WO2022053567A1 - Pesticidally active heterocyclic derivatives with sulfur containing substituents - Google Patents

Pesticidally active heterocyclic derivatives with sulfur containing substituents Download PDF

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WO2022053567A1
WO2022053567A1 PCT/EP2021/074837 EP2021074837W WO2022053567A1 WO 2022053567 A1 WO2022053567 A1 WO 2022053567A1 EP 2021074837 W EP2021074837 W EP 2021074837W WO 2022053567 A1 WO2022053567 A1 WO 2022053567A1
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spp
methyl
compound
pyrazolo
formula
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PCT/EP2021/074837
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French (fr)
Inventor
André Stoller
Michel Muehlebach
Vikas SIKERVAR
Daniel EMERY
André Jeanguenat
Swarnendu SASMAL
Anke Buchholz
Benedikt KURTZ
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Syngenta Crop Protection Ag
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Publication of WO2022053567A1 publication Critical patent/WO2022053567A1/en

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    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D471/00—Heterocyclic compounds containing nitrogen atoms as the only ring hetero atoms in the condensed system, at least one ring being a six-membered ring with one nitrogen atom, not provided for by groups C07D451/00 - C07D463/00
    • C07D471/02—Heterocyclic compounds containing nitrogen atoms as the only ring hetero atoms in the condensed system, at least one ring being a six-membered ring with one nitrogen atom, not provided for by groups C07D451/00 - C07D463/00 in which the condensed system contains two hetero rings
    • C07D471/04—Ortho-condensed systems

Definitions

  • the present invention relates to pesticidally active, in particular insecticidally active 2-heteroaryl- indazoles with sulfur substituents, to processes for their preparation, to compositions comprising those compounds, and to their use for controlling animal pests, including arthropods and in particular insects or representatives of the order Acarina.
  • Heterocyclic compounds with pesticidal action are known and described, for example, in WO2013191112 and W02020182577.
  • Gi and G2 are, independently from each other, CH or N;
  • R2 is Ci-Cehaloalkyl
  • X is S, SO, or SO2
  • R1 is Ci-C4alkyl or C3-C6cycloalkyl-Ci-C4alkyl
  • Y1 and Y2 are, independently from each other, hydrogen, halogen, Ci-C4alkyl, Ci-Cehaloalkyl, C3- Cecycloalkyl, Cs-Cecycloalkyl monosubstituted by cyano, Ci-Cecyanoalkyl, Ci-Cecyanoalkoxy, cyano, Ci-C4alkoxy, Ci-Cehaloalkoxy, -N(R3)2, -N(R3)COR4; and each R3 and R4 are independently from each other, hydrogen, Ci-C4alkyl, Ci-Cehaloalkyl or C3- Cecycloalkyl.
  • the present invention also provides agrochemically acceptable salts, stereoisomers, enantiomers, tautomers and N-oxides of the compounds of formula I.
  • Compounds of formula I which have at least one basic centre can form, for example, acid addition salts, for example with strong inorganic acids such as mineral acids, for example perchloric acid, sulfuric acid, nitric acid, nitrous acid, a phosphorus acid or a hydrohalic acid, with strong organic carboxylic acids, such as Ci-C4alkanecarboxylic acids which are unsubstituted or substituted, for example by halogen, for example acetic acid, such as saturated or unsaturated dicarboxylic acids, for example oxalic acid, malonic acid, succinic acid, maleic acid, fumaric acid or phthalic acid, such as hydroxycarboxylic acids, for example ascorbic acid, lactic acid, malic acid, tartaric acid or citric acid, or such as benzoic acid, or with organic sulfonic acids, such as Ci-C4alkane- or arylsulfonic acids which are unsubstituted or substituted, for example by
  • Compounds of formula I which have at least one acidic group can form, for example, salts with bases, for example mineral salts such as alkali metal or alkaline earth metal salts, for example sodium, potassium or magnesium salts, or salts with ammonia or an organic amine, such as morpholine, piperidine, pyrrolidine, a mono-, di- or tri-lower-alkylamine, for example ethyl-, diethyl-, triethyl- or dimethylpropylamine, or a mono-, di- or trihydroxy-lower-alkylamine, for example mono-, di- or triethanolamine.
  • bases for example mineral salts such as alkali metal or alkaline earth metal salts, for example sodium, potassium or magnesium salts
  • salts with ammonia or an organic amine such as morpholine, piperidine, pyrrolidine, a mono-, di- or tri-lower-alkylamine, for example ethyl-, diethy
  • the compounds of formula (I) according to the invention are in free form, in oxidized form as a N-oxide or in salt form, e.g. an agronomically usable salt form.
  • N-oxides are oxidized forms of tertiary amines or oxidized forms of nitrogen containing heteroaromatic compounds. They are described for instance in the book “Heterocyclic N-oxides” by A. Albini and S. Pietra, CRC Press, Boca Raton 1991.
  • the compounds of formula (I) according to the invention also include hydrates or solvates which may be formed during the salt formation.
  • substituents are indicated as being themselves further substituted, this means that they carry one or more identical or different substituents, e.g. one to four substituents. Normally not more than three such optional substituents are present at the same time. Preferably not more than two such substituents are present at the same time (i.e. the group is substituted by one or two of the substituents indicated). Where the additional substituent group is a larger group, such as cycloalkyl or phenyl, it is most preferred that only one such optional substituent is present. Where a group is indicated as being substituted, e.g. alkyl, this includes those groups that are part of other groups, e.g. the alkyl in alkylthio.
  • Ci-C n alkyl refers to a saturated straight-chain or branched hydrocarbon radical attached via any of the carbon atoms having 1 to n carbon atoms, for example, any one of the radicals methyl, ethyl, n-propyl, 1 -methylbutyl, 2-methylbutyl, 3-methylbutyl, 2, 2-dimethylpropyl, 1 -ethylpropyl, n-hexyl, n-pentyl, 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 -ethylbut
  • Ci-C n haloalkyl refers to a straight-chain or branched saturated alkyl radical attached via any of the carbon atoms having 1 to n carbon atoms (as mentioned above), where some or all of the hydrogen atoms in these radicals may be replaced by fluorine, chlorine, bromine and/or iodine, i.e., for example, any one of chloromethyl, dichloromethyl, trichloro methyl, fluoromethyl, difluoromethyl, trifluoromethyl, chlorofluoromethyl, dichlorofluoromethyl, chlorodifluoromethyl, 2- fluoroethyl, 2-chloroethyl, 2-bromoethyl, 2-iodoethyl, 2, 2-difluoroethyl, 2,2, 2-trifluoroethyl, 2-chloro-2- fluoroethyl, 2-chloro-2, 2-difluoroeth
  • Ci-C2-fluoroalkyl would refer to a Ci-C2-alkyl radical which carries 1 ,2, 3,4, or 5 fluorine atoms, for example, any one of difluoromethyl, trifluoromethyl, 1- fluoroethyl, 2-fluoroethyl, 2, 2-difluoroethyl, 2,2, 2-trifluoroethyl, 1 ,1 , 2, 2-tetrafluoroethyl or pentafluoroethyl.
  • Ci-C n alkoxy refers to a straight-chain or branched saturated alkyl radical having 1 to n carbon atoms (as mentioned above) which is attached via an oxygen atom, i.e., for example, any one of methoxy, ethoxy, n-propoxy, 1 -methylethoxy, n-butoxy, 1 -methylpropoxy, 2- methylpropoxy or 1 , 1 -dimethylethoxy.
  • Ci-C n haloalkoxy refers to a Ci-C n alkoxy radical as mentioned above which is partially or fully substituted by fluorine, chlorine, bromine and/or iodine, i.e., for example, any one of chloromethoxy, dichloromethoxy, trichloromethoxy, fluoromethoxy, difluoromethoxy, trifluoromethoxy, chlorofluoromethoxy, dichlorofluoromethoxy, chlorodifluoromethoxy, 2- fluoroethoxy, 2-chloroethoxy, 2-bromoethoxy, 2-iodoethoxy, 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, pentafluorine, chlorine, bromine and/
  • Ci-C n cyanoalkyl refers to a straight chain or branched saturated alkyl radicals having 1 to n carbon atoms (as mentioned above) which is substituted by a cyano group, for example cyanomethyl, cyanoethyl, and 1 ,1 -dimethylcyanomethyl.
  • Ci-C n cyanoalkoxy refers to a straight-chain or branched saturated alkyl radical having 1 to n carbon atoms which is substituted by a cyano group (as mentioned above) but which is attached via an oxygen atom.
  • n is an integer from 1-6, as used herein refers to a straight chain or branched saturated alkyl radicals which is substituted by Cs-Cncycloalkyl.
  • An example of C3-C n cycloalkyl-Ci-C n alkyl is for example, cyclopropylmethyl.
  • Cs-Cncycloalkyl refers to 3-6 membered cycloylkyl groups such as cyclopropyl, cyclobutyl, cyclopentyl and cyclohexyl.
  • Halogen is generally fluorine, chlorine, bromine or iodine. This also applies, correspondingly, to halogen in combination with other meanings, such as haloalkyl.
  • Embodiment 1 provides compounds of formula (I), or an agrochemically acceptable salt, stereoisomer, enantiomer, tautomer or N-oxide thereof, as defined above.
  • Embodiment 2 provides compounds, or an agrochemically acceptable salt, stereoisomer, enantiomer, tautomer or N-oxide thereof, according to embodiment 1 having preferred values of Ri, R2, X, R3, R4, G1, G2, Y1 and Y2 as set out below.
  • R1, R2, X, R3, R4, G1, G2, Y1 and Y2 are, in any combination thereof, as set out below:
  • R2 is Ci-Cehaloalkyl.
  • R2 is Ci-Cefluoroalkyl.
  • R2 is -CH2CH2CF3, -CH2CF2CHF2 or -CH2CF2CF3.
  • X is S or SO2
  • X is SO2.
  • R1 is Ci-C4alkyl or cyclopropyl-Ci-C4alkyl.
  • R1 is ethyl or cyclopropylmethyl.
  • R1 is ethyl
  • Y1 is hydrogen, halogen, Ci-C4alkyl, Ci-Cehaloalkyl, Cs-Cecycloalkyl, Cs-Cecycloalkyl monosubstituted by cyano, Ci-Cecyanoalkyl, Ci-Cecyanoalkoxy, cyano, Ci-C4alkoxy, Ci-Cehaloalkoxy, -N(R 3 ) 2 , -N(R 3 )COR4.
  • Y1 is hydrogen, halogen, trifluoromethyl, difluoroethyl, cyclopropyl, cyanocyclopropyl, cyanoisopropyl, 2,2,2-trifluoroethoxy, -N(R3)2, -N(R3)COR4, in each of which R3 is independently either hydrogen or methyl and R4 is either methyl, trifluoromethyl or cyclopropyl.
  • Even more preferably Yi is hydrogen, chlorine, bromine, trifluoromethyl, -CF2CH3, cyclopropyl, 1- cyanocyclopropyl, 1-cyano-1-methyl-ethyl, 2,2,2-trifluoroethoxy, -NH(CH3), -N(CH3)COCH3 or - N(CH 3 )COCF3.
  • Y1 is hydrogen, trifluoromethyl, -CF2CH3, cyclopropyl, 1 -cyanocyclopropyl, 1-cyano-1- methyl-ethyl, -NH(CH 3 ), -N(CH 3 )COCH3 or -N(CH 3 )COCF3.
  • Y2 is hydrogen, halogen, Ci-C4alkyl, Ci-Cehaloalkyl, Cs-Cecycloalkyl, Cs-Cecycloalkyl monosubstituted by cyano, Ci-Cecyanoalkyl, Ci-Cecyanoalkoxy, cyano, Ci-C4alkoxy, Ci-Cehaloalkoxy, -N(R 3 ) 2 , -N(R 3 )COR4.
  • Y2 is hydrogen, halogen, trifluoromethyl, difluoroethyl, cyclopropyl, cyanocyclopropyl, cyanoisopropyl, 2,2,2-trifluoroethoxy, -N(R3)2, -N(R3)COR4, in which R3 is independently either hydrogen or methyl and R4 is either methyl, trifluoromethyl or cyclopropyl.
  • Y2 is hydrogen, chlorine, bromine, trifluoromethyl, -CF2CH3, cyclopropyl, 1- cyanocyclopropyl, 1-cyano-1-methyl-ethyl, 2,2,2-trifluoroethoxy, -NH(CH3), -N(CH3)COCH3 or - N(CH 3 )COCF3.
  • Y2 is hydrogen, trifluoromethyl, -CF2CH3, cyclopropyl, 1 -cyanocyclopropyl, 1-cyano-1- methyl-ethyl, -NH(CH 3 ), -N(CH 3 )COCH3 or -N(CH 3 )COCF3.
  • Y1 is H and Y2 is H, -Me, -OCH2CHF2, Br, -CF2CH3, CF3, -OCF3, -O-/-Pr, - OCH3.-OCHF2, -NH(CH3), -N(CH3)COCH3, -N(CH3)COCF3, cyclopropyl, 1 -cyanocyclopropyl, 1-cyano- 1-methyl-ethyl, -OCH2CF3 or -OC(CH3)2CN; or
  • Y 2 is H and Y1 is H, -Me, -OCH2CHF2, Br, -CF2CH3, CF 3 , -OCF3, -O-/-Pr, -OCH 3 ,-OCHF 2 , -NH(CH 3 ), - N(CH3)COCH3, -N(CH3)COCF3, cyclopropyl, 1 -cyanocyclopropyl, 1-cyano-1-methyl-ethyl, -OCH2CF3 or -OC(CH 3 )2CN.
  • Y2 is H and Y1 is halogen, trifluoromethyl, 1 ,1 -difluoroethyl, cyclopropyl, cyanocyclopropyl, cyanoisopropyl or trifluoroethoxy; preferably Y2 is H and Y1 is -Br, -CF2CH3, -CF3, cyclopropyl, 1 -cyanocyclopropyl, 1-cyano-1-methyl-ethyl or -OCH2CF3; more preferably Y2 is H and Y1 is -CF3, 1 -cyanocyclopropyl or 1-cyano-1-methyl-ethyl; or
  • Y1 is H and Y2 is halogen, trifluoromethyl, 1 ,1-difluoroethyl, cyclopropyl, cyanocyclopropyl, cyanoisopropyl or trifluoroethoxy; preferably Y1 is H and Y2 is -Br, -CF2CH3, -CF3, cyclopropyl, 1- cyanocyclopropyl, 1-cyano-1-methyl-ethyl or -OCFhCFs; more preferably Y1 is H and Y2 is -CF3, 1- cyanocyclopropyl or 1-cyano-1-methyl-ethyl.
  • Y2 is H and Y1 is trifluoromethyl, difluoroethyl, cyclopropyl, cyanocyclopropyl, cyanoisopropyl, -NH(CH 3 ), -N(CH 3 )COCH3 or -N(CH3)COCF 3 ;
  • Y 2 is H and Y1 is -CF 3 , - CF2CH3, cyclopropyl, 1 -cyanocyclopropyl, 1-cyano-1-methyl-ethyl, -NH(CH3), -N(CH3)COCH3 or - N(CH3)COCF3;
  • Y2 is H and Y1 is cyclopropyl, 1 -cyanocyclopropyl or 1-cyano-1- methyl-ethyl; or
  • Y1 is H and Y2 is trifluoromethyl, difluoroethyl, cyclopropyl, cyanocyclopropyl, cyanoisopropyl, - NH(CH 3 ), -N(CH 3 )COCH3 or -N(CH3)COCF 3 ; preferably Y1 is H and Y 2 is -CF 3 , -CF2CH3, cyclopropyl, 1 -cyanocyclopropyl, 1-cyano-1-methyl-ethyl, -NH(CH3), -N(CH3)COCH3 or -N(CH3)COCF3; more preferably Yi is H and Y2 is -CF3, -CF2CH3, 1 -cyanocyclopropyl, 1-cyano-1-methyl-ethyl, -NH(CH3), - N(CH 3 )COCH3 or -N(CH 3 )COCF3.
  • each R3 is independently hydrogen or Ci-C4alkyl.
  • each R3 is independently hydrogen or methyl.
  • R4 is Ci-Cealkyl, Ci-Cehaloalkyl or Cs-Cecycloalkyl.
  • R4 is methyl, trifluoromethyl or cyclopropyl.
  • R4 is methyl or trifluoromethyl.
  • R4 is methyl
  • G1 and G2 are, independently from each other, CH or N.
  • G2 is N and G1 is CH.
  • G2 and G1 are both CH.
  • G2 is CH and G1 is N.
  • G1 and G2 are N.
  • G1 is CH or N.
  • G1 is CH.
  • G2 is CH or N.
  • G2 is N.
  • G1 is CH and G2 is N.
  • R1, R2, X, R3, R4, G1, G2 and Y1 are as defined for compounds of formula I (above), or an agrochemically acceptable salt, stereoisomer, enantiomer, tautomer or N-oxide thereof, and wherein Y1 is preferably hydrogen, halogen, Ci-C4alkyl, Ci-Cehaloalkyl, Cs-Cecycloalkyl, Cs-Cecycloalkyl monosubstituted by cyano, Ci-Cecyanoalkyl, Ci-Cecyanoalkoxy, cyano, Ci-C4alkoxy, Ci-Cehaloalkoxy, -N(R 3 ) 2 , -N(R 3 )COR4; and each R3 and R4 are independently from each other, hydrogen, Ci-C4alkyl, Ci-Cehaloalkyl or C3- Cecycloalkyl.
  • each R3 is independently hydrogen or Ci-C4alkyl
  • R4 is preferably Ci-Cealkyl or Cs-Cecycloalkyl.
  • Y1 is hydrogen, chlorine, bromine, trifluoromethyl, -CF2CH3, cyclopropyl, 1 -cyanocyclopropyl, 1-cyano-1-methyl-ethyl, 2,2,2-trifluoroethoxy, -NH(CH3), - N(CH3)COCH3 or -N(CH3)COCF3; more preferably Yi is hydrogen, trifluoromethyl, -CF2CH3, cyclopropyl, 1 -cyanocyclopropyl, 1-cyano-1-methyl-ethyl, -NH(CH3), -N(CH3)COCH3 or - N(CH 3 )COCF3
  • R1, R2, X, R3, R4, G1, G2 are as defined for compounds of formula I (above), and more preferably R2 is Ci-Cefluoroalkyl; more preferably R2 is -CH2CH2CF3, -CH2CF2CHF2 or - CH2CF2CF3; preferably X is S or SO2; more preferably X is SO2; R1 is Ci-C4alkyl or cyclopropyl-Ci- C4alkyl; preferably R1 is ethyl or cyclopropylmethyl; more preferably R1 is ethyl; Y1 is halogen, trifluoromethyl, 1 ,1 -difluoroethyl, cyclopropyl, cyanocyclopropyl, cyanoisopropyl or trifluoroethoxy; more preferably Y1 is cyclopropyl, 1 -cyanocyclopropyl or 1-cyano-1-methyl-methyl-methyl-
  • One group of compounds according to this embodiment are compounds of formula (1-1 a) which are compounds of formula (1-1) wherein G2 is N and G1 is CH. wherein R1, R2, X, R3, R4 and Y1 are as defined for compounds of formula I (above), or an agrochemically acceptable salt, stereoisomer, enantiomer, tautomer or N-oxide thereof, and wherein Y1 is preferably hydrogen, halogen, Ci-C4alkyl, Ci-Cehaloalkyl, Cs-Cecycloalkyl, Cs-Cecycloalkyl monosubstituted by cyano, Ci-Cecyanoalkyl, Ci-Cecyanoalkoxy, cyano, Ci-C4alkoxy, Ci-Cehaloalkoxy, -N(R 3 ) 2 , -N(R 3 )COR4; and each R3 and R4 are independently from each other, hydrogen, Ci-C4alkyl, Ci-C
  • each R3 is independently hydrogen or Ci-C4alkyl
  • R4 is preferably Ci-Cealkyl or Cs-Cecycloalkyl.
  • Y1 is hydrogen, chlorine, bromine, trifluoromethyl, -CF2CH3, cyclopropyl, 1 -cyanocyclopropyl, 1-cyano-1-methyl-ethyl, 2,2,2-trifluoroethoxy, -NH(CH3), - N(CH3)COCH3 or -N(CH3)COCF3; more preferably Y1 is hydrogen, trifluoromethyl, -CF2CH3, cyclopropyl, 1 -cyanocyclopropyl, 1-cyano-1-methyl-ethyl, -NH(CH3), -N(CH3)COCH3 or - N(CH 3 )COCF3
  • R1, R2, X, R3 and R4 are as defined for compounds of formula I (above), and more preferably R2 is Ci-Cefluoroalkyl; more preferably R2 is -CH2CH2CF3, -CH2CF2CHF2 or - CH2CF2CF3; preferably X is S or SO2; more preferably X is SO2; R1 is Ci-C4alkyl or cyclopropyl-Ci- C4alkyl; preferably R1 is ethyl or cyclopropylmethyl; more preferably R1 is ethyl; Y1 is halogen, trifluoromethyl, 1 ,1-difluoroethyl, cyclopropyl, cyanocyclopropyl, cyanoisopropyl or trifluoroethoxy; more preferably Yi is cyclopropyl, 1 -cyanocyclopropyl or 1-cyano-1-methyl-ethyl.
  • Another group of compounds according to this embodiment are compounds of formula (1-1 b) which are compounds of formula (1-1) wherein G2 and G1 are both CH. wherein R1, R2, X, R3, R4 and Y1 are as defined for compounds of formula I (above), or an agrochemically acceptable salt, stereoisomer, enantiomer, tautomer or N-oxide thereof, and wherein Y1 is preferably hydrogen, halogen, Ci-C4alkyl, Ci-Cehaloalkyl, Cs-Cecycloalkyl, Cs-Cecycloalkyl monosubstituted by cyano, Ci-Cecyanoalkyl, Ci-Cecyanoalkoxy, cyano, Ci-C4alkoxy, Ci-Cehaloalkoxy, -N(R 3 ) 2 , -N(R 3 )COR4; and each R 3 and R4 are independently from each other, hydrogen, Ci-C4alkyl, Ci-Ce
  • each R3 is independently hydrogen or Ci-C4alkyl
  • R4 is preferably Ci-Cealkyl or Cs-Cecycloalkyl.
