wherein Ra' denotes B7 and Q1, Ra", RA and RB in each case correspond to a row of Table A.
Table C179
Compounds of formula (I-5-9) wherein Ra' denotes B8 and Q1, Ra", RA and RB in each case correspond to a row of Table A.
Table C180
Compounds of formula (I-5-9) wherein Ra' denotes B9 and Q1, Ra", RA and RB in each case correspond to a row of Table A.
Table C181
Compounds of formula (1-5-10) wherein Ra' denotes B2 and Q1, Ra", RA and RB in each case correspond to a row of Table A.
Table d 82
Compounds of formula (1-5-10) wherein Ra' denotes B3 and Q1, Ra", RA and RB in each case correspond to a row of Table A.
Table C183
Compounds of formula (1-5-10) wherein Ra' denotes B4 and Q1, Ra", RA and RB in each case correspond to a row of Table A.
Table C184
Compounds of formula (1-5-10) wherein Ra' denotes B5 and Q1, Ra", RA and RB in each case correspond to a row of Table A.
Table C185
Compounds of formula (1-5-10) wherein Ra' denotes B6 and Q1, Ra", RA and RB in each case correspond to a row of Table A.
Table C186
Compounds of formula (1-5-10) wherein Ra' denotes B7 and Q1, Ra", RA and RB in each case correspond to a row of Table A.
Table d 87
Compounds of formula (1-5-10) wherein Ra' denotes B8 and Q1, Ra", RA and RB in each case correspond to a row of Table A.
Table C188
Compounds of formula (1-5-10) wherein Ra' denotes B9 and Q1, Ra", RA and RB in each case correspond to a row of Table A.
Table C189
Compounds of formula (1-5-1 1 ) wherein Ra' denotes B2 and Q1, Ra", RA and RB in each case correspond to a row of Table A.
Table C190
Compounds of formula (1-5-1 1 ) wherein Ra' denotes B3 and Q1, Ra", RA and RB in each case correspond to a row of Table A.
Table C191
Compounds of formula (1-5-1 1 ) wherein Ra' denotes B4 and Q1, Ra", RA and RB in each case correspond to a row of Table A. Table C192
Compounds of formula (1-5-1 1 ) wherein Ra' denotes B5 and Q1, Ra", RA and RB in each case correspond to a row of Table A.
Table C193
Compounds of formula (1-5-1 1 ) wherein Ra' denotes B6 and Q1, Ra", RA and RB in each case correspond to a row of Table A.
Table C194
Compounds of formula (1-5-1 1 ) wherein Ra' denotes B7 and Q1, Ra", RA and RB in each case correspond to a row of Table A.
Table C195
Compounds of formula (1-5-1 1 ) wherein Ra' denotes B8 and Q1, Ra", RA and RB in each case correspond to a row of Table A.
Table C196
Compounds of formula (1-5-1 1 ) wherein Ra' denotes B9 and Q , Ra", RA and RB in each case correspond to a row of Table A.
Table C197
Compounds of formula (1-5-12) wherein Ra' denotes B2 and Q1, Ra", RA and RB in each case correspond to a row of Table A.
Table C198
Compounds of formula (1-5-12) wherein Ra' denotes B3 and Q1, Ra", RA and RB in each case correspond to a row of Table A.
Table C199
Compounds of formula (1-5-12) wherein Ra' denotes B4 and Q1, Ra", RA and RB in each case correspond to a row of Table A.
Table C200
Compounds of formula (1-5-12) wherein Ra' denotes B5 and Q1, Ra", RA and RB in each case correspond to a row of Table A.
Table C201
Compounds of formula (1-5-12) wherein Ra' denotes B6 and Q1, Ra", RA and RB in each case correspond to a row of Table A.
Table C202
Compounds of formula (1-5-12) wherein Ra' denotes B7 and Q1, Ra", RA and RB in each case correspond to a row of Table A.
Table C203
Compounds of formula (1-5-12) wherein Ra' denotes B8 and Q1, Ra", RA and RB in each case correspond to a row of Table A.
Table C204
Compounds of formula (1-5-12) wherein Ra' denotes B9 and Q1, Ra", RA and RB in each case correspond to a row of Table A.
Table C205
Compounds of formula (1-5-13) wherein Ra' denotes B2 and Q1, Ra", RA and RB in each case correspond to a row of Table A.
Table C206 Compounds of formula (1-5-13) wherein Ra' denotes B3 and Q1, Ra", RA and RB in each case correspond to a row of Table A.
Table C207
Compounds of formula (1-5-13) wherein Ra' denotes B4 and Q1, Ra", RA and RB in each case correspond to a row of Table A.
Table C208
Compounds of formula (1-5-13) wherein Ra' denotes B5 and Q1, Ra", RA and RB in each case correspond to a row of Table A.
Table C209
Compounds of formula (1-5-13) wherein Ra' denotes B6 and Q1, Ra", RA and RB in each case correspond to a row of Table A.
Table C210
Compounds of formula (1-5-13) wherein Ra' denotes B7 and Q1, Ra", RA and RB in each case correspond to a row of Table A.
Table C21 1
Compounds of formula (1-5-13) wherein Ra' denotes B8 and Q1, Ra", RA and RB in each case correspond to a row of Table A.
Table C212
Compounds of formula (1-5-13) wherein Ra' denotes B9 and Q1, Ra", RA and RB in each case correspond to a row of Table A.
Table C213
Compounds of formula (1-5-14) wherein Ra' denotes B2 and Q1, Ra", RA and RB in each case correspond to a row of Table A.
Table C214
Compounds of formula (1-5-14) wherein Ra' denotes B3 and Q1, Ra", RA and RB in each case correspond to a row of Table A.
Table C215
Compounds of formula (1-5-14) wherein Ra' denotes B4 and Q1, Ra", RA and RB in each case correspond to a row of Table A.
Table C216
Compounds of formula (1-5-14) wherein Ra' denotes B5 and Q1, Ra", RA and RB in each case correspond to a row of Table A.
Table C217
Compounds of formula (1-5-14) wherein Ra' denotes B6 and Q1, Ra", RA and RB in each case correspond to a row of Table A.
Table C218
Compounds of formula (1-5-14) wherein Ra' denotes B7 and Q1, Ra", RA and RB in each case correspond to a row of Table A.
Table C219
Compounds of formula (1-5-14) wherein Ra' denotes B8 and Q1, Ra", RA and RB in each case correspond to a row of Table A.
Table C220
Compounds of formula (1-5-14) wherein Ra' denotes B9 and Q1, Ra", RA and RB in each case correspond to a row of Table A. Table C221
Compounds of formula (1-5-15) wherein Ra' denotes B2 and Q1, Ra", RA and RB in each case correspond to a row of Table A.
Table C222
Compounds of formula (1-5-15) wherein Ra' denotes B3 and Q1, Ra", RA and RB in each case correspond to a row of Table A.
Table C223
Compounds of formula (1-5-15) wherein Ra' denotes B4 and Q1, Ra", RA and RB in each case correspond to a row of Table A.
Table C224
Compounds of formula (1-5-15) wherein Ra' denotes B5 and Q1, Ra", RA and RB in each case correspond to a row of Table A.
Table C225
Compounds of formula (1-5-15) wherein Ra' denotes B6 and Q1, Ra", RA and RB in each case correspond to a row of Table A.
Table C226
Compounds of formula (I-5-3) wherein Ra' denotes B7 and Q1, Ra", RA and RB in each case correspond to a row of Table A.
Table C227
Compounds of formula (1-5-15) wherein Ra' denotes B8 and Q1, Ra", RA and RB in each case correspond to a row of Table A.
Table C228
Compounds of formula (1-5-15) wherein Ra' denotes B9 and Q1, Ra", RA and RB in each case correspond to a row of Table A.
Table C229
Compounds of formula (1-5-16) wherein Ra' denotes B2 and Q1, Ra", RA and RB in each case correspond to a row of Table A.
Table C230
Compounds of formula (1-5-16) wherein Ra' denotes B3 and Q1, Ra", RA and RB in each case correspond to a row of Table A.
Table C231
Compounds of formula (1-5-16) wherein Ra' denotes B4 and Q1, Ra", RA and RB in each case correspond to a row of Table A.
Table C232
Compounds of formula (1-5-16) wherein Ra' denotes B5 and Q1, Ra", RA and RB in each case correspond to a row of Table A.
Table C233
Compounds of formula (1-5-16) wherein Ra' denotes B6 and Q1, Ra", RA and RB in each case correspond to a row of Table A.
Table C234
Compounds of formula (1-5-16) wherein Ra' denotes B7 and Q1, Ra", RA and RB in each case correspond to a row of Table A.
Table C235 Compounds of formula (1-5-16) wherein Ra' denotes B8 and Q1, Ra", RA and RB in each case correspond to a row of Table A.
Table C236
Compounds of formula (1-5-16) wherein Ra' denotes B9 and Q1, Ra", RA and RB in each case correspond to a row of Table A.
Table C237
Compounds of formula (1-5-17) wherein Ra' denotes B2 and Q1, Ra", RA and RB in each case correspond to a row of Table A.
Table C238
Compounds of formula (1-5-17) wherein Ra' denotes B3 and Q1, Ra", RA and RB in each case correspond to a row of Table A.
Table C239
Compounds of formula (1-5-17) wherein Ra' denotes B4 and Q1, Ra", RA and RB in each case correspond to a row of Table A.
Table C240
Compounds of formula (1-5-17) wherein Ra' denotes B5 and Q1, Ra", RA and RB in each case correspond to a row of Table A.
Table C241
Compounds of formula (1-5-17) wherein Ra' denotes B6 and Q1, Ra", RA and RB in each case correspond to a row of Table A.
Table C242
Compounds of formula (1-5-17) wherein Ra' denotes B7 and Q1, Ra", RA and RB in each case correspond to a row of Table A.
Table C243
Compounds of formula (1-5-17) wherein Ra' denotes B8 and Q1, Ra", RA and RB in each case correspond to a row of Table A.
Table C244
Compounds of formula (1-5-17) wherein Ra' denotes B9 and Q1, Ra", RA and RB in each case correspond to a row of Table A.
Table C245
Compounds of formula (1-5-18) wherein Ra' denotes B2 and Q1, Ra", RA and RB in each case correspond to a row of Table A.
Table C246
Compounds of formula (1-5-18) wherein Ra' denotes B3 and Q1, Ra", RA and RB in each case correspond to a row of Table A.
Table C247
Compounds of formula (1-5-18) wherein Ra' denotes B4 and Q1, Ra", RA and RB in each case correspond to a row of Table A.
Table C248
Compounds of formula (1-5-18) wherein Ra' denotes B5 and Q1, Ra", RA and RB in each case correspond to a row of Table A.
Table C249
Compounds of formula (1-5-18) wherein Ra' denotes B6 and Q1, Ra", RA and RB in each case correspond to a row of Table A. Table C250
Compounds of formula (1-5-18) wherein Ra' denotes B7 and Q1, Ra", RA and RB in each case correspond to a row of Table A.
Table C251
Compounds of formula (1-5-18) wherein Ra' denotes B8 and Q1, Ra", RA and RB in each case correspond to a row of Table A.
Table C252
Compounds of formula (1-5-18) wherein Ra' denotes B9 and Q1, Ra", RA and RB in each case correspond to a row of Table A.
Table C253
Compounds of formula (1-5-19) wherein Ra' denotes B2 and Q1, Ra", RA and RB in each case correspond to a row of Table A.
Table C254
Compounds of formula (1-5-19) wherein Ra' denotes B3 and Q , Ra", RA and RB in each case correspond to a row of Table A.
Table C255
Compounds of formula (1-5-19) wherein Ra' denotes B4 and Q1, Ra", RA and RB in each case correspond to a row of Table A.
Table C256
Compounds of formula (1-5-19) wherein Ra' denotes B5 and Q1, Ra", RA and RB in each case correspond to a row of Table A.
Table C257
Compounds of formula (1-5-19) wherein Ra' denotes B6 and Q1, Ra", RA and RB in each case correspond to a row of Table A.
Table C258
Compounds of formula (1-5-19) wherein Ra' denotes B7 and Q1, Ra", RA and RB in each case correspond to a row of Table A.
Table C259
Compounds of formula (1-5-19) wherein Ra' denotes B8 and Q1, Ra", RA and RB in each case correspond to a row of Table A.
Table C260
Compounds of formula (1-5-19) wherein Ra' denotes B9 and Q1, Ra", RA and RB in each case correspond to a row of Table A.
Table C261
Compounds of formula (I-5-20) wherein Ra' denotes B2 and Q1, Ra", RA and RB in each case correspond to a row of Table A.
Table C262
Compounds of formula (I-5-20) wherein Ra' denotes B3 and Q1, Ra", RA and RB in each case correspond to a row of Table A.
Table C263
Compounds of formula (I-5-20) wherein Ra' denotes B4 and Q1, Ra", RA and RB in each case correspond to a row of Table A.
Table C264 Compounds of formula (1-5-20) wherein Ra' denotes B5 and Q1, Ra", RA and RB in each case correspond to a row of Table A.
Table C265
Compounds of formula (I-5-20) wherein Ra' denotes B6 and Q1, Ra", RA and RB in each case correspond to a row of Table A.
Table C266
Compounds of formula (I-5-20) wherein Ra' denotes B7 and Q1, Ra", RA and RB in each case correspond to a row of Table A.
Table C267
Compounds of formula (I-5-20) wherein Ra' denotes B8 and Q1, Ra", RA and RB in each case correspond to a row of Table A.
Table C268
Compounds of formula (I-5-20) wherein Ra' denotes B9 and Q1, Ra", RA and RB in each case correspond to a row of Table A.
Table C269
Compounds of formula (1-5-21 ) wherein Ra' denotes B2 and Q , Ra", RA and RB in each case correspond to a row of Table A.
Table C270
Compounds of formula (1-5-21 ) wherein Ra' denotes B3 and Q1, Ra", RA and RB in each case correspond to a row of Table A.
Table C271
Compounds of formula (1-5-21 ) wherein Ra' denotes B4 and Q1, Ra", RA and RB in each case correspond to a row of Table A.
Table C272
Compounds of formula (1-5-21 ) wherein Ra' denotes B5 and Q1, Ra", RA and RB in each case correspond to a row of Table A.
Table C273
Compounds of formula (1-5-21 ) wherein Ra' denotes B6 and Q1, Ra", RA and RB in each case correspond to a row of Table A.
Table C274
Compounds of formula (1-5-21 ) wherein Ra' denotes B7 and Q1, Ra", RA and RB in each case correspond to a row of Table A.
Table C275
Compounds of formula (1-5-21 ) wherein Ra' denotes B8 and Q1, Ra", RA and RB in each case correspond to a row of Table A.
Table C276
Compounds of formula (1-5-21 ) wherein Ra' denotes B9 and Q1, Ra", RA and RB in each case correspond to a row of Table A.
Table C277
Compounds of formula (I-5-22) wherein Ra' denotes B1 and Q1, Ra", RA and RB in each case correspond to a row of Table A.
Table C278
Compounds of formula (I-5-22) wherein Ra' denotes B2 and Q1, Ra", RA and RB in each case correspond to a row of Table A. Table C279
Compounds of formula (1-5-22) wherein Ra' denotes B3 and Q1, Ra", RA and RB in each case correspond to a row of Table A.
Table C280
Compounds of formula (I-5-22) wherein Ra' denotes B4 and Q1, Ra", RA and RB in each case correspond to a row of Table A.
Table C281
Compounds of formula (I-5-22) wherein Ra' denotes B5 and Q1, Ra", RA and RB in each case correspond to a row of Table A.
Table C282
Compounds of formula (I-5-22) wherein Ra' denotes B6 and Q1, Ra", RA and RB in each case correspond to a row of Table A.
Table C283
Compounds of formula (I-5-22) wherein Ra' denotes B7 and Q1, Ra", RA and RB in each case correspond to a row of Table A.
Table C284
Compounds of formula (I-5-22) wherein Ra' denotes B8 and Q1, Ra", RA and RB in each case correspond to a row of Table A.
Table C285
Compounds of formula (I-5-22) wherein Ra' denotes B9 and Q1, Ra", RA and RB in each case correspond to a row of Table A.
Table C286
Compounds of formula (1-8-1 ) wherein Ra' denotes B1 and Q1, Ra", RA and RB in each case correspond to a row of Table A.
Table C287
Compounds of formula (1-8-1 ) wherein Ra' denotes B2 and Q , Ra", RA and RB in each case correspond to a row of Table A.
Table C288
Compounds of formula (1-8-1 ) wherein Ra' denotes B3 and Q1, Ra", RA and RB in each case correspond to a row of Table A.
Table C289
Compounds of formula (1-8-1 ) wherein Ra' denotes B4 and Q1, Ra", RA and RB in each case correspond to a row of Table A.
Table C290
Compounds of formula (1-8-1 ) wherein Ra' denotes B5 and Q1, Ra", RA and RB in each case correspond to a row of Table A.
Table C291
Compounds of formula (1-8-1 ) wherein Ra' denotes B6 and Q1, Ra", RA and RB in each case correspond to a row of Table A.
Table C292
Compounds of formula (1-8-1 ) wherein Ra' denotes B7 and Q1, Ra", RA and RB in each case correspond to a row of Table A.
Table C293 Compounds of formula (1-8-1 ) wherein Ra' denotes B8 and Q1, Ra", RA and RB in each case correspond to a row of Table A.
Table C294
Compounds of formula (1-8-1 ) wherein Ra' denotes B9 and Q1, Ra", RA and RB in each case correspond to a row of Table A.
Table C295
Compounds of formula (I-8-2) wherein Ra' denotes B2 and Q1, Ra", RA and RB in each case correspond to a row of Table A.
Table C296
Compounds of formula (I-8-2) wherein Ra' denotes B3 and Q1, Ra", RA and RB in each case correspond to a row of Table A.
Table C297
Compounds of formula (I-8-2) wherein Ra' denotes B4 and Q1, Ra", RA and RB in each case correspond to a row of Table A.
Table C298
Compounds of formula (I-8-2) wherein Ra' denotes B5 and Q , Ra", RA and RB in each case correspond to a row of Table A.