  • Y1 is hydrogen, chlorine, bromine, trifluoromethyl, -CF2CH3, cyclopropyl, 1 -cyanocyclopropyl, 1-cyano-1-methyl-ethyl, 2,2,2-trifluoroethoxy, -NH(CH3), - N(CH3)COCH3 or -N(CH3)COCF3; more preferably Y1 is hydrogen, trifluoromethyl, -CF2CH3, cyclopropyl, 1 -cyanocyclopropyl, 1-cyano-1-methyl-ethyl, -NH(CH3), -N(CH3)COCH3 or - N(CH 3 )COCF3.
  • R1, R2, X, R3 and R4 are as defined for compounds of formula I (above), and more preferably R2 is Ci-Cefluoroalkyl; more preferably R2 is -CH2CH2CF3, -CH2CF2CHF2 or - CH2CF2CF3; preferably X is S or SO2; more preferably X is SO2; R1 is Ci-C4alkyl or cyclopropyl-Ci- C4alkyl; preferably R1 is ethyl or cyclopropylmethyl; more preferably R1 is ethyl; Y1 is halogen, trifluoromethyl, 1 ,1-difluoroethyl, cyclopropyl, cyanocyclopropyl, cyanoisopropyl or trifluoroethoxy; more preferably Y1 is cyclopropyl, 1 -cyanocyclopropyl or 1-cyano-1-methyl-ethyl
  • Another group of compounds according to this embodiment are compounds of formula (1-1 c) which are compounds of formula (1-1) wherein G2 is CH and G1 is N.
  • Ri, R2, X, R3, R4 and Y1 are as defined for compounds of formula I (above), or an agrochemically acceptable salt, stereoisomer, enantiomer, tautomer or N-oxide thereof, and wherein Y1 is preferably hydrogen, halogen, Ci-C4alkyl, Ci-Cehaloalkyl, Cs-Cecycloalkyl, Cs-Cecycloalkyl monosubstituted by cyano, Ci-Cecyanoalkyl, Ci-Cecyanoalkoxy, cyano, Ci-C4alkoxy, Ci-Cehaloalkoxy, -N(R 3 ) 2 , -N(R 3 )COR4; and each R 3 and R4 are independently from each other, hydrogen, Ci-C4alkyl, Ci-C
  • each R3 is independently hydrogen or Ci-C4alkyl
  • R4 is preferably Ci-Cealkyl or Cs-Cecycloalkyl.
  • Y1 is hydrogen, chlorine, bromine, trifluoromethyl, -CF2CH3, cyclopropyl, 1 -cyanocyclopropyl, 1-cyano-1-methyl-ethyl, 2,2,2-trifluoroethoxy, -NH(CH3), - N(CH3)COCH3 or -N(CH3)COCF3; more preferably Y1 is hydrogen, trifluoromethyl, -CF2CH3, cyclopropyl, 1 -cyanocyclopropyl, 1-cyano-1-methyl-ethyl, -NH(CH3), -N(CH3)COCH3 or - N(CH 3 )COCF3.
  • R1, R2, X, R3 and R4 are as defined for compounds of formula I (above), and more preferably R2 is Ci-Cefluoroalkyl; more preferably R2 is -CH2CH2CF3, -CH2CF2CHF2 or - CH2CF2CF3; preferably X is S or SO2; more preferably X is SO2; R1 is Ci-C4alkyl or cyclopropyl-Ci- C4alkyl; preferably R1 is ethyl or cyclopropylmethyl; more preferably R1 is ethyl; Y1 is halogen, trifluoromethyl, 1 ,1-difluoroethyl, cyclopropyl, cyanocyclopropyl, cyanoisopropyl or trifluoroethoxy; more preferably Y1 is cyclopropyl, 1 -cyanocyclopropyl or 1-cyano-1-methyl-ethyl
  • R1, R2, X, R3, R4, G1, G2 and Y2 are as defined for compounds of formula I (above), or an agrochemically acceptable salt, stereoisomer, enantiomer, tautomer or N-oxide thereof, and wherein Y2 is preferably hydrogen, halogen, Ci-C4alkyl, Ci-Cehaloalkyl, Cs-Cecycloalkyl, Cs-Cecycloalkyl monosubstituted by cyano, Ci-Cecyanoalkyl, Ci-Cecyanoalkoxy, cyano, Ci-C4alkoxy, Ci-Cehaloalkoxy, -N(R 3 ) 2 , -N(R 3 )COR4; and each R3 and R4 are independently from each other, hydrogen, Ci-C4alkyl, Ci-Cehaloalkyl or C3- Cecycloalkyl.
  • each R3 is independently hydrogen or Ci-C4alkyl; and R4 is preferably Ci-Cealkyl or Cs-Cecycloalkyl.
  • Y2 is hydrogen, chlorine, bromine, trifluoromethyl, -CF2CH3, cyclopropyl, 1 -cyanocyclopropyl, 1-cyano-1-methyl-ethyl, 2,2,2-trifluoroethoxy, -NH(CH3), - N(CH3)COCH3 or -N(CH3)COCF3; more preferably Y2 is hydrogen, trifluoromethyl, -CF2CH3, cyclopropyl, 1 -cyanocyclopropyl, 1-cyano-1-methyl-ethyl, -NH(CH3), -N(CH3)COCH3 or - N(CH 3 )COCF3.
  • R1, R2, X, R3, R4, G1, G2 are as defined for compounds of formula I (above), and more preferably R2 is Ci-Cefluoroalkyl; more preferably R2 is -CH2CH2CF3, -CH2CF2CHF2 or - CH2CF2CF3; preferably X is S or SO2; more preferably X is SO2; R1 is Ci-C4alkyl or cyclopropyl-Ci- C4alkyl; preferably R1 is ethyl or cyclopropylmethyl; more preferably R1 is ethyl; Y2 is halogen, trifluoromethyl, 1 ,1-difluoroethyl, cyclopropyl, cyanocyclopropyl, cyanoisopropyl or trifluoroethoxy; more preferably Y2 is cyclopropyl, 1 -cyanocyclopropyl or 1-cyano-1-methyl-e
  • One group of compounds according to this embodiment are compounds of formula (l-2a) which are compounds of formula (I-2) wherein G2 is N and G1 is CH.
  • R1, R2, X, R3, R4 and Y2 are as defined for compounds of formula I (above), or an agrochemically acceptable salt, stereoisomer, enantiomer, tautomer or N-oxide thereof, and wherein Y2 is preferably hydrogen, halogen, Ci-C4alkyl, Ci-Cehaloalkyl, Cs-Cecycloalkyl, Cs-Cecycloalkyl monosubstituted by cyano, Ci-Cecyanoalkyl, Ci-Cecyanoalkoxy, cyano, Ci-C4alkoxy, Ci-Cehaloalkoxy, -N(R 3 ) 2 , -N(R 3 )COR4; and each R3 and R4 are independently from each other, hydrogen, Ci-C4alkyl, Ci-
  • each R3 is independently hydrogen or Ci-C4alkyl
  • R4 IS preferably Ci-Cealkyl or Cs-Cecycloalkyl.
  • Y2 is hydrogen, chlorine, bromine, trifluoromethyl, -CF2CH3, cyclopropyl, 1 -cyanocyclopropyl, 1-cyano-1-methyl-ethyl, 2,2,2-trifluoroethoxy, -NH(CH3), - N(CH3)COCH3 or -N(CH3)COCF3; more preferably Y2 is hydrogen, trifluoromethyl, -CF2CH3, cyclopropyl, 1 -cyanocyclopropyl, 1-cyano-1-methyl-ethyl, -NH(CH3), -N(CH3)COCH3 or - N(CH 3 )COCF3.
  • R1, R2, X, R3 and R4 are as defined for compounds of formula I (above), and more preferably R2 is Ci-Cefluoroalkyl; more preferably R2 is -CH2CH2CF3, -CH2CF2CHF2 or - CH2CF2CF3; preferably X is S or SO2; more preferably X is SO2; R1 is Ci-C4alkyl or cyclopropyl-Ci- C4alkyl; preferably R1 is ethyl or cyclopropylmethyl; more preferably R1 is ethyl; Y2 is halogen, trifluoromethyl, 1 ,1-difluoroethyl, cyclopropyl, cyanocyclopropyl, cyanoisopropyl or trifluoroethoxy; more preferably Y2 is cyclopropyl, 1 -cyanocyclopropyl or 1-cyano-1-methyl-ethyl
  • Another group of compounds according to this embodiment are compounds of formula (l-2b) which are compounds of formula (I-2) wherein G2 and G1 are both CH. wherein R1, R2, X, R3, R4 and Y2 are as defined for compounds of formula I (above), or an agrochemically acceptable salt, stereoisomer, enantiomer, tautomer or N-oxide thereof, and wherein Y2 is preferably hydrogen, halogen, Ci-C4alkyl, Ci-Cehaloalkyl, Cs-Cecycloalkyl, Cs-Cecycloalkyl monosubstituted by cyano, Ci-Cecyanoalkyl, Ci-Cecyanoalkoxy, cyano, Ci-C4alkoxy, Ci-Cehaloalkoxy, -N(R 3 ) 2 , -N(R 3 )COR4; and each R3 and R4 are independently from each other, hydrogen, Ci-C4alkyl, Ci-C
  • each R3 is independently hydrogen or Ci-C4alkyl
  • R4 is preferably Ci-Cealkyl or Cs-Cecycloalkyl.
  • Y2 is hydrogen, chlorine, bromine, trifluoromethyl, -CF2CH3, cyclopropyl, 1 -cyanocyclopropyl, 1-cyano-1-methyl-ethyl, 2,2,2-trifluoroethoxy, -NH(CH3), - N(CH3)COCH3 or -N(CH3)COCF3; more preferably Y2 is hydrogen, trifluoromethyl, -CF2CH3, cyclopropyl, 1 -cyanocyclopropyl, 1-cyano-1-methyl-ethyl, -NH(CH3), -N(CH3)COCH3 or - N(CH 3 )COCF3.
  • R1, R2, X, R3 and R4 are as defined for compounds of formula I (above), and more preferably R2 is Ci-Cefluoroalkyl; more preferably R2 is -CH2CH2CF3, -CH2CF2CHF2 or - CH2CF2CF3; preferably X is S or SO2; more preferably X is SO2; R1 is Ci-C4alkyl or cyclopropyl-Ci- C4alkyl; preferably R1 is ethyl or cyclopropylmethyl; more preferably R1 is ethyl; Y2 is halogen, trifluoromethyl, 1 ,1-difluoroethyl, cyclopropyl, cyanocyclopropyl, cyanoisopropyl or trifluoroethoxy; more preferably Y2 is cyclopropyl, 1 -cyanocyclopropyl or 1-cyano-1-methyl-ethyl
  • Another group of compounds according to this embodiment are compounds of formula (l-2c) which are compounds of formula (I-2) wherein G2 is CH and G1 is N.
  • R1, R2, X, R3, R4 and Y2 are as defined for compounds of formula I (above), or an agrochemically acceptable salt, stereoisomer, enantiomer, tautomer or N-oxide thereof, and wherein Y2 is preferably hydrogen, halogen, Ci-C4alkyl, Ci-Cehaloalkyl, Cs-Cecycloalkyl, Cs-Cecycloalkyl monosubstituted by cyano, Ci-Cecyanoalkyl, Ci-Cecyanoalkoxy, cyano, Ci-C4alkoxy, Ci-Cehaloalkoxy, -N(R 3 ) 2 , -N(R 3 )COR4; and each R3 and R4 are independently from each other, hydrogen, Ci-C4alkyl, Ci-
  • each R3 is independently hydrogen or Ci-C4alkyl
  • R4 is preferably Ci-Cealkyl or Cs-Cecycloalkyl.
  • Y2 is hydrogen, chlorine, bromine, trifluoromethyl, -CF2CH3, cyclopropyl, 1 -cyanocyclopropyl, 1-cyano-1-methyl-ethyl, 2,2,2-trifluoroethoxy, -NH(CH3), - N(CH3)COCH3 or -N(CH3)COCF3; more preferably Y2 is hydrogen, trifluoromethyl, -CF2CH3, cyclopropyl, 1 -cyanocyclopropyl, 1-cyano-1-methyl-ethyl, -NH(CH3), -N(CH3)COCH3 or - N(CH 3 )COCF3.
  • R1, R2, X, R3 and R4 are as defined for compounds of formula I (above), and more preferably R2 is Ci-Cefluoroalkyl; more preferably R2 is -CH2CH2CF3, -CH2CF2CHF2 or - CH2CF2CF3; preferably X is S or SO2; more preferably X is SO2; R1 is Ci-C4alkyl or cyclopropyl-Ci- C4alkyl; preferably R1 is ethyl or cyclopropylmethyl; more preferably R1 is ethyl; Y2 is halogen, trifluoromethyl, 1 ,1-difluoroethyl, cyclopropyl, cyanocyclopropyl, cyanoisopropyl or trifluoroethoxy; more preferably Y2 is cyclopropyl, 1 -cyanocyclopropyl or 1-cyano-1-methyl-ethyl
  • R2, R3, R4, G1, G2 and Y1 are as defined for compounds of formula I (above), or an agrochemically acceptable salt, stereoisomer, enantiomer, tautomer or N-oxide thereof, and wherein Y1 is preferably hydrogen, halogen, Ci-C4alkyl, Ci-Cehaloalkyl, Cs-Cecycloalkyl, Cs-Cecycloalkyl monosubstituted by cyano, Ci-Cecyanoalkyl, Ci-Cecyanoalkoxy, cyano, Ci-C4alkoxy, Ci-Cehaloalkoxy, -N(R 3 ) 2 , -N(R 3 )COR4; and each R3 and R4 are independently from each other, hydrogen, Ci-C4alkyl, Ci-Cehaloalkyl or C3- Cecycloalkyl.
  • each R3 is independently hydrogen or Ci-C4alkyl
  • R4 is preferably Ci-Cealkyl or Cs-Cecycloalkyl.
  • Y1 is hydrogen, chlorine, bromine, trifluoromethyl, -CF2CH3, cyclopropyl, 1 -cyanocyclopropyl, 1-cyano-1-methyl-ethyl, 2,2,2-trifluoroethoxy, -NH(CH3), - N(CH3)COCH3 or -N(CH3)COCF3; more preferably Y1 is hydrogen, trifluoromethyl, -CF2CH3, cyclopropyl, 1 -cyanocyclopropyl, 1-cyano-1-methyl-ethyl, -NH(CH3), -N(CH3)COCH3 or - N(CH 3 )COCF3.
  • R2 is Ci-Cefluoroalkyl; more preferably R2 is -CH2CH2CF3, -CH2CF2CHF2 or -CH2CF2CF3; Y1 is halogen, trifluoromethyl, 1 ,1-difluoroethyl, cyclopropyl, cyanocyclopropyl, cyanoisopropyl or trifluoroethoxy; more preferably Y1 is cyclopropyl, 1 -cyanocyclopropyl or 1-cyano-1-methyl-ethyl.
  • Another group of compounds according to this embodiment are those of formula l-3a which are compounds of formula (I-3) wherein R1 is ethyl, X is SO2, G2 is N and G1 is CH.
  • R2, R3, R4 and Y1 are as defined for compounds of formula I (above), or an agrochemically acceptable salt, stereoisomer, enantiomer, tautomer or N-oxide thereof, and wherein Y1 is preferably hydrogen, halogen, Ci-C4alkyl, Ci-Cehaloalkyl, Cs-Cecycloalkyl, Cs-Cecycloalkyl monosubstituted by cyano, Ci-Cecyanoalkyl, Ci-Cecyanoalkoxy, cyano, Ci-C4alkoxy, Ci-Cehaloalkoxy, -N(R 3 )2, - N(R 3 )COR 4 ; and each R 3 and R 4 are independently from each other, hydrogen, Ci-C
  • each R 3 is independently hydrogen or Ci-C 4 alkyl
  • R 4 is preferably Ci-Cealkyl or C 3 -C6cycloalkyl.
  • Yi is hydrogen, chlorine, bromine, trifluoromethyl, -CF2CH 3 , cyclopropyl, 1 -cyanocyclopropyl, 1-cyano-1-methyl-ethyl, 2,2,2-trifluoroethoxy, -NH(CH 3 ), - N(CH 3 )COCH 3 or -N(CH 3 )COCF 3 ; more preferably Yi is hydrogen, trifluoromethyl, -CF2CH 3 , cyclopropyl, 1 -cyanocyclopropyl, 1-cyano-1-methyl-ethyl, -NH(CH 3 ), -N(CH 3 )COCH 3 or - N(CH 3 )COCF 3 .
  • R2, R 3 and R 4 are as defined for compounds of formula I (above), and more preferably Yi is halogen, trifluoromethyl, 1 ,1-difluoroethyl, cyclopropyl, cyanocyclopropyl, cyanoisopropyl or trifluoroethoxy.
  • One group of compounds according to this embodiment are compounds of formula (l-3a-1) which are compounds of formula (l-3a), or of any of the preferred embodiments of the compounds of formula (I- 3a), wherein
  • R 2 is -CH 2 CH 2 CF 3 , -CH2CF2CHF2 or -CH 2 CF 2 CF 3 ; preferably -CH 2 CH 2 CF 3 or -CH 2 CF 2 CF 3 ;
  • Yi is trifluoromethyl, difluoroethyl, cyclopropyl, cyanocyclopropyl, cyanoisopropyl, -NH(CH 3 ), - N(CH 3 )COCH 3 or -N(CH 3 )COCF 3 ; preferably -CF 3 , -CF2CH 3 , cyclopropyl, 1 -cyanocyclopropyl, 1- cyano-1-methyl-ethyl, -NH(CH 3 ), -N(CH 3 )COCH 3 or -N(CH 3 )COCF 3 ; more preferably Yi is cyclopropyl, 1 -cyanocyclopropyl or 1-cyano-1-methyl-ethyl.
  • Another group of compounds according to this embodiment are compounds of formula (l-3b) which are compounds of formula (I-3) wherein R1 is ethyl, X is SO2, G2 is CH and G1 is CH.
  • R2, R 3 , R 4 and Yi are as defined for compounds of formula I (above), or an agrochemically acceptable salt, stereoisomer, enantiomer, tautomer or N-oxide thereof, and wherein Yi is preferably hydrogen, halogen, Ci-C 4 alkyl, Ci-Cehaloalkyl, C 3 -C6cycloalkyl, C 3 -C6cycloalkyl monosubstituted by cyano, Ci-Cecyanoalkyl, Ci-Cecyanoalkoxy, cyano, Ci-C 4 alkoxy, Ci-Cehaloalkoxy, -N(R 3 )2, - N(R 3 )COR 4 ; and each R 3 and R4 are independently from each other, hydrogen, Ci-
  • each R 3 is independently hydrogen or Ci-C4alkyl
  • R4 is preferably Ci-Cealkyl or C 3 -C6cycloalkyl.
  • Y1 is hydrogen, chlorine, bromine, trifluoromethyl, -CF2CH 3 , cyclopropyl, 1 -cyanocyclopropyl, 1-cyano-1-methyl-ethyl, 2,2,2-trifluoroethoxy, -NH(CH 3 ), - N(CH 3 )COCH 3 or -N(CH 3 )COCF 3 ; more preferably Y1 is hydrogen, trifluoromethyl, -CF2CH 3 , cyclopropyl, 1 -cyanocyclopropyl, 1-cyano-1-methyl-ethyl, -NH(CH 3 ), -N(CH 3 )COCH 3 or - N(CH 3 )COCF 3 .
  • R2 is Ci-Cefluoroalkyl; more preferably R2 is -CH2CH2CF 3 , -CH2CF2CHF2 or -CH2CF2CF 3 ; Y1 is halogen, trifluoromethyl, 1 ,1-difluoroethyl, cyclopropyl, cyanocyclopropyl, cyanoisopropyl or trifluoroethoxy; more preferably Y1 is cyclopropyl, 1 -cyanocyclopropyl or 1-cyano-1-methyl-ethyl.
  • Another group of compounds according to this embodiment are compounds of formula (l-3c) which are compounds of formula (I-3) wherein R1 is ethyl, X is SO2, G2 is CH and G1 is N.
  • R2, R 3 , R4 and Y1 are as defined for compounds of formula I (above), or an agrochemically acceptable salt, stereoisomer, enantiomer, tautomer or N-oxide thereof, and wherein Y1 is preferably hydrogen, halogen, Ci-C4alkyl, Ci-Cehaloalkyl, C 3 -C6cycloalkyl, C 3 -C6cycloalkyl monosubstituted by cyano, Ci-Cecyanoalkyl, Ci-Cecyanoalkoxy, cyano, Ci-C4alkoxy, Ci-Cehaloalkoxy, -N(R 3 )2, - N(R 3 )COR 4 ; and each R 3 and R4 are independently from each other,
  • each R 3 is independently hydrogen or Ci-C4alkyl
  • R4 is preferably Ci-Cealkyl or C 3 -C6cycloalkyl.