Table C299
Compounds of formula (I-8-2) wherein Ra' denotes B6 and Q1, Ra", RA and RB in each case correspond to a row of Table A.
Table C300
Compounds of formula (I-8-2) wherein Ra' denotes B7 and Q1, Ra", RA and RB in each case correspond to a row of Table A.
Table C301
Compounds of formula (I-8-2) wherein Ra' denotes B8 and Q1, Ra", RA and RB in each case correspond to a row of Table A.
Table C302
Compounds of formula (I-8-2) wherein Ra' denotes B9 and Q1, Ra", RA and RB in each case correspond to a row of Table A.
Table C303
Compounds of formula (I-8-3) wherein Ra' denotes B2 and Q1, Ra", RA and RB in each case correspond to a row of Table A.
Table C304
Compounds of formula (I-8-3) wherein Ra' denotes B3 and Q1, Ra", RA and RB in each case correspond to a row of Table A.
Table C305
Compounds of formula (I-8-3) wherein Ra' denotes B4 and Q1, Ra", RA and RB in each case correspond to a row of Table A.
Table C306
Compounds of formula (I-8-3) wherein Ra' denotes B5 and Q1, Ra", RA and RB in each case correspond to a row of Table A.
Table C307
Compounds of formula (I-8-3) wherein Ra' denotes B6 and Q1, Ra", RA and RB in each case correspond to a row of Table A. Table C308
Compounds of formula (1-8-3) wherein Ra' denotes B7 and Q1, Ra", RA and RB in each case correspond to a row of Table A.
Table C309
Compounds of formula (1-8-3) wherein Ra' denotes B8 and Q1, Ra", RA and RB in each case correspond to a row of Table A.
Table C310
Compounds of formula (I-8-3) wherein Ra' denotes B9 and Q1, Ra", RA and RB in each case correspond to a row of Table A.
Table C31 1
Compounds of formula (I-8-4) wherein Ra' denotes B2 and Q1, Ra", RA and RB in each case correspond to a row of Table A.
Table C312
Compounds of formula (I-8-4) wherein Ra' denotes B3 and Q1, Ra", RA and RB in each case correspond to a row of Table A.
Table C313
Compounds of formula (I-8-4) wherein Ra' denotes B4 and Q1, Ra", RA and RB in each case correspond to a row of Table A.
Table C314
Compounds of formula (I-8-4) wherein Ra' denotes B5 and Q1, Ra", RA and RB in each case correspond to a row of Table A.
Table C315
Compounds of formula (I-8-4) wherein Ra' denotes B6 and Q1, Ra", RA and RB in each case correspond to a row of Table A.
Table C316
Compounds of formula (I-8-4) wherein Ra' denotes B7 and Q1, Ra", RA and RB in each case correspond to a row of Table A.
Table C317
Compounds of formula (I-8-4) wherein Ra' denotes B8 and Q1, Ra", RA and RB in each case correspond to a row of Table A.
Table C318
Compounds of formula (I-8-4) wherein Ra' denotes B9 and Q1, Ra", RA and RB in each case correspond to a row of Table A.
Table C319
Compounds of formula (I-8-5) wherein Ra' denotes B2 and Q1, Ra", RA and RB in each case correspond to a row of Table A.
Table C320
Compounds of formula (I-8-5) wherein Ra' denotes B3 and Q1, Ra", RA and RB in each case correspond to a row of Table A.
Table C321
Compounds of formula (I-8-5) wherein Ra' denotes B4 and Q1, Ra", RA and RB in each case correspond to a row of Table A.
Table C322 Compounds of formula (1-8-5) wherein Ra' denotes B5 and Q1, Ra", RA and RB in each case correspond to a row of Table A.
Table C323
Compounds of formula (I-8-5) wherein Ra' denotes B6 and Q1, Ra", RA and RB in each case correspond to a row of Table A.
Table C324
Compounds of formula (I-8-5) wherein Ra' denotes B7 and Q1, Ra", RA and RB in each case correspond to a row of Table A.
Table C325
Compounds of formula (I-8-5) wherein Ra' denotes B8 and Q1, Ra", RA and RB in each case correspond to a row of Table A.
Table C326
Compounds of formula (I-8-5) wherein Ra' denotes B9 and Q1, Ra", RA and RB in each case correspond to a row of Table A.
Table C327
Compounds of formula (I-8-6) wherein Ra' denotes B2 and Q1, Ra", RA and RB in each case correspond to a row of Table A.
Table C328
Compounds of formula (I-8-6) wherein Ra' denotes B3 and Q1, Ra", RA and RB in each case correspond to a row of Table A.
Table C329
Compounds of formula (I-8-6) wherein Ra' denotes B4 and Q1, Ra", RA and RB in each case correspond to a row of Table A.
Table C330
Compounds of formula (I-8-6) wherein Ra' denotes B5 and Q1, Ra", RA and RB in each case correspond to a row of Table A.
Table C331
Compounds of formula (I-8-6) wherein Ra' denotes B6 and Q1, Ra", RA and RB in each case correspond to a row of Table A.
Table C332
Compounds of formula (I-8-6) wherein Ra' denotes B7 and Q1, Ra", RA and RB in each case correspond to a row of Table A.
Table C333
Compounds of formula (I-8-6) wherein Ra' denotes B8 and Q1, Ra", RA and RB in each case correspond to a row of Table A.
Table C334
Compounds of formula (I-8-6) wherein Ra' denotes B9 and Q1, Ra", RA and RB in each case correspond to a row of Table A.
Table C335
Compounds of formula (I-8-7) wherein Ra' denotes B2 and Q1, Ra", RA and RB in each case correspond to a row of Table A.
Table C336
Compounds of formula (I-8-7) wherein Ra' denotes B3 and Q1, Ra", RA and RB in each case correspond to a row of Table A. Table C337
Compounds of formula (1-8-7) wherein Ra' denotes B4 and Q1, Ra", RA and RB in each case correspond to a row of Table A.
Table C338
Compounds of formula (I-8-7) wherein Ra' denotes B5 and Q1, Ra", RA and RB in each case correspond to a row of Table A.
Table C339
Compounds of formula (I-8-7) wherein Ra' denotes B6 and Q1, Ra", RA and RB in each case correspond to a row of Table A.
Table C340
Compounds of formula (I-8-7) wherein Ra' denotes B7 and Q1, Ra", RA and RB in each case correspond to a row of Table A.
Table C341
Compounds of formula (I-8-7) wherein Ra' denotes B8 and Q1, Ra", RA and RB in each case correspond to a row of Table A.
Table C342
Compounds of formula (I-8-7) wherein Ra' denotes B9 and Q1, Ra", RA and RB in each case correspond to a row of Table A.
Table C343
Compounds of formula (I-8-8) wherein Ra' denotes B2 and Q1, Ra", RA and RB in each case correspond to a row of Table A.
Table C344
Compounds of formula (I-8-8) wherein Ra' denotes B3 and Q1, Ra", RA and RB in each case correspond to a row of Table A.
Table C345
Compounds of formula (I-8-8) wherein Ra' denotes B4 and Q1, Ra", RA and RB in each case correspond to a row of Table A.
Table C346
Compounds of formula (I-8-8) wherein Ra' denotes B5 and Q1, Ra", RA and RB in each case correspond to a row of Table A.
Table C347
Compounds of formula (I-8-8) wherein Ra' denotes B6 and Q1, Ra", RA and RB in each case correspond to a row of Table A.
Table C348
Compounds of formula (I-8-8) wherein Ra' denotes B7 and Q1, Ra", RA and RB in each case correspond to a row of Table A.
Table C349
Compounds of formula (I-8-8) wherein Ra' denotes B8 and Q1, Ra", RA and RB in each case correspond to a row of Table A.
Table C350
Compounds of formula (I-8-8) wherein Ra' denotes B9 and Q1, Ra", RA and RB in each case correspond to a row of Table A.
Table C351 Compounds of formula (1-8-9) wherein Ra' denotes B2 and Q1, Ra", RA and RB in each case correspond to a row of Table A.
Table C352
Compounds of formula (I-8-9) wherein Ra' denotes B3 and Q1, Ra", RA and RB in each case correspond to a row of Table A.
Table C353
Compounds of formula (I-8-9) wherein Ra' denotes B4 and Q1, Ra", RA and RB in each case correspond to a row of Table A.
Table C354
Compounds of formula (I-8-9) wherein Ra' denotes B5 and Q1, Ra", RA and RB in each case correspond to a row of Table A.
Table C355
Compounds of formula (I-8-9) wherein Ra' denotes B6 and Q1, Ra", RA and RB in each case correspond to a row of Table A.
Table C356
Compounds of formula (I-8-9) wherein Ra' denotes B7 and Q1, Ra", RA and RB in each case correspond to a row of Table A.
Table C357
Compounds of formula (I-8-9) wherein Ra' denotes B8 and Q1, Ra", RA and RB in each case correspond to a row of Table A.
Table C358
Compounds of formula (I-8-9) wherein Ra' denotes B9 and Q1, Ra", RA and RB in each case correspond to a row of Table A.
Table C359
Compounds of formula (1-8-10) wherein Ra' denotes B2 and Q1, Ra", RA and RB in each case correspond to a row of Table A.
Table C360
Compounds of formula (1-8-10) wherein Ra' denotes B3 and Q1, Ra", RA and RB in each case correspond to a row of Table A.
Table C361
Compounds of formula (1-8-10) wherein Ra' denotes B4 and Q1, Ra", RA and RB in each case correspond to a row of Table A.
Table C362
Compounds of formula (1-8-10) wherein Ra' denotes B5 and Q1, Ra", RA and RB in each case correspond to a row of Table A.
Table C363
Compounds of formula (1-8-10) wherein Ra' denotes B6 and Q1, Ra", RA and RB in each case correspond to a row of Table A.
Table C364
Compounds of formula (1-8-10) wherein Ra' denotes B7 and Q1, Ra", RA and RB in each case correspond to a row of Table A.
Table C365
Compounds of formula (1-8-10) wherein Ra' denotes B8 and Q1, Ra", RA and RB in each case correspond to a row of Table A. Table C366
Compounds of formula (1-8-10) wherein Ra' denotes B9 and Q1, Ra", RA and RB in each case correspond to a row of Table A.
Table C367
Compounds of formula (1-8-1 1 ) wherein Ra' denotes B2 and Q1, Ra", RA and RB in each case correspond to a row of Table A.
Table C368
Compounds of formula (1-8-1 1 ) wherein Ra' denotes B3 and Q1, Ra", RA and RB in each case correspond to a row of Table A.
Table C369
Compounds of formula (1-8-1 1 ) wherein Ra' denotes B4 and Q1, Ra", RA and RB in each case correspond to a row of Table A.
Table C370
Compounds of formula (1-8-1 1 ) wherein Ra' denotes B5 and Q1, Ra", RA and RB in each case correspond to a row of Table A.
Table C371
Compounds of formula (1-8-1 1 ) wherein Ra' denotes B6 and Q1, Ra", RA and RB in each case correspond to a row of Table A.
Table C372
Compounds of formula (1-8-1 1 ) wherein Ra' denotes B7 and Q1, Ra", RA and RB in each case correspond to a row of Table A.
Table C373
Compounds of formula (1-8-1 1 ) wherein Ra' denotes B8 and Q1, Ra", RA and RB in each case correspond to a row of Table A.
Table C374
Compounds of formula (1-8-1 1 ) wherein Ra' denotes B9 and Q1, Ra", RA and RB in each case correspond to a row of Table A.
Table C375
Compounds of formula (1-8-12) wherein Ra' denotes B2 and Q1, Ra", RA and RB in each case correspond to a row of Table A.
Table C376
Compounds of formula (1-8-12) wherein Ra' denotes B3 and Q1, Ra", RA and RB in each case correspond to a row of Table A.
Table C377
Compounds of formula (1-8-12) wherein Ra' denotes B4 and Q1, Ra", RA and RB in each case correspond to a row of Table A.
Table C378
Compounds of formula (1-8-12) wherein Ra' denotes B5 and Q1, Ra", RA and RB in each case correspond to a row of Table A.
Table C379
Compounds of formula (1-8-12) wherein Ra' denotes B6 and Q1, Ra", RA and RB in each case correspond to a row of Table A.
Table C380 Compounds of formula (1-8-12) wherein Ra' denotes B7 and Q1, Ra", RA and RB in each case correspond to a row of Table A.
Table C381
Compounds of formula (1-8-12) wherein Ra' denotes B8 and Q1, Ra", RA and RB in each case correspond to a row of Table A.
Table C382
Compounds of formula (1-8-12) wherein Ra' denotes B9 and Q1, Ra", RA and RB in each case correspond to a row of Table A.
Table C383
Compounds of formula (1-8-12) wherein Ra' denotes B2 and Q1, Ra", RA and RB in each case correspond to a row of Table A.
Table C384
Compounds of formula (1-8-13) wherein Ra' denotes B3 and Q1, Ra", RA and RB in each case correspond to a row of Table A.
Table C385
Compounds of formula (1-8-13) wherein Ra' denotes B4 and Q , Ra", RA and RB in each case correspond to a row of Table A.
Table C386
Compounds of formula (1-8-13) wherein Ra' denotes B5 and Q1, Ra", RA and RB in each case correspond to a row of Table A.
Table C387
Compounds of formula (1-8-13) wherein Ra' denotes B6 and Q1, Ra", RA and RB in each case correspond to a row of Table A.
Table C388
Compounds of formula (1-8-13) wherein Ra' denotes B7 and Q1, Ra", RA and RB in each case correspond to a row of Table A.
Table C389
Compounds of formula (1-8-13) wherein Ra' denotes B8 and Q1, Ra", RA and RB in each case correspond to a row of Table A.
Table C390
Compounds of formula (1-8-13) wherein Ra' denotes B9 and Q1, Ra", RA and RB in each case correspond to a row of Table A.
Table C391
Compounds of formula (1-8-14) wherein Ra' denotes B2 and Q1, Ra", RA and RB in each case correspond to a row of Table A.
Table C392
Compounds of formula (1-8-14) wherein Ra' denotes B3 and Q1, Ra", RA and RB in each case correspond to a row of Table A.
Table C393
Compounds of formula (1-8-14) wherein Ra' denotes B4 and Q1, Ra", RA and RB in each case correspond to a row of Table A.
Table C394
Compounds of formula (1-8-14) wherein Ra' denotes B5 and Q1, Ra", RA and RB in each case correspond to a row of Table A. Table C395
Compounds of formula (1-8-14) wherein Ra' denotes B6 and Q1, Ra", RA and RB in each case correspond to a row of Table A.
Table C396
Compounds of formula (1-8-14) wherein Ra' denotes B7 and Q1, Ra", RA and RB in each case correspond to a row of Table A.
Table C397
Compounds of formula (1-8-14) wherein Ra' denotes B8 and Q1, Ra", RA and RB in each case correspond to a row of Table A.
Table C398
Compounds of formula (1-8-14) wherein Ra' denotes B9 and Q1, Ra", RA and RB in each case correspond to a row of Table A.
Table C399
Compounds of formula (1-8-15) wherein Ra' denotes B2 and Q1, Ra", RA and RB in each case correspond to a row of Table A.
Table C400
Compounds of formula (1-8-15) wherein Ra' denotes B3 and Q1, Ra", RA and RB in each case correspond to a row of Table A.
Table C401
Compounds of formula (1-8-15) wherein Ra' denotes B4 and Q1, Ra", RA and RB in each case correspond to a row of Table A.
Table C402
Compounds of formula (1-8-15) wherein Ra' denotes B5 and Q1, Ra", RA and RB in each case correspond to a row of Table A.
Table C403
Compounds of formula (1-8-15) wherein Ra' denotes B6 and Q1, Ra", RA and RB in each case correspond to a row of Table A.
Table C404
Compounds of formula (1-8-15) wherein Ra' denotes B7 and Q1, Ra", RA and RB in each case correspond to a row of Table A.
Table C405
Compounds of formula (1-8-15) wherein Ra' denotes B8 and Q1, Ra", RA and RB in each case correspond to a row of Table A.
Table C406
Compounds of formula (1-8-15) wherein Ra' denotes B9 and Q1, Ra", RA and RB in each case correspond to a row of Table A.
Table C407
General Synthesis
Heterocycles of the formula P-3 can be prepared by reaction of compounds of the formula P-1 with active esters of the formula P-2 as described by, for example, Holyoke et al, WO
2009/099929 (Scheme 1 ). Reaction temperatures are typically between 50 and 180°C and the reactions can be performed neat or in solution (e.g. toluene, xylene, bromobenzene) as solvent Scheme 1
Figure imgf000074_0001
P-1 P-2
Bisphenyl esters of the formula P-9 can be prepared by reaction of phenyl esters of the formula P-8 with a base (e.g. sodium hydride, lithium bis(trimethylsilyl)amide, lithium diisopropylamide) followed by phenyl chloroformate or diphenyl carbonate (Scheme 2). Phenyl esters of the formula P-8 can in turn be prepared from acids P-7 by reaction with phenol and a coupling agent (e.g. Ν,Ν'-dicyclohexylcarbodiimide, 1 -ethyl-3-(3-dimethylaminopropyl) carbodiimide) with or without a base (e.g. triethylamine) or catalyst (e.g. 4-dimethylaminopyridine). Acids P-7 are in turn available from esters P-6 via base-promoted hydrolysis reactions of, for example, methyl esters P-6 (Rxx = Me). Finally esters P-5 can be prepared from halides P-4 and boronic acids P- 5 in Suzuki coupling reactions.
Scheme 2
Figure imgf000074_0002
P-4 P-5 P-6
base-promoted coupling agent
hydrolysis O phenol
j^A-A°— C-RB
HO
P-7 base
Figure imgf000074_0003
Bis(2,4,6-trichlorophenyl) esters of the formula P-14 can be prepared from malonic acids P-13 by reaction with phosphorus oxychloride or oxalyl chloride then 2,4,6-trichlorophenol as described, for example, by Holyoke et al, WO 2009/099929 (Scheme 3). Malonic acids of the formula P-13 can be prepared by base- or acid-promoted hydrolysis of esters of the formula P-12. Finally esters of the formula P-11 can be prepared by copper- or palladium-catalyzed coupling reactions of dialkyi malonates P-10 and halides P-11 as described by, for example, Moore et al, WO 2010/045379 or Birch et al, WO 2010/146395.
Scheme 3
Figure imgf000075_0001
Compounds of the formula P-3 can also be prepared in Suzuki couplings between compounds of the formula P-15, where X is an appropriate leaving group (e.g. CI, Br, I, triflate), and boronic acids of the formula P-16 as described, for example, by Holyoke et al, WO 2009/099929 (Scheme 4).
Scheme 4
Figure imgf000075_0002
Compounds of the formula P-17, P-18 and P-19 (where RA is, e.g., alkyl, aryl) can be condensation reactions involving P-3 (e.g. RB = alkyl, aryl) and amines (RANH2), hydroxylamine (RA0NH2) or hydrazines [(RA1)2lMNH2], respectively, as described in, for example, J. March, Advanced Organic Chemistry, 6th ed., John Wiley & Sons (Scheme 5). Scheme 5
Figure imgf000076_0001
Compounds of the formula P-21 , P-23 and P-25 can be condensation reactions involving P-3 (where RA and Raa are, e.g., H, alkyl, aryl) and semicarbazides P-22 , N-aminocarbamates P-24 or acylhydrazides P-22, respectively, as described in, for example, J. March, Advanced Organic Chemistry, 6th ed., John Wiley & Sons (Scheme 6).
Scheme 6
Figure imgf000077_0001
Compounds of the formula P-26 can be prepared from compounds of the formula P-27 by reaction with, for example, hydroxylamine hydrochloride in the presence of a base (e.g. NaOH, pyridine, triethylamine, K2CO3, NaH) as described by, for example, Sanders et al, J. Am. Chem. Soc. 201 1 , 133, 949-957 (Scheme 2). Compounds of the formula P-28 can be prepared from compounds of the formula P-27 by reaction with a chlorinating reagent (e.g. N-chlorosuccin- imide, NaOCI, t-butylhypochlorite) as described by, for example, Sanders et al, J. Am. Chem. Soc. 201 1 , 133, 949-957. Compounds of the formula P-29 can be prepared from compounds of the formula P-28 by reaction with an amine nucleophile as described by, for example, Altug et al, Tetrahedron Lett. 2009, 50, 7392-7394. Compounds of the formula P-30 can be prepared from compounds of the formula P-29 by reaction with an electrophile (e.g. methyl iodide, cyanogen bromide, acetyl chloride etc.) in the presence of a base (e.g. NaOH, pyridine, triethylamine, K2CO3, NaH) as described by, for example, Lui et al, Pest. Manag. Sci. 2009, 65, 229-234. Scheme 7
Figure imgf000078_0001
amine
nucleophile
Figure imgf000078_0002
Compounds of the formula P-32 can be prepared from compounds of the formula P-31 by reaction with, for example, hydroxylamine hydrochloride in the presence of a base (e.g. NaOH, pyridine, triethylamine, K2CO3) as described by, for example, Neshida et al, WO 2010/065717 (Scheme 8). Compounds of the formula P-34 can be prepared from compounds of the formula P-32 by reaction with an electophile (e.g. methyl iodide) in the presence of a base (e.g. NaOH, pyridine, triethylamine, K2CO3, NaH) as described by, for example, Branowska et al, Bioorg. Med. Chem. Lett. 2010, 18, 3551 -3558. Compounds of the formula P-33 can be prepared from compounds of the formula P-32 by reaction with an acylating agent (e.g. acetic anhydride where Rbb is Me) as described by, for example, Jeong et al, US 2006/0106017.
Scheme 8
Figure imgf000078_0003
Compounds of the formula P-35 can be prepared from compounds of the formula P-31 by reaction with, for example, hydrochloric acid in methanol as described by, for example, Laurent et al, Molecules, 2010, 15, 4283-4293 (Scheme 9). Compounds of the formula P-36 can be prepared from compounds of the formula P-35 by reaction with an amine nucleophile as described by, for example, Arnold et al, WO 2008/124849.
Scheme 9
Figure imgf000079_0001
Compounds of the formula P-37 (where Raa is, e.g. H, alkyl, aryl) can be prepared from com- pounds of the formula 2 by reaction with a hydrazine as described by, for example, Chambers et al, WO 2006/097766 (Scheme 10).
Scheme 10
Figure imgf000079_0002
The compounds of formula (I), N-oxides and their salts are in particular suitable for efficiently controlling arthropodal pests such as arachnids, myriapedes and insects as well as nematodes.
The compounds of formula (I), their N-oxides and their salts 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, Autogra- pha gamma, Bupalus piniarius, Cacoecia murinana, Capua reticulana, Cheimatobia brumata, Choristoneura fumiferana, Choristoneura occidentalis, Cirphis unipuncta, Cydia pomonella, Dendrolimus pini, Diaphania nitidalis, Diatraea grandiosella, 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 defoliaria, Hyphantria cunea, Hyponomeuta malinellus, Keiferia lycopersicella, Lambdina fiscellaria, Laphygma exigua, Leucoptera coffeella, Leucoptera scitel- la, Lithocolletis blancardella, Lobesia botrana, Loxostege sticticalis, Lymantria dispar, Lymantria monacha, Lyonetia clerkella, Malacosoma neustria, Mamestra brassicae, Orgyia pseudotsuga- ta, 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, Sito- troga cerealella, Sparganothis pilleriana, Spodoptera frugiperda, Spodoptera littoralis, Spodop- tera litura, Thaumatopoea pityocampa, Tortrix viridana, Trichoplusia ni and Zeiraphera canadensis;
beetles (Coleoptera), for example Agrilus sinuatus, Agriotes lineatus, Agriotes obscurus, Am- phimallus solstitialis, Anisandrus dispar, Anthonomus grandis, Anthonomus pomorum, Aphtho- na euphoridae, Athous haemorrhoidalis, Atomaria linearis, Blastophagus piniperda, Blitophaga undata, Bruchus rufimanus, Bruchus pisorum, Bruchus lentis, Byctiscus betulae, Cassida nebu- losa, Cerotoma trifurcata, Cetonia aurata, Ceuthorrhynchus assimilis, Ceuthorrhynchus napi, Chaetocnema tibialis, Conoderus vespertinus, Crioceris asparagi, Ctenicera ssp., Diabrotica longicornis, Diabrotica semipunctata, Diabrotica 12-punctata Diabrotica speciosa, Diabrotica virgifera, Epilachna varivestis, Epitrix hirtipennis, Eutinobothrus brasiliensis, Hylobius abietis, Hypera brunneipennis, Hypera postica, Ips typographus, Lema bilineata, Lema melanopus, Leptinotarsa decemlineata, Limonius californicus, Lissorhoptrus oryzophilus, Melanotus communis, Meligethes aeneus, Melolontha hippocastani, Melolontha melolontha, Oulema oryzae, Otiorrhynchus sulcatus, Otiorrhynchus ovatus, Phaedon cochleariae, Phyllobius pyri, Phyllotreta chrysocephala, Phyllophaga sp., Phyllopertha horticola, Phyllotreta nemorum, Phyllotreta stri- olata, Popillia japonica, Sitona lineatus and Sitophilus granaria;
flies, mosquitoes (Diptera), e.g. Aedes aegypti, Aedes albopictus, Aedes vexans, Anastrepha ludens, Anopheles maculipennis, Anopheles crucians, Anopheles albimanus, Anopheles gam- biae, Anopheles freeborni, Anopheles leucosphyrus, Anopheles minimus, Anopheles quadri- maculatus, Calliphora vicina, Ceratitis capitata, Chrysomya bezziana, Chrysomya hominivorax, Chrysomya macellaria, Chrysops discalis, Chrysops silacea, Chrysops atlanticus, Cochliomyia hominivorax, Contarinia sorghicola Cordylobia anthropophaga, Culicoides furens, Culex pipiens, Culex nigripalpus, Culex quinquefasciatus, Culex tarsalis, Culiseta inornata, Culiseta melanura, Dacus cucurbitae, Dacus oleae, Dasineura brassicae, Delia antique, Delia coarctata, Delia pla- tura, Delia radicum, Dermatobia hominis, Fannia canicularis, Geomyza Tripunctata, Gasterophi- lus 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 cu- prina, Lucilia sericata, Lycoria pectoralis, Mansonia titillanus, Mayetiola destructor, Musca au- tumnalis, Musca domestica, Muscina stabulans, Oestrus ovis, Opomyza florum, Oscinella frit, Pegomya hysocyami, Phorbia antiqua, Phorbia brassicae, Phorbia coarctata, Phlebotomus ar- gentipes, Psorophora columbiae, Psila rosae, Psorophora discolor, Prosimulium mixtum, Rhag- oletis cerasi, Rhagoletis pomonella, Sarcophaga haemorrhoidalis, Sarcophaga spp., Simulium vittatum, Stomoxys calcitrans, Tabanus bovinus, Tabanus atratus, Tabanus lineola, and Taba- nus 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 pa Imi and Thrips tabaci,
termites (Isoptera), e.g. Calotermes flavicollis, Leucotermes flavipes, Heterotermes aureus, Re- ticulitermes flavipes, Reticulitermes virginicus, Reticulitermes lucifugus, Reticulitermes san- tonensis, Reticulitermes grassei, Termes natalensis, and Coptotermes formosanus; cockroaches (Blattaria - Blattodea), e.g. Blattella germanica, Blattella asahinae, Periplaneta americana, Periplaneta japonica, Periplaneta brunnea, Periplaneta fuligginosa, Periplaneta aus- tralasiae, and Blatta orientalis;
bugs, aphids, leafhoppers, whiteflies, scale insects, cicadas (Hemiptera), e.g. Acrosternum hi- lare, Blissus leucopterus, Cyrtopeltis notatus, Dysdercus cingulatus, Dysdercus intermedius, Eurygaster integriceps, Euschistus impictiventris, Leptoglossus phyllopus, Lygus lineolaris, Ly- gus pratensis, Nezara viridula, Piesma quadrata, Solubea insularis , Thyanta perditor, Acyrtho- siphon onobrychis, Adelges laricis, Aphidula nasturtii, Aphis fabae, Aphis forbesi, Aphis pomi, Aphis gossypii, Aphis grossulariae, Aphis schneideri, Aphis spiraecola, Aphis sambuci, Acyrtho- siphon pisum, Aulacorthum solani, Bemisia argentifolii, Brachycaudus cardui, Brachycaudus helichrysi, Brachycaudus persicae, Brachycaudus prunicola, Brevicoryne brassicae, Capitopho- rus horni, Cerosipha gossypii, Chaetosiphon fragaefolii, Cryptomyzus ribis, Dreyfusia nordman- nianae, Dreyfusia piceae, Dysaphis radicola, Dysaulacorthum pseudosolani, Dysaphis plantagi- nea, Dysaphis pyri, Empoasca fabae, Hyalopterus pruni, Hyperomyzus lactucae, Macrosiphum avenae, Macrosiphum euphorbiae, Macrosiphon rosae, Megoura viciae, Melanaphis pyrarius, Metopolophium dirhodum, Myzus persicae, Myzus ascalonicus, Myzus cerasi, Myzus varians, Nasonovia ribis-nigri, Nilaparvata lugens, Pemphigus bursarius, Perkinsiella saccharicida, Pho- rodon humuli, Psylla mail, Psylla piri, Rhopalomyzus ascalonicus, Rhopalosiphum maidis, Rho- palosiphum padi, Rhopalosiphum insertum, Sappaphis mala, Sappaphis mail, Schizaphis gra- minum, Schizoneura lanuginosa, Sitobion avenae, Trialeurodes vaporariorum, Toxoptera auran- tiiand, Viteus vitifolii, Cimex lectularius, Cimex hemipterus, Reduvius senilis, Triatoma 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, Monomorium pharaonis, Solenopsis geminata, Solenopsis invicta, Solenopsis richteri, Solenopsis xyloni, Pogonomyrmex barbatus, Pogonomyrmex californicus, Pheidole megacephala, Dasymutilla occidentalis, Bombus spp., Vespula squamosa, Paravespula vulgaris, Paravespula pennsylvanica, Paravespula germanica, Dolichovespula maculata, Vespa crabro, Polistes rubiginosa, Camponotus floridanus, and Linepithema humile;
crickets, grasshoppers, locusts (Orthoptera), e.g. Acheta domestica, Gryllotalpa gryllotalpa, Lo- custa migratoria, Melanoplus bivittatus, Melanoplus femurrubrum, Melanoplus mexicanus, Me- lanoplus sanguinipes, Melanoplus spretus, Nomadacris septemfasciata, Schistocerca americana, Schistocerca gregaria, Dociostaurus maroccanus, Tachycines asynamorus, Oedaleus se- negalensis, Zonozerus variegatus, Hieroglyphus daganensis, Kraussaria angulifera, Callip- tamus italicus, Chortoicetes terminifera, and Locustana pardalina;
arachnoidea, such as arachnids (Acarina), e.g. of the families Argasidae, Ixodidae and Sar- coptidae, such as Amblyomma americanum, Amblyomma variegatum, Ambryomma maculatum, Argas persicus, Boophilus annulatus, Boophilus decoloratus, Boophilus microplus, Dermacentor silvarum, Dermacentor andersoni, Dermacentor variabilis, Hyalomma truncatum, Ixodes ricinus, Ixodes rubicundus, Ixodes scapularis, Ixodes holocyclus, Ixodes pacificus, Ornithodorus mou- bata, Ornithodorus hermsi, Ornithodorus turicata, Ornithonyssus bacoti, Otobius megnini, Der- manyssus 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 palli- dus and Polyphagotarsonemus latus; Tenuipalpidae spp. such as Brevipalpus phoenicis; Tetra- nychidae spp. such as Tetranychus cinnabarinus, Tetranychus kanzawai, Tetranychus pacifi- cus, Tetranychus telarius and Tetranychus urticae, Panonychus ulmi, 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, Bovicola bovis, Menopon gallinae, Menacanthus stramineus and Solenopotes capillatus.
Collembola (springtails), e.g. Onychiurus ssp..
They are also suitable for controlling Nematodes: plant parasitic 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 species; Sting nematodes, Belonolaimus longicaudatus and other Belono- laimus 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, Ditylenchus dip- saci 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 rootknot nematodes, Nacobbus species; Needle nematodes, Longidorus elongatus and other Longidorus species; Lesion nematodes, Pratylen- chus 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 du- bius and other Tylenchorhynchus species; Citrus nematodes, Tylenchulus species; Dagger nematodes, Xiphinema species; and other plant parasitic nematode species.
The compounds of formula (I) and their salts are also useful for controlling arachnids (Arachnoidea), such as acarians (Acarina), e.g. of the families Argasidae, Ixodidae and Sar- coptidae, such as Amblyomma americanum, Amblyomma variegatum, Argas persicus, Boophi- lus annulatus, Boophilus decoloratus, Boophilus microplus, Dermacentor silvarum, Hyalomma truncatum, Ixodes ricinus, Ixodes rubicundus, Ornithodorus moubata, Otobius megnini, Der- manyssus gallinae, Psoroptes ovis, Rhipicephalus appendiculatus, Rhipicephalus evertsi, Sar- coptes scabiei, and Eriophyidae spp. such as Aculus schlechtendali, Phyllocoptrata oleivora and Eriophyes sheldoni; Tarsonemidae spp. such as Phytonemus pallidus and Polyphagotar- sonemus latus; Tenuipalpidae spp. such as Brevipalpus phoenicis; Tetranychidae spp. such as Tetranychus cinnabarinus, Tetranychus kanzawai, Tetranychus pacificus, Tetranychus telarius and Tetranychus urticae, Panonychus ulmi, Panonychus citri, and oligonychus pratensis.
Compounds of formula (I) are particularly useful for controlling insects, preferably sucking or piercing insects such as insects from the genera Thysanoptera, Diptera and Hemiptera, in particular the following species:
Thysanoptera: Frankliniella fusca, Frankliniella occidentalis, Frankliniella tritici, Scirtothrips citri, Thrips oryzae, Thrips palmi and Thrips tabaci,
Diptera, e.g. Aedes aegypti, Aedes albopictus, Aedes vexans, Anastrepha ludens, Anopheles maculipennis, Anopheles crucians, Anopheles albimanus, Anopheles gambiae, Anopheles free- borni, Anopheles leucosphyrus, Anopheles minimus, Anopheles quadrimaculatus, Calliphora vicina, Ceratitis capitata, Chrysomya bezziana, Chrysomya hominivorax, Chrysomya macellaria, Chrysops discalis, Chrysops silacea, Chrysops atlanticus, Cochliomyia hominivorax, Contarinia sorghicola Cordylobia anthropophaga, Culicoides furens, Culex pipiens, Culex nigripalpus, Cu- lex quinquefasciatus, Culex tarsalis, Culiseta inornata, Culiseta melanura, Dacus cucurbitae, Dacus oleae, Dasineura brassicae, Delia antique, Delia coarctata, Delia platura, Delia radicum, Dermatobia hominis, Fannia canicularis, Geomyza Tripunctata, Gasterophilus intestinalis, Glossina morsitans, Glossina palpalis, Glossina fuscipes, Glossina tachinoides, Haematobia irritans, Haplodiplosis equestris, Hippelates spp., Hylemyia platura, Hypoderma lineata, Lepto- conops torrens, Liriomyza sativae, Liriomyza trifolii, Lucilia caprina, Lucilia cuprina, Lucilia seri- cata, Lycoria pectoralis, Mansonia titillanus, Mayetiola destructor, Musca autumnalis, Musca domestica, Muscina stabulans, Oestrus ovis, Opomyza florum, Oscinella frit, Pegomya hysocy- ami, Phorbia antiqua, Phorbia brassicae, Phorbia coarctata, Phlebotomus argentipes, Psoro- phora 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, and Tabanus similis, Tipula oleracea, and Tipula paludosa;
Hemiptera, in particular aphids: 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, Brachycaudus car- dui, Brachycaudus helichrysi, Brachycaudus persicae, Brachycaudus prunicola, Brevicoryne brassicae, Capitophorus horni, Cerosipha gossypii, Chaetosiphon fragaefolii, Cryptomyzus ribis, Dreyfusia nordmannianae, 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, Myzodes persicae, Myzus ascalonicus, Myzus cerasi, Myzus varians, Nasonovia ribis-nigri, Nilaparvata lugens, Pemphigus bursarius,
Perkinsiella saccharicida, Phorodon humuli, Psylla mail, Psylla piri, Rhopalomyzus ascalonicus, Rhopalosiphum maidis, Rhopalosiphum padi, Rhopalosiphum insertum, Sappaphis mala, Sap- paphis mali, Schizaphis graminum, Schizoneura lanuginosa, Sitobion avenae, Trialeurodes va- porariorum, Toxoptera aurantiiand, and Viteus vitifolii.