  • Y1 is hydrogen, chlorine, bromine, trifluoromethyl, -CF2CH 3 , cyclopropyl, 1 -cyanocyclopropyl, 1-cyano-1-methyl-ethyl, 2,2,2-trifluoroethoxy, -NH(CH 3 ), - N(CH 3 )COCH 3 or -N(CH 3 )COCF 3 ; more preferably Y1 is hydrogen, trifluoromethyl, -CF2CH 3 , cyclopropyl, 1 -cyanocyclopropyl, 1-cyano-1-methyl-ethyl, -NH(CH 3 ), -N(CH 3 )COCH 3 or -
  • R2 is Ci-Cefluoroalkyl; more preferably R2 is -CH2CH2CF3, -CH2CF2CHF2 or -CH2CF2CF3; Y1 is halogen, trifluoromethyl, 1 ,1-difluoroethyl, cyclopropyl, cyanocyclopropyl, cyanoisopropyl or trifluoroethoxy; more preferably Y1 is cyclopropyl, 1 -cyanocyclopropyl or 1-cyano-1-methyl-ethyl.
  • R2, R3, R4, G1, G2 and Y2 are as defined for compounds of formula I (above), or an agrochemically acceptable salt, stereoisomer, enantiomer, tautomer or N-oxide thereof, and wherein Y2 is preferably hydrogen, halogen, Ci-C4alkyl, Ci-Cehaloalkyl, Cs-Cecycloalkyl, Cs-Cecycloalkyl monosubstituted by cyano, Ci-Cecyanoalkyl, Ci-Cecyanoalkoxy, cyano, Ci-C4alkoxy, Ci-Cehaloalkoxy, -N(R 3 ) 2 , -N(R 3 )COR4; and each R3 and R4 are independently from each other, hydrogen, Ci-C4alkyl, Ci-Cehaloalkyl or C3- Cecycloalkyl.
  • each R3 is independently hydrogen or Ci-C4alkyl
  • R4 is preferably Ci-Cealkyl or Cs-Cecycloalkyl.
  • Y2 is hydrogen, chlorine, bromine, trifluoromethyl, -CF2CH3, cyclopropyl, 1 -cyanocyclopropyl, 1-cyano-1-methyl-ethyl, 2,2,2-trifluoroethoxy, -NH(CH3), - N(CH3)COCH3 or -N(CH3)COCF3; more preferably Y2 is hydrogen, trifluoromethyl, -CF2CH3, cyclopropyl, 1 -cyanocyclopropyl, 1-cyano-1-methyl-ethyl, -NH(CH3), -N(CH3)COCH3 or - N(CH 3 )COCF3.
  • R2 is Ci-Cefluoroalkyl; more preferably R2 is -CH2CH2CF3, -CH2CF2CHF2 or -CH2CF2CF3; Y2 is halogen, trifluoromethyl, 1 ,1-difluoroethyl, cyclopropyl, cyanocyclopropyl, cyanoisopropyl or trifluoroethoxy; more preferably Y2 is cyclopropyl, 1 -cyanocyclopropyl or 1-cyano-1-methyl-ethyl.
  • Another group of compounds according to this embodiment are those of formula l-4a which are compounds of formula (I-4) wherein R1 is ethyl, X is SO2, G2 is N and G1 is CH.
  • R2, R3, R4 and Y2 are as defined for compounds of formula I (above), or an agrochemically acceptable salt, stereoisomer, enantiomer, tautomer or N-oxide thereof, and wherein Y2 is preferably hydrogen, halogen, Ci-C4alkyl, Ci-Cehaloalkyl, Cs-Cecycloalkyl, Cs-Cecycloalkyl monosubstituted by cyano, Ci-Cecyanoalkyl, Ci-Cecyanoalkoxy, cyano, Ci-C4alkoxy, Ci-Cehaloalkoxy, -N(Rs)2, - N(R 3 )COR 4 ; and each R3 and R4 are independently from each other, hydrogen, Ci-C4
  • each R3 is independently hydrogen or Ci-C4alkyl
  • R4 is preferably Ci-Cealkyl or Cs-Cecycloalkyl.
  • Y2 is hydrogen, chlorine, bromine, trifluoromethyl, -CF2CH3, cyclopropyl, 1 -cyanocyclopropyl, 1-cyano-1-methyl-ethyl, 2,2,2-trifluoroethoxy, -NH(CH3), - N(CH3)COCH3 or -N(CH3)COCF3; more preferably Y2 is hydrogen, trifluoromethyl, -CF2CH3, cyclopropyl, 1 -cyanocyclopropyl, 1-cyano-1-methyl-ethyl, -NH(CH3), -N(CH3)COCH3 or - N(CH 3 )COCF3.
  • R2, R3 and R4 are as defined for compounds of formula I (above), and more preferably Y2 is halogen, trifluoromethyl, 1 ,1-difluoroethyl, cyclopropyl, cyanocyclopropyl, cyanoisopropyl or trifluoroethoxy.
  • One group of compounds according to this embodiment are compounds of formula (l-4a-1) which are compounds of formula (l-4a), or of any of the preferred embodiments of the compounds of formula (I- 4a), wherein
  • R 2 is -CH2CH2CF3, -CH2CF2CHF2 or -CH2CF2CF3; preferably -CH2CH2CF3 or -CH2CF2CF3; and
  • Y2 is trifluoromethyl, difluoroethyl, cyclopropyl, cyanocyclopropyl, cyanoisopropyl, -NH(CH3), - N(CH3)COCH3 or -N(CH3)COCF3; preferably -CF3, -CF2CH3, cyclopropyl, 1 -cyanocyclopropyl, 1- cyano-1-methyl-ethyl, -NH(CH3), -N(CH3)COCH3 or -N(CH3)COCF3; more preferably Y2 is -CF3, - CF2CH3, 1 -cyanocyclopropyl, 1-cyano-1-methyl-ethyl, -NH(CH3), -N(CH3)COCH3 or -N(CH3)COCF3.
  • Another group of compounds according to this embodiment are compounds of formula (l-4b) which are compounds of formula (I-4) wherein R1 is ethyl, X is SO2, G2 is CH and G1 is CH.
  • R2, R3, R4 and Y2 are as defined for compounds of formula I (above), or an agrochemically acceptable salt, stereoisomer, enantiomer, tautomer or N-oxide thereof, and wherein Y2 is preferably hydrogen, halogen, Ci-C4alkyl, Ci-Cehaloalkyl, Cs-Cecycloalkyl, Cs-Cecycloalkyl monosubstituted by cyano, Ci-Cecyanoalkyl, Ci-Cecyanoalkoxy, cyano, Ci-C4alkoxy, Ci-Cehaloalkoxy, -N(Rs)2, - N(R 3 )COR 4 ; and each R3 and R4 are independently from each other, hydrogen, Ci-C
  • each R3 is independently hydrogen or Ci-C4alkyl; and R4 is preferably Ci-Cealkyl or Cs-Cecycloalkyl.
  • Y2 is hydrogen, chlorine, bromine, trifluoromethyl, -CF2CH3, cyclopropyl, 1 -cyanocyclopropyl, 1-cyano-1-methyl-ethyl, 2,2,2-trifluoroethoxy, -NH(CH3), - N(CH3)COCH3 or -N(CH3)COCF3; more preferably Y2 is hydrogen, trifluoromethyl, -CF2CH3, cyclopropyl, 1 -cyanocyclopropyl, 1-cyano-1-methyl-ethyl, -NH(CH3), -N(CH3)COCH3 or - N(CH 3 )COCF3.
  • R2 is Ci-Cefluoroalkyl; more preferably R2 is -CH2CH2CF3, -CH2CF2CHF2 or -CH2CF2CF3; Y2 is halogen, trifluoromethyl, 1 ,1-difluoroethyl, cyclopropyl, cyanocyclopropyl, cyanoisopropyl or trifluoroethoxy; more preferably Y2 is cyclopropyl, 1 -cyanocyclopropyl or 1-cyano-1-methyl-ethyl.
  • Another group of compounds according to this embodiment are compounds of formula (l-4c) which are compounds of formula (I-4) wherein R1 is ethyl, X is SO2, G2 is CH and G1 is N.
  • R2, R3, R4 and Y2 are as defined for compounds of formula I (above), or an agrochemically acceptable salt, stereoisomer, enantiomer, tautomer or N-oxide thereof, and wherein Y2 is preferably hydrogen, halogen, Ci-C4alkyl, Ci-Cehaloalkyl, Cs-Cecycloalkyl, Cs-Cecycloalkyl monosubstituted by cyano, Ci-Cecyanoalkyl, Ci-Cecyanoalkoxy, cyano, Ci-C4alkoxy, Ci-Cehaloalkoxy, -N(R 3 )2, - N(R 3 )COR 4 ; and each R 3 and R 4 are independently from each other, hydrogen, Ci-
  • each R 3 is independently hydrogen or Ci-C 4 alkyl
  • R 4 is preferably Ci-Cealkyl or C 3 -C6cycloalkyl.
  • Y2 is hydrogen, chlorine, bromine, trifluoromethyl, -CF2CH 3 , cyclopropyl, 1 -cyanocyclopropyl, 1-cyano-1-methyl-ethyl, 2,2,2-trifluoroethoxy, -NH(CH 3 ), - N(CH 3 )COCH 3 or -N(CH 3 )COCF 3 ; more preferably Y2 is hydrogen, trifluoromethyl, -CF2CH 3 , cyclopropyl, 1 -cyanocyclopropyl, 1-cyano-1-methyl-ethyl, -NH(CH 3 ), -N(CH 3 )COCH 3 or - N(CH 3 )COCF 3 .
  • R2 is Ci-Cefluoroalkyl; more preferably R2 is -CH2CH2CF 3 , -CH2CF2CHF2 or -CH2CF2CF 3 ; Y2 is halogen, trifluoromethyl, 1 ,1-difluoroethyl, cyclopropyl, cyanocyclopropyl, cyanoisopropyl or trifluoroethoxy; more preferably Y2 is cyclopropyl, 1 -cyanocyclopropyl or 1-cyano-1-methyl-ethyl.
  • Compounds according to the invention may possess any number of benefits including, inter alia, advantageous levels of biological activity for protecting plants against insects or superior properties for use as agrochemical active ingredients (for example, greater biological activity, an advantageous spectrum of activity, an increased safety profile, improved physico-chemical properties, or increased biodegradability or environmental profile).
  • advantageous levels of biological activity for protecting plants against insects or superior properties for use as agrochemical active ingredients for example, greater biological activity, an advantageous spectrum of activity, an increased safety profile, improved physico-chemical properties, or increased biodegradability or environmental profile.
  • certain compounds of formula (I) may show an advantageous safety profile with respect to non-target arthropods, in particular pollinators such as honey bees, solitary bees, and bumble bees.
  • Apis mellifera is particularly, bumble bees.
  • the present invention provides a composition
  • a composition comprising an insecticidally, acaricidally, nematicidally or molluscicidally effective amount of a compound of formula (I), or an agrochemically acceptable salt, stereoisomer, enantiomer, tautomer or N-oxide thereof, as defined in any of the embodiments under compounds of formula (I), (1-1), (I-2), (I-3) or (I-4) (above), and, optionally, an auxiliary or diluent.
  • the present invention provides a method of combating and controlling insects, acarines, nematodes or molluscs which comprises applying to a pest, to a locus of a pest, or to a plant susceptible to attack by a pest an insecticidally, acaricidally, nematicidally or molluscicidally effective amount of a compound of formula (I), or an agrochemically acceptable salt, stereoisomer, enantiomer, tautomer or N-oxide thereof, as defined in any of the embodiments under compounds of formula (I), (I- 1), (I-2), (I-3) or (I-4) (above) or a composition as defined above.
  • the present invention provides a method for the protection of plant propagation material from the attack by insects, acarines, nematodes or molluscs, which comprises treating the propagation material or the site, where the propagation material is planted, with a composition as defined above.
  • the process according to the invention for preparing compounds of formula I is carried out in principle by methods known to those skilled in the art as depicted in scheme 1 .
  • the subgroup of compounds of formula I, wherein X is SO (sulfoxide) and/or SO2 (sulfone) may be obtained by means of an oxidation reaction of the corresponding sulfide compounds of formula II defined as compounds of formula I, wherein X is S, involving reagents such as, for example, m-chloroperoxy- benzoic acid (mCPBA), hydrogen peroxide, oxone, sodium periodate, sodium hypochlorite or tert-butyl hypochlorite amongst other oxidants.
  • mCPBA m-chloroperoxy- benzoic acid
  • the oxidation reaction is generally conducted in the presence of a solvent.
  • the solvent to be used in the reaction include aliphatic halogenated hydrocarbons such as dichloromethane and chloroform; alcohols such as methanol and ethanol; acetic acid; water; and mixtures thereof.
  • the amount of the oxidant to be used in the reaction is generally 1 to 3 moles, preferably 1 to 1.2 moles, relative to 1 mole of the sulfide compounds I to produce the sulfoxide compounds I, and preferably 2 to 2.2 moles of oxidant, relative to 1 mole of of the sulfide compounds I to produce the sulfone compounds I.
  • Such oxidation reactions are disclosed, for example, in WO 2013/018928.
  • Xa is preferentially chlorine, bromine or iodine, more preferentially bromine or iodine and the reaction is performed with a base, for example a tertiary amine or a mineral base, as for example an alkali metal carbonate, in a non-participating solvent, like dimethoxyethane or acetonitrile, at a temperature between 0°C and the boiling point of the reaction mixture.
  • a base for example a tertiary amine or a mineral base, as for example an alkali metal carbonate
  • a non-participating solvent like dimethoxyethane or acetonitrile
  • Xa is preferably a halogen, preferably chlorine, bromine or iodine and the solvent is preferably a polar aprotic solvent, as for example dimethylformamide.
  • the reaction can be performed preferably between -20°C and 100°C, most preferably between 0°C and 80°C. An excess of reagent III or Illa maybe used for a good conversion.
  • Compounds of formula IV maybe conveniently obtained by treating compounds of formula V, wherein G1, G2, R2, Y1 and Y2 are as defined in formula I with an electrophilic halogenating reagent, as for example N-chlorosuccinimide, N-bromosuccinimide, N-iodosuccinimide or a molecular halogen, like bromine, just to cite a few.
  • an electrophilic halogenating reagent as for example N-chlorosuccinimide, N-bromosuccinimide, N-iodosuccinimide or a molecular halogen, like bromine, just to cite a few.
  • R2, Y1 and Y2 are as defined in formula I above;
  • Xa is a halogen, are novel, especially developed for the preparation of the compounds of formula I according to the invention and therefore represent a further object of the invention.
  • the preferences and preferred embodiments of the substituents of the compounds of formula I are also valid for the compounds of formula IV-a.
  • Xa preferably is chlorine, bromine or iodine; even more preferably bromine or iodine.
  • Compounds of formula V can be obtained by cyclization of compounds of formula VI, wherein G1, G2, R2, Y1 and Y2 are as defined in formula I.
  • the reaction can be performed with a large range of reducing agents.
  • Trialkylphosphines for example tributylphosphine, are convenient reagents for this purpose.
  • the reaction can be performed in a inert solvent, like acetonitrile or dimethoxyethane, at temperatures between -30°C and 100°C.
  • R2, Y1 and Y2 are as defined in formula I above, are novel, especially developed for the preparation of the compounds of formula I according to the invention and therefore represent a further object of the invention.
  • the preferences and preferred embodiments of the substituents of the compounds of formula I are also valid for the compounds of formula V-a.
  • Compounds of formula VI can be prepared by condensing an amino compound of formula VIII, wherein G1, G2 and R2 are as defined in formula I and an aldehyde of formula VII, wherein Y1 and Y2 are as defined in formula I.
  • the dehydration can be preferably performed in an inert solvent, like toluene, at a temperature between 20°C and the boiling point of the solvent. It is convenient to use a dehydrating agent, like molecular sieves.
  • R2, Y1 and Y2 are as defined in formula I above, are novel, especially developed for the preparation of the compounds of formula I according to the invention and therefore represent a further object of the invention.
  • the preferences and preferred embodiments of the substituents of the compounds of formula I are also valid for the compounds of formula Vl-a.
  • Compounds of formula IX can be prepared from compounds of formula X, wherein G1, G2 and R2 are as defined in formula I and Rr is a Ci-C4alkyl group, preferably methyl or ethyl.
  • the first step of this transformation consists of the hydrolysis of the ester function to the carboxylic acid, which is standardwise performed under aqueous alkaline conditions followed by acidification, leading to an intermediate of formula X wherein Rr is H.
  • This intermediate can then be treated with an azidocontaining reagent, for example diphenylphosphoryl azide, and heated in presence of t-butyl alcohol to effect the Curtius rearrangement to lead to the BOC-protected amine.
  • an azidocontaining reagent for example diphenylphosphoryl azide
  • Compounds of formula X can be obtained from compounds of formula XI, wherein G1, G2 and R2 are as defined in formula I, and Xb is a leaving group, like a trifluoro methanesulfonate or a halogen, preferentially chloro, bromo or iodo, most preferably bromo.
  • the transformation can best be carried out under pressure of carbon monoxide, in an autoclave, in presence of an lower alcohol Rr-OH, wherein Rr is C1-C4 alkyl, preferably methanol or ethanol.
  • the reaction is best catalyzed by a palladium-based catalyst. Alkoxycarbonylation reactions are standard reactions very often encountered in the chemical literature and are known to the person skilled in the art.
  • compounds of formula VIII can be prepared directly from compounds of formula XI (same definition as above) by treatment with ammonia.
  • the reaction is preferably performed with a large excess of ammonia, in a solvent that could be a lower alcohol or water, eventually mixed with another organic solvent.
  • the reaction mixture may need to be heated so, because of the volatility of ammonia, an autoclave should be used. Copper salts can be added to facilitate the reaction.
  • Another preparation method of compounds of formula VIII from compounds of formula XI consists of coupling with te/Y-butyl carbamate, in presence of a base and with a palladium-based catalyst. This type of reaction is also well described in the literature.
  • the coupling product is a compound of formula IX, which conversion to compound of formula VIII has been described hereabove.
  • Compounds of formula XI can be prepared by reacting compounds of formula XII, wherein Gi and G2 are as defined in formula I, and Xb is a halogen (or a pseudo-halogen leaving group, such as a triflate), preferably chloro, bromo or iodo, most preferably bromo with a compound R2-LG, wherein R2 is as defined in formula I and LG is a halogen, preferably iodo, bromo or chloro or a pseudo-halogen leaving group, such as a (halo)alkyl or aryl sulfonate ester, for example triflate, in the presence of a base, such as sodium hydride or an alkali metal hydride, carbonate (e.g.
  • a base such as sodium hydride or an alkali metal hydride, carbonate
  • sodium carbonate, potassium carbonate or cesium carbonate) or hydroxide in an inert solvent such as tetra hydrofuran, dioxane, N,N-dimethylformamide DMF, N,N-dimethylacetamide or acetonitrile and the like, at temperatures between 0 and 120°C, by procedures well known to those skilled in the art.
  • an inert solvent such as tetra hydrofuran, dioxane, N,N-dimethylformamide DMF, N,N-dimethylacetamide or acetonitrile and the like, at temperatures between 0 and 120°C, by procedures well known to those skilled in the art.
  • R2 is as defined in formula I, are novel, especially developed for the preparation of the compounds of formula I according to the invention and therefore represent a further object of the invention.
  • the preferences and preferred embodiments of the substituents of the compounds of formula I are also valid for the compounds of formula Vlll-a.
  • the reactants can be reacted in the presence of a base.
  • suitable bases are alkali metal or alkaline earth metal hydroxides, alkali metal or alkaline earth metal hydrides, alkali metal or alkaline earth metal amides, alkali metal or alkaline earth metal alkoxides, alkali metal or alkaline earth metal acetates, alkali metal or alkaline earth metal carbonates, alkali metal or alkaline earth metal dialkylamides or alkali metal or alkaline earth metal alkylsilylamides, alkylamines, alkylenediamines, free or N-alkylated saturated or unsaturated cycloalkylamines, basic heterocycles, ammonium hydroxides and carbocyclic amines.
  • Examples which may be mentioned are sodium hydroxide, sodium hydride, sodium amide, sodium methoxide, sodium acetate, sodium carbonate, potassium tert- butoxide, potassium hydroxide, potassium carbonate, potassium hydride, lithium diisopropylamide, potassium bis(trimethylsilyl)amide, calcium hydride, triethylamine, diisopropylethylamine, triethylenediamine, cyclohexylamine, N-cyclohexyl-N,N-dimethylamine, N,N-diethylaniline, pyridine, 4- (N,N-dimethylamino)pyridine, quinuclidine, N-methylmorpholine, benzyltrimethylammonium hydroxide and 1 ,8-diazabicyclo[5.4.0]undec-7-ene (DBU).
  • the reactants can be reacted with each other as such, i.e. without adding a solvent or diluent. In most cases, however, it is advantageous to add an inert solvent or diluent or a mixture of these. If the reaction is carried out in the presence of a base, bases which are employed in excess, such as triethylamine, pyridine, N-methylmorpholine or N , N-diethylaniline , may also act as solvents or diluents.
  • the reactions are advantageously carried out in a temperature range from approximately -80°C to approximately +140°C, preferably from approximately -30°C to approximately +100°C, in many cases in the range between ambient temperature and approximately +80°C.
  • a compound of formula I can be converted in a manner known per se into another compound of formula I by replacing one or more substituents of the starting compound of formula I in the customary manner by (an)other substituent(s) according to the invention, and by post modification of compounds of with reactions such as oxidation, alkylation, reduction, acylation and other methods known by those skilled in the art.
  • Salts of compounds of formula I can be prepared in a manner known per se.
  • acid addition salts of compounds of formula I are obtained by treatment with a suitable acid or a suitable ion exchanger reagent and salts with bases are obtained by treatment with a suitable base or with a suitable ion exchanger reagent.
  • Salts of compounds of formula I can be converted in the customary manner into the free compounds I, acid addition salts, for example, by treatment with a suitable basic compound or with a suitable ion exchanger reagent and salts with bases, for example, by treatment with a suitable acid or with a suitable ion exchanger reagent.