Compounds of formula (I), their N-oxides and salts are particularly useful for controlling insects of the orders Hemiptera and Thysanoptera. Compositions (formulations)
The invention also relates to agrochemical compositions comprising an auxiliary and at least one compound (I) or an N-oxide or salt thereof.
An agrochemical composition comprises a pesticidally effective amount of a compound (I) or an N-oxide or salt thereof. The term "effective amount" denotes an amount of the composition or of the compound (I) or an N-oxide or salt thereof, which is sufficient for controlling harmful animal pests 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 pest to be controlled the treated cultivated plant or material, the climatic conditions and the specific compound (I) or an N-oxide or salt thereof used.
The compounds (I), their N-oxides and salts 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 suspen- sions (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 pes- ticide 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 Grube- mann, Formulation technology, Wiley VCH, Weinheim, 2001 ; or Knowles, New developments in crop protection product formulation, Agrow Reports DS243, T&F Informa, London, 2005.
Examples for suitable auxiliaries are solvents, liquid carriers, solid carriers or fillers, surfactants, dispersants, emulsifiers, wetters, adjuvants, solubilizers, penetration enhancers, protective colloids, adhesion agents, thickeners, humectants, repellents, attractants, feeding stimulants, compatibilizers, bactericides, anti-freezing 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, tetrahydronaphthalene, alkylated naphthalenes; alcohols, e.g. ethanol, propanol, butanol, benzylalcohol, cyclohexanol; glycols; DMSO; ketones, e.g. cyclohexanone; esters, e.g. lactates, carbonates, fatty acid esters, gamma-butyrolactone; 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, limestone, lime, chalk, clays, dolomite, diatomaceous earth, bentonite, calcium sulfate, magnesium sulfate, magnesium oxide; polysaccharide powders, e.g. cellulose, starch; fertilizers, e.g. am- monium 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 emusifier, dispersant, solubilizer, wetter, penetration enhancer, protective col- loid, 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, sulfosuccinates 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-subsituted 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-subsititued 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 al- kylpolyglucosides. Examples of polymeric surfactants are home- or copolymers of vinylpyrroli- done, vinylalcohols, 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 polyethylene oxide and polypropylene oxide, or of the A-B-C type comprising alkanol, polyethylene oxide and polypropylene oxide. Suitable polyelectrolytes are polyacids or polybases. Examples of polyacids are alkali salts of polyacrylic acid or polyacid comb polymers. Examples of polybases are polyvinylamines or pol- yethyleneamines.
Suitable adjuvants are compounds, which have a neglectable or even no pesticidal activity themselves, and which improve the biological performance of the compound I on the target. Examples are surfactants, mineral or vegetable oils, and other auxilaries. 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 alkylisothiazolinones and benzisothiazolinones.
Suitable anti-freezing agents are ethylene glycol, propylene glycol, urea and glycerin.
Suitable anti-foaming 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 hexacyanofer- rate) and organic colorants (e.g. alizarin-, azo- and phthalocyanine colorants). Suitable tackifiers or binders are polyvinylpyrrolidone, polyvinylacetates, polyvinyl alcohols, pol- yacrylates, 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 (I) or an N-oxide or salt thereof 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 (I) or an N-oxide or salt thereof and 1 -10 wt% dispersant (e. g. polyvi- nylpyrrolidone) 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 (I) or an N-oxide or salt thereof 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 (I) or an N-oxide or salt thereof 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 (I) or an N-oxide or salt thereof 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 (I) or an N-oxide or salt thereof 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 (I) or an N-oxide or salt thereof are ground in a rotor-stator mill with addition of 1 -5 wt% dispersants (e.g. sodium lignosulfonate), 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 (I) or an N-oxide or salt thereof are comminuted with addition of 3-10 wt% dispersants (e.g. sodium lignosulfonate), 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 (I) or an N-oxide or salt thereof 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 (I) or an N-oxide or salt thereof, 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 radi- cal 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 monomer (e.g. diphenylme- thene-4,4'-diisocyanatae) are dispersed into an aqueous solution of a protective colloid (e.g. polyvinyl alcohol). The addition of a polyamine (e.g. hexamethylenediamine) results in the for- mation of a polyurea microcapsules. The monomers amount to 1 -10 wt%. The wt% relate to the total CS composition,
ix) Dustable powders (DP, DS)
1 -10 wt% of a compound (I) or an N-oxide or salt thereof 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 (I) or an N-oxide or salt thereof 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 (I) or an N-oxide or salt thereof 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% anti-freezing agents, 0,1 -1 wt% anti-foaming 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. The active substances are 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 in question give, after two-to-tenfold dilution, active substance concentrations of from 0.01 to 60% by weight, preferably from 0.1 to 40% by weight, in the ready-to-use preparations. Appli- cation can be carried out before or during sowing. Methods for applying or treating compound 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 I or the compositions thereof, respectively, are ap- plied on to the plant propagation 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 pesticides (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. Usually, 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, 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 I and/or active substances from the groups A) to O), 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 at least one and/or compound (I) or an N-oxide or salt thereof active substances from the groups M1 -M27 and Fl- FXII below, can be applied jointly (e.g. after tank mix) or consecutively.
The following list M of pesticides 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 combinations, but not to impose any limitation:
M.1 . Organo(thio)phosphate compounds: acephate, azamethiphos, azinphos-ethyl, az- inphos-methyl, chlorethoxyfos, chlorfenvinphos, chlormephos, chlorpyrifos, chlorpyrifos-methyl, coumaphos, cyanophos, demeton-S-methyl, diazinon, dichlorvos/ DDVP, dicrotophos, dimetho- ate, dimethylvinphos, disulfoton, EPN, ethion, ethoprophos, famphur, fenamiphos, fenitrothion, fenthion, flupyrazophos, fosthiazate, heptenophos, isoxathion, malathion, mecarbam, methamidophos, methidathion, mevinphos, monocrotophos, naled, omethoate, oxydemeton- methyl, parathion, parathion-methyl, phenthoate, phorate, phosalone, phosmet, phosphamidon, phoxim, pirimiphos-methyl, profenofos, propetamphos, prothiofos, pyraclofos, pyridaphenthion, quinalphos, sulfotep, tebupirimfos, temephos, terbufos, tetrachlorvinphos, thiometon, triazo- phos, trichlorfon, vamidothion;
M.2. Carbamate compounds: aldicarb, alanycarb, bendiocarb, benfuracarb, butocar- boxim, butoxycarboxim, carbaryl, carbofuran, carbosulfan, ethiofencarb, fenobucarb, formetan- ate, furathiocarb, isoprocarb, methiocarb, methomyl, metolcarb, oxamyl, pirimicarb, propoxur, thiodicarb, thiofanox, trimethacarb, XMC, xylylcarb, triazamate;
M.3. Pyrethroid compounds: acrinathrin, allethrin, d-cis-trans allethrin, d-trans allethrin, bifenthrin, bioallethrin, bioallethrin S-cylclopentenyl, bioresmethrin, cycloprothrin, cyfluthrin, be- ta-cyfluthrin, cyhalothrin, lambda-cyhalothrin, gamma-cyhalothrin, cypermethrin, alpha- cypermethrin, beta-cypermethrin, theta-cypermethrin, zeta-cypermethrin, cyphenothrin, del- tamethrin, empenthrin, esfenvalerate, etofenprox, fenpropathrin, fenvalerate, flucythrinate, flumethrin, tau-fluvalinate, halfenprox, imiprothrin, metofluthrin, permethrin, phenothrin, prallethrin, profluthrin, pyrethrin (pyrethrum), resmethrin, silafluofen, tefluthrin, tetramethrin, tral- omethrin, transfluthrin;
M.4. Juvenile hormone mimics: hydroprene, kinoprene, methoprene, fenoxycarb, pyriproxyfen;
M.5. Nicotinic receptor agonists/antagonists compounds: acetamiprid, bensultap, cartap hydrochloride, clothianidin, dinotefuran, imidacloprid, thiamethoxam, nitenpyram, nicotine, spi- nosad (allosteric agonist), spinetoram (allosteric agonist), thiacloprid, thiocyclam, thiosultap- sodium and AKD1022.
M.6. GABA gated chloride channel antagonist compounds: chlordane, endosulfan, gam- ma-HCH (lindane); ethiprole, fipronil, pyrafluprole, pyriprole
M.7. Chloride channel activators: abamectin, emamectin benzoate, milbemectin, lepimec- tin;
M.8. METI I compounds: fenazaquin, fenpyroximate, pyrimidifen, pyridaben,
tebufenpyrad, tolfenpyrad, flufenerim, rotenone;
M.9. METI II and III compounds: acequinocyl, fluacyprim, hydramethylnon;
M.10. Uncouplers of oxidative phosphorylation: chlorfenapyr, DNOC;
M.1 1 . Inhibitors of oxidative phosphorylation: azocyclotin, cyhexatin, diafenthiuron, fenbu- tatin oxide, propargite, tetradifon;
M.12. Moulting disruptors: cyromazine, chromafenozide, halofenozide, methoxyfenozide, tebufenozide;
M.13. Synergists: piperonyl butoxide, tribufos;
M.14. Sodium channel blocker compounds: indoxacarb, metaflumizone;
M.15. Fumigants: methyl bromide, chloropicrin sulfuryl fluoride;
M.16. Selective feeding blockers: crylotie, pymetrozine, flonicamid;
M.17. Mite growth inhibitors: clofentezine, hexythiazox, etoxazole;
M.18. Chitin synthesis inhibitors: buprofezin, bistrifluron, chlorfluazuron, diflubenzuron, flucycloxuron, flufenoxuron, hexaflumuron, lufenuron, novaluron, noviflumuron, teflubenzuron, triflumuron;
M.19. Lipid biosynthesis inhibitors: spirodiclofen, spiromesifen, spirotetramat; M.20. Octapaminergic agonsits: amitraz;
M.21. Ryanodine receptor modulators: flubendiamide and the phtalamid compound (R)-, (S)- 3- Chlor-N 1 -{2-methyl-4-[1 ,2,2,2 -tetrafluor-1 -(trifluormethyl)ethyl]phenyl}-N2-(1 -methyl-2- methylsulfonylethyl)phthalamid (M21.1 )
M.22. Isoxazoline compounds: 4-[5-(3,5-Dichloro-phenyl)-5-trifluoromethyl-4,5-dihydro- isoxazol-3-yl]-2-methyl-N-pyridin-2-ylmethyl-benzamide (M22.1 ), 4-[5-(3,5-Dichlorophenyl)-5- trifluoromethyl-4,5-dihydro-isoxazol-3-yl]-2-methyl-N-(2,2,2-trifluoro-ethyl)-benzamide (M22.2), 4-[5-(3,5-Dichloro-phenyl)-5-trifluoromethyl-4,5-dihydro-isoxazol-3-yl]-2-methyl-N-[(2,2,2- trifluoro-ethylcarbamoyl)-methyl]-benzamide (M22.3), 4-[5-(3,5-Dichloro-phenyl)-5- trifluoromethyl-4,5-dihydro-isoxazol-3-yl]-naphthalene-1 -carboxylic acid [(2,2,2-trifluoro- ethylcarbamoyl)-methyl]-amide (M22.4), 4-[5-(3,5-Dichlorophenyl)-5-trifluoromethyl-4,5-dihydro- isoxazol-3-yl]-N-[(methoxyimino)methyl]-2-methylbenzamide (M22.5) 4-[5-(3-Chloro-5- trifluoromethyl-phenyl)-5-trifluoromethyl-4,5-dihydro-isoxazol-3-yl]-2-methyl-N-[(2,2,2-trifluoro- ethylcarbamoyl)-methyl]-benzamide (M22.6), 4-[5-(3-Chloro-5-trifluoromethyl-phenyl)-5- trifluoromethyl-4,5-dihydro-isoxazol-3-yl]-naphthalene-1 -carboxylic acid [(2,2,2-trifluoro-ethyl- carbamoyl)-methyl]-amide (M22.7) and 5-[5-(3,5-Dichloro-4-fluoro-phenyl)-5-trifluoromethyl-4,5- dihydro-isoxazol-3-yl]-2-[1 ,2,4]triazol-1 -yl-benzonitrile (M22.8);
M.23. Anthranilamide compounds: chloranthraniliprole, cyantraniliprole, 5-Bromo-2-(3- chloro-pyridin-2-yl)-2H-pyrazole-3-carboxylic acid [4-cyano-2-(1 -cyclopropyl-ethylcarbamoyl)-6- methyl-phenyl]-amide (M23.1 ), 5-Bromo-2-(3-chloro-pyridin-2-yl)-2H-pyrazole-3-carboxylic acid [2-chloro-4-cyano-6-(1 -cyclopropyl-ethylcarbamoyl)-phenyl]-amide (M23.2), 5-Bromo-2-(3- chloro-pyridin-2-yl)-2H-pyrazole-3-carboxylic acid [2-bromo-4-cyano-6-(1 -cyclopropyl- ethylcarbamoyl)-phenyl]-amide(M23.3), 5-Bromo-2-(3-chloro-pyridin-2-yl)-2H-pyrazole-3- carboxylic acid [2-bromo-4-chloro-6-(1 -cyclopropyl-ethylcarbamoyl)-phenyl]-amide(M23.4), 5- Bromo-2-(3-chloro-pyridin-2-yl)-2H-pyrazole-3-carboxylic acid [2,4-dichloro-6-(1 -cyclopropyl- ethylcarbamoyl)-phenyl]-amide (M23.5), 5-Bromo-2-(3-chloro-pyridin-2-yl)-2H-pyrazole-3- carboxylic acid [4-chloro-2-(1 -cyclopropyl-ethylcarbamoyl)-6-methyl-phenyl]-amide (M23.6), N'- (2-{[5-Bromo-2-(3-chloro-pyridin-2-yl)-2H-pyrazole-3-carbonyl]-amino}-5-chloro-3-methyl- benzoyl)-hydrazinecarboxylic acid methyl ester (M23.7), N'-(2-{[5-Bromo-2-(3-chloro-pyridin-2- yl)-2H-pyrazole-3-carbonyl]-amino}-5-chloro-3-methyl-benzoyl)-N'-methyl-hydrazinecarboxylic acid methyl ester (M23.8), N'-(2-{[5-Bromo-2-(3-chloro-pyridin-2-yl)-2H-pyrazole-3-carbonyl]- amino}-5-chloro-3-methyl-benzoyl)-N,N'-dimethyl-hydrazinecarboxylic acid methyl ester (M23.9), N'-(3,5-Dibromo-2-{[5-bromo-2-(3-chloro-pyridin-2-yl)-2H-pyrazole-3-carbonyl]-amino}- benzoyl)-hydrazinecarboxylic acid methyl ester (M23.10), N'-(3,5-Dibromo-2-{[5-bromo-2-(3- chloro-pyridin-2-yl)-2H-pyrazole-3-carbonyl]-amino}-benzoyl)-N'-methyl-hydrazinecarboxylic acid methyl ester (M23.1 1 ) and N'-(3,5-Dibromo-2-{[5-bromo-2-(3-chloro-pyridin-2-yl)-2H- pyrazole-3-carbonyl]-amino}-benzoyl)-N,N'-dimethyl-hydrazinecarboxylic acid methyl ester (M23.12);
M.24. Malononitrile compounds: 2-(2,2,3,3,4,4,5,5-octafluoropentyl)-2-(3,3,3-trifluoro- propyl)malononitrile (CF2HCF2CF2CF2CH2C(CN)2CH2CH2CF3) (M24.1 ) and 2-(2,2,3,3, 4,4,5,5- octafluoropentyl)-2-(3,3,4,4,4-pentafluorobutyl)-malonodinitrile (CF2HCF2CF2- CF2CH2C(CN)2CH2CH2CF2CF3) (M24.2); M.25. Microbial disruptors: Bacillus thuringiensis subsp. Israelensi, Bacillus sphaericus, Bacillus thuringiensis subsp. Aizawai, Bacillus thuringiensis subsp. Kurstaki, Bacillus thuringiensis subsp. Tenebrionis;
M.26. Aminofuranone compounds:
4-{[(6-Bromopyrid-3-yl)methyl](2-fluoroethyl)amino}furan-2(5H)-on (M26.1 ), 4-{[(6-Fluoropyrid-3- yl)methyl](2,2-difluoroethyl)amino}furan-2(5H)-on (M26.2), 4-{[(2-Chloro1 ,3-thiazolo-5- yl)methyl](2-fluoroethyl)amino}furan-2(5H)-on (M26.3), 4-{[(6-Chloropyrid-3-yl)methyl](2- fluoroethyl)amino}furan-2(5H)-on (M26.4), 4-{[(6-Chloropyrid-3-yl)methyl] (2,2- difluoroethyl)amino}furan-2(5H)-on (M26.5), 4-{[(6-Chloro-5-fluoropyrid-3-yl)me- thyl](methyl)amino}furan-2(5H)-on (M26.6), 4-{[(5,6-Dichloropyrid-3-yl)methyl](2-fluoro- ethyl)amino}furan-2(5H)-on (M26.7), 4-{[(6-Chloro-5-fluoropyrid-3-yl)methyl](cyclopro- pyl)amino}furan-2(5H)-on (M26.8), 4-{[(6-Chloropyrid-3-yl)methyl](cyclopropyl)amino}furan- 2(5H)-on (M26.9) and 4-{[(6-Chloropyrid-3-yl)methyl](methyl)amino}furan-2(5H)-on (M26.10); M.27. Various compounds: aluminium phosphide, amidoflumet, benclothiaz, benzoximate, bifenazate, borax, bromopropylate, cyanide, cyenopyrafen, cyflumetofen, chinomethionate, di- cofol, fluoroacetate, phosphine, pyridalyl, pyrifluquinazon, sulfur, organic sulfur compounds, tartar emetic, sulfoxaflor, N-R'-2,2-dihalo-1 -R"cyclo-propanecarboxamide-2-(2,6-dichloro-a,a,a- trifluoro-p-tolyl)hydrazone or N-R'-2,2-di (R"')propionamide-2-(2,6-dichloro-a,a,a-trifluoro-p- tolyl)-hydrazone, wherein R' is methyl or ethyl, halo is chloro or bromo, R" is hydrogen or methyl and R'" is methyl or ethyl, 4-But-2-ynyloxy-6-(3,5-dimethyl-piperidin-1 -yl)-2-fluoro-pyrimidine
(M27.1 ), Cyclopropaneacetic acid, 1 ,1 '-[(3S,4R,4aR,6S,6aS,12R,12aS,12bS)-4-[[(2-cyclopropyl- acetyl)oxy]methyl]-1 ,3,4,4a,5,6,6a,12,12a,12b-decahydro-12-hydroxy-4,6a,12b-trimethyl-1 1 - oxo-9-(3-pyridinyl)-2H,1 1 H-naphtho[2,1 -b]pyrano[3,4-e]pyran-3,6-diyl]ester
(M27.2) and 8-(2-Cyclopropylmethoxy-4-trifluoromethyl-phenoxy)-3-(6-trifluoromethyl-pyridazin- 3-yl)-3-aza-bicyclo[3.2.1 ]octane(M27.3).
The commercially available compounds of the group M may be found in The Pesticide Manual, 14th Edition, British Crop Protection Council (2006) among other publications.
Paraoxon and their preparation have been described in Farm Chemicals Handbook, Volume 88, Meister Publishing Company, 2001 . Flupyrazofos has been described in Pesticide Sci- ence 54, 1988, p.237-243 and in US 4,822,779. AKD 1022 and its preparation have been described in US 6,300,348. M21 .1 is known from WO 2007/101540. Isoxazolines M22.1 to M22.8 have been described in e.g. WO 2005/085216, WO 2007/079162, WO 2007/026965, WO 2009/126668 and WO 2009/051956. Anthranilamides M23.1 to M23.6 have been described in WO 2008/72743 and WO 2008/72783, those M23.7 to M23.12 in WO 2007/043677. Malono- nitriles M24.1 and M24.2 have been described in WO 02/089579, WO 02/090320, WO
02/090321 , WO 04/006677, WO 05/068423, WO 05/ 068432 and WO 05/063694. Amino- furanones M26.1 to M6.10 have been described eg. in WO 2007/1 15644. Alkynylether M27.1 is described e.g. in JP 2006131529. Organic sulfur compounds have been described in WO 2007060839. Pyripyropene derivative M27.2 has been described in WO 2008/66153 and WO 2008/108491 . Pyridazin M27.3 has been described in JP 2008/1 15155.
The following list of active 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.I-1 ) Inhibitors of complex III at Qo site (e.g. strobilurins)
strobilurins: azoxystrobin, coumethoxystrobin, coumoxystrobin, dimoxystrobin, enestroburin, fluoxastrobin, kresoxim-methyl, metominostrobin, orysastrobin, picoxystrobin, pyraclostrobin, pyrametostrobin, pyraoxystrobin, pyribencarb, triclopyricarb/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, bixafen, boscalid, carboxin, fenfuram, fenhexamid, fluopyram, flutolanil, furametpyr, isopyrazam, isotianil, mepronil, oxycarboxin, 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, N-(4'- trifluoromethylthiobiphenyl-2-yl)-3-difluoromethyl-1-methyl-1 H pyrazole-4-carboxamide and N- (2-(1 ,3,3-trimethyl-butyl)-phenyl)-1 ,3-dimethyl-5-fluoro-1 H-pyrazole-4-carboxamide;
F.I-3) Inhibitors of complex III at Qi site: cyazofamid, amisulbrom;
F.I-4) Other respiration inhibitors (complex I, uncouplers)
diflumetorim; tecnazen; ferimzone; ametoctradin; silthiofam;
nitrophenyl derivates: binapacryl, dinobuton, dinocap, fluazinam, nitrthal-isopropyl,
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, dinicona- zole, diniconazole-M, epoxiconazole, fenbuconazole, fluquinconazole, flusilazole, flutriafol, hexaconazole, imibenconazole, ipconazole, metconazole, myclobutanil, paclobutrazole, penco- nazole, propiconazole, prothioconazole, simeconazole, tebuconazole, tetraconazole, triadime- fon, triadimenol, triticonazole, uniconazole;
imidazoles: imazalil, pefurazoate, oxpoconazole, prochloraz, triflumizole;
pyrimidines, pyridines and piperazines: fenarimol, nuarimol, pyrifenox, triforine;
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, metalaxyl, metalaxyl-M (mefenoxam), ofurace, oxadixyl;
isoxazoles and iosothiazolones: hymexazole, octhilinone;
F.III-2) DNA topisomerase inhibitors: oxolinic acid;
F.III-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, fluopicolide, zox- amide;
F.IV-3) Actin inhibitors: benzophenones: metrafenone;
F.V) Inhibitors of amino acid and protein synthesis
F.V-1 ) Mmethionine 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, mildiomycin, 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 acides
carbamates: propamocarb, propamocarb-hydrochlorid
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, flusulfamide, hexachlorobenzene, pentachlorphenole and its salts, phthalide, tolylfluanid, N-(4-chloro-2-nitro- phenyl)-N-ethyl-4-methyl-benzenesulfonamide;
F.VIII-4) Guanidines: guanidine, dodine, dodine free base, guazatine, guazatine-acetate, imi- noctadine, iminoctadine-triacetate, iminoctadine-tris(albesilate);
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, difen- zoquat, difenzoquat-methylsulfate, diphenylamin, flumetover, flusulfamide, flutianil, methasul- focarb, 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, pyrisoxa- zole, 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) cyclopropanecarboxylic 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, flurprimidol, fluthiacet, forchlorfenuron, gibberellic acid, inabenfide, indole-3-acetic acid , maleic hydrazide, mefluidide, mepiquat (mepiquat chloride), naphthaleneacetic acid, N 6 benzyladenine, paclobutrazol, prohexadione (prohexadione- calcium), prohydrojasmon, thidiazuron, triapenthenol, tributyl phosphorotrithioate, 2,3,5- triiodobenzoic acid , trinexapac-ethyl and uniconazole;
F.XI I) Biological control agents
antifungal biocontrol agents: Bacillus substilis strain with NRRL No. B-21661 (e.g. RHAPSODY®, SERENADE® MAX and SERENADE® ASO from AgraQuest, Inc., USA.), Bacillus pu- milus strain with NRRL No. B-30087 (e.g. SONATA® and BALLAD® Plus from AgraQuest, Inc., USA), Ulocladium oudemansii (e.g. the product BOTRY-ZEN from BotriZen Ltd., New Zealand), Chitosan (e.g. ARMOUR-ZEN from BotriZen Ltd., New Zealand).
Applications 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 compounds of formula (I), their N-oxides and salts or composition(s) containing them by any application method known in the art. As such, "contacting" includes both direct contact (applying the compounds/compositions directly 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 the invention 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 at least one compound of the invention. The term "crop" refers both to growing and harvested crops.
The compounds of the 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, 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 compounds of the 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 a insecticidally effective amount of the active compounds. 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 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 materi- als, plants, seeds, soils, surfaces or spaces to be protected from animal attack or infestation with a pesticidally effective amount of at least one compound of the invention or a composition comprising such a compound.
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 at least one com- pound of the invention. 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 the invention may be also used to protect growing plants from attack or infestation by pests by contacting the plant with a pesticidally effective amount of at least one compound of the invention. 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 limited to targeted post-transtional modification of protein(s) (oligo- or polypeptides) poly for example by glycosylation or polymer additions such as prenyl- ated, 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 hydroxy 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 0 242 236, EP-A 242 246) 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 commercially 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, truncated 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 disclosed, 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 taxo- nomic 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 So- lanum bulbocastanum) or T4-lysozym (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 environmental 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 example 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 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 com- pounds/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 compound 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 the invention 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 the invention 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 particular necessities in terms of stickyness, 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 compound.
Formulations of compounds of the invention 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 compound, 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, dimethylformamide, N-methylpyrrolidone, dimethyl sulfoxide, aromatic hydrocarbons such as toluene, xylene, water, furthermore auxiliaries such as emulsifi- ers 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 carbonyl 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 compounds of the invention and their 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 im- pregnation 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 including 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, Methyl- neodecanamide (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 aliphatic 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 material into emulsions or dispersions of the insecticide or spraying them onto the nets.
The compounds of the invention and their 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, elec- trie 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 the invention 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 concrete, 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, a compound of the invention is applied to the crops or the surrounding soil, or is directly applied to the nest of ants or the like.
Seed treatment
The compounds of the invention 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 the invention 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 invention therefore comprises a method for the protection of seeds from insects, in particular from soil insects and of the seedlings' 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 invention 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 form 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 invention also comprises seeds coated with or containing the active compound.
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, sugarbeet, 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 compounds of the invention may be used for treating seed from plants, which tolerate the action of herbicides or fungicides or insecticides owing to breeding, including genetic engineering methods.
For example, the compound of the invention can be employed in treatment of seeds from plants, which are resistant to herbicides from the group consisting of the sulfonylureas, imidazo- linones, glufosinate-ammonium or glyphosate-isopropylammonium and analogous active substances (see for example, EP-A 242 236, EP-A 242 246) (WO 92/00377) (EP-A 257 993, US 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 142 924, EP-A 193 259),
Furthermore, the compound of the invention can be used for the treatment of seed 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 the invention 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, solu- tions 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. Typcially, a FS formulation may comprise 1 -800 g/l of active ingredient, 1 -200 g/l Surfactant, 0 to 200 g/l anti- freezing 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 the invention 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 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 polyethylenepyrimidines, polysaccharides like celluloses, tylose and starch, polyolefin homo- and copolymers like olefin/maleic anhydride copolymers, polyure- thanes, 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.
An example of a gelling agent is carrageen (Satiagel®)
In the treatment of seed, the application rates of the compounds of the invention 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 provides 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.
Animal health
The compounds of formula (I), their N-oxides and/or veterinarily acceptable salts thereof are in particular also suitable for being used for combating parasites in and on animals.
One object of the invention is therefore 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 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 control of parasites.
The invention also relates to compositions containing a parasiticidally effective amount of at least one compound of formula (I), N-oxide or veterinarily acceptable salt thereof and an acceptable carrier, for combating parasites in and on animals.
The invention also provides a method for treating, controlling, preventing and protecting animals against infestation and infection by parasites, which comprises orally, topically or parenteral^ administering or applying to the animals a parasiticidally effective amount of a compound of the invention 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 the invention 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 the invention are suitable for combating endo- and ectoparasites in and on animals.
Compounds of the invention 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 the invention 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, chiggers, gnats, mosquitoes and fleas.
The compounds of the invention and compositions comprising them are suitable for systemic and/or non-systemic control of ecto- and/or endoparasites. They can be active against all or some stages of development.
The compounds of the invention are especially useful for combating ectoparasites.
The compounds of the invention are especially useful for combating parasites of the following orders and species, respectively:
fleas (Siphonaptera), e.g. Ctenocephalides felis, Ctenocephalides cams, Xenopsylla cheopis, Pulex irritans, Tunga penetrans, and Nosopsyllus fasciatus,
cockroaches (Blattaria - Blattodea), e.g. Blattella germanica, Blattella asahinae, Periplaneta americana, Periplaneta japonica, Periplaneta brunnea, Periplaneta fuligginosa, Periplaneta australasiae, and Blatta orientalis,
flies, mosquitoes (Diptera), e.g. Aedes aegypti, Aedes albopictus, Aedes vexans, Anastrepha ludens, Anopheles maculipennis, Anopheles crucians, Anopheles albimanus, Anopheles gambiae, Anopheles freeborni, Anopheles leucosphyrus, Anopheles minimus, Anopheles quadrimaculatus, Calliphora vicina, Chrysomya bezziana, Chrysomya hominivorax, Chrysomya macellaria, Chrysops discalis, Chrysops silacea, Chrysops atlanticus, Cochliomyia hominivorax, Cordylobia anthropophaga, Culicoides furens, Culex pi pi ens, Culex nigripalpus, Culex quinquefasciatus, Culex tarsalis, Culiseta inornata, Culiseta melanura, Dermatobia hominis, Fannia canicularis, Gasterophilus intestinalis, Glossina morsitans, Glossina palpalis, Glossina fuscipes, Glossina tachinoides, Haematobia irritans, Haplodiplosis equestris, Hippelates spp., Hypoderma lineata, Leptoconops torrens, Lucilia caprina, Lucilia cuprina, Lucilia sericata, Lycoria pectoralis, Mansonia spp., Musca domestica, Muscina stabulans, Oestrus ovis, Phlebotomus argentipes, Psorophora columbiae, Psorophora discolor, Prosimulium mixtum, Sarcophaga haemorrhoidalis, Sarcophaga sp., Simulium vittatum, Stomoxys calcitrans, Tabanus bovinus, Tabanus atratus, Tabanus lineola, and Tabanus similis,
lice (Phthiraptera), e.g. Pediculus humanus capitis, Pediculus humanus corporis, Pthirus pubis, Haematopinus eurysternus, Haematopinus suis, Linognathus vituli, Bovicola bovis, Menopon gallinae, Menacanthus stramineus and Solenopotes capillatus.
ticks and parasitic mites (Parasitiformes): ticks (Ixodida), e.g. Ixodes scapularis, Ixodes holocyclus, Ixodes pacificus, Rhiphicephalus sanguineus, Dermacentor andersoni, Dermacentor variabilis, Amblyomma americanum, Ambryomma maculatum, Ornithodorus hermsi,
Ornithodorus turicata and parasitic mites (Mesostigmata), e.g. Ornithonyssus bacoti and Dermanyssus gallinae,
Actinedida (Prostigmata) und Acaridida (Astigmata) e.g. Acarapis spp., Cheyletiella spp., Ornithocheyletia spp., Myobia spp., Psorergates spp., Demodex spp., Trombicula spp.,
Listrophorus spp., Acarus spp., Tyrophagus spp., Caloglyphus spp., Hypodectes spp.,
Pterolichus spp., Psoroptes spp., Chorioptes spp., Otodectes spp., Sarcoptes spp., Notoedres spp.,Knemidocoptes spp., Cytodites spp., and Laminosioptes spp,
Bugs (Heteropterida): Cimex lectularius, Cimex hemipterus, Reduvius senilis, Triatoma spp., Rhodnius ssp., Panstrongylus ssp. and Arilus critatus,
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:
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, Bunostomum spp. (Hookworm), Trichostrongylus spp., Haemonchus contortus., Ostertagia spp., Cooperia spp., Nematodirus spp., Dictyocaulus spp., Cyathostoma spp., Oesophagostomum spp.,
Stephanurus dentatus, Ollulanus spp., Chabertia spp., Stephanurus dentatus , Syngamus trachea, Ancylostoma spp., Uncinaria spp., Globocephalus spp., Necator spp., Metastrongylus spp., Muellerius capillaris, Protostrongylus spp., Angiostrongylus spp., Parelaphostrongylus spp. Aleurostrongylus abstrusus, and Dioctophyma 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 Habronema 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., Dicrocoelium spp., Fasciolopsis buski, Clonorchis sinensis, Schistosoma spp., Trichobilharzia spp., Alaria a lata, 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 (I) and compositions containing them for combating mosquitoes is especially preferred.
The use of the compounds of the invention and compositions containing them for combating flies is a further preferred embodiment of the present invention.
Furthermore, the use of the compounds of the invention and compositions containing them for combating fleas is especially preferred.
The use of the compounds of the invention and compositions containing them for combating ticks is a further preferred embodiment of the present invention.
The compounds of the invention also are especially useful for combating endoparasites (roundworms nematoda, thorny headed worms and planarians).
Administration can be carried out both prophylactically and therapeutically.
Administration of the compounds of the invention is carried out directly or in the form of suitable preparations, orally, topically/dermally or parenterally.
For oral administration to warm-blooded animals, compounds of the invention 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 the invention 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 compound of the invention, preferably with 0.5 mg/kg to 100 mg/kg of animal body weight per day.
Alternatively, the compounds of the invention may be administered to animals parenterally, for example, by intraruminal, intramuscular, intravenous or subcutaneous injection. The compounds of the invention may be dispersed or dissolved in a physiologically acceptable carrier for subcutaneous injection. Alternatively, the compounds of the invention may be formulated into an implant for subcutaneous administration. In addition the compound of the invention 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 the invention.
The compounds of the invention 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 the invention. In addition, the compounds of the invention 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 compound 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, tablets, boluses, capsules; aerosols and inhalants, and active compound-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, pre- servatives, 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 compounds can optionally be dissolved in physiologically tolerable vegetable or synthetic oils which are suitable for injection.
Suitable solubilizers are solvents which promote the dissolution of the active compound 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 esters, 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.
Further suitable solvents are polypropylene glycol, phenyl ethanol, phenoxy ethanol, ester such as ethyl or butyl acetate, benzyl benzoate, ethers such as alkyleneglycol alkylether, e.g. dipropylenglycol monomethylether, ketons such as acetone, methylethylketone, aromatic hydrocarbons, vegetable and synthetic oils, dimethylformamide, dimethylacetamide, transcutol, solketal, propylencarbonate, and mixtures thereof.
It may be advantageous to add thickeners during preparation. Suitable thickeners are in- organic thickeners such as bentonites, colloidal silicic acid, aluminium monostearate, organic thickeners such as cellulose derivatives, polyvinyl alcohols and their copolymers, acrylates and methacrylates.
Gels are applied to or spread on the skin or introduced into body cavities. Gels are prepared by treating solutions which have been prepared as described in the case of the injection solutions with sufficient thickener that a clear material having an ointment-like consistency results. The thickeners employed are the thickeners given above.