  • Salts of compounds of formula I can be converted in a manner known per se into other salts of compounds of formula I, acid addition salts, for example, into other acid addition salts, for example by treatment of a salt of inorganic acid such as hydrochloride with a suitable metal salt such as a sodium, barium or silver salt, of an acid, for example with silver acetate, in a suitable solvent in which an inorganic salt which forms, for example silver chloride, is insoluble and thus precipitates from the reaction mixture.
  • a salt of inorganic acid such as hydrochloride
  • a suitable metal salt such as a sodium, barium or silver salt
  • the compounds of formula I which have saltforming properties can be obtained in free form or in the form of salts.
  • the compounds of formula I and, where appropriate, the tautomers thereof, in each case in free form or in salt form, can be present in the form of one of the isomers which are possible or as a mixture of these, for example in the form of pure isomers, such as antipodes and/or diastereomers, or as isomer mixtures, such as enantiomer mixtures, for example racemates, diastereomer mixtures or racemate mixtures, depending on the number, absolute and relative configuration of asymmetric carbon atoms which occur in the molecule and/or depending on the configuration of non-aromatic double bonds which occur in the molecule; the invention relates to the pure isomers and also to all isomer mixtures which are possible and is to be understood in each case in this sense hereinabove and hereinbelow, even when stereochemical details are not mentioned specifically in each case.
  • Diastereomer mixtures or racemate mixtures of compounds of formula I, in free form or in salt form, which can be obtained depending on which starting materials and procedures have been chosen can be separated in a known manner into the pure diasteromers or racemates on the basis of the physicochemical differences of the components, for example by fractional crystallization, distillation and/or chromatography.
  • Enantiomer mixtures such as racemates, which can be obtained in a similar manner can be resolved into the optical antipodes by known methods, for example by recrystallization from an optically active solvent, by chromatography on chiral adsorbents, for example high-performance liquid chromatography (HPLC) on acetyl celulose, with the aid of suitable microorganisms, by cleavage with specific, immobilized enzymes, via the formation of inclusion compounds, for example using chiral crown ethers, where only one enantiomer is complexed, or by conversion into diastereomeric salts, for example by reacting a basic end-product racemate with an optically active acid, such as a carboxylic acid, for example camphor, tartaric or malic acid, or sulfonic acid, for example camphorsulfonic acid, and separating the diastereomer mixture which can be obtained in this manner, for example by fractional crystallization based on their differing solubilities, to give the
  • N-oxides can be prepared by reacting a compound of the formula I with a suitable oxidizing agent, for example the H2C>2/urea adduct in the presence of an acid anhydride, e.g. trifluoroacetic anhydride.
  • oxidizing agent for example the H2C>2/urea adduct
  • acid anhydride e.g. trifluoroacetic anhydride
  • the compounds of formula I and, where appropriate, the tautomers thereof, in each case in free form or in salt form, can, if appropriate, also be obtained in the form of hydrates and/or include other solvents, for example those which may have been used for the crystallization of compounds which are present in solid form.
  • Table A-1 provides 18 compounds A-1 .001 to A-1 .018 of formula l-la wherein Ri is CH2CH3, R2 is CH2CF2CF3, X is S and Y1 is Y as defined in table Y.
  • Table A-2 provides 18 compounds A-2.001 to A-2.018 of formula l-la wherein R1 is CH2CH3, R2 is CH2CF2CF3, X is SO and Y1 is Y as defined in table Y.
  • Table A-3 provides 18 compounds A-3.001 to A-3.018 of formula l-la wherein R1 is CH2CH3, R2 is CH2CF2CF3, X is SO2 and Y1 is Y as defined in table Y.
  • Table A-4 provides 18 compounds A-4.001 to A-4.018 of formula l-la wherein R1 is CH2CH3, R2 is CH2CF2CHF2, X is S and Y1 is Y as defined in table Y.
  • Table A-5 provides 18 compounds A-5.001 to A-5.018 of formula l-la wherein R1 is CH2CH3, R2 is CH2CF2CHF2, X is SO and Y1 is Y as defined in table Y.
  • Table A-6 provides 18 compounds A-6.001 to A-6.018 of formula l-la wherein R1 is CH2CH3, R2 is CH2CF2CHF2, X is SO2 and Y1 is Y as defined in table Y.
  • Table B-1 provides 18 compounds B-1 .001 to B-1.018 of formula l-la wherein R1 is CH2CH3, R2 is CH2CH2CF3, X is S and Y1 is Y as defined in table Y.
  • Table B-2 provides 18 compounds B-2.001 to B-2.018 of formula l-la wherein R1 is CH2CH3, R2 is CH2CH2CF3, X is SO and Y1 is Y as defined in table Y.
  • Table B-3 provides 18 compounds B-3.001 to B-3.018 of formula l-la wherein R1 is CH2CH3, R2 is CH2CH2CF3, X is SO2 and Y1 is Y as defined in table Y.
  • Table B-4 provides 18 compounds B-4.001 to B-4.018 of formula l-la wherein R1 is CH2CH3, R2 is CH2CF3, X is S and Y1 is Y as defined in table Y.
  • Table B-5 provides 18 compounds B-5.001 to B-5.018 of formula l-la wherein R1 is CH2CH3, R2 is CH2CF3, X is SO and Y1 is Y as defined in table Y.
  • Table B-6 provides 18 compounds B-6.001 to B-6.018 of formula l-la wherein R1 is CH2CH3, R2 is CH2CF3, X is SO2 and Y1 is Y as defined in table Y.
  • Table A- 7 provides 18 compounds A-7.001 to A-7.018 of formula l-2a wherein Ri is CH2CH3, R2 is CH2CF2CF3, X is S and Y2 is Y as defined in table Y.
  • Table A-8 provides 18 compounds A-8.001 to A-8.018 of formula l-2a wherein R1 is CH2CH3, R2 is CH2CF2CF3, X is SO and Y2 is Y as defined in table Y.
  • Table A-9 provides 18 compounds A-9.001 to A-9.018 of formula l-2a wherein R1 is CH2CH3, R2 is CH2CF2CF3, X is SO2 and Y2 is Y as defined in table Y.
  • Table A-10 provides 18 compounds A-10.001 to A-10.018 of formula l-2a wherein R1 is CH2CH3, R2 is CH2CF2CHF2, X is S and Y2 is Y as defined in table Y.
  • Table A-11 provides 18 compounds A-11 .001 to A-11 .018 of formula l-2a wherein R1 is CH2CH3, R2 is CH2CF2CHF2, X is SO and Y2 is Y as defined in table Y.
  • Table A-12 provides 18 compounds A-12.001 to A-12.018 of formula l-2a wherein R1 is CH2CH3, R2 is CH2CF2CHF2, X is SO2 and Y2 is Y as defined in table Y.
  • Table B-7 provides 18 compounds B-7.001 to B-7.018 of formula l-2a wherein R1 is CH2CH3, R2 is CH2CH2CF3, X is S and Y2 is Y as defined in table Y.
  • Table B-8 provides 18 compounds B-8.001 to B-8.018 of formula l-2a wherein R1 is CH2CH3, R2 is CH2CH2CF3, X is SO and Y2 is Y as defined in table Y.
  • Table B-9 provides 18 compounds B-9.001 to B-9.018 of formula l-2a wherein R1 is CH2CH3, R2 is CH2CH2CF3, X is SO2 and Y2 is Y as defined in table Y.
  • Table B-10 provides 18 compounds B-10.001 to B-10.018 of formula l-2a wherein R1 is CH2CH3, R2 is CH2CF3, X is S and Y2 is Y as defined in table Y.
  • Table B-11 provides 18 compounds B-11.001 to B-11.018 of formula l-2a wherein R1 is CH2CH3, R2 is CH2CF3, X is SO and Y2 is Y as defined in table Y.
  • Table B-12 provides 18 compounds B-12.001 to B-12.018 of formula l-2a wherein R1 is CH2CH3, R2 is CH2CF3, X is SO2 and Y2 is Y as defined in table Y.
  • the compounds of formula I according to the invention are preventively and/or curatively valuable active ingredients in the field of pest control, even at low rates of application, which have a very favorable biocidal spectrum and are well tolerated by warm-blooded species, fish and plants.
  • the active ingredients according to the invention act against all or individual developmental stages of normally sensitive, but also resistant, animal pests, such as insects or representatives of the order Acarina.
  • the insecticidal or acaricidal activity of the active ingredients according to the invention can manifest itself directly, i. e.
  • Examples of the above mentioned animal pests are: from the order Acarina, for example,
  • Tetranychus spp. from the order Anoplura, for example, Haematopinus spp., Linognathus spp., Pediculus spp., Pemphigus spp. and Phylloxera spp.; from the order Coleoptera, for example,
  • Agriotes spp. Amphimallon majale, Anomala orientalis, Anthonomus spp., Aphodius spp, Astylus atromaculatus, Ataenius spp, Atomaria linearis, Chaetocnema tibialis, Cerotoma spp, Conoderus spp, Cosmopolites spp., Cotinis nitida, Curculio spp., Cyclocephala spp, Dermestes spp., Diabrotica spp., Diloboderus abderus, Epilachna spp., Eremnus spp., Heteronychus arator, Hypothenemus hampei, Lagria vilosa, Leptinotarsa decemLineata, Lissorhoptrus spp., Liogenys spp, Maecolaspis spp, Maladera castanea, Megas
  • Hemiptera for example, Acanthocoris scabrator, Acrosternum spp, Adelphocoris lineolatus, Amblypelta nitida, Bathycoelia thalassina, Blissus spp, Cimex spp., Clavigralla tomentosicollis, Creontiades spp, Distantiella theobroma, Dichelops furcatus, Dysdercus spp., Edessa spp, Euschistus spp., Eurydema pulchrum, Eurygaster spp., Halyomorpha halys, Horcias nobilellus, Leptocorisa spp., Lygus spp, Margarodes spp, Murgantia histrionic, Neomegalotomus spp, Nesidiocoris tenuis, Nezara spp., Nysius si
  • Acyrthosium pisum Adalges spp, Agalliana ensigera, Agonoscena targionii, Aleurodicus spp, Aleurocanthus spp, Aleurolobus barodensis, Aleurothrixus floccosus, Aleyrodes brassicae, Amarasca biguttula, Amritodus atkinsoni, Aonidiella spp., Aphididae, Aphis spp., Aspidiotus spp., Aulacorthum solani, Bactericera cockerelli, Bemisia spp, Brachycaudus spp, Brevicoryne brassicae, Cacopsylla spp, Cavariella aegopodii Scop., Ceroplaster spp., Chrysomphalus aonidium, Chrysomphalus dictyospermi, Cicadella spp, Cofana spec
  • Vespa spp. from the order Isoptera, for example, Coptotermes spp, Corniternes cumulans, Incisitermes spp, Macrotermes spp, Mastotermes spp, Microtermes spp, Reticulitermes spp.; Solenopsis geminate from the order Lepidoptera, for example,
  • Trichodectes spp. from the order Orthoptera, for example, Blatta spp., Blattella spp., Gryllotalpa spp., Leucophaea maderae, Locusta spp., Neocurtilla hexadactyla, Periplaneta spp. , Scapteriscus spp, and Schistocerca spp.; from the order Psocoptera, for example, Liposcelis spp.; from the order Siphonaptera, for example, Ceratophyllus spp., Ctenocephalides spp.
  • Orthoptera for example, Blatta spp., Blattella spp., Gryllotalpa spp., Leucophaea maderae, Locusta spp., Neocurtilla hexadactyla, Periplaneta spp. , Scapteriscus spp, and Schisto
  • Thysanoptera for example, Calliothrips phaseoli, Frankliniella spp., Heliothrips spp, Hercinothrips spp., Parthenothrips spp, Scirtothrips aurantii, Sericothrips variabilis, Taeniothrips spp., Thrips spp; from the order Thysanura, for example, Lepisma saccharina.
  • the active ingredients according to the invention can be used for controlling, i. e. containing or destroying, pests of the abovementioned type which occur in particular on plants, especially on useful plants and ornamentals in agriculture, in horticulture and in forests, or on organs, such as fruits, flowers, foliage, stalks, tubers or roots, of such plants, and in some cases even plant organs which are formed at a later point in time remain protected against these pests.
  • Suitable target crops are, in particular, cereals, such as wheat, barley, rye, oats, rice, maize or sorghum; beet, such as sugar or fodder beet; fruit, for example pomaceous fruit, stone fruit or soft fruit, such as apples, pears, plums, peaches, almonds, cherries or berries, for example strawberries, raspberries or blackberries; leguminous crops, such as beans, lentils, peas or soya; oil crops, such as oilseed rape, mustard, poppies, olives, sunflowers, coconut, castor, cocoa or ground nuts; cucurbits, such as pumpkins, cucumbers or melons; fibre plants, such as cotton, flax, hemp or jute; citrus fruit, such as oranges, lemons, grapefruit or tangerines; vegetables, such as spinach, lettuce, asparagus, cabbages, carrots, onions, tomatoes, potatoes or bell peppers; Lauraceae, such as avocado, Cinnamonium or camphor; and also tobacco, nuts,
  • compositions and/or methods of the present invention may be also used on any ornamental and/or vegetable crops, including flowers, shrubs, broad-leaved trees and evergreens.
  • the invention may be used on any of the following ornamental species: Ageratum spp., Alonsoa spp., Anemone spp., Anisodontea capsenisis, Anthemis spp., Antirrhinum spp., Aster spp., Begonia spp. (e.g. B. elatior, B. semperflorens, B. tubereux), Bougainvillea spp., Brachycome spp., Brassica spp.
  • Ageratum spp. Ageratum spp., Alonsoa spp., Anemone spp., Anisodontea capsenisis, Anthemis spp., Antirrhinum spp., Aster spp., Begonia spp. (e.g. B. elatior, B. semperflorens, B. tubereux), Bougainvillea spp., Brachycome spp.
  • Coreopsis spp. Crassula coccinea, Cuphea ignea, Dahlia spp., Delphinium spp., Dicentra spectabilis, Dorotheantus spp., Eustoma grandiflorum, Forsythia spp., Fuchsia spp., Geranium gnaphalium, Gerbera spp., Gomphrena globosa, Heliotropium spp., Helianthus spp., Hibiscus spp., Hortensia spp., Hydrangea spp., Hypoestes phyllostachya, I mpatiens spp. (/.
  • Iresines spp. Kalanchoe spp., Lantana camara, Lavatera trimestris, Leonotis leonurus, Lilium spp., Mesembryanthemum spp., Mimulus spp., Monarda spp., Nemesia spp., Tagetes spp., Dianthus spp. (carnation), Canna spp., Oxalis spp., Bellis spp., Pelargonium spp. (P. peltatum, P. Zonale), Viola spp.
  • the invention may be used on any of the following vegetable species: Allium spp. (A sativum, A., cepa, A. oschaninii, A. Porrum, A. ascalonicum, A. fistulosum), Anthriscus cerefolium, Apium graveolus, Asparagus officinalis, Beta vulgarus, Brassica spp. (B. Oleracea, B. Pekinensis, B. rapa), Capsicum annuum, Cicer arietinum, Cichorium endivia, Cichorum spp. (C. intybus, C. endivia), Citrillus lanatus, Cucumis spp. (C. sativus, C.
  • Preferred ornamental species include African violet, Begonia, Dahlia, Gerbera, Hydrangea, Verbena, Rosa, Kalanchoe, Poinsettia, Aster, Centaurea, Coreopsis, Delphinium, Monarda, Phlox, Rudbeckia, Sedum, Petunia, Viola, Impatiens, Geranium, Chrysanthemum, Ranunculus, Fuchsia, Salvia, Hortensia, rosemary, sage, St. Johnswort, mint, sweet pepper, tomato and cucumber.
  • the active ingredients according to the invention are especially suitable for controlling Aphis craccivora, Diabrotica balteata, Heliothis virescens, Myzus persicae, Plutella xylostella and Spodoptera littoralis in cotton, vegetable, maize, rice and soya crops.
  • the active ingredients according to the invention are further especially suitable for controlling Mamestra (preferably in vegetables), Cydia pomonella (preferably in apples), Empoasca(preferably in vegetables, vineyards), Leptinotarsa (preferably in potatos) and Chilo supressalis (preferably in rice).
  • the active ingredients according to the invention are especially suitable for controlling Aphis craccivora, Diabrotica balteata, Heliothis virescens, Myzus persicae, Plutella xylostella and Spodoptera littoralis in cotton, vegetable, maize, rice and soya crops.
  • the active ingredients according to the invention are further especially suitable for controlling Mamestra (preferably in vegetables), Cydia pomonella (preferably in apples), Empoasca(preferably in vegetables, vineyards), Leptinotarsa (preferably in potatos) and Chilo supressalis (preferably in rice).
  • the invention may also relate to a method of controlling damage to plant and parts thereof by plant parasitic nematodes (Endoparasitic-, Semiendoparasitic- and Ectoparasitic nematodes), especially plant parasitic nematodes such as root knot nematodes, Meloidogyne hapla, Meloidogyne incognita, Meloidogyne javanica, Meloidogyne arenaria and other Meloidogyne species; cyst-forming nematodes, Globodera rostochiensis and other Globodera species; Heterodera avenae, Heterodera glycines, Heterodera schachtii, Heterodera trifolii, and other Heterodera species; Seed gall nematodes, Anguina species; Stem and foliar nematodes, Aphelenchoides species; Sting nematodes, Belonolai
  • Needle nematodes Longidorus elongatus and other Longidorus species; Pin nematodes, Pratylenchus species; Lesion nematodes, Pratylenchus neglectus, Pratylenchus penetrans, Pratylenchus curvitatus, Pratylenchus goodeyi and other Pratylenchus species; Burrowing nematodes, Radopholus similis and other Radopholus species; Reniform nematodes, Rotylenchus robustus, Rotylenchus reniformis and other Rotylenchus species; Scutellonema species; Stubby root nematodes, Trichodorus primitivus and other Trichodorus species, Paratrichodorus species; Stunt nematodes, Tylenchorhynchus claytoni, Tylenchorhynchus dubius and other Tylenchorhynchus species; Citrus nematodes, Tyle
  • the compounds of the invention may also have activity against the molluscs.
  • Examples of which include, for example, Ampullariidae; Arion (A. ater, A. circumscriptus, A. hortensis, A. rufus); Bradybaenidae (Bradybaena fruticum); Cepaea (C. hortensis, C. Nemoralis); ochlodina; Deroceras (D. agrestis, D. empiricorum, D. laeve, D. reticulatum); Discus (D. rotundatus); Euomphalia; Galba (G. trunculata); Helicelia (H. itala, H.
  • H. aperta Limax (L. cinereoniger, L. flavus, L. marginatus, L. maximus, L. tenellus); Lymnaea; Milax (M. gagates, M. marginatus, M. sowerbyi); Opeas; Pomacea (P. canaticulata); Vallonia and Zanitoides.
  • crops is to be understood as including also crop plants which have been so transformed by the use of recombinant DNA techniques that they are capable of synthesising one or more selectively acting toxins, such as are known, for example, from toxin-producing bacteria, especially those of the genus Bacillus.
  • Toxins that can be expressed by such transgenic plants include, for example, insecticidal proteins, for example insecticidal proteins from Bacillus cereus or Bacillus popilliae; or insecticidal proteins from Bacillus thuringiensis, such as 8-endotoxins, e.g. CrylAb, CrylAc, Cry1 F, Cry1 Fa2, Cry2Ab, Cry3A, Cry3Bb1 or Cry9C, or vegetative insecticidal proteins (Vip), e.g. Vip1 , Vip2, Vip3 or Vip3A; or insecticidal proteins of bacteria colonising nematodes, for example Photorhabdus spp.
  • insecticidal proteins for example insecticidal proteins from Bacillus cereus or Bacillus popilliae
  • Bacillus thuringiensis such as 8-endotoxins, e.g. CrylAb, CrylAc, Cry1 F, Cry1 Fa2, Cry2Ab,
  • Xenorhabdus spp. such as Photorhabdus luminescens, Xenorhabdus nematophilus
  • toxins produced by animals such as scorpion toxins, arachnid toxins, wasp toxins and other insect-specific neurotoxins
  • toxins produced by fungi such as Streptomycetes toxins, plant lectins, such as pea lectins, barley lectins or snowdrop lectins
  • agglutinins proteinase inhibitors, such as trypsin inhibitors, serine protease inhibitors, patatin, cystatin, papain inhibitors
  • steroid metabolism enzymes such as 3-hydroxysteroidoxidase, ecdysteroid-UDP-glycosyl-transferase, cholesterol oxidases, ecd
  • 8-endotoxins for example CrylAb, CrylAc, Cry1 F, Cry1 Fa2, Cry2Ab, Cry3A, Cry3Bb1 or Cry9C, or vegetative insecticidal proteins (Vip), for example Vip1 , Vip2, Vip3 or Vip3A, expressly also hybrid toxins, truncated toxins and modified toxins.
  • Hybrid toxins are produced recombinantly by a new combination of different domains of those proteins (see, for example, WO 02/15701).
  • Truncated toxins for example a truncated CrylAb, are known.
  • modified toxins one or more amino acids of the naturally occurring toxin are replaced.
  • preferably non-naturally present protease recognition sequences are inserted into the toxin, such as, for example, in the case of Cry3A055, a cathepsin-G-recognition sequence is inserted into a Cry3A toxin (see WO 03/018810).
  • Examples of such toxins or transgenic plants capable of synthesising such toxins are disclosed, for example, in EP-A-0 374 753, WO 93/07278, WO 95/34656, EP-A-0 427 529, EP-A-451 878 and WO 03/052073.
  • Cryl-type deoxyribonucleic acids and their preparation are known, for example, from WO 95/34656, EP-A-0 367 474, EP-A-0 401 979 and WO 90/13651.
  • the toxin contained in the transgenic plants imparts to the plants tolerance to harmful insects.
  • insects can occur in any taxonomic group of insects, but are especially commonly found in the beetles (Coleoptera), two-winged insects (Diptera) and moths (Lepidoptera).
  • Transgenic plants containing one or more genes that code for an insecticidal resistance and express one or more toxins are known and some of them are commercially available. Examples of such plants are: YieldGard® (maize variety that expresses a Cry1 Ab toxin); YieldGard Rootworm® (maize variety that expresses a Cry3Bb1 toxin); YieldGard Plus® (maize variety that expresses a Cry1 Ab and a Cry3Bb1 toxin); Starlink® (maize variety that expresses a Cry9C toxin); Herculex I® (maize variety that expresses a Cry1 Fa2 toxin and the enzyme phosphinothricine N-acetyltransferase (PAT) to achieve tolerance to the herbicide glufosinate ammonium); NuCOTN 33B® (cotton variety that expresses a Cry1 Ac toxin); Bollgard I® (cotton variety that expresses
  • transgenic crops are:
  • MIR604 Maize from Syngenta Seeds SAS, Chemin de I'Hobit 27, F-31 790 St. Sauveur, France, registration number C/FR/96/05/10. Maize which has been rendered insect-resistant by transgenic expression of a modified Cry3A toxin. This toxin is Cry3A055 modified by insertion of a cathepsin-G- protease recognition sequence. The preparation of such transgenic maize plants is described in WO 03/018810.
  • MON 863 Maize from Monsanto Europe S.A. 270-272 Avenue de Tervuren, B-1150 Brussels, Belgium, registration number C/DE/02/9. MON 863 expresses a Cry3Bb1 toxin and has resistance to certain Coleoptera insects.
  • NK603 x MON 810 Maize from Monsanto Europe S.A. 270-272 Avenue de Tervuren, B-1150 Brussels, Belgium, registration number C/GB/02/M3/03. Consists of conventionally bred hybrid maize varieties by crossing the genetically modified varieties NK603 and MON 810.
  • NK603 x MON 810 Maize transgenically expresses the protein CP4 EPSPS, obtained from Agrobacterium sp. strain CP4, which imparts tolerance to the herbicide Roundup® (contains glyphosate), and also a Cry1 Ab toxin obtained from Bacillus thuringiensis subsp. kurstaki which brings about tolerance to certain Lepidoptera, include the European corn borer.
  • crops is to be understood as including also crop plants which have been so transformed by the use of recombinant DNA techniques that they are capable of synthesising antipathogenic substances having a selective action, such as, for example, the so-called "pathogenesis-related proteins" (PRPs, see e.g. EP-A-0 392 225).
  • PRPs pathogenesis-related proteins
  • Examples of such antipathogenic substances and transgenic plants capable of synthesising such antipathogenic substances are known, for example, from EP-A-0 392225, WO 95/33818 and EP-A-0 353 191.
  • the methods of producing such transgenic plants are generally known to the person skilled in the art and are described, for example, in the publications mentioned above.
  • Crops may also be modified for enhanced resistance to fungal (for example Fusarium, Anthracnose, or Phytophthora), bacterial (for example Pseudomonas) or viral (for example potato leafroll virus, tomato spotted wilt virus, cucumber mosaic virus) pathogens.
  • fungal for example Fusarium, Anthracnose, or Phytophthora
  • bacterial for example Pseudomonas
  • viral for example potato leafroll virus, tomato spotted wilt virus, cucumber mosaic virus
  • Crops also include those that have enhanced resistance to nematodes, such as the soybean cyst nematode.
  • Crops that are tolerance to abiotic stress include those that have enhanced tolerance to drought, high salt, high temperature, chill, frost, or light radiation, for example through expression of NF-YB or other proteins known in the art.
  • Antipathogenic substances which can be expressed by such transgenic plants include, for example, ion channel blockers, such as blockers for sodium and calcium channels, for example the viral KP1 , KP4 or KP6 toxins; stilbene synthases; bibenzyl synthases; chitinases; glucanases; the so-called "pathogenesis-related proteins" (PRPs; see e.g. EP-A-0 392 225); antipathogenic substances produced by microorganisms, for example peptide antibiotics or heterocyclic antibiotics (see e.g.
  • compositions according to the invention are the protection of stored goods and store rooms and the protection of raw materials, such as wood, textiles, floor coverings or buildings, and also in the hygiene sector, especially the protection of humans, domestic animals and productive livestock against pests of the mentioned type.
  • the present invention also provides a method for controlling pests (such as mosquitoes and other disease vectors; see also http://www.who.int/malaria/vector_control/irs/en/).
  • the method for controlling pests comprises applying the compositions of the invention to the target pests, to their locus or to a surface or substrate by brushing, rolling, spraying, spreading or dipping.
  • an IRS (indoor residual spraying) application of a surface such as a wall, ceiling or floor surface is contemplated by the method of the invention.
  • the method for controlling such pests comprises applying a pesticidally effective amount of the compositions of the invention to the target pests, to their locus, or to a surface or substrate so as to provide effective residual pesticidal activity on the surface or substrate.
  • a pesticidally effective amount of the compositions of the invention to the target pests, to their locus, or to a surface or substrate so as to provide effective residual pesticidal activity on the surface or substrate.
  • Such application may be made by brushing, rolling, spraying, spreading or dipping the pesticidal composition of the invention.
  • an IRS application of a surface such as a wall, ceiling or floor surface is contemplated by the method of the invention so as to provide effective residual pesticidal activity on the surface.
  • it is contemplated to apply such compositions for residual control of pests on a substrate such as a fabric material in the form of (or which can be used in the manufacture of) netting, clothing, bedding, curtains and tents.
  • Substrates including non-woven, fabrics or netting to be treated may be made of natural fibres such as cotton, raffia, jute, flax, sisal, hessian, or wool, or synthetic fibres such as polyamide, polyester, polypropylene, polyacrylonitrile or the like.
  • the polyesters are particularly suitable.
  • the methods of textile treatment are known, e.g. WO 2008/151984, WO 2003/034823, US 5631072, WO 2005/64072, W02006/128870, EP 1724392, WO 2005113886 or WO 2007/090739.
  • Further areas of use of the compositions according to the invention are the field of tree injection/trunk treatment for all ornamental trees as well all sort of fruit and nut trees.
  • the compounds according to the present invention are especially suitable against wood-boring insects from the order Lepidoptera as mentioned above and from the order Coleoptera, especially against woodborers listed in the following tables A and B:
  • the present invention may be also used to control any insect pests that may be present in turfgrass, including for example beetles, caterpillars, fire ants, ground pearls, millipedes, sow bugs, mites, mole crickets, scales, mealybugs ticks, spittlebugs, southern chinch bugs and white grubs.
  • the present invention may be used to control insect pests at various stages of their life cycle, including eggs, larvae, nymphs and adults.
  • the present invention may be used to control insect pests that feed on the roots of turfgrass including white grubs (such as Cyclocephala spp. (e.g. masked chafer, C. lurida), Rhizotrogus spp. (e.g. European chafer, R. majalis), Cotinus spp. (e.g. Green June beetle, C. nitida), Popillia spp. (e.g. Japanese beetle, P. japonica), Phyllophaga spp. (e.g. May/June beetle), Ataenius spp. (e.g. Black turfgrass ataenius, A.
  • white grubs such as Cyclocephala spp. (e.g. masked chafer, C. lurida), Rhizotrogus spp. (e.g. European chafer, R. majalis), Cotinus spp
  • Maladera spp. e.g. Asiatic garden beetle, M. castanea
  • Tomarus spp. ground pearls
  • mole crickets tawny, southern, and short-winged; Scapteriscus spp., Gryllotalpa africana) and leatherjackets (European crane fly, Tipula spp.).
  • the present invention may also be used to control insect pests of turfgrass that are thatch dwelling, including armyworms (such as fall armyworm Spodoptera frugiperda, and common armyworm Pseudaletia unipuncta), cutworms, billbugs (Sphenophorus spp., such as S. venatus verstitus and S. parvulus), and sod webworms (such as Crambus spp. and the tropical sod webworm, Herpetogramma phaeopteralis).
  • armyworms such as fall armyworm Spodoptera frugiperda, and common armyworm Pseudaletia unipuncta
  • cutworms such as S. venatus verstitus and S. parvulus
  • sod webworms such as Crambus spp. and the tropical sod webworm, Herpetogramma phaeopteralis.
  • the present invention may also be used to control insect pests of turfgrass that live above the ground and feed on the turfgrass leaves, including chinch bugs (such as southern chinch bugs, B/issus insularis), Bermudagrass mite (Eriophyes cynodoniensis), rhodesgrass mealybug (Antonina graminis), two-lined spittlebug (Propsapia bicincta), leafhoppers, cutworms (Noctuidae family), and greenbugs.
  • the present invention may also be used to control other pests of turfgrass such as red imported fire ants (Solenopsis invicta) that create ant mounds in turf.
  • compositions according to the invention are active against ectoparasites such as hard ticks, soft ticks, mange mites, harvest mites, flies (biting and licking), parasitic fly larvae, lice, hair lice, bird lice and fleas.
  • ectoparasites such as hard ticks, soft ticks, mange mites, harvest mites, flies (biting and licking), parasitic fly larvae, lice, hair lice, bird lice and fleas.
  • Anoplurida Haematopinus spp., Linognathus spp., Pediculus spp. and Phtirus spp., Solenopotes spp..
  • Nematocerina and Brachycerina for example Aedes spp., Anopheles spp., Culex spp., Simulium spp., Eusimulium spp., Phlebotomus spp., Lutzomyia spp., Culicoides spp., Chrysops spp., Hybomitra spp., Atylotus spp., Tabanus spp., Haematopota spp., Philipomyia spp., Braula spp., Musca spp., Hydrotaea spp., Stomoxys spp., Haematobia spp., Morellia spp., Fannia spp., Glossina spp., Calliphora spp., Glossina spp., Calliphora spp., Glossina spp., Call
  • Siphonaptrida for example Pulex spp., Ctenocephalides spp., Xenopsylla spp., Ceratophyllus spp..
  • Heteropterida for example Cimex spp., Triatoma spp., Rhodnius spp., Panstrongylus spp..
  • Actinedida Prostigmata
  • Acaridida Acaridida
  • Acarapis spp. Cheyletiella spp., Ornitrocheyletia spp., Myobia spp., Psorergatesspp., Demodex spp., Trombicula spp., Listrophorus spp., Acarus spp., Tyrophagus spp., Caloglyphus spp., Hypodectes spp., Pterolichus spp., Psoroptes spp., Chorioptes spp., Otodectes spp., Sarcoptes spp., Notoedres spp., Knemidocoptes spp., Cytodites spp. and Laminosioptes spp..
  • compositions according to the invention are also suitable for protecting against insect infestation in the case of materials such as wood, textiles, plastics, adhesives, glues, paints, paper and card, leather, floor coverings and buildings.
  • compositions according to the invention can be used, for example, against the following pests: beetles such as Hylotrupes bajulus, Chlorophorus pilosis, Anobium punctatum, Xestobium rufovillosum, Ptilinuspecticornis, Dendrobium pertinex, Ernobius mollis, Priobium carpini, Lyctus brunneus, Lyctus africanus, Lyctus planicollis, Lyctus linearis, Lyctus pubescens, Trogoxylon aequale, Minthesrugicollis, Xyleborus spec.,Tryptodendron spec., Apate monachus, Bostrychus capucins, Heterobostrychus brunneus, Sinoxylon spec, and Dinoderus minutus, and also hymenopterans such as Sirex juvencus, Urocerus gigas, Urocerus gigas taign
  • the compounds according to the invention can be used as pesticidal agents in unmodified form, but they are generally formulated into compositions in various ways using formulation adjuvants, such as carriers, solvents and surface-active substances.
  • formulation adjuvants such as carriers, solvents and surface-active substances.
  • the formulations can be in various physical forms, e.g.
  • Such formulations can either be used directly or diluted prior to use.
  • the dilutions can be made, for example, with water, liquid fertilisers, micronutrients, biological organisms, oil or solvents.
  • the formulations can be prepared e.g. by mixing the active ingredient with the formulation adjuvants in order to obtain compositions in the form of finely divided solids, granules, solutions, dispersions or emulsions.
  • the active ingredients can also be formulated with other adjuvants, such as finely divided solids, mineral oils, oils of vegetable or animal origin, modified oils of vegetable or animal origin, organic solvents, water, surface-active substances or combinations thereof.
  • the active ingredients can also be contained in very fine microcapsules.
  • Microcapsules contain the active ingredients in a porous carrier. This enables the active ingredients to be released into the environment in controlled amounts (e.g. slow-release).
  • Microcapsules usually have a diameter of from 0.1 to 500 microns. They contain active ingredients in an amount of about from 25 to 95 % by weight of the capsule weight.
  • the active ingredients can be in the form of a monolithic solid, in the form of fine particles in solid or liquid dispersion or in the form of a suitable solution.
  • the encapsulating membranes can comprise, for example, natural or synthetic rubbers, cellulose, styrene/butadiene copolymers, polyacrylonitrile, polyacrylate, polyesters, polyamides, polyureas, polyurethane or chemically modified polymers and starch xanthates or other polymers that are known to the person skilled in the art.
  • very fine microcapsules can be formed in which the active ingredient is contained in the form of finely divided particles in a solid matrix of base substance, but the microcapsules are not themselves encapsulated.
  • the formulation adjuvants that are suitable for the preparation of the compositions according to the invention are known perse.
  • liquid carriers there may be used: water, toluene, xylene, petroleum ether, vegetable oils, acetone, methyl ethyl ketone, cyclohexanone, acid anhydrides, acetonitrile, acetophenone, amyl acetate, 2-butanone, butylene carbonate, chlorobenzene, cyclohexane, cyclohexanol, alkyl esters of acetic acid, diacetone alcohol, 1 ,2-dichloropropane, diethanolamine, p- diethylbenzene, diethylene glycol, diethylene glycol abietate, diethylene glycol butyl ether, diethylene glycol ethyl ether, diethylene glycol methyl ether, A/,A/-dimethylformamide, dimethyl sulfoxide, 1 ,4- dioxan
  • Suitable solid carriers are, for example, talc, titanium dioxide, pyrophyllite clay, silica, attapulgite clay, kieselguhr, limestone, calcium carbonate, bentonite, calcium montmorillonite, cottonseed husks, wheat flour, soybean flour, pumice, wood flour, ground walnut shells, lignin and similar substances.
  • a large number of surface-active substances can advantageously be used in both solid and liquid formulations, especially in those formulations which can be diluted with a carrier prior to use.
  • Surfaceactive substances may be anionic, cationic, non-ionic or polymeric and they can be used as emulsifiers, wetting agents or suspending agents or for other purposes.
  • Typical surface-active substances include, for example, salts of alkyl sulfates, such as diethanolammonium lauryl sulfate; salts of alkylarylsulfonates, such as calcium dodecylbenzenesulfonate; alkylphenol/alkylene oxide addition products, such as nonylphenol ethoxylate; alcohol/alkylene oxide addition products, such as tridecylalcohol ethoxylate; soaps, such as sodium stearate; salts of alkylnaphthalenesulfonates, such as sodium dibutylnaphthalenesulfonate; dialkyl esters of sulfosuccinate salts, such as sodium di(2- ethylhexyl)sulfosuccinate; sorbitol esters, such as sorbitol oleate; quaternary amines, such as lauryltrimethylammonium chloride, polyethylene glycol esters of
  • compositions according to the invention can include an additive comprising an oil of vegetable or animal origin, a mineral oil, alkyl esters of such oils or mixtures of such oils and oil derivatives.
  • the amount of oil additive in the composition according to the invention is generally from 0.01 to 10 %, based on the mixture to be applied.
  • the oil additive can be added to a spray tank in the desired concentration after a spray mixture has been prepared.
  • Preferred oil additives comprise mineral oils or an oil of vegetable origin, for example rapeseed oil, olive oil or sunflower oil, emulsified vegetable oil, alkyl esters of oils of vegetable origin, for example the methyl derivatives, or an oil of animal origin, such as fish oil or beef tallow.
  • Preferred oil additives comprise alkyl esters of C8-C22 fatty acids, especially the methyl derivatives of C12-C18 fatty acids, for example the methyl esters of lauric acid, palmitic acid and oleic acid (methyl laurate, methyl palmitate and methyl oleate, respectively).
  • Many oil derivatives are known from the Compendium of Herbicide Adjuvants, 10 th Edition, Southern Illinois University, 2010.
  • inventive compositions generally comprise from 0.1 to 99 % by weight, especially from 0.1 to 95 % by weight, of compounds of the present invention and from 1 to 99.9 % by weight of a formulation adjuvant which preferably includes from 0 to 25 % by weight of a surface-active substance.
  • a formulation adjuvant which preferably includes from 0 to 25 % by weight of a surface-active substance.
  • commercial products may preferably be formulated as concentrates, the end user will normally employ dilute formulations.
  • the rates of application vary within wide limits and depend on the nature of the soil, the method of application, the crop plant, the pest to be controlled, the prevailing climatic conditions, and other factors governed by the method of application, the time of application and the target crop.
  • a general guideline compounds may be applied at a rate of from 1 to 2000 l/ha, especially from 10 to 1000 l/ha.
  • Preferred formulations can have the following compositions (weight %):
  • Emulsifiable concentrates active ingredient: 1 to 95 %, preferably 60 to 90 % surface-active agent: 1 to 30 %, preferably 5 to 20 % liquid carrier: 1 to 80 %, preferably 1 to 35 %
  • Dusts active ingredient: 0.1 to 10 %, preferably 0.1 to 5 % solid carrier: 99.9 to 90 %, preferably 99.9 to 99 %
  • Suspension concentrates active ingredient: 5 to 75 %, preferably 10 to 50 % water: 94 to 24 %, preferably 88 to 30 % surface-active agent: 1 to 40 %, preferably 2 to 30 %
  • Wettable powders active ingredient: 0.5 to 90 %, preferably 1 to 80 % surface-active agent: 0.5 to 20 %, preferably 1 to 15 % solid carrier: 5 to 95 %, preferably 15 to 90 %
  • Granules active ingredient: 0.1 to 30 %, preferably 0.1 to 15 % solid carrier: 99.5 to 70 %, preferably 97 to 85 %
  • the combination is thoroughly mixed with the adjuvants and the mixture is thoroughly ground in a suitable mill, affording wettable powders that can be diluted with water to give suspensions of the desired concentration.
  • the combination is thoroughly mixed with the adjuvants and the mixture is thoroughly ground in a suitable mill, affording powders that can be used directly for seed treatment.
  • Emulsions of any required dilution which can be used in plant protection, can be obtained from this concentrate by dilution with water.
  • Ready-for-use dusts are obtained by mixing the combination with the carrier and grinding the mixture in a suitable mill. Such powders can also be used for dry dressings for seed.
  • the combination is mixed and ground with the adjuvants, and the mixture is moistened with water.
  • the mixture is extruded and then dried in a stream of air.
  • the finely ground combination is uniformly applied, in a mixer, to the kaolin moistened with polyethylene glycol. Non-dusty coated granules are obtained in this manner.
  • the finely ground combination is intimately mixed with the adjuvants, giving a suspension concentrate from which suspensions of any desired dilution can be obtained by dilution with water.
  • a suspension concentrate from which suspensions of any desired dilution can be obtained by dilution with water.
  • living plants as well as plant propagation material can be treated and protected against infestation by microorganisms, by spraying, pouring or immersion.
  • the finely ground combination is intimately mixed with the adjuvants, giving a suspension concentrate from which suspensions of any desired dilution can be obtained by dilution with water.
  • a suspension concentrate from which suspensions of any desired dilution can be obtained by dilution with water.
  • living plants as well as plant propagation material can be treated and protected against infestation by microorganisms, by spraying, pouring or immersion.
  • 28 parts of the combination are mixed with 2 parts of an aromatic solvent and 7 parts of toluene diisocyanate/polymethylene-polyphenylisocyanate-mixture (8:1).
  • This mixture is emulsified in a mixture of 1 .2 parts of polyvinylalcohol, 0.05 parts of a defoamer and 51 .6 parts of water until the desired particle size is achieved.
  • To this emulsion a mixture of 2.8 parts 1 ,6-diaminohexane in 5.3 parts of water is added. The mixture is agitated until the polymerization reaction is completed.
  • the obtained capsule suspension is stabilized by adding 0.25 parts of a thickener and 3 parts of a dispersing agent.
  • the capsule suspension formulation contains 28% of the active ingredients.
  • the medium capsule diameter is 8-15 microns.
  • the resulting formulation is applied to seeds as an aqueous suspension in an apparatus suitable forthat purpose.
  • Formulation types include an emulsion concentrate (EC), a suspension concentrate (SC), a suspo- emulsion (SE), a capsule suspension (CS), a water dispersible granule (WG), an emulsifiable granule (EG), an emulsion, water in oil (EG), an emulsion, oil in water (EW), a micro-emulsion (ME), an oil dispersion (OD), an oil miscible flowable (OF), an oil miscible liquid (OL), a soluble concentrate (SL), an ultra-low volume suspension (SU), an ultra-low volume liquid (UL), a technical concentrate (TK), a dispersible concentrate (DC), a wettable powder (WP), a soluble granule (SG) or any technically feasible formulation in combination with agriculturally acceptable adjuvants.
  • EC emulsion concentrate
  • SC suspension concentrate
  • SE suspo- emulsion
  • CS capsule suspension
  • WG water dispersible granule
  • Mp means melting point in °C. Free radicals represent methyl groups. 1 H NMR measurements were recorded on a Brucker 400MHz spectrometer, chemical shifts are given in ppm relevant to a TMS standard. Spectra measured in deuterated solvents as indicated. Either one of the LCMS methods below was used to characterize the compounds. The characteristic LCMS values obtained for each compound were the retention time (“Rt”, recorded in minutes) and the measured molecular ion (M+H) H or (M-H)-.