Pour-on formulations are poured or sprayed onto limited areas of the skin, the active compound penetrating the skin and acting systemically. Pour-on formulations are prepared by dissolving, suspending or emulsifying the active compound in suitable skin-compatible solvents or solvent mixtures. If appropriate, other auxiliaries such as colorants, bioabsorption-promoting substances, antioxidants, light stabilizers, ad- hesives are added.
Suitable solvents which are: water, alkanols, glycols, polyethylene glycols, polypropylene glycols, glycerol, aromatic alcohols such as benzyl alcohol, phenylethanol, phenoxyethanol, esters such as ethyl acetate, butyl acetate, benzyl benzoate, ethers such as alkylene glycol al- kyl ethers such as dipropylene glycol monomethyl ether, diethylene glycol mono-butyl ether, ketones such as acetone, methyl ethyl ketone, cyclic carbonates such as propylene carbonate, ethylene carbonate, aromatic and/or aliphatic hydrocarbons, vegetable or synthetic oils, DMF, dimethylacetamide, n-alkylpyrrolidones such as methylpyrrolidone, n-butylpyrrolidone or n- octylpyrrolidone, N-methylpyrrolidone, 2-pyrrolidone, 2,2-dimethyl-4-oxy-methylene-1 ,3-diox- olane and glycerol formal.
Suitable colorants are all colorants permitted for use on animals and which can be dissolved or suspended.
Suitable absorption-promoting substances are, for example, DMSO, spreading oils such as isopropyl myristate, dipropylene glycol pelargonate, silicone oils and copolymers thereof with polyethers, fatty acid esters, triglycerides, fatty alcohols.
Suitable antioxidants are sulfites or metabisulfites such as potassium metabisulfite, ascor- bic acid, butylhydroxytoluene, butylhydroxyanisole, tocopherol.
Suitable light stabilizers are, for example, novantisolic acid.
Suitable adhesives are, for example, cellulose derivatives, starch derivatives, polyacry- lates, natural polymers such as alginates, gelatin.
Emulsions can be administered orally, dermally or as injections.
Emulsions are either of the water-in-oil type or of the oil-in-water type.
They are prepared by dissolving the active compound either in the hydrophobic or in the hydrophilic phase and homogenizing this with the solvent of the other phase with the aid of suitable emulsifiers and, if appropriate, other auxiliaries such as colorants, absorption-promoting substances, preservatives, antioxidants, light stabilizers, viscosity-enhancing substances.
Suitable hydrophobic phases (oils) are:
liquid paraffins, silicone oils, natural vegetable oils such as sesame oil, almond oil, castor oil, synthetic triglycerides such as caprylic/capric biglyceride, triglyceride mixture with vegetable fatty acids of the chain length Cs-Ci2 or other specially selected natural fatty acids, partial gly- ceride mixtures of saturated or unsaturated fatty acids possibly also containing hydroxyl groups, mono- and diglycerides of the Cs-do fatty acids,
fatty acid esters such as ethyl stearate, di-n-butyryl adipate, hexyl laurate, dipropylene glycol perlargonate, esters of a branched fatty acid of medium chain length with saturated fatty alcohols of chain length C16-C18, isopropyl myristate, isopropyl palmitate, caprylic/capric acid esters of saturated fatty alcohols of chain length C12-C18, isopropyl stearate, oleyl oleate, decyl oleate, ethyl oleate, ethyl lactate, waxy fatty acid esters such as synthetic duck coccygeal gland fat, dibutyl phthalate, diisopropyl adipate, and ester mixtures related to the latter, fatty alcohols such as isotridecyl alcohol, 2-octyldodecanol, cetylstearyl alcohol, oleyl alcohol, and fatty acids such as oleic acid and mixtures thereof. Suitable hydrophilic phases are: water, alcohols such as propylene glycol, glycerol, sorbitol and mixtures thereof.
Suitable emulsifiers are:
non-ionic surfactants, e.g. polyethoxylated castor oil, polyethoxylated sorbitan monooleate, sor- bitan monostearate, glycerol monostearate, polyoxyethyl stearate, alkylphenol polyglycol ether; ampholytic surfactants such as di-sodium N-lauryl-p-iminodipropionate or lecithin;
anionic surfactants, such as sodium lauryl sulfate, fatty alcohol ether sulfates, mono/dialkyl polyglycol ether orthophosphoric acid ester monoethanolamine salt;
cation-active surfactants, such as cetyltrimethylammonium chloride.
Suitable further auxiliaries are: substances which enhance the viscosity and stabilize the emulsion, such as carboxymethylcellulose, methylcellulose and other cellulose and starch derivatives, polyacrylates, alginates, gelatin, gum arabic, polyvinylpyrrolidone, polyvinyl alcohol, copolymers of methyl vinyl ether and maleic anhydride, polyethylene glycols, waxes, colloidal silicic acid or mixtures of the substances mentioned.
Suspensions can be administered orally or topically/dermally. They are prepared by suspending the active compound in a suspending agent, if appropriate with addition of other auxiliaries such as wetting agents, colorants, bioabsorption-promoting substances, preservatives, antioxidants, light stabilizers.
Liquid suspending agents are all homogeneous solvents and solvent mixtures.
Suitable wetting agents (dispersants) are the emulsifiers given above.
Other auxiliaries which may be mentioned are those given above.
Semi-solid preparations can be administered orally or topically/dermally. They differ from the suspensions and emulsions described above only by their higher viscosity.
For the production of solid preparations, the active compound is mixed with suitable excip- ients, if appropriate with addition of auxiliaries, and brought into the desired form.
Suitable excipients are all physiologically tolerable solid inert substances. Those used are inorganic and organic substances. Inorganic substances are, for example, sodium chloride, carbonates such as calcium carbonate, hydrogencarbonates, aluminium oxides, titanium oxide, silicic acids, argillaceous earths, precipitated or colloidal silica, or phosphates. Organic sub- stances are, for example, sugar, cellulose, foodstuffs and feeds such as milk powder, animal meal, grain meals and shreds, starches.
Suitable auxiliaries are preservatives, antioxidants, and/or colorants which have been mentioned above.
Other suitable auxiliaries are lubricants and glidants such as magnesium stearate, stearic acid, talc, bentonites, disintegration-promoting substances such as starch or crosslinked polyvinylpyrrolidone, binders such as starch, gelatin or linear polyvinylpyrrolidone, and dry binders such as microcrystalline cellulose.
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, retarda- tion, 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 generally comprisefrom about 0.001 to 95% of the compound of the invention.
Generally it is favorable to apply the compounds of the invention 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 ectopar- asites 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 the invention against endopar- asites 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, the compositions comprising the compounds of the invention 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 the inven- tion 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 derivatives, polyamides and polyester which are sufficiently compatible with the compounds of the invention. 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 invention is now illustrated in further details by the following examples, without imposing any limitation thereto.
Examples
The compounds can be characterized e.g. by coupled High Performance Liquid Chromatography / mass spectrometry (HPLC/MS), by 1 H-NMR and/or by their melting points. The following analytical procedures were employed:
Method A: Analytical HPLC column: RP-18 column Chromolith Speed ROD from Merck KgaA (Germany). Elution: acetonitrile + 0.1 % trifluoroacetic acid (TFA) / water + 0.1 % trifluoroacetic acid (TFA) in a ratio of from 5:95 to 95:5 in 5 minutes at 40 °C.
Method B: Analytical UPLC column: Phenomenex Kinetex 1 ,7 μηι XB-C18 100A; 50 x 2.1 mm; mobile phase: A: water + 0.1 % trifluoroacetic acid (TFA); B: acetonitrile + 0.1 % TFA; gradient: 5-100% B in 1.50 minutes; 100% B 0.20 min; flow: 0,8-1 ,0mL/min in 1 ,50 minutes at 60°C. MS-method: ESI positive.
1 H-NMR. The signals are characterized by chemical shift (ppm) vs. tetramethylsilane, by their multiplicity and by their integral (relative number of hydrogen atoms given). The following ab- breviations are used to characterize the multiplicity of the signals: m = multiplett, q = quartet, t = triplet, d = doublet and s = singlet.
S. Synthesis Examples
Figure imgf000110_0001
A suspension of iodide S-1 (130 mg, 0.27 mmol), boronic acid S-2 (40 mg, 0.27 mmol), cesium carbonate (216 mg, 0.66 mmol) and 1 ,1 -bis(diphenylphosphino)ferrocene] dichloropalladium(ll) (43 mg, 0.05 mmol) in dioxane (5 ml.) was heated at 80°C for 16 h. The reaction mixture was then concentrated under reduced pressure and purified directly by flash chromatography eluting with a dichloromethane/methanol gradient afforded the aldehyde S-3 (23 mg, 18%).
Figure imgf000110_0002
A solution of aldehyde S-3 (23 mg, 0.05 mmol) and hydroxylamine hydrochloride (6 mg, 0.07 mmol) in ethanol (10 ml.) was stirred at room temperature for 16 h. The reaction mixture was then concentrated under reduced pressure and purified directly by flash chromatography eluting with a dichloromethane/methanol gradient afforded the oxime C-1 (14 mg, 57%).
C. Compound examples Compound examples of the present invention are shown in the synthesis examples
above.
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.
Analytical HPLC: 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.
RT or r.t. = HPLC retention time; m/z of the [M+H]+, [M+Na]+ or [M+K]+ peaks. 1H-NMR, respectively 13C-NMR: The signals are characterized by chemical shift (ppm) vs. tet- ramethylsilane, 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 = multiplet, q = quartet, t = triplet, d = doublet and s = singlet.
The compounds of formula (l-A) in the following Table D were obtained by analogous methods:
Figure imgf000111_0001
Table D Compound Examples
Figure imgf000112_0001
Figure imgf000113_0001
Figure imgf000114_0001
Figure imgf000115_0001
Figure imgf000116_0001
Figure imgf000117_0001
Figure imgf000118_0001
Figure imgf000119_0001
Figure imgf000120_0001
Figure imgf000121_0001
Figure imgf000122_0001
Figure imgf000123_0001
Figure imgf000124_0001
Figure imgf000125_0001
Figure imgf000126_0001
B. Biological examples
The biological activity of the compounds of formula (I) of the invention can
evaluated in biological tests as described in the following.
B.1. 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 Kinetic HV at a rate of 0.01 % v/v.
Thrips potency of each compound was evaluated by using a floral-immersion technique. All petals of individual, intact orchid flowers were dipped into treatment solution and allowed to dry in Petri dishes. Treated petals were placed into individual re-sealable plastic along with about 20 adult thrips. 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 petal. The percent mortality was recorded 72 hours after treatment.
In this test, compounds C-1 1 , C-18, C-19, C-30, C-35, C-39, C-41 , C-47, C-56, C-58, C-63, C-71 , C-77, C-79, C-80 at 500 ppm showed over 75 % mortality in comparison with untreated controls.
B.2. 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-5, C-15, C-16, C-17, C-19, C-21 , C-22, C-23, C-24, C-25, C-34, C-35, C-51 , C-61 , C-65, C-67, C-69, C-70, C-71 , C-80, C-83 at 1415 ppm showed over 75 % mortality in comparison with untreated controls.
B.3. Cowpea aphid {aphis craccivora)
The active compound is dissolved at the desired concentration in a mixture of 1 :1 (vohvol) distilled water : acetone. Surfactant (Kinetic HV) is added at a rate of 0.01 % (vol/vol). The test solution is prepared at the day of use.
Potted cowpea plants were colonized with approximately 50 - 100 aphids of various stages by manually transferring a leaf tissue cut from infested plant 24 hours before application. Plants were sprayed after the pest population has been recorded. Treated plants are maintained on light carts at about 28°C. Percent mortality was assessed after 72 hours.
In this test, compounds C-4, C-75, C-76, C-77 at 500 ppm showed over 75 % mortality in comparison with untreated controls. B.4. Silverleaf whitefly (Bemisia argentifolii)
The active compounds were formulated by a Tecan liquid handler in 100% cyclohexanone as a 10,000 ppm solution supplied in tubes. The 10,000 ppm solution was serially diluted in 100% cyclohexanone to make interim solutions. These served as stock solutions for which final dilutions were made by the Tecan in 50% acetone:50% water (v/v) into 5 or 10ml glass vials. A nonionic surfactant (Kinetic®) was included in the solution at a volume of 0.01 % (v/v). The vials were then inserted into an automated electrostatic sprayer equipped with an atomizing nozzle for application to plants/insects.
Cotton plants at the cotyledon stage (one plant per pot) were sprayed by an automated electrostatic plant sprayer equipped with an atomizing spray nozzle. The plants were dried in the sprayer fume hood and then removed from the sprayer. Each pot was pla-ced into a plastic cup and about 10 to 12 whitefly adults (approximately 3-5 days old) were introduced. The insects were collected using an aspirator and a nontoxic Tygon® tubing connected to a barrier pipette tip. The tip, containing the collected insects, was then gently inserted into the soil containing the treated plant, allowing insects to crawl out of the tip to reach the foliage for feeding. Cups were covered with a reusable screened lid. Test plants were maintained in a growth room at about 25°C and about 20-40% relative humidity for 3 days, avoiding direct exposure to fluorescent light (24 hour photoperiod) to prevent trapping of heat inside the cup. Mortality was assessed 3 days after treatment, compared to untreated control plants.
In this test, compounds C-4, C-22, C-23, C-24 at 500 ppm showed over 75 % mortality in comparison with untreated controls. B.5. Mediterranean fruitfly {Ceratitis capitata)
For evaluating control of Mediterranean fruitfly (Ceratitis capitata) the test unit consisted of microtiter plates containing an insect diet and 50-80 C. capitata 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 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-25, C-32, C-43, C-55, C-61 , C-84 at 1415 ppm showed over 75 % mortality in comparison with untreated controls.
B.6. 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-19, C-22, C-23, C-24, C-25, C-31 , C-32, C-33, C-34, C-35, C-37, C-39, C-46, C-51 , C-52, C-61 , C-67, C-70, C-71 , C-77, C-79, C-84 at 1415 ppm showed over 75 % mortality in comparison with untreated controls.
B.7. 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 mortali- ty and fecundity was then visually assessed.
In this test, compounds C-2, C-3, C-4, C-16, C-17, C-18, C-19, C-20, C-22, C-25, C-26, C-32, C-33, C-34, C-35, C-37, C-38, C-39, C-41 , C-42, C-43, C-45, C-46, C-47, C-49, C-50, C-51 , C-52, C-55, C-56, C-58, C-61 , C-63, C-65, C-71 , C-73, C-77, C-78, C-79, C-80, C-81 , C-84 at 1415 ppm showed over 75 % mortality in comparison with untreated controls.
B.8. Green Peach Aphid (Myzus persicae), mixed population
The active compounds were formulated by a Tecan liquid handler in 100% cyclohexanone as a 10,000 ppm solution supplied in tubes. The 10,000 ppm solution was serially diluted in 100% cyclohexanone to make interim solutions. These served as stock solutions for which final dilutions were made by the Tecan in 50% acetone:50% water (v/v) into 5 or 10ml glass vials. A nonionic surfactant (Kinetic®) was included in the solution at a volume of 0.01 % (v/v). The vials were then inserted into an automated electrostatic sprayer equipped with an atomizing nozzle for application to plants/insects.
Bell pepper plants at the first true-leaf stage were infested prior to treatment by placing heavily infested leaves from the main colony on top of the treatment plants. Aphids were allowed to transfer overnight to accomplish an infestation of 30-50 aphids per plant and the host leaves were removed. The infested plants were then sprayed by an automated electrostatic plant sprayer equipped with an atomizing spray nozzle. The plants were dried in the sprayer fume hood, removed, and then maintained in a growth room under fluorescent lighting in a 24-hr pho- toperiod at about 25°C and about 20-40% relative humidity. Aphid mortality on the treated plants, relative to mortality on untreated control plants, was determined after 5 days.
In this test, compounds C-31 , C-33, C-37, C-38, C-42, C-45, C-46, C-49, C-51 , C-55, C-56, C-76, C-77 at 300 ppm showed over 75 % mortality in comparison with untreated controls.
B.9. Rice green leafhopper {Nephotettix virescens)
Rice seedlings were cleaned and washed 24 hours before spraying. The active compounds were formulated in 1 :1 acetone:water (vohvol), and 0.01 % vol/vol surfactant (Kinetic HV) was added. Potted rice seedlings were sprayed with 5-6 ml test solution, air dried, covered with Mylar cages 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-4, C-30, C-32, C-39, C-41 , C-42, C-63 at 500 ppm showed over 75 % mortality in comparison with untreated controls.
B.10. Rice brown plant hopper {Nilaparvata lugens)
Rice seedlings were cleaned and washed 24 hours before spraying. The active compounds were formulated in 1 :1 acetone:water (vohvol) and 0.01 % vol/vol surfactant (Kinetic HV) was added. Potted rice seedlings were sprayed with 5 ml test solution, air dried, covered with Mylar 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-18, C-20, C-25, C-26, C-30, C-32, C-39, C-41 , C-42, C-43, C-47, C-63 at 500 ppm showed over 75 % mortality in comparison with untreated controls.
B.1 1. Diamond back moth {Plutella xylostella)
The active compound is dissolved at the desired concentration in a mixture of 1 :1 (vohvol) dis- tilled water : aceteone. Surfactant (Kinetic HV) is added at a rate of 0.01 % (vol/vol). The test solution is prepared at the day of use.
Leaves of cabbage were dipped in test solution and air-dried. Treated leaves were placed in petri dishes lined with moist filter paper and inoculated with ten 3rd instar larvae. Mortality was recorded 72 hours after treatment. Feeding damages were also recorded using a scale of 0- 100%.
In this test, compounds C-1 , C-17, C-18, C-19, C-22, C-23, C-24, C-25, C-26, C-30, C-31 , C-32, C-33, C-34, C-35, C-39, C-42, C-45, C-49, C-50, C-51 , C-52, C-71 , C-78, C-79, C-83 at 500 ppm showed over 75 % mortality in comparison with untreated controls.