  • Spectra were recorded on a Mass Spectrometer from Waters Corporation (SQD, SQDII or QDA Single quadrupole mass spectrometer) equipped with an electrospray source (Polarity: positive and negative ions), Capillary: 0.8-3.00 kV, Cone: 5-30 V, Source Temperature: 120-150°C, Desolvation Temperature: 350-600°C, Cone Gas Flow: 50-150 l/h, Desolvation Gas Flow: 650-1000 l/h, Mass range: 50 to 900 Da and an Acquity UPLC from Waters Corporation: Binary pump, heated column compartment , diode-array detector and ELSD.
  • Spectra were recorded on a Mass Spectrometer from Waters Corporation (SQD, SQDII or QDA Single quadrupole mass spectrometer) equipped with an electrospray source (Polarity: positive and negative ions), Capillary: 0.8-3.00 kV, Cone: 5-30 V, Source Temperature: 120-150°C, Desolvation Temperature: 350-600°C, Cone Gas Flow: 50-150 l/h, Desolvation Gas Flow: 650-1000 l/h, Mass range: 50 to 900 Da and an Acquity UPLC from Waters Corporation: Binary pump, heated column compartment , diode-array detector and ELSD.
  • Step 1 Preparation of 5-bromo-1-(2,2,3,3,3-pentafluoropropyl)pyrazolo[3,4-clpyridine
  • Step 2 Preparation of methyl 1-(2,2,3,3,3-pentafluoropropyl)pyrazolo[3,4-clpyridine-5-carboxylate
  • Step 3 Preparation of 1-(2,2,3,3,3-pentafluoropropyl)pyrazolo[3,4-clpyridine-5-carboxylic acid
  • Methyl 1-(2,2,3,3,3-pentafluoropropyl)pyrazolo[3,4-c]pyridine-5-carboxylate (3.68 g, 11.90 mmol, 1.0 eq.) (synthesis described hereabove) was dissolved in tetrahydrofuran (35.7 mL) and diluted with water (35.7 mL). The mixture was cooled to 0-5°C. Lithium hydroxide monohydrate (0.76 g, 17.90 mmol, 1 .5 eq.) was added. The orange mixture was stirred at 0-5°C. After 1 .5 hours the reaction mixture was carefully poured onto HC1 1 M (50ml). The pH was 1-2.
  • Step 4 Preparation of tert-butyl N-[1-(2, 2,3,3, 3-pentafluoropropyl)pyrazolo[3,4-clpyridin-5- yllcarbamate
  • Step 5 Preparation of 1-(2, 2,3,3, 3-pentafluoropropyl)pyrazolo[3,4-clpyridin-5-amine
  • Step 6 Preparation of (E)-1-[2-nitro-4-(trifluoromethyl)phenyl1-N-[1-(2,2,3,3,3- pentafluoropropyl)pyrazolo[3,4-clpyridin-5-yl1methanimine
  • Step 7 Preparation of 1-(2,2,3,3,3-pentafluoropropyl)-5-[6-(trifluoromethyl)indazol-2-yllpyrazolo[3,4- clpyridine
  • tributylphosphine (1 .60 g, 6.9 mmol, 3.0 eq.) was added and the mixture stirred at reflux for around 2 hours. Heating was stopped and the reaction mixture was cooled to room temperature. Then the mixture was extracted twice between ethyl acetate and brine. The combined organic layers were dried over Na2SO4, filtered and evaporated under vacuo to give 3.05 g crude of a black oil which was purified by chromatography with 0-70% ethyl acetate in cyclohexane using combiflash to get the title compound as a beige solid.
  • Step 8 Preparation of 5-[3-iodo-6-(trifluoromethyl)indazol-2-yl1-1-(2,2,3,3,3- pentafluoropropyl)pyrazolo[3,4-clpyridine
  • Step 9 Preparation of example P1 : 5-[3-ethylsulfanyl-6-(trifluoromethyl)indazol-2-yl1-1-(2,2,3,3,3- pentafluoropropyl)pyrazolo[3,4-clpyridine (compound P1)
  • Step 2 Preparation of 2-[4-(1 ,3-dioxolan-2-yl)-3-nitro-phenyl1-2-methyl-propanenitrile
  • Step 4 Preparation of 2-methyl-2-[3-nitro-4-[(E)-[1-(2,2,3,3,3-pentafluoropropyl)-pyrazolo[3,4-clpyridin- 5-ylliminomethyllphenyllpropanenitrile
  • Step 5 Preparation of 2-methyl-2-[2-[1-(2,2,3,3,3-pentafluoropropyl)pyrazolo[3,4-clpyridin-5-yl1indazol- 6-yllpropanenitrile
  • tributylphosphine (0.89 g, 1.08 mL, 3.72 mmol, 3.00 eq.) was added and the mixture was stirred further at reflux. After 75 minutes the suspension was diluted with ethyl acetate and water and the molecular sieves were filtered off. The mixture was extracted twice with ethyl acetate and brine and the combined organic layers were dried over sodium sulfate, filtered and evaporated to give 0.81 g crude. The solid residue was treated with small amounts of ethyl acetate, methanol and dichloromethane, then filtered and washed with diisopropylether.
  • Step 6 Preparation of 2-[3-iodo-2-[1-(2,2,3,3,3-pentafluoropropyl)pyrazolo[3,4-clpyridin-5-yl1indazol-6- yll-2-methyl-propanenitrile
  • Step 7 Preparation of example P3: 2-[3-ethylsulfanyl-2-[1-(2,2,3,3,3-pentafluoro-propyl)pyrazolo[3,4- clpyridin-5-yl1indazol-6-yl1-2-methyl-propanenitrile
  • the bright yellow solution was degassed with argon and xantphos (0.01 g, 0.02 mmol, 0.05 eq.) and Pd2(dba)3 (0.01 g, 0.01 mmol, 0.04 eq.) were added.
  • the dark reaction mixture was further degassed with argon for another 5 minutes.
  • Ethanethiol (0.02 g, 0.03 mL, 0.36 mmol, 1 .10 eq.) was added and the reaction mixture was heated to 100°C overnight. The heating was then stopped and the reaction mixture was extracted twice between ethyl acetate and brine.
  • Step 8 Preparation of example P4: 2-[3-ethylsulfonyl-2-[1-(2,2,3,3,3-pentafluoro-propyl)pyrazolo[3,4- clpyridin-5-yl1indazol-6-yl1-2-methyl-propanenitrile
  • Example H3 Preparation of 1-[3-ethylsulfonyl-2-[1-(2,2,3,3,3-pentafluoropropyl)-pyrazolo[3,4-clpyridin-
  • Step 1 Preparation of 2-[4-(1 ,3-dioxolan-2-yl)-3-nitro-phenyl1acetonitrile
  • the reaction mixture was stirred and degassed with argon for further 5 minutes.
  • the suspension was stirred and heated to 130°C. After 4.5 hours the mixture was extracted twice with ethyl acetate and brine. The combined organic layers were dried over MgSO4, filtered and evaporated using high vacuum to remove mesitylene to give 3.70 g crude as a black oil which was absorbed on “isolute” and purified by chromatography with 0-100% EtOAc in cyclohexane using combiflash to give the title product as a dark orange oil.
  • Step 2 Preparation of 1-[4-(1 ,3-dioxolan-2-yl)-3-nitro-phenyl1cyclopropanecarbonitrile
  • Step 4 Preparation of 1-[3-nitro-4-[(E)-[1-(2,2,3,3,3-pentafluoropropyl)pyrazolo[3,4-clpyridin-5- ylliminomethyllphenyllcyclopropanecarbonitrile
  • Step 5 Preparation of 1-[2-[1-(2,2,3,3,3-pentafluoropropyl)pyrazolo[3,4-clpyridin-5-yl1indazol-6- yllcyclopropanecarbonitrile
  • tributylphosphine (1 .40 g, 1 .7 mL, 5.70 mmol, 3.00 equiv.) was added and the mixture was stirred further at reflux. After 95 minutes, the heating was stopped and the suspension was stirred at room temperature overnight. The mixture was diluted with ethyl acetate and water. After filtration, the crude solution was extracted twice with ethyl acetate and brine and the combined organic layers were dried over sodium sulfate, filtered and evaporated to give a black oil. This was absorbed on “isolute” and purified by chromatography with 0-70% ethyl acetate in cyclohexane using combiflash to yield the title compound as a yellow powder.
  • Step 6 Preparation of 1-[3-iodo-2-[1-(2,2,3,3,3-pentafluoropropyl)pyrazolo[3,4-clpyridin-5-yl1indazol-6- yllcyclopropanecarbonitrile
  • Step 7 Preparation of example P5: 1-[3-ethylsulfanyl-2-[1-(2,2,3,3,3-pentafluoropropyl)pyrazolo[3,4- clpyridin-5-yl1indazol-6-yl1cyclopropanecarbonitrile
  • the yellow suspension was degassed with argon for 10 minutes and xantphos (0.02 g, 0.03 mmol, 0.05 equiv.) and Pd2(dba)3 (0.02 g, 0.02 mmol, 0.04 equiv.) were added.
  • the reaction mixture was degassed with argon for another 5 minutes.
  • Ethanethiol (0.05 g, 0.05 mL, 0.70 mmol, 1 .30 equiv.) was added and the reaction mixture was heated to 100°C overnight. The heating was stopped and the reaction mixture was extracted twice between ethyl acetate and brine. The combined organic layers were dried over sodium sulfate, filtered and evaporated to give 0.38 g crude.
  • the crude product was absorbed on “isolute” and purified by chromatography with 0-100% EtOAc in cyclohexane using combiflash to yield the title compound as a beige solid.
  • Step 8 Preparation of example P6: 1-[3-ethylsulfonyl-2-[1-(2,2,3,3,3-pentafluoropropyl)pyrazolo[3,4- clpyridin-5-yl1indazol-6-yl1cyclopropanecarbonitrile
  • Step 1 Preparation of 2-(5-bromo-2-nitro-phenyl)-1 ,3-dioxolane
  • 5-bromo-2-nitro-benzaldehyde (2.50 g, 10.70 mmol, 1 .00 equiv.) in toluene (27 mL) and p-toluenesulfonic acid monohydrate (0.06 g, 0.32 mmol, 0.03 equiv.) was added ethylene glycol (3.48 g, 3.13 mL, 53.30 mmol, 5.00 equiv.). The mixture was heated to reflux overnight under a Dean- Stark trap.
  • Step 4 Preparation of 2-methyl-2-[4-nitro-3-[(E)-[1-(2,2,3,3,3-pentafluoropropyl)-pyrazolo[3,4-clpyridin-
  • step 5 To the hot reaction mixture of step 5 was added tributylphosphine (0.54 g, 0.65 mL, 2.30 mmol, 3.00 equiv.) and the mixture stirred further at reflux for 30 minutes and then at room temperature overnight. Some more tributylphosphine (0.18 g, 0.22 mL, 0.75 mmol, 1 .00 equiv.) was added and the suspension was heated again to reflux for 90 minutes. After cooling down, the yellow-beige suspension was diluted with EtOAc and water and the molecular sieves were filtered off. The mixture was extracted 2x with ethyl acetate.
  • Step 6 Preparation of 2-[3-iodo-2-[1-(2,2,3,3,3-pentafluoropropyl)pyrazolo[3,4-clpyridin-5-yl1indazol-5- yll-2-methyl-propanenitrile
  • Step 7 Preparation of example P7: 2-[3-ethylsulfanyl-2-[1-(2,2,3,3,3-pentafluoro-propyl)pyrazolo[3,4- clpyridin-5-yl1indazol-5-yl1-2-methyl-propanenitrile
  • Step 8 Preparation of P8: 2-[3-ethylsulfonyl-2-[1-(2,2,3,3,3-pentafluoropropyl)-pyrazolo[3,4-clpyridin-
  • Step 1 Preparation of 2-[3-(1 ,3-dioxolan-2-yl)-4-nitro-phenyl1acetonitrile
  • the vial was closed and the mixture was heated to 130°C for 2.5 hours. Then the mixture was extracted 2x between ethyl acetate and brine. The combined organic layers were dried over MgSO4, filtered and evaporated to give 30 ml of a dark-green oil. The crude oil was absorbed on “isolute” and purified by chromatography with 0-100% EtOAc in cyclohexane using the rf-machine. The title compound was obtained as a dark-green amorphous substance.
  • Step 2 Preparation of 1-[3-(1 ,3-dioxolan-2-yl)-4-nitro-phenyl1cyclopropanecarbonitrile
  • Step 4 Preparation of 1-[4-nitro-3-[(E)-[1-(2,2,3,3,3-pentafluoropropyl)pyrazolo[3,4-clpyridin-5- ylliminomethyllphenyllcyclopropanecarbonitrile
  • Step 5 Preparation of 1-[2-[1-(2,2,3,3,3-pentafluoropropyl)pyrazolo[3,4-clpyridin-5-yl1indazol-5- yllcyclopropanecarbonitrile
  • step 4 To the refluxing reaction mixture of step 4 was added tributylphosphine (0.45 g, 0.55 mL, 1 .90 mmol, 1 .00 equiv.) and stirring at this temperature was continued for 1 hour, then overnight, at room temperature. More tributylphosphine (0.45 g, 0.55 mL, 1 .90 mmol, 1 .00 equiv.) was added and the mixture was heated again at reflux for 6 hours. After cooling down, the suspension was diluted with EtOAc and water and molecular sieve was filtered off. The phases were separated and the aqueous phase was extracted twice with ethyl acetate.
  • Step 6 Preparation of 1-[3-iodo-2-[1-(2,2,3,3,3-pentafluoropropyl)pyrazolo[3,4-clpyridin-5-yl1indazol-5- yllcyclopropanecarbonitrile
  • Step 7 Preparation of example P9: 1-[3-ethylsulfanyl-2-[1-(2,2,3,3,3-pentafluoro-propyl)pyrazolo[3,4- clpyridin-5-yl1indazol-5-yl1cyclopropanecarbonitrile
  • reaction mixture was cooled down and N,N-diisopropylethylamine (0.17 g, 0.23 mL, 1.30 mmol, 2.60 equiv.), xantphos (0.02 g, 0.03 mmol, 0.05 equiv.), Pd2(dba)3 (0.02 g, 0.02 mmol, 0.04 equiv.) and ethanethiol (0.04 g, 0.05 mL, 0.65 mmol, 1 .30 equiv.) were added and the reaction mixture was heated again to 100°C for another 5 hours. The heating was stopped and the mixture was extracted twice between ethyl acetate and brine.
  • Step 8 Preparation of example P10: 1-[3-ethylsulfonyl-2-[1-(2,2,3,3,3-pentafluoro-propyl)pyrazolo[3,4- clpyridin-5-yl1indazol-5-yl1cyclopropanecarbonitrile
  • Example H6 Preparation of 5-[6-(1 ,1-difluoroethyl)-3-ethylsulfonyl-indazol-2-yl1-1-(2,2,3,3,3-penta- fluoropropyl)pyrazolo[3,4-clpyridine (compound P12)
  • Step 2 Preparation of 2-(4-isopropenyl-2-nitro-phenyD-1 ,3-dioxolane
  • Step 3 Preparation of 1-[4-(1 ,3-dioxolan-2-yl)-3-nitro-phenyl1ethanone
  • Step 4 Preparation of 2-[4-(1 ,1-difluoroethyl)-2-nitro-phenyl1-1 ,3-dioxolane
  • Step 5 Preparation of 4-(1 ,1-difluoroethyl)-2-nitro-benzaldehyde
  • Step 7 Preparation of 5-[6-(1 ,1-difluoroethyr)indazol-2-yl1-1-(2,2,3,3,3-pentafluoropropyDpyrazolo[3,4- clpyridine
  • Step 8 Preparation of S-fG-d .l-difluoroethyD-S-iodo-indazol ⁇ -yll-l- ⁇ .S.S.S-pentafluoropropyD- pyrazolofS ⁇ -clpyridine
  • Step 9 Preparation of example P11 : 5-[6-(1 ,1-difluoroethyl)-3-ethylsulfanyl-indazol-2-yl1-1-(2,2,3,3,3- pentafluoropropyl)pyrazolo[3,4-clpyridine
  • Step 10 Preparation of example P12: 5-[6-(1 ,1-difluoroethyl)-3-ethylsulfonyl-indazol-2-yl1-1-(2,2,3,3,3- pentafluoropropyl)pyrazolo[3,4-clpyridine
  • Step 2 Preparation of (E)-1-(5-cyclopropyl-2-nitro-phenyl)-N-[1-(2,2,3,3,3-pentafluoropropyl)pyra- zolo[3,4-clpyridin-5-yl1methanimine
  • Step 3 Preparation of 5-(5-cyclopropylindazol-2-yl)-1-(2,2,3,3,3-pentafluoropropyl)pyrazolo[3,4- clpyridine
  • Step 5 Preparation of example P13: 5-(5-cyclopropyl-3-ethylsulfanyl-indazol-2-yl)-1-(2,2,3,3,3- pentafluoropropyl)pyrazolo[3,4-clpyridine
  • Step 6 Preparation of example P14: 5-(5-cyclopropyl-3-ethylsulfonyl-indazol-2-yl)-1-(2, 2,3,3, 3-penta- fluoropropyl)pyrazolo[3,4-clpyridine
  • the example P14 5-(5-cyclopropyl-3-ethylsulfonyl-indazol-2-yl)-1 -(2,2,3,3,3-pentafluoropropyl)pyra- zolo[3,4-c]pyridine, was prepared from 5-(5-cyclopropyl-3-ethylsulfanyl-indazol-2-yl)-1-(2,2,3,3,3- pentafluoropropyl)pyrazolo[3,4-c]pyridine (preparation described hereabove) in a similar way as for 2- [3-ethylsulfonyl-2-[1-(2,2,3,3,3-pentafluoro-propyl)pyrazolo[3,4-c]pyridin-5-yl]indazol-6-yl]-2-methyl- propanenitrile (Preparation example H2, step 8).
  • Example H8 Preparation of 1-[3-ethylsulfonyl-2-[1-(3,3,3-trifluoropropyl)pyrazolo[3,4-clpyridin-5-yl1- indazol-6-yllcyclopropanecarbonitrile (compound P16)
  • Step 1 Preparation of 2-(4-bromo-2-nitro-phenyl)-1 ,3-dioxolane
  • Step 2 Preparation of 2-[4-(1 ,3-dioxolan-2-yl)-3-nitro-phenyl1acetonitrile
  • Step 3 Preparation of 1-[4-(1 ,3-dioxolan-2-yl)-3-nitro-phenyl1cyclopropanecarbonitrile
  • Step 5 Preparation of 5-bromo-1-(3,3,3-trifluoropropyl)pyrazolo[3,4-clpyridine
  • a suspension of 5-bromo-1 H-pyrazolo[3,4-c]pyridine (CAS 929617-35-6) (1.50 g, 7.35 mmol, 1.0 equiv.) in acetonitrile (15 mL) was added potassium carbonate (2.63 g, 11.0 mmol, 1.50 equiv.) and the mixture was stirred at room temperature for 30 minutes.
  • Step 6 Preparation of tert-butyl N-[1-(3,3,3-trifluoropropyl)pyrazolo[3,4-clpyridin-5-yl1carbamate
  • Xantphos (0.0487 g, 0.0816 mmol, 0.16 equiv.) and tris(dibenzylideneacetone)dipalladium(0) (0.0385 g, 0.041 mmol, 0.08 equiv.) were added and the mixture was heated at 90°C for 2 hours. After cooling down to room temperature, water was added and the resulting mixture was extracted twice with ethyl acetate. The combined organic layers were washed with sat.aq.
  • Step 7 Preparation of 1-(3,3,3-trifluoropropyl)pyrazolo[3,4-clpyridin-5-amine tert-Butyl N-[1-(3,3,3-trifluoropropyl)pyrazolo[3,4-c]pyridin-5-yl]carbamate (1.06 g, 3.21 mmol, 1.0 equiv.) was suspended in HCI (4M in dioxane, 16mL, 64 mmol, 20.0 equiv.) and the reaction mixture was stirred at room temperature overnight. The suspension was filtered and solid was washed three times with diisopropylether.
  • Step 8 Preparation of 1-[3-nitro-4-[(E)-[1-(3,3,3-trifluoropropyl)pyrazolo[3,4-clpyridin-5-yl1iminomethyl1- phenyllcyclopropanecarbonitrile
  • Step 9 Preparation of 1-[2-[1-(3,3,3-trifluoropropyl)pyrazolo[3,4-clpyridin-5-yl1indazol-6-yl1cyclopro- panecarbonitrile
  • Step 10 Preparation of 1-[3-iodo-2-[1-(3,3,3-trifluoropropyl)pyrazolo[3,4-clpyridin-5-yl1indazol-6-yl1- cyclopropanecarbonitrile
  • Step 11 Preparation of example P15: 1-[3-ethylsulfanyl-2-[1-(3,3,3-trifluoropropyl)pyrazolo[3,4-c1- pyridin-5-yl1indazol-6-yl1cyclopropanecarbonitrile
  • Step 12 Preparation of example P16: 1-[3-ethylsulfonyl-2-[1-(3,3,3-trifluoropropyl)pyrazolo[3,4-c1 pyridin-5-yl1indazol-6-yl1cyclopropanecarbonitrile
  • Step 1 Preparation of 2-(4-fluoro-2-nitro-phenyl)-1 ,3-dioxolane
  • Step 3 Preparation of N-[4-(1 ,3-dioxolan-2-yl)-3-nitro-phenyl1-N-methyl-acetamide
  • Step 4 Preparation of N-(4-formyl-3-nitro-phenyl)-N-methyl-acetamide
  • N-[4-(1 ,3-dioxolan-2-yl)-3-nitro-phenyl]-N-methyl-acetamide (preparation described hereabove) (19.3 g, 72.5 mmol, 1 .0 equiv.) in acetone (123 mL) and water (40.6 mL) was added concentrated aqueous hydrochloric acid (7.12 mL, 72.5 mmol, 1.0 equiv.). The reaction mixture was stirred at 50°C for 4 hours.