B.12. Southern armyworm {Spodoptera eridania), 2nd instar larvae
The active compounds were formulated by a Tecan liquid handler in 100% cyclohexanone as a 10,000 ppm solution supplied in tubes. The 10,000 ppm solution was serially diluted in 100% cyclohexanone to make interim solutions. These served as stock solutions for which final dilu- tions were made by the Tecan in 50% acetone:50% water (v/v) into 5 or 10ml glass vials. A nonionic surfactant (Kinetic®) was included in the solution at a volume of 0.01 % (v/v). The vials were then inserted into an automated electrostatic sprayer equipped with an atomizing nozzle for application to plants/insects.
Lima bean plants (variety Sieva) were grown 2 plants to a pot and selected for treatment at the 1 st true leaf stage. Test solutions were sprayed onto the foliage by an automated electrostatic plant sprayer equipped with an atomizing spray nozzle. The plants were dried in the sprayer fume hood and then removed from the sprayer. Each pot was placed into perforated plastic bags with a zip closure. About 10 to 1 1 armyworm larvae were placed into the bag and the bags zipped closed. Test plants were maintained in a growth room at about 25°C and about 20-40% relative humidity for 4 days, avoiding direct exposure to fluorescent light (24 hour photoperiod) to prevent trapping of heat inside the bags. Mortality and reduced feeding were assessed 4 days after treatment, compared to untreated control plants. In this test, compounds C-23, C-24, C-45, C-51 at 300 ppm showed over 75 % mortality in comparison with untreated controls.

Claims

Claims
1 . A substituted mesoionic compound of formula (I),
Figure imgf000132_0001
wherein
X is O or S;
Y is O or S;
A, A0 is independently phenyl, naphthyl or a 5- or 6-membered heteroaromatic ring system, or a 8-10 -membered heteroaromatic bicyclic ring system, each unsubstituted or substituted with up to 6 substituents Ra;
R1 , R2 is independently hydrogen, Ci-C6-alkyl, Cs-Cs-cycloalkyl, C2-C6-alkenyl, C2-C6- alkynyl, wherein the carbon atoms of the aforementioned aliphatic and cyclo- aliphatic radicals are unsubstituted or substituted with one or more Rb; or
R1 and R2 together with the nitrogen and carbon atom to which they are bonded, form the following substituted heterocyclic ring system:
Figure imgf000132_0002
k is 0, 1 , 2, 3 or 4;
R3 is (CR30R31)aQ1 , Ci-C6-alkyl unsubstituted or substituted with one or more halogen or
C3-C6-cycloalkyl unsubstituted or substituted with 1 to 4 substituents selected from the group consisting of halogen, Ci-C2-alkyl, 1 cyclopropyl and 1 CF3;
a is O or l ;
each R30 and R31 is independently hydrogen or halogen, and one of R30, R31 is hy- drogen, halogen or cyano, hydroxy, amino, nitro, OCN, SCN,
CHO, C(=0)OH, C(=0)NH2, C(=S)NH2 or SO2NH2,
or Ci-C6-alkyl, C2-C6-alkenyl, C2-C6-alkynyl, Cs-Cs-cycloalkyl, C4- Cs-alkylcycloalkyl, C4-Cs-cycloalkylalkyl, Ci-C6-alkoxy, C3-C6- cycloalkoxy, C4-C8-cycloalkylalkoxy, C2-C6-alkenyloxy or C2-C6- alkynyloxy, each unsubstituted or substituted with at least one halogen;
Q1 is a three to eleven-membered heterocyclic ring system, which contains from 1 to 6 heteroatoms selected from N(R)eb, O and S(0)c, , and wherein 1 , 2 or 3 carbon-atoms of the heterocyclic ring are optionally selected from C(=0), C(=NRe) and (C=S), wherein the heterocyclic ring is unsubstituted or substituted with one or more radicals Ra;
RA is hydrogen, Ci-C8-alkyl, C3-C8-cycloalkyl, C2-C8-alkenyl, C2-C8-alkynyl, C4-C8- cycloalkenyl, wherein the carbon atoms of the aforementioned aliphatic and cyclo- aliphatic radicals are unsubstituted or substituted with one or more Rb,
or
RA is ORA0 or N(RA1)2;
RA0, RA1 is hydrogen, C C8-alkyl, C3-C8-cycloalkyl, C2-C8-alkenyl, C2-C8-alkynyl, C4-C8- cycloalkenyl, wherein the carbon atoms of the aforementioned aliphatic and cyclo-aliphatic radicals are unsubstituted or substituted with one or more Rb or is C(=0)N(Re)2, C(=S)N(Re)2, C(=0)Re, C(=0)ORe, C(=S)Re or C(=S)ORe; RB is hydrogen, CrC8-alkyl, C2-C8-alkenyl, C2-C8-alkynyl, wherein the carbon atoms of the aforementioned aliphatic radicals are unsubstituted or substituted with one or more Rb,
or
RB is N(R9)2;
each Ra is independently halogen, cyano, azido, nitro, SCN, SF5, Ci-C8-alkyl, C2-C8- alkenyl, C2-C8-alkynyl, C3-C8-cycloalkyl, C4-C8-cycloalkenyl, wherein the carbon atoms of the aforementioned aliphatic and cyclo-aliphatic radicals are unsubstituted or substituted with one or more Rb,
Si(Rc)3, ORe, OS(0)cRd, S(0)cRd, S(0)cN(Re)2, N(Re)2, C(=0)Re, C(=0)ORe,
C(=NRe)Rd, C(=0)N(Re)2, C(=S)N(Re)2 or Q2; or
two Ra together on one ring atom are =0, =C(Re)2, =NRe, =NORd or =NN(Rd)2;
each Rb is independently halogen, cyano, azido, nitro, -SCN, SF5, Ci-C6-alkoxy, C1-C6- haloalkoxy, Ci-C6-alkylthio, Ci-C6-alkylsulfinyl, Ci-C6-alkylsulfonyl, C1-C6- haloalkylthio, C3-C8-cycloalkyl, C3-C8-halocycloalkyl, C2-C6-alkenyl, C2-C6- haloalkenyl, C2-C6-alkynyl, C2-C6-haloalkynyl, Si(Rc)3, ORe, OS02Rd, S(0)cRd, S(0)cN(Re)2, N(Re)2, C(=0)N(Re)2, C(=S)N(Re)2, C(=0)ORe or Q2;
each Rc is independently hydrogen, Ci-C6-alkyl, Ci-C6-haloalkyl, C2-C6-alkenyl, C2-C6- haloalkenyl, C2-C6-alkynyl, C2-C6-haloalkynyl, C3-C8-cycloalkyl, C3-C8-halocycloalkyl,
Ci-C6-alkoxyalkyl, Ci-C6-haloalkoxyalkyl or phenyl which is unsubstituted or substituted with one or more substituents selected independently from halogen, cyano, NO2, Ci-C6-alkyl, Ci-C6-haloalkyl, Ci-C6-alkoxy and Ci-C6-haloalkoxy;
each Rd is independently Ci-C6-alkyl, Ci-C6-haloalkyl, C2-C6-alkenyl, C2-C6-haloalkenyl, C2-C6-alkynyl, C2-C6-haloalkynyl, C3-C8-cycloalkyl, C3-C8-halocycloalkyl, or phenyl which is unsubstituted or substituted with one or more substituents selected independently from halogen, cyano, NO2, CiC6-alkyl, Ci-C6-haloalkyl, Ci-C6-alkoxy and Ci-C6-haloalkoxy;
each Re is independently hydrogen, Ci-C6-alkyl, Ci-C6-haloalkyl, C2-C6-alkenyl, C2-C6- haloalkenyl, C2-C6-alkynyl, C2-C6-haloalkynyl, C3-C8-cycloalkyl, C3-C8-halocycloalkyl,
Ci-C6-alkoxyalkyl, Ci-C6-haloalkoxyalkyl or phenyl which is unsubstituted or substituted with one or more substituents selected independently from halogen, cyano, NO2, Ci-C6-alkyl, Ci-C6-haloalkyl, Ci-C6-alkoxy and Ci-C6-haloalkoxy; each Q2 is independently a 3- to 10-membered ring or a 7- to 1 1 -membered ring system, each ring or ring system containing ring members 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, 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)c, each ring or ring system unsubstituted or substituted with up to 5 substitu- ents Rf;
each Rf is independently hydrogen, halogen, cyano, nitro, OH, SH, SCN, SF5, C1-C6- alkoxy, Ci-C6-haloalkoxy, Ci-C6-alkylthio, Ci-C6-alkylsulfinyl, Ci-C6-alkylsulfonyl, Ci- C6-haloalkylthio, trimethylsilyl, triethylsilyl, tert-butyldimethylsilyl, Ci-C6-alkyl, C2-C6- alkenyl, C2-C6-alkynyl or Cs-Cs-cycloalkyl, wherein the four last mentioned aliphatic and cyclo-aliphatic radicals are unsubstituted, partially or fully halogenated and/or substituted with (=0) and/or carry 1 or 2 radicals selected from Ci-C4-alkoxy; Q3; or two Rf present on the same carbon atom are together =CH(Ci-C4), =C(Ci-C4-alkyl)2, =N(Ci-C6-alkyl) or =NO(Ci-C6-alkyl);
each R9 is independently hydrogen, Ci-C6-alkyl, Ci-C6-haloalkyl, Ci-C6-alkoxyalkyl, C2- C6-alkenyl, C2-C6-haloalkenyl, C2-C6-alkynyl, C2-C6-haloalkynyl or C1-C6- haloalkoxyalkyl;
each Q3 is independently phenyl, unsubstituted or substituted with at least one
substituent selected from halogen, cyano, nitro, Ci-C6-alkyl, Ci-C6-haloalkyl, C1-C6- alkoxy and Ci-C6-haloalkoxy,
a 3-, 4-, 5-, 6- or 7- membered saturated, partly saturated or unsaturated aromatic heterocyclic ring comprising 1 , 2 or 3 heteroatoms or heteroatom groups selected from oxygen, nitrogen, sulfur, NO, SO and SO2 unsubstituted or substituted with up to four substituents selected independently from halogen, cyano, NO2, Ci-C6-alkyl, Ci-C6-haloalkyl, Ci-C6-alkoxy and Ci-C6-haloalkoxy;
each b is independently 0 or 1 ;
each c is independently 0, 1 or 2;
and N-oxides and salts thereof.
The compound according to claim 1 or an N-oxide or salt thereof, wherein the symbols in formula (I), each independently, have the following meanings:
X is O or S;
Y is O or S;
A, A0 is independently phenyl, naphthyl or a 5- or 6-membered heteroaromatic ring system, or a 8-10-membered heteroaromatic bicyclic ring system, each unsubstituted or substituted with up to 6 substituents Ra.
R1, R2 is independently hydrogen, Ci-C6-alkyl, Cs-Cs-cycloalkyl, C2-C6-alkenyl, C2-C6- alkynyl, wherein the carbon atoms of the aforementioned aliphatic and cyclo- aliphatic radicals are unsubstituted or substituted with one or more Rb; or
R1 and R2 together with the nitrogen and carbon atom to which they are bonded, form the following substituted heterocyclic ring system:
Figure imgf000135_0001
k is 0, 1 or 2;
Figure imgf000135_0002
a is 1 ;
each R30 and R31 is independently hydrogen or halogen, and one of R30, R31 is hydrogen, halogen, cyano, or methyl;
Q1 is a heterocyclic ring system:
Figure imgf000135_0003
D-1 D-2 D-3 D-5
Figure imgf000135_0004
D-6 D-7 D-8 D-9 D-10
Figure imgf000135_0005
D-16 D-17 D-18 D-19 D-20
Figure imgf000135_0006
D-21 D-22 D-23 D-24 D-25
Figure imgf000136_0001
D-26 D-27 D-28 D-29 D-30
Figure imgf000136_0002
D-36 D-37 D-38 D-39 D-40
,N¾ (R')K N¾/(R,)K
Figure imgf000136_0003
Figure imgf000136_0004
D-46 D-47 D-48 D-49 D-50
Figure imgf000136_0005
D-51 D-52 D-53 D-54 D-55
RA is hydrogen, Ci-C3-alkyl, C3-C6-cycloalkyl, C2-C4-alkenyl, C2-C4-alkynyl, C4-C6- cycloalkenyl, wherein the carbon atoms of the aforementioned aliphatic and cyclo- aliphatic radicals are unsubstituted or substituted with one or more Rb,
or
RA is ORA0 or N(RA )2;
RA0, RA1 is hydrogen, Ci-C3-alkyl, C3-C6-cycloalkyl, C2-C4-alkenyl, C2-C4-alkynyl, C4-C6- cycloalkenyl, wherein the carbon atoms of the aforementioned aliphatic and cyclo- aliphatic radicals are unsubstituted or substituted with one or more Rb or is
C(=0)N(Re)2, C(=S)N(Re)2, C(=0)Re, C(=S)ORe or C(=S)ORe;
RB is hydrogen, CrC3-alkyl, C2-C4-alkenyl, C2-C4-alkynyl, wherein the carbon atoms of the aforementioned aliphatic radicals are unsubstituted or substituted with one or more Rb,
or RB is N(R9)2;
each Ra is independently halogen, cyano, Ci-C3-alkyl, C2-C4-alkenyl, C2-C4-alkynyl, C3- C6-cycloalkyl, C4-C6-cycloalkenyl, wherein the carbon atoms of the aforementioned aliphatic and cyclo-aliphatic radicals are unsubstituted or substituted with one or more Rb;
each Rb is independently halogen, cyano, nitro, Ci-C3-alkoxy, Ci-C3-haloalkoxy, C1-C3- alkylthio, Ci-C3-alkylsulfinyl, Ci-C3-alkylsulfonyl, Ci-C3-haloalkylthio, C3-C6- cycloalkyl, C3-C6-halocycloalkyl, C2-C4-alkenyl, C2-C4-haloalkenyl, C2-C4-alkynyl or C2-C4 haloalkynyl;
each Rc is independently hydrogen, Ci-C6-alkyl, Ci-C6-haloalkyl, Ci-C6-alkoxyalkyl, C2-
C6-alkenyl, C2-C6-haloalkenyl, C2-C6-alkynyl, C2-C6-haloalkynyl, Cs-Cs-cycloalkyl, C3- Cs-halocycloalkyl, Ci-C6-alkoxyalkyl, Ci-C6-haloalkoxyalkyl or phenyl which is unsubstituted or substituted with one or more substituents selected independently from halogen, cyano, NO2, Ci-C6-alkyl, Ci-C6-haloalkyl, Ci-C6-alkoxy and C1-C6- haloalkoxy;
each Rd is independently Ci-C6-alkyl, Ci-C6-haloalkyl, C2-C6-alkenyl, C2-C6-haloalkenyl, C2-C6-alkynyl, C2-C6-haloalkynyl, Cs-Cs-cycloalkyl, C3-Cs-halocycloalkyl, or phenyl which is unsubstituted or substituted with one or more substituents selected independently from halogen, cyano, NO2, CiC6-alkyl, Ci-C6-haloalkyl, Ci-C6-alkoxy and Ci-C6-haloalkoxy;
each Re is independently hydrogen, Ci-C6-alkyl, Ci-C6-haloalkyl, C2-C6-alkenyl, C2-C6- haloalkenyl, C2-C6-alkynyl, C2-C6-haloalkynyl, Cs-Cs-cycloalkyl, C3-Cs-halocycloalkyl, Ci-C6-alkoxyalkyl, Ci-C6-haloalkoxyalkyl or phenyl which is unsubstituted or substituted with one or more substituents selected independently from halogen, cyano, N02, d-Ce-alkyl, Ci-C6-haloalkyl, Ci-C6-alkoxy and Ci-C6-haloalkoxy;
each Q2 is independently a 3- to 10-membered ring or a 7- to 1 1-membered ring system, each ring or ring system containing ring members 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, 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)c, each ring or ring system unsubstituted or substituted with up to 5 substituents Rf;
each Rf is independently hydrogen, halogen, cyano, nitro, OH, SH, SCN, SF5, C1-C6- alkoxy, Ci-C6-haloalkoxy, Ci-C6-alkylthio, Ci-C6-alkylsulfinyl, Ci-C6-alkylsulfonyl, Ci- C6-haloalkylthio, trimethylsilyl, triethylsilyl, tert-butyldimethylsilyl, Ci-C6-alkyl, C2-C6- alkenyl, C2-C6-alkynyl or Cs-Cs-cycloalkyl, wherein the four last mentioned aliphatic and cyclo-aliphatic radicals are unsubstituted, partially or fully halogenated and/or substituted with (=0) and/or carry 1 or 2 radicals selected from Ci-C4-alkoxy; Q3; or two Rf present on the same carbon atom are together =CH(Ci-C4), =C(Ci-C4-alkyl)2, =N(Ci-C6-alkyl) or =NO(Ci-C6-alkyl);
each Ra is independently hydrogen, Ci-C6-alkyl, Ci-C6-haloalkyl, Ci-C6-alkoxyalkyl, C2- C6-alkenyl, C2-C6-haloalkenyl, C2-C6-alkynyl, C2-C6-haloalkynyl, Ci-C6-alkoxyalkyl or Ci-C6-haloalkoxyalkyl; each Q3 is independently phenyl, unsubstituted or substituted with at least one substit- uent selected from halogen, cyano, nitro, Ci-C6-alkyl, Ci-C6-haloalkyl, Ci-C6-alkoxy and Ci-C6-haloalkoxy;
a 3-, 4-, 5-, 6- or 7- membered saturated, partly saturated or unsaturated aromatic heterocyclic ring comprising 1 , 2 or 3 heteroatoms or heteroatom groups selected from oxygen, nitrogen, sulfur, NO, SO and SO2 unsubstituted or substituted with up to four substituents selected independently from halogen, cyano, NO2, Ci-C6-alkyl, Ci-C6-haloalkyl, Ci-C6-alkoxy and Ci-C6-haloalkoxy.
each b is independently 0 or 1 and
each c is independently 0, 1 or 2.