  • reaction mixture was then neutralized by addition of sodium hydroxide (2M, 30 mL) followed by addition of sat.aqueous NaHCOs at 0°C.
  • the aqueous layer was extracted three times with ethyl acetate.
  • the combined organic layers were washed with brine, dried over sodium sulfate, filtered, and evaporated to yield the title compound as an orange solid.
  • the crude was used in the next step without further purification.
  • Step 5 Preparation of N-methyl-N-[3-nitro-4-[(E)-[1-(2,2,3,3,3-pentafluoropropyl)pyrazolo[3,4-clpyridin- 5-ylliminomethyllphenyllacetamide
  • Step 6 Preparation of N-methyl-N-[2-[1-(2, 2,3,3, 3-pentafluoropropyl)pyrazolo[3,4-clpyridin-5- yllindazol-6-yllacetamide
  • Step 7 Preparation of N-methyl-2-[1-(2,2,3,3,3-pentafluoropropyl)pyrazolo[3,4-clpyridin-5-yl1indazol-6- amine
  • Step 8 Preparation of 2,2,2-trifluoro-N-methyl-N-[2-[1-(2,2,3,3,3-pentafluoropropyl)pyrazolo[3,4- clpyridin-5-yl1indazol-6-yl1acetamide
  • Step 9 Preparation of 2,2,2-trifluoro-N-[3-iodo-2-[1-(2,2,3,3,3-pentafluoropropyl)pyrazolo[3,4-clpyridin-
  • Step 10 Preparation of example P17: N-[3-ethylsulfanyl-2-[1-(2,2,3,3,3- pentafluoropropyl)pyrazolo[3,4-clpyridin-5-yl1indazol-6-yl1-2,2,2-trifluoro-N-methyl-acetamide
  • Step 1 1 Preparation of example P18: N-[3-ethylsulfonyl-2-[1-(2,2,3,3,3- pentafluoropropyl)pyrazolo[3,4-clpyridin-5-yl1indazol-6-yl1-2,2,2-trifluoro-N-methyl-acetamide
  • Step 12 Preparation of example P19: 3-ethylsulfonyl-N-methyl-2-[1-(2,2,3,3,3-pentafluoropropyl)- pyrazolo[3,4-clpyridin-5-yl1indazol-6-amine
  • Step 13 Preparation of example P20: N-[3-ethylsulfonyl-2-[1-(2,2,3,3,3- pentafluoropropyl)pyrazolo[3,4-clpyridin-5-yl1indazol-6-yl1-N-methyl-acetamide
  • Table P Examples of compounds of formula (I)
  • the activity of the compositions according to the invention can be broadened considerably, and adapted to prevailing circumstances, by adding other insecticidally, acaricidally and/or fungicidally active ingredients.
  • the mixtures of the compounds of formula I with other insecticidally, acaricidally and/or fungicidally active ingredients may also have further surprising advantages which can also be described, in a wider sense, as synergistic activity. For example, better tolerance by plants, reduced phytotoxicity, insects can be controlled in their different development stages or better behaviour during their production, for example during grinding or mixing, during their storage or during their use.
  • Suitable additions to active ingredients here are, for example, representatives of the following classes of active ingredients: organophosphorus compounds, nitrophenol derivatives, thioureas, juvenile hormones, formamidines, benzophenone derivatives, ureas, pyrrole derivatives, carbamates, pyrethroids, chlorinated hydrocarbons, acylureas, pyridylmethyleneamino derivatives, macrolides, neonicotinoids and Bacillus thuringiensis preparations.
  • TX means “one compound selected from the group consisting of the compounds described in Tables A-1 to A-12 and Tables B-1 to B-12 and Table P of the present invention
  • an adjuvant selected from the group of substances consisting of petroleum oils (alternative name) (628) + TX
  • an insect control active substance selected from abamectin + TX, acequinocyl + TX, acetamiprid + TX, acetoprole + TX, acrinathrin + TX, acynonapyr + TX, afidopyropen + TX, afoxolaner + TX, alanycarb + TX, allethrin + TX, alpha-cypermethrin + TX, alphamethrin + TX, amidoflumet + TX, aminocarb + TX, azocyclotin + TX, bensultap + TX
  • TX Neem tree based products + TX, Paecilomyces fumosoroseus + TX, Paecilomyces lilacinus + TX, Pasteuria nishizawae + TX, Pasteuria penetrans + TX, Pasteuria ramosa + TX, Pasteuria thornei + TX, Pasteuria usgae + TX, P- cymene + TX, Plutella xylostella Granulosis virus + TX, Plutella xylostella Nucleopolyhedrovirus + TX, Polyhedrosis virus + TX, pyrethrum + TX, QRD 420 (a terpenoid blend) + TX, QRD 452 (a terpenoid blend) + TX, QRD 460 (a terpenoid blend) + TX, Quillaja saponaria + TX, Rhodoc
  • TX Streptomyces sp. (NRRL Accession No. B- 30145) + TX, Terpenoid blend + TX, and Verticillium spp.; an algicide selected from the group of substances consisting of bethoxazin [CON] + TX, copper dioctanoate (IUPAC name) (170) + TX, copper sulfate (172) + TX, cybutryne [CON] + TX, dichlone (1052) + TX, dichlorophen (232) + TX, endothal (295) + TX, fentin (347) + TX, hydrated lime [CON] + TX, nabam (566) + TX, quinoclamine (714) + TX, quinonamid (1379) + TX, simazine (730) + TX, triphenyltin acetate (IUPAC name) (347) and triphenyltin hydroxide (IUPAC name) (347) +
  • TX Paecilomyces fumosoroseus + TX, Phytoseiulus persimilis + TX, Steinernema bibionis + TX, Steinernema carpocapsae + TX, Steinernema feltiae + TX, Steinernema glaseri + TX, Steinernema riobrave + TX, Steinernema riobravis + TX, Steinernema scapterisci + TX, Steinernema spp. + TX, Trichogramma spp.
  • the compounds in this paragraph may be prepared from the methods described in WO 2017/055473, WO 2017/055469, WO 2017/093348 and WO 2017/118689; 2-[6-(4-chlorophenoxy)-2-(trifluoromethyl)-3- pyridyl]-1-(1 ,2,4-triazol-1-yl)propan-2-ol + TX (this compound may be prepared from the methods described in WO 2017/029179); 2-[6-(4-bromophenoxy)-2-(trifluoromethyl)-3-pyridyl]-1-(1 ,2,4-triazol-1- yl)propan-2-ol + TX (this compound may be prepared from the methods described in WO 2017/029179); 3-[2-(1-chlorocyclopropyl)-3-(2-fluorophenyl)-2-hydroxy-propyl]imidazole-4-carbonitrile + TX (this compound may be prepared from the methods described in
  • Bacillus subtilis strain AQ178 + TX Bacillus subtilis strain QST 713 (CEASE® + TX, Serenade® + TX, Rhapsody®) + TX, Bacillus subtilis strain QST 714 (JAZZ®) + TX, Bacillus subtilis strain AQ153 + TX, Bacillus subtilis strain AQ743 + TX, Bacillus subtilis strain QST3002 + TX, Bacillus subtilis strain QST3004 + TX, Bacillus subtilis var.
  • amyloliquefaciens strain FZB24 (Taegro® + TX, Rhizopro®) + TX, Bacillus thuringiensis Cry 2Ae + TX, Bacillus thuringiensis Cry1 Ab + TX, Bacillus thuringiensis aizawai GC 91 (Agree®) + TX, Bacillus thuringiensis israelensis (BMP123® + TX, Aquabac® + TX, VectoBac®) + TX, Bacillus thuringiensis kurstaki (Javelin® + TX, Deliver® + TX, CryMax® + TX, Bonide® + TX, Scutella WP® + TX, Turilav WP ® + TX, Astuto® + TX, Dipel WP® + TX, Biobit® + TX, Foray®) + TX, Bacillus thuringiensis kurstaki BMP 123 (Baritone
  • aizawai (XenTari® + TX, DiPei®) + TX, bacteria spp. (GROWMEND® + TX, GROWSWEET® + TX, Shootup®) + TX, bacteriophage of Clavipacter michiganensis (AgriPhage®) + TX, Bakflor® + TX, Beauveria bassiana (Beaugenic® + TX, Brocaril WP®) + TX, Beauveria bassiana GHA (Mycotrol ES® + TX, Mycotrol O® + TX, BotaniGuard®) + TX, Beauveria brongniartii (Engerlingspilz® + TX, Schweizer Beauveria® + TX, Melocont®) + TX, Beauveria spp.
  • TX Botrytis cineria + TX, Bradyrhizobium japonicum (TerraMax®) + TX, Brevibacillus brevis + TX, Bacillus thuringiensis tenebrionis (Novodor®) + TX, BtBooster + TX, Burkholderia cepacia (Deny® + TX, Intercept® + TX, Blue Circle®) + TX, Burkholderia gladii + TX, Burkholderia gladioli + TX, Burkholderia spp.
  • TX Canadian thistle fungus (CBH Canadian Bioherbicide®) + TX, Candida butyri + TX, Candida famata + TX, Candida fructus + TX, Candida glabrata + TX, Candida guilliermondii + TX, Candida melibiosica + TX, Candida oleophila strain O + TX, Candida parapsilosis + TX, Candida pelliculosa + TX, Candida pulcherrima + TX, Candida reuêtii + TX, Candida saitoana (Bio-Coat® + TX, Biocure®) + TX, Candida sake + TX, Candida spp.
  • TX Cladosporium tenuissimum + TX, Clonostachys rosea (EndoFine®) + TX, Colletotrichum acutatum + TX, Coniothyrium minitans (Cotans WG®) + TX, Coniothyrium spp.
  • TX Filobasidium floriforme + TX, Fusarium acuminatum + TX, Fusarium chlamydosporum + TX, Fusarium oxysporum (Fusaclean® I Biofox C®) + TX, Fusarium proliferatum + TX, Fusarium spp. + TX, Galactomyces geotrichum + TX, Gliocladium catenulatum (Primastop® + TX, Prestop®) + TX, Gliocladium roseum + TX, Gliocladium spp.
  • Pasteuria spp. Econem® + TX, Pasteuria nishizawae + TX, Penicillium aurantiogriseum + TX, Penicillium billai (Jumpstart® + TX, TagTeam®) + TX, Penicillium brevicompactum + TX, Penicillium frequentans + TX, Penicillium griseofulvum + TX, Penicillium purpurogenum + TX, Penicillium spp.
  • TX Penicillium viridicatum + TX, Phlebiopsis gigantean (Rotstop®) + TX, phosphate solubilizing bacteria (Phosphomeal®) + TX, Phytophthora cryptogea + TX, Phytophthora palmivora (Devine®) + TX, Pichia anomala + TX, Pichia guilermondii + TX, Pichia membranaefaciens + TX, Pichia onychis + TX, Pichia stipites + TX, Pseudomonas aeruginosa + TX, Pseudomonas aureofasciens (Spot-Less Biofungicide®) + TX, Pseudomonas cepacia + TX, Pseudomonas chlororaphis (AtEze®) + TX, Pseudomonas corrugate + TX, Ps
  • Rhodosporidium diobovatum + TX Rhodosporidium toruloides + TX, Rhodotorula spp.
  • Trichoderma asperellum T34 Biocontrol®
  • Trichoderma gamsii TX
  • Trichoderma atroviride Plant®
  • Trichoderma harzianum rifai Mycostar®
  • Trichoderma harzianum T-22 Trianum-P® + TX, Plantshield HC® + TX, Rootshield® + TX, Trianum-G®) + TX, Trichoderma harzianum T-39 (Trichodex®) + TX, Trichoderma inhamatum + TX, Trichoderma koningii + TX, Trichoderma spp.
  • LC 52 (Sentinel®) + TX, Trichoderma lignorum + TX, Trichoderma longibrachiatum + TX, Trichoderma polysporum (Binab T®) + TX, Trichoderma taxi + TX, Trichoderma virens + TX, Trichoderma virens (formerly Gliocladium virens GL-21) (SoilGuard®) + TX, Trichoderma viride + TX, Trichoderma viride strain ICC 080 (Remedier®) + TX, Trichosporon pullulans + TX, Trichosporon spp. + TX, Trichothecium spp.
  • TX Trichothecium roseum + TX, Typhula phacorrhiza strain 94670 + TX, Typhula phacorrhiza strain 94671 + TX, Ulocladium atrum + TX, Ulocladium oudemansii (Botry-Zen®) + TX, Ustilago maydis + TX, various bacteria and supplementary micronutrients (Natural II®) + TX, various fungi (Millennium Microbes®) + TX, Verticillium chlamydosporium + TX, Verticillium lecanii (Mycotal® + TX, Vertalec®) + TX, Vip3Aa20 (VIPtera®) + TX, Virgibaclillus marismortui + TX, Xanthomonas campestris pv. Poae (Camperico®) + TX, Xenorhabdus bovienii + TX, Xenorhab
  • Plant extracts including: pine oil (Retenol®) + TX, azadirachtin (Plasma Neem Oil® + TX, AzaGuard® + TX, MeemAzal® + TX, Molt-X® + TX, Botanical IGR (Neemazad® + TX, Neemix®) + TX, canola oil (Lilly Miller Vegol®) + TX, Chenopodium ambrosioides near ambrosioides (Requiem®) + TX, Chrysanthemum extract (Crisant®) + TX, extract of neem oil (Trilogy®) + TX, essentials oils of Labiatae (Botania®) + TX, extracts of clove rosemary peppermint and thyme oil (Garden insect killer®) + TX, Glycinebetaine (Greenstim®) + TX, garlic + TX, lemongrass oil (GreenMatch®) + TX, neem oil +
  • TX Coccidoxenoides perminutus (Pianopar®) + TX, Coccophagus cowperi + TX, Coccophagus lycimnia + TX, Cotesia flavipes + TX, Cotesia plutellae + TX, Cryptolaemus montrouzieri (Cryptobug® + TX, Cryptoline®) + TX, Cybocephalus nipponicus + TX, Dacnusa sibirica + TX, Dacnusa sibirica (Minusa®) + TX, Diglyphus isaea (Diminex®) + TX, Delphastus catalinae (Delphastus®) + TX, Delphastus pusillus + TX, Diachasmimorpha krausii + TX, Diachasmimorpha longicaudata + TX, Diaparsis jucunda + TX, Diaphorencyrtus aligarhensis
  • TX Steinemematid spp. (Guardian Nematodes®) + TX, Stethorus punctillum (Stethorus®) + TX, Tamarixia radiate + TX, Tetrastichus setifer + TX, Thripobius semiluteus + TX, Torymus sinensis + TX, Trichogramma brassicae (Tricholine b®) + TX, Trichogramma brassicae (Tricho-Strip®) + TX, Trichogramma evanescens + TX, Trichogramma minutum + TX, Trichogramma ostriniae + TX, Trichogramma platneri + TX, Trichogramma pretiosum + TX, Xanthopimpla stemmator, other biologicals including: abscisic acid + TX, bioSea® + TX, Chondrostereum purpureum (Chontrol Paste®) + TX, Colletotrichum gloeosporio
  • the active ingredient mixture of the compounds of formula I selected from Tables A-1 to A-12 and Tables B-1 to B-12 and Table P with active ingredients described above comprises a compound selected from Tables A-1 to A-12 and Tables B-1 to B-12 and Table P and an active ingredient as described above preferably in a mixing ratio of from 100:1 to 1 :6000, especially from 50:1 to 1 :50, more especially in a ratio of from 20:1 to 1 :20, even more especially from 10:1 to 1 :10, very especially from 5:1 and 1 :5, special preference being given to a ratio of from 2:1 to 1 :2, and a ratio of from 4:1 to 2:1 being likewise preferred, above all in a ratio of 1 :1 , or 5:1 , or 5:2, or 5:3, or 5:4, or 4:1 , or 4:2, or 4:3, or 3:1 , or 3:2, or 2:1 , or 1 :5, or 2:5, or 3:5, or 4:5, or 1 :4, or 2:4, or 3:4, or 1
  • the mixtures as described above can be used in a method for controlling pests, which comprises applying a composition comprising a mixture as described above to the pests or their environment, with the exception of a method for treatment of the human or animal body by surgery or therapy and diagnostic methods practised on the human or animal body.
  • the mixtures comprising a compound of formula I selected from Tables A-1 to A-12 and Tables B-1 to B-12 and Table P and one or more active ingredients as described above can be applied, for example, in a single “ready-mix” form, in a combined spray mixture composed from separate formulations of the single active ingredient components, such as a “tank-mix”, and in a combined use of the single active ingredients when applied in a sequential manner, i.e. one after the other with a reasonably short period, such as a few hours or days.
  • the order of applying the compounds of formula I selected from Tables A-1 to A-12 and Tables B-1 to B-12 and Table P and the active ingredients as described above is not essential for working the present invention.
  • compositions according to the invention can also comprise further solid or liquid auxiliaries, such as stabilizers, for example unepoxidized or epoxidized vegetable oils (for example epoxidized coconut oil, rapeseed oil or soya oil), antifoams, for example silicone oil, preservatives, viscosity regulators, binders and/or tackifiers, fertilizers or other active ingredients for achieving specific effects, for example bactericides, fungicides, nematocides, plant activators, molluscicides or herbicides.
  • auxiliaries such as stabilizers, for example unepoxidized or epoxidized vegetable oils (for example epoxidized coconut oil, rapeseed oil or soya oil), antifoams, for example silicone oil, preservatives, viscosity regulators, binders and/or tackifiers, fertilizers or other active ingredients for achieving specific effects, for example bactericides, fungicides, nematocides
  • compositions according to the invention are prepared in a manner known per se, in the absence of auxiliaries for example by grinding, screening and/or compressing a solid active ingredient and in the presence of at least one auxiliary for example by intimately mixing and/or grinding the active ingredient with the auxiliary (auxiliaries).
  • auxiliaries for example by grinding, screening and/or compressing a solid active ingredient and in the presence of at least one auxiliary for example by intimately mixing and/or grinding the active ingredient with the auxiliary (auxiliaries).
  • compositions that is the methods of controlling pests of the abovementioned type, such as spraying, atomizing, dusting, brushing on, dressing, scattering or pouring - which are to be selected to suit the intended aims of the prevailing circumstances - and the use of the compositions for controlling pests of the abovementioned type are other subjects of the invention.
  • Typical rates of concentration are between 0.1 and 1000 ppm, preferably between 0.1 and 500 ppm, of active ingredient.
  • the rate of application per hectare is generally 1 to 2000 g of active ingredient per hectare, in particular 10 to 1000 g/ha, preferably 10 to 600 g/ha.
  • a preferred method of application in the field of crop protection is application to the foliage of the plants (foliar application), it being possible to select frequency and rate of application to match the danger of infestation with the pest in question.
  • the active ingredient can reach the plants via the root system (systemic action), by drenching the locus of the plants with a liquid composition or by incorporating the active ingredient in solid form into the locus of the plants, for example into the soil, for example in the form of granules (soil application). In the case of paddy rice crops, such granules can be metered into the flooded paddy-field.
  • the compounds of the invention and compositions thereof are also be suitable for the protection of plant propagation material, for example seeds, such as fruit, tubers or kernels, or nursery plants, against pests of the abovementioned type.
  • the propagation material can be treated with the compound prior to planting, for example seed can be treated prior to sowing.
  • the compound can be applied to seed kernels (coating), either by soaking the kernels in a liquid composition or by applying a layer of a solid composition. It is also possible to apply the compositions when the propagation material is planted to the site of application, for example into the seed furrow during drilling.
  • These treatment methods for plant propagation material and the plant propagation material thus treated are further subjects of the invention.
  • Typical treatment rates would depend on the plant and pest/fungi to be controlled and are generally between 1 to 200 grams per 100 kg of seeds, preferably between 5 to 150 grams per 100 kg of seeds, such as between 10 to 100 grams per 100 kg of seeds.
  • seed embraces seeds and plant propagules of all kinds including but not limited to true seeds, seed pieces, suckers, corns, bulbs, fruit, tubers, grains, rhizomes, cuttings, cut shoots and the like and means in a preferred embodiment true seeds.
  • the present invention also comprises seeds coated or treated with or containing a compound of formula I.
  • coated or treated with and/or containing generally signifies that the active ingredient is for the most part on the surface of the seed at the time of application, although a greater or lesser part of the ingredient may penetrate into the seed material, depending on the method of application.
  • the seed product When the said seed product is (re)planted, it may absorb the active ingredient.
  • the present invention makes available a plant propagation material adhered thereto with a compound of formula (I). Further, it is hereby made available, a composition comprising a plant propagation material treated with a compound of formula (I).
  • Seed treatment comprises all suitable seed treatment techniques known in the art, such as seed dressing, seed coating, seed dusting, seed soaking and seed pelleting.
  • the seed treatment application of the compound formula (I) can be carried out by any known methods, such as spraying or by dusting the seeds before sowing or during the sowing/planting of the seeds.
  • Example B1 Activity against Bemisia tabaci (Cotton white fly): Feedinq/contact activity
  • Cotton leaf discs were placed on agar in 24-well microtiter plates and sprayed with aqueous test solutions prepared from 10'000 ppm DMSO stock solutions. After drying the leaf discs were infested with adult white flies. The samples were checked for mortality 6 days after incubation.
  • Example B2 Activity against Diabrotica balteata (Corn root worm)
  • Maize sprouts placed onto an agar layer in 24-well microtiter plates were treated with aqueous test solutions prepared from 10'000 ppm DMSO stock solutions by spraying. After drying, the plates were infested with L2 larvae (6 to 10 per well). The samples were assessed for mortality and growth inhibition in comparison to untreated samples 4 days after infestation.