The compound according to claim 1 or 2, or N-oxide or salt thereof, wherein the symbols in formula (I), each independently, have the following meanings:
X is O;
Y is O;
A is phenyl with up to 3 substituents Ra:
A0 is phenyl with up to 3 substituents Ra or pyridyl, with up to 2 substituents Ra;
R1 , R2 is independently hydrogen, Ci-C6-alkyl, Cs-Cs-cycloalkyl, C2-C6-alkenyl, C2-C6- alkynyl, wherein the carbon atoms of the aforementioned aliphatic and cyclo- aliphatic radicals are unsubstituted or substituted with one or more Rb; or
R1 and R2 together with the nitrogen and carbon atom to which they are bonded, form the following substituted heterocyclic ring system:
Figure imgf000138_0001
k is O, 1 or 2;
Figure imgf000138_0002
a is 1 ;
each R30 and R31 is hydrogen and one of R30, R31 is hydrogen or methyl;
Q1 is a heterocyclic ring system:
Figure imgf000138_0003
D-1 D-2 D-3 D-5
Figure imgf000138_0004
D-6 D-7
Figure imgf000139_0001
D-16 D-17 D-20 D-22
Figure imgf000139_0002
D-23 D-24 D-25
<R ™ i
Figure imgf000139_0003
<RV N (R"¾ N 4 (RT N i
D-26 D-27 D-28 D-29 D-30
Figure imgf000139_0004
D-35
Figure imgf000139_0005
D-36 D-54 D-55
RA is Ci-C3-alkyl, C3-C6-cycloalkyl, wherein the carbon atoms of the aforementioned aliphatic and cyclo-aliphatic radicals are unsubstituted or substituted with one or more Rb,
or
RA is ORA0 or N(RA )2;
RA0, RA1 is Ci-C3-alkyl, C3-C6-cycloalkyl, wherein the carbon atoms of the aforementioned aliphatic and cyclo-aliphatic radicals are unsubstituted or substituted with one or more Rb or is C(=0)N(Re)2, C(=S)N(Re)2 or C(=0)Re;
RB is hydrogen, Ci-C3-alkyl, wherein the carbon atoms of the aforementioned aliphatic radicals are unsubstituted or substituted with one or more Rb,
or
RB is N(R9)2;
each Ra is independently halogen, cyano, OCH3, CF3, OCF3, SCF3 or OCF2H;
each Rb is independently halogen, cyano, Ci-C3-alkoxy, Ci-C3-haloalkoxy, C1-C3- alkylthio, Ci-C3-alkylsulfinyl, Ci-C3-alkylsulfonyl or Ci-C3-haloalkylthio;
each Rc is independently hydrogen, Ci-C6-alkyl, Ci-C6-haloalkyl, Ci-C6-alkoxyalkyl, C2- C6-alkenyl, C2-C6-haloalkenyl, C2-C6-alkynyl, C2-C6-haloalkynyl, Cs-Cs-cycloalkyl, C3- Cs-halocycloalkyl, Ci-C6-alkoxyalkyl or Ci-C6-haloalkoxyalkyl; each Rd is independently Ci-C6-alkyl, Ci-C6-haloalkyl, C2-C6-alkenyl, C2-C6-haloalkenyl, C2-C6-alkynyl, C2-C6-haloalkynyl, Cs-Cs-cycloalkyl or Cs-Cs-halocycloalkyl;
each Re is independently hydrogen, Ci-C6-alkyl, Ci-C6-haloalkyl, C2-C6-alkenyl, C2-C6- haloalkenyl, C2-C6-alkynyl, C2-C6-haloalkynyl, Cs-Cs-cycloalkyl, Cs-Cs-halocycloalkyl, Ci-C6-alkoxyalkyl or Ci-C6-haloalkoxyalkyl;
each Q2 is independently a 3- to 10-membered ring or a 7- to 1 1 -membered ring system, each ring or ring system containing ring members 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, 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)c, each ring or ring system unsubstituted or substituted with up to 5 substitu- ents Rf;
each Rf is independently hydrogen, halogen, cyano, nitro, OH, SH, SCN, SF5, C1-C6- alkoxy, Ci-C6-haloalkoxy, Ci-C6-alkylthio, Ci-C6-alkylsulfinyl, Ci-C6-alkylsulfonyl, Ci- C6-haloalkylthio, trimethylsilyl, triethylsilyl, tert-butyldimethylsilyl, Ci-C6-alkyl, C2-C6- alkenyl, C2-C6-alkyl, Cs-Cs-cycloalkyl, wherein the four last mentioned aliphatic and cyclo-aliphatic radicals are unsubstituted, partially or fully halogenated and/or substituted with (=0) and/or carry 1 or 2 radicals selected from Ci-C4-alkoxy; Q3;
each R9 is independently hydrogen, Ci-C6-alkyl, Ci-C6-haloalkyl, Ci-C6-alkoxyalkyl, C2- C6-alkenyl, C2-C6-haloalkenyl, C2-C6-alkynyl, C2-C6-haloalkynyl, Ci-C6-alkoxyalkyl or Ci-C6-haloalkoxyalkyl.
each Q3 is independently phenyl, unsubstituted or substituted with at least one
substituent selected from halogen, cyano, nitro, Ci-C6-alkyl, Ci-C6-haloalkyl, C1-C6- alkoxy and Ci-C6-haloalkoxy,
a 3-, 4-, 5-, 6- or 7- membered saturated, partly saturated or unsaturated aromatic heterocyclic ring comprising 1 , 2 or 3 heteroatoms or heteroatom groups selected from oxygen, nitrogen, sulfur, NO, SO and SO2 unsubstituted or substituted with up to four substituents selected independently from halogen, cyano, NO2, Ci-C6-alkyl, Ci-C6-haloalkyl, Ci-C6-alkoxy and Ci-C6-haloalkoxy;
each b is independently 0 or 1 and
each c is independently 0, 1 or 2.
The compound according to any one of claims 1 to 3 or an N-oxide or salt thereof, wherein the symbols in formula (I), each independently, have the following meanings:
X is O;
Y is O;
A is phenyl with up to 3 substituents Ra;
A0 is phenyl with up to 3 substituents Ra or pyridyl, with up to 2 substituents Ra;
R1 and R2 together with the nitrogen and carbon atom to which they are bonded, form the following substituted heterocyclic ring system:
Figure imgf000141_0001
is 0, 1 or 2;
is CH2Q1 or CH(CH3)Q1;
is a heterocyclic ring system
Figure imgf000141_0002
RA is Ci-C3-alkyl, C3-C6-cycloalkyl, wherein the carbon atoms of the aforementioned aliphatic and cyclo-aliphatic radicals are unsubstituted or substituted with one or more Rb,
or
RA is ORA0 or N(RA )2;
RA0, RA1 is Ci-C3-alkyl, C3-C6-cycloalkyl, wherein the carbon atoms of the aforementioned aliphatic and cyclo-aliphatic radicals are unsubstituted or substituted with one or more Rb or is C(=0)N(Re)2, C(=S)NRe)2 or C(=0)Re;
RB is hydrogen, Ci-C3-alkyl, wherein the carbon atoms of the aforementioned aliphatic radicals are unsubstituted or substituted with one or more Rb,
or
Figure imgf000141_0003
each Rc is independently hydrogen, Ci-C6-alkyl, Ci-C6-haloalkyl, Ci-C6-alkoxyalkyl, C2- C6-alkenyl, C2-C6-haloalkenyl, C2-C6-alkynyl, C2-C6-haloalkynyl, Cs-Cs-cycloalkyl, C3- Cs-halocycloalkyl, Ci-C6-alkoxyalkyl or Ci-C6-haloalkoxyalkyl;
each Rd is independently Ci-C6-alkyl, Ci-C6-haloalkyl, C2-C6-alkenyl, C2-C6-haloalkenyl, C2-C6-alkynyl, C2-C6-haloalkynyl, Cs-Cs-cycloalkyl or C3-Cs-halocycloalkyl;
each Re is independently hydrogen, Ci-C6-alkyl, Ci-C6-haloalkyl, C2-C6-alkenyl, C2-C6- haloalkenyl, C2-C6-alkynyl, C2-C6-haloalkynyl, Cs-Cs-cycloalkyl, C3-Cs-halocycloalkyl, Ci-C6-alkoxyalkyl or Ci-C6-haloalkoxyalkyl.
each Q2 is independently a 3- to 10-membered ring or a 7- to 1 1 -membered ring system, each ring or ring system containing ring members 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, 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)c, each ring or ring system unsubstituted or substituted with up to 5 substitu- ents Rf;
each Rf is independently hydrogen, halogen, cyano, nitro, OH, SH , SCN, SF5, C1-C6- alkoxy, Ci-C6-haloalkoxy, Ci-C6-alkylthio, Ci-C6-alkylsulfinyl, Ci-C6-alkylsulfonyl, Ci- C6-haloalkylthio, trimethylsilyl, triethylsilyl, tert-butyldimethylsilyl, Ci-C6-alkyl, C2-C6- alkenyl, C2-C6-alkyl, Cs-Cs-cycloalkyl, wherein the four last mentioned aliphatic and cyclo-aliphatic radicals are unsubstituted, partially or fully halogenated and/or substituted with (=0) and/or carry 1 or 2 radicals selected from Ci-C4-alkoxy; Q3;
each R9 is independently hydrogen, Ci-C6-alkyl, Ci-C6-haloalkyl, Ci-C6-alkoxyalkyl, C2- C6-alkenyl, C2-C6-haloalkenyl, C2-C6-alkynyl, C2-C6-haloalkynyl, Ci-C6-alkoxyalkyl or Ci-C6-haloalkoxyalkyl;
each Q3 is independently phenyl, unsubstituted or substituted with at least one
substituent selected from halogen, cyano, nitro, Ci-C6-alkyl, Ci-C6-haloalkyl, C1-C6- alkoxy and Ci-C6-haloalkoxy,
a 3-, 4-, 5-, 6- or 7- membered saturated, partly saturated or unsaturated aromatic heterocyclic ring comprising 1 , 2 or 3 heteroatoms or heteroatom groups selected from oxygen, nitrogen, sulfur, NO, SO and SO2 unsubstituted or substituted with up to four substituents selected independently from halogen, cyano, NO2, Ci-C6-alkyl, Ci-C6-haloalkyl, Ci-C6-alkoxy and Ci-C6-haloalkoxy.
each b is independently 0 or 1 and
each c is independently 0, 1 or 2.
The compound according to any one of claims 1 to 4 or an N-oxide or salt thereof, wherein symbols in formula (I), each independently, have the following meanings:
X is O;
Y is O;
A, A0 is independently phenyl, unsubstituted or substituted with up to 4 substituents Ra; R1 and R2 together with the nitrogen and carbon atom to which they are bonded, form the following substituted heterocyclic ring system:
Figure imgf000142_0001
is preferred 0, 1 or 2; is 1 ;
is a heterocyclic ring system
Figure imgf000142_0002
D-2 D-25 D-54
is Ci-C3-alkyl, C3-C6-cycloalkyl, Ci-C3-haloalkyl or C3-C6-halocycloalkyl,
or RA0, RA1 is Ci-C3-alkyl, C3-C6-cycloalkyl, wherein the carbon atoms of the aforementioned aliphatic and cyclo-aliphatic radicals are unsubstituted or substituted with one or more Rb or is C(=0)N(Re)2, C(=S)N(Re)2, C(=0)Re.
RB is hydrogen, Ci-C3-alkyl, Ci-C3-haloalkyl or C3-C6-halocycloalkyl;
each Rc is independently hydrogen, Ci-C6-alkyl, Ci-C6-haloalkyl, Ci-C6-alkoxyalkyl, C2- C6-alkenyl, C2-C6-haloalkenyl, C2-C6-alkynyl, C2-C6-haloalkynyl, Cs-Cs-cycloalkyl, C3- Cs-halocycloalkyl, Ci-C6-alkoxyalkyl or Ci-C6-haloalkoxyalkyl;
each Rd is independently Ci-C6-alkyl, Ci-C6-haloalkyl, C2-C6-alkenyl, C2-C6-haloalkenyl, C2-C6-alkynyl, C2-C6-haloalkynyl, Cs-Cs-cycloalkyl, C3-Cs-halocycloalkyl;
each Re is independently hydrogen, Ci-C6-alkyl, Ci-C6-haloalkyl, Ci-C6-alkoxyalkyl, C2- C6-alkenyl, C2-C6-haloalkenyl, C2-C6-alkynyl, C2-C6-haloalkynyl, Cs-Cs-cycloalkyl, C3- Cs-halocycloalkyl, Ci-C6-alkoxyalkyl or Ci-C6-haloalkoxyalkyl;
each Q2 is independently a 3- to 6-membered ring, each ring or ring system containing ring members 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, 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)c, each ring or ring system unsubstituted or substituted with up to 5 substituents Rf;
each Rf is independently hydrogen, halogen, cyano, nitro, Ci-C6-alkoxy, C1-C6- haloalkoxy, Ci-C6-alkylthio, Ci-C6-alkylsulfinyl, Ci-C6-alkylsulfonyl, C1-C6- haloalkylthio, Ci-C6-alkyl, C2-C6-alkenyl, C2-C6-alkynyl, Cs-Cs-cycloalkyl, wherein the four last mentioned aliphatic and cyclo-aliphatic radicals are unsubstituted, partially or fully halogenated;
each Q3 is independently phenyl, unsubstituted or substituted with at least one
substituent selected from halogen, cyano, nitro, Ci-C6-alkyl, Ci-C6-haloalkyl, C1-C6- alkoxy and Ci-C6-haloalkoxy,
a 3-, 4-, 5-, 6- or 7- membered saturated, partly saturated or unsaturated aromatic heterocyclic ring comprising 1 , 2 or 3 heteroatoms or heteroatom groups selected from oxygen, nitrogen, sulfur, NO, SO and SO2 unsubstituted or substituted with up to four substituents selected independently from halogen, cyano, NO2, Ci-C6-alkyl, Ci-C6-haloalkyl, Ci-C6-alkoxy and Ci-C6-haloalkoxy;
each b is independently 0 or 1 and
each c is independently 0, 1 or 2. the compound according to any one of claims 1 to 5 or an N-oxide or salt thereof, which is a compound of formulae (1-1 ) to (I-9);
Figure imgf000143_0001
(1-1 ) 143
Figure imgf000144_0001
Figure imgf000145_0001
wherein
Z is the group C(=NRA)RB,
each A1, A2, A3, A4 is independently N or C-Ra',
with the proviso that no more than two of A1, A2, A3 and A4 are N,
each Ra' is independently H or Ra
and X, Y, R1, R2, R3, RA, RB and Ra have the meaning given in formula (I).
7. The compound according to any one of claim 1 to 6 or an N-oxide or salt thereof, which is a compound selected from formulae (1-2-1 ) to (1-8-15), or an N-oxide or salt thereof:
Figure imgf000145_0002
Figure imgf000146_0001
Figure imgf000146_0002
N (1-2-13)
Ra'' C(=NRA)RB
Figure imgf000147_0001
(I-5-2)
Figure imgf000147_0002
(I-5-4)
Figure imgf000147_0003
(I-5-8)
Figure imgf000148_0001
Figure imgf000149_0001
(1-5-17) (1-5-18)
Figure imgf000149_0002
1-5-19) (I-5-20)
Figure imgf000149_0003
Figure imgf000150_0001
Figure imgf000150_0002
Figure imgf000151_0001
Figure imgf000151_0002
Figure imgf000152_0001
Figure imgf000152_0002
3)
5)
Figure imgf000152_0003
wherein the symbols have the following meanings:
A is
Figure imgf000152_0004
Ra', Ra" each independently are H or Ra, and
Ra, Q1, RA, RB have the meanings given in formula (I). 8. The compound according to claim 7, wherein the symbols have the following meanings:
Q1 is
Figure imgf000153_0001
RA is Me, Et, c-Pr, CH2CF3, OMe, OEt, O-c-Pr, 0-CH2CF3, NHMe, NH-c-Pr, NHCH2CF3, NHC(=0)Me, NHC(=0)NHMe, NHC(=0)NHCH2CF3, N(Me)C(=0)Me,
N(Me)C(=0)OMe, N(Me)C(=0)NHCH2CF3, N(Me)2, N(Me)(Et), N(Et)2, OH, OMe,
OEt, O-c-Pr, 0-CH2CF3 or 0-C(=0)Me;
RB is H, Me, Et, i-Pr, CH2CF3, NH2, NHMe, NHEt, NH-i-Pr, NHCH2CF3, NMe2, NMeEt or
NEt2.
Ra' is H, F, CI, CH3, OCH3, CF3, OCF3, SCF3 or OCF2H and
Ra" is H or CH3.
9. An agricultural and/or veterinary composition comprising at least one compound of formula (I) according to any one of claims 1 to 8, N-oxide or a salt thereof.
10. The use of a compound of formula (I) according to any one of claims 1 to 8, N-oxide or salt thereof for combating animal pests.
1 1 . A method of combating animal pests which comprises contacting the animal pests, their habit, breeding ground, food supply, plant, 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 at least one compound of formula (I) according to any one of claims 1 to 8, N-oxide or salt thereof.
12. A method for protecting crops from attack or infestation by animal pests, which comprises contacting the crop with a pesticidally effective amount of at least one compound of formula (I) according to any one of claims 1 to 8, N-oxide or salt thereof. 13. A method for the protection of seeds from soil insects and of the seedlings' roots and shoots from soil and foliar insects comprising contacting the seeds before sowing and/or after pregermination with at least one compound of formula (I) according to any one of claims 1 to 8, N-oxide or salt thereof.
Seeds comprising at least one compound of formula (I) according to any one of claims 1 to 8, N-oxide or salt thereof.
15. The use of a compound of formula (I) according to any one of claims 1 to 8, N-oxide or veterinarily acceptable salt thereof for combating parasites in and on animals.
16. A method for treating 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 at least one compound of formula (I) according to any one of claims 1 to 8, N-oxide or veterinary acceptable salt thereof.
7. A process for the preparation of a composition for treating or protecting animals against infestation or infection by parasites which comprises mixing a parasiticidally effective amount of at least one compound of formula (I) according to any one of claims 1 to 8, N- oxide or veterinary acceptable salt thereof and an acceptable carrier.
8. The use of a compound of formula (I) according to any one of claims 1 to 8, N-oxide or veterinarily acceptable salt thereof for the preparation of a medicament for treating or protecting animals against infestation or infection by parasites.
9. A compound of formula (I) according to any one of claims 1 to 8, N-oxide or a veterinarily acceptable salt thereof as a medicament.
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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

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