  • the following compounds gave an effect of at least 80% in at least one of the two categories (mortality or growth inhibition) at an application rate of 200 ppm: P2, P3, P4, P5, P6, P7, P8, P9, P10, P12, P14, P16, P18, P20.
  • Example B3 Activity against Euschistus heros (Neotropical Brown Stink Bug)
  • Soybean leaves on agar in 24-well microtiter plates were sprayed with aqueous test solutions prepared from 10'000 ppm DMSO stock solutions. After drying the leaves were infested with N2 nymphs. The samples were assessed for mortality and growth inhibition in comparison to untreated samples 5 days after infestation. The following compounds gave an effect of at least 80% in at least one of the two categories (mortality or growth inhibition) at an application rate of 200 ppm: P2, P5, P6, P9, P10, P12, P16, P17, P18, P20.
  • Example B4 Activity against Myzus persicae (Green peach aphid) Feedinq/Contact activity Sunflower leaf discs were placed onto agar in a 24-well microtiter plate and sprayed with aqueous test solutions prepared from 10'000 ppm DMSO stock solutions. After drying, the leaf discs were infested with an aphid population of mixed ages. The samples were assessed for mortality 6 days after infestation.
  • the following compounds resulted in at least 80% mortality at an application rate of 200 ppm: P3, P5, P9, P10, P16, P18, P20.
  • Example B5 Activity against Plutella xylostella (Diamond back moth) 24-well microtiter plates with artificial diet were treated with aqueous test solutions prepared from 10'000 ppm DMSO stock solutions by pipetting. After drying, Plutella eggs were pipetted through a plastic stencil onto a gel blotting paper and the plate was closed with it. The samples were assessed for mortality and growth inhibition in comparison to untreated samples 8 days after infestation.
  • the following compounds gave an effect of at least 80% in at least one of the two categories (mortality or growth inhibition) at an application rate of 200 ppm: P2, P3, P4, P5, P6, P7, P8, P9, P10, P12, P14, P16, P17, P18, P19, P20.
  • Example B6 Activity against Spodoptera litoralis (Egyptian cotton leaf worm)
  • Cotton leaf discs were placed onto agar in 24-well microtiter plates and sprayed with aqueous test solutions prepared from 10'000 ppm DMSO stock solutions. After drying the leaf discs were infested with five L1 larvae. The samples were assessed for mortality, anti-feeding effect, and growth inhibition in comparison to untreated samples 3 days after infestation. Control of Spodoptera littoralis by a test sample is given when at least one of the categories mortality, anti-feedant effect, and growth inhibition is higher than the untreated sample.
  • Example B7 Activity against Chilo suppressalis (Striped rice stemborer)
  • 24-well microtiter plates with artificial diet were treated with aqueous test solutions prepared from 10'000 ppm DMSO stock solutions by pipetting. After drying, the plates were infested with L2 larvae (6-8 per well). The samples were assessed for mortality, anti-feeding effect, and growth inhibition in comparison to untreated samples 6 days after infestation. Control of Chilo suppressalis by a test sample is given when at least one of the categories mortality, anti-feedant effect, and growth inhibition is higher than the untreated sample.
  • Example B8 Activity against Myzus persicae (Green peach aphid) Systemic activity
  • Roots of pea seedlings infested with an aphid population of mixed ages were placed directly into aqueous test solutions prepared from 10'000 DMSO stock solutions. The samples were assessed for mortality 6 days after placing seedlings into test solutions.
  • Example B9 Activity against Carpocapsa (Cydia) pomonella (Codling moth)

Abstract

Compounds of the formula (I) (I), wherein the substituents are as defined in claim 1. Furthermore, the present invention relates to agrochemical compositions which comprise compounds of formula (I), to preparation of these compositions, and to the use of the compounds or compositions in agriculture or horticulture for combating, preventing or controlling animal pests, including arthropods and in particular insects, nematodes, molluscs or representatives of the order Acarina.

Description

Pesticidally active heterocyclic derivatives with sulfur containing substituents
The present invention relates to pesticidally active, in particular insecticidally active 2-heteroaryl- indazoles with sulfur substituents, to processes for their preparation, to compositions comprising those compounds, and to their use for controlling animal pests, including arthropods and in particular insects or representatives of the order Acarina.
Heterocyclic compounds with pesticidal action are known and described, for example, in WO2013191112 and W02020182577.
It has now surprisingly been found that certain novel pesticidally active 2-heteroaryl-indazoles with sulfur substituents have favourable properties as pesticides.
The present invention therefore provides compounds of formula I,
Figure imgf000002_0001
wherein
Gi and G2 are, independently from each other, CH or N;
R2 is Ci-Cehaloalkyl;
X is S, SO, or SO2 and
R1 is Ci-C4alkyl or C3-C6cycloalkyl-Ci-C4alkyl;
Y1 and Y2 are, independently from each other, hydrogen, halogen, Ci-C4alkyl, Ci-Cehaloalkyl, C3- Cecycloalkyl, Cs-Cecycloalkyl monosubstituted by cyano, Ci-Cecyanoalkyl, Ci-Cecyanoalkoxy, cyano, Ci-C4alkoxy, Ci-Cehaloalkoxy, -N(R3)2, -N(R3)COR4; and each R3 and R4 are independently from each other, hydrogen, Ci-C4alkyl, Ci-Cehaloalkyl or C3- Cecycloalkyl.
The present invention also provides agrochemically acceptable salts, stereoisomers, enantiomers, tautomers and N-oxides of the compounds of formula I.
Compounds of formula I which have at least one basic centre can form, for example, acid addition salts, for example with strong inorganic acids such as mineral acids, for example perchloric acid, sulfuric acid, nitric acid, nitrous acid, a phosphorus acid or a hydrohalic acid, with strong organic carboxylic acids, such as Ci-C4alkanecarboxylic acids which are unsubstituted or substituted, for example by halogen, for example acetic acid, such as saturated or unsaturated dicarboxylic acids, for example oxalic acid, malonic acid, succinic acid, maleic acid, fumaric acid or phthalic acid, such as hydroxycarboxylic acids, for example ascorbic acid, lactic acid, malic acid, tartaric acid or citric acid, or such as benzoic acid, or with organic sulfonic acids, such as Ci-C4alkane- or arylsulfonic acids which are unsubstituted or substituted, for example by halogen, for example methane- or p-toluenesulfonic acid. Compounds of formula I which have at least one acidic group can form, for example, salts with bases, for example mineral salts such as alkali metal or alkaline earth metal salts, for example sodium, potassium or magnesium salts, or salts with ammonia or an organic amine, such as morpholine, piperidine, pyrrolidine, a mono-, di- or tri-lower-alkylamine, for example ethyl-, diethyl-, triethyl- or dimethylpropylamine, or a mono-, di- or trihydroxy-lower-alkylamine, for example mono-, di- or triethanolamine.
In each case, the compounds of formula (I) according to the invention are in free form, in oxidized form as a N-oxide or in salt form, e.g. an agronomically usable salt form.
N-oxides are oxidized forms of tertiary amines or oxidized forms of nitrogen containing heteroaromatic compounds. They are described for instance in the book “Heterocyclic N-oxides” by A. Albini and S. Pietra, CRC Press, Boca Raton 1991.
The compounds of formula (I) according to the invention also include hydrates or solvates which may be formed during the salt formation.
Where substituents are indicated as being themselves further substituted, this means that they carry one or more identical or different substituents, e.g. one to four substituents. Normally not more than three such optional substituents are present at the same time. Preferably not more than two such substituents are present at the same time (i.e. the group is substituted by one or two of the substituents indicated). Where the additional substituent group is a larger group, such as cycloalkyl or phenyl, it is most preferred that only one such optional substituent is present. Where a group is indicated as being substituted, e.g. alkyl, this includes those groups that are part of other groups, e.g. the alkyl in alkylthio.
The term "Ci-Cnalkyl" as used herein refers to a saturated straight-chain or branched hydrocarbon radical attached via any of the carbon atoms having 1 to n carbon atoms, for example, any one of the radicals methyl, ethyl, n-propyl, 1 -methylbutyl, 2-methylbutyl, 3-methylbutyl, 2, 2-dimethylpropyl, 1 -ethylpropyl, n-hexyl, n-pentyl, 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, or 1-ethyl-2-methylpropyl. The term "Ci-Cnhaloalkyl" as used herein refers to a straight-chain or branched saturated alkyl radical attached via any of the carbon atoms having 1 to n carbon atoms (as mentioned above), where some or all of the hydrogen atoms in these radicals may be replaced by fluorine, chlorine, bromine and/or iodine, i.e., for example, any one of chloromethyl, dichloromethyl, trichloro methyl, fluoromethyl, difluoromethyl, trifluoromethyl, chlorofluoromethyl, dichlorofluoromethyl, chlorodifluoromethyl, 2- fluoroethyl, 2-chloroethyl, 2-bromoethyl, 2-iodoethyl, 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, 2-fluoropropyl, 3-fluoropropyl, 2,2- difluoropropyl, 2, 3-difluoropropyl, 2-chloropropyl, 3-chloropropyl, 2, 3-dichloropropyl, 2- bromopropyl, 3-bromopropyl, 3,3, 3-trifluoropropyl, 3,3, 3- trichloropropyl, 2,2, 3,3, 3- pentafluoropropyl, heptafluoropropyl, 1-(fluoromethyl)-2-fluoroethyl, 1- (chloromethyl)-2-chloroethyl, 1-(bromomethyl)-2-bromoethyl, 4-fluorobutyl, 4-ch loro butyl, 4-bromobutyl or nonafluorobutyl. According a term "Ci-C2-fluoroalkyl" would refer to a Ci-C2-alkyl radical which carries 1 ,2, 3,4, or 5 fluorine atoms, for example, any one of difluoromethyl, trifluoromethyl, 1- fluoroethyl, 2-fluoroethyl, 2, 2-difluoroethyl, 2,2, 2-trifluoroethyl, 1 ,1 , 2, 2-tetrafluoroethyl or pentafluoroethyl.
The term "Ci-Cnalkoxy" as used herein refers to a straight-chain or branched saturated alkyl radical having 1 to n carbon atoms (as mentioned above) which is attached via an oxygen atom, i.e., for example, any one of methoxy, ethoxy, n-propoxy, 1 -methylethoxy, n-butoxy, 1 -methylpropoxy, 2- methylpropoxy or 1 , 1 -dimethylethoxy.
The term "Ci-Cnhaloalkoxy" as used herein refers to a Ci-Cnalkoxy radical as mentioned above which is partially or fully substituted by fluorine, chlorine, bromine and/or iodine, i.e., for example, any one of chloromethoxy, dichloromethoxy, trichloromethoxy, fluoromethoxy, difluoromethoxy, trifluoromethoxy, chlorofluoromethoxy, dichlorofluoromethoxy, chlorodifluoromethoxy, 2- fluoroethoxy, 2-chloroethoxy, 2-bromoethoxy, 2-iodoethoxy, 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, pentafluoroeth- oxy, 2-fluoropropoxy, 3-fluoropropoxy, 2, 2-difluoropropoxy, 2, 3-difluoropropoxy, 2- chloropropoxy, 3-chloropropoxy, 2, 3-dichloropropoxy, 2-bromopropoxy, 3- bromopropoxy, 3,3, 3-trifluoropropoxy, 3,3, 3-trichloropropoxy, 2,2, 3,3, 3- pentafluoropropoxy, heptafluoropropoxy, 1- (fluoromethyl)-2-fluoroethoxy, 1- (chloromethyl)-2-chloroethoxy, 1- (bromomethyl)-2-bromoethoxy, 4-fluorobutoxy, 4- chlorobutoxy, or 4-bromobutoxy.
The term “Ci-Cncyanoalkyl” as used herein refers to a straight chain or branched saturated alkyl radicals having 1 to n carbon atoms (as mentioned above) which is substituted by a cyano group, for example cyanomethyl, cyanoethyl, and 1 ,1 -dimethylcyanomethyl. The term "Ci-Cncyanoalkoxy” as used herein refers to a straight-chain or branched saturated alkyl radical having 1 to n carbon atoms which is substituted by a cyano group (as mentioned above) but which is attached via an oxygen atom.
The suffix “-Ci-Cnalkyl” after terms such as “Cs-Cncycloalkyl”, wherein n is an integer from 1-6, as used herein refers to a straight chain or branched saturated alkyl radicals which is substituted by Cs-Cncycloalkyl. An example of C3-Cncycloalkyl-Ci-Cnalkyl is for example, cyclopropylmethyl.
The term “Cs-Cncycloalkyl” as used herein refers to 3-6 membered cycloylkyl groups such as cyclopropyl, cyclobutyl, cyclopentyl and cyclohexyl.
Halogen is generally fluorine, chlorine, bromine or iodine. This also applies, correspondingly, to halogen in combination with other meanings, such as haloalkyl.
Certain embodiments according to the invention are provided as set out below.
Embodiment 1 provides compounds of formula (I), or an agrochemically acceptable salt, stereoisomer, enantiomer, tautomer or N-oxide thereof, as defined above.
Embodiment 2 provides compounds, or an agrochemically acceptable salt, stereoisomer, enantiomer, tautomer or N-oxide thereof, according to embodiment 1 having preferred values of Ri, R2, X, R3, R4, G1, G2, Y1 and Y2 as set out below.
With respect to embodiments 1 - 2, preferred values of R1, R2, X, R3, R4, G1, G2, Y1 and Y2 are, in any combination thereof, as set out below:
Preferably R2 is Ci-Cehaloalkyl.
More preferably R2 is Ci-Cefluoroalkyl.
Most preferably R2 is -CH2CH2CF3, -CH2CF2CHF2 or -CH2CF2CF3.
Preferably X is S or SO2
Most preferably X is SO2.
Preferably R1 is Ci-C4alkyl or cyclopropyl-Ci-C4alkyl.
More preferably R1 is ethyl or cyclopropylmethyl.
Most preferably R1 is ethyl.
Preferably Y1 is hydrogen, halogen, Ci-C4alkyl, Ci-Cehaloalkyl, Cs-Cecycloalkyl, Cs-Cecycloalkyl monosubstituted by cyano, Ci-Cecyanoalkyl, Ci-Cecyanoalkoxy, cyano, Ci-C4alkoxy, Ci-Cehaloalkoxy, -N(R3)2, -N(R3)COR4.
More preferably Y1 is hydrogen, halogen, trifluoromethyl, difluoroethyl, cyclopropyl, cyanocyclopropyl, cyanoisopropyl, 2,2,2-trifluoroethoxy, -N(R3)2, -N(R3)COR4, in each of which R3 is independently either hydrogen or methyl and R4 is either methyl, trifluoromethyl or cyclopropyl. Even more preferably Yi is hydrogen, chlorine, bromine, trifluoromethyl, -CF2CH3, cyclopropyl, 1- cyanocyclopropyl, 1-cyano-1-methyl-ethyl, 2,2,2-trifluoroethoxy, -NH(CH3), -N(CH3)COCH3 or - N(CH3)COCF3.
Most preferably Y1 is hydrogen, trifluoromethyl, -CF2CH3, cyclopropyl, 1 -cyanocyclopropyl, 1-cyano-1- methyl-ethyl, -NH(CH3), -N(CH3)COCH3 or -N(CH3)COCF3.
Preferably Y2 is hydrogen, halogen, Ci-C4alkyl, Ci-Cehaloalkyl, Cs-Cecycloalkyl, Cs-Cecycloalkyl monosubstituted by cyano, Ci-Cecyanoalkyl, Ci-Cecyanoalkoxy, cyano, Ci-C4alkoxy, Ci-Cehaloalkoxy, -N(R3)2, -N(R3)COR4.
More preferably Y2 is hydrogen, halogen, trifluoromethyl, difluoroethyl, cyclopropyl, cyanocyclopropyl, cyanoisopropyl, 2,2,2-trifluoroethoxy, -N(R3)2, -N(R3)COR4, in which R3 is independently either hydrogen or methyl and R4 is either methyl, trifluoromethyl or cyclopropyl.
Even more preferably Y2 is hydrogen, chlorine, bromine, trifluoromethyl, -CF2CH3, cyclopropyl, 1- cyanocyclopropyl, 1-cyano-1-methyl-ethyl, 2,2,2-trifluoroethoxy, -NH(CH3), -N(CH3)COCH3 or - N(CH3)COCF3.
Most preferably Y2 is hydrogen, trifluoromethyl, -CF2CH3, cyclopropyl, 1 -cyanocyclopropyl, 1-cyano-1- methyl-ethyl, -NH(CH3), -N(CH3)COCH3 or -N(CH3)COCF3.
Also preferred is when Y1 is H and Y2 is H, -Me, -OCH2CHF2, Br, -CF2CH3, CF3, -OCF3, -O-/-Pr, - OCH3.-OCHF2, -NH(CH3), -N(CH3)COCH3, -N(CH3)COCF3, cyclopropyl, 1 -cyanocyclopropyl, 1-cyano- 1-methyl-ethyl, -OCH2CF3 or -OC(CH3)2CN; or
Y2 is H and Y1 is H, -Me, -OCH2CHF2, Br, -CF2CH3, CF3, -OCF3, -O-/-Pr, -OCH3,-OCHF2, -NH(CH3), - N(CH3)COCH3, -N(CH3)COCF3, cyclopropyl, 1 -cyanocyclopropyl, 1-cyano-1-methyl-ethyl, -OCH2CF3 or -OC(CH3)2CN.
Also prefered is when Y2 is H and Y1 is halogen, trifluoromethyl, 1 ,1 -difluoroethyl, cyclopropyl, cyanocyclopropyl, cyanoisopropyl or trifluoroethoxy; preferably Y2 is H and Y1 is -Br, -CF2CH3, -CF3, cyclopropyl, 1 -cyanocyclopropyl, 1-cyano-1-methyl-ethyl or -OCH2CF3; more preferably Y2 is H and Y1 is -CF3, 1 -cyanocyclopropyl or 1-cyano-1-methyl-ethyl; or
Y1 is H and Y2 is halogen, trifluoromethyl, 1 ,1-difluoroethyl, cyclopropyl, cyanocyclopropyl, cyanoisopropyl or trifluoroethoxy; preferably Y1 is H and Y2 is -Br, -CF2CH3, -CF3, cyclopropyl, 1- cyanocyclopropyl, 1-cyano-1-methyl-ethyl or -OCFhCFs; more preferably Y1 is H and Y2 is -CF3, 1- cyanocyclopropyl or 1-cyano-1-methyl-ethyl.
Also prefered is when Y2 is H and Y1 is trifluoromethyl, difluoroethyl, cyclopropyl, cyanocyclopropyl, cyanoisopropyl, -NH(CH3), -N(CH3)COCH3 or -N(CH3)COCF3; preferably Y2 is H and Y1 is -CF3, - CF2CH3, cyclopropyl, 1 -cyanocyclopropyl, 1-cyano-1-methyl-ethyl, -NH(CH3), -N(CH3)COCH3 or - N(CH3)COCF3; more preferably Y2 is H and Y1 is cyclopropyl, 1 -cyanocyclopropyl or 1-cyano-1- methyl-ethyl; or
Y1 is H and Y2 is trifluoromethyl, difluoroethyl, cyclopropyl, cyanocyclopropyl, cyanoisopropyl, - NH(CH3), -N(CH3)COCH3 or -N(CH3)COCF3; preferably Y1 is H and Y2 is -CF3, -CF2CH3, cyclopropyl, 1 -cyanocyclopropyl, 1-cyano-1-methyl-ethyl, -NH(CH3), -N(CH3)COCH3 or -N(CH3)COCF3; more preferably Yi is H and Y2 is -CF3, -CF2CH3, 1 -cyanocyclopropyl, 1-cyano-1-methyl-ethyl, -NH(CH3), - N(CH3)COCH3 or -N(CH3)COCF3.
Preferably each R3 is independently hydrogen or Ci-C4alkyl.
Most preferably each R3 is independently hydrogen or methyl.
Preferably R4 is Ci-Cealkyl, Ci-Cehaloalkyl or Cs-Cecycloalkyl.
More preferably R4 is methyl, trifluoromethyl or cyclopropyl.
Even more preferably R4 is methyl or trifluoromethyl.
Most preferably R4 is methyl.
Preferably G1 and G2 are, independently from each other, CH or N.
Also prefered is when G2 is N and G1 is CH.
Also prefered is when G2 and G1 are both CH.
Also preferred is when G2 is CH and G1 is N.
Preferably either one of G1 and G2 is N.
Preferably G1 is CH or N.
More preferably G1 is CH.
Preferably G2 is CH or N.
More preferably G2 is N.
Most preferably G1 is CH and G2 is N.
One group of compounds according to the invention are those of formula 1-1
Figure imgf000007_0001
wherein R1, R2, X, R3, R4, G1, G2 and Y1 are as defined for compounds of formula I (above), or an agrochemically acceptable salt, stereoisomer, enantiomer, tautomer or N-oxide thereof, and wherein Y1 is preferably hydrogen, halogen, Ci-C4alkyl, Ci-Cehaloalkyl, Cs-Cecycloalkyl, Cs-Cecycloalkyl monosubstituted by cyano, Ci-Cecyanoalkyl, Ci-Cecyanoalkoxy, cyano, Ci-C4alkoxy, Ci-Cehaloalkoxy, -N(R3)2, -N(R3)COR4; and each R3 and R4 are independently from each other, hydrogen, Ci-C4alkyl, Ci-Cehaloalkyl or C3- Cecycloalkyl.
Preferably each R3 is independently hydrogen or Ci-C4alkyl; and
R4 is preferably Ci-Cealkyl or Cs-Cecycloalkyl.
Preferably in compounds of formula (1-1), Y1 is hydrogen, chlorine, bromine, trifluoromethyl, -CF2CH3, cyclopropyl, 1 -cyanocyclopropyl, 1-cyano-1-methyl-ethyl, 2,2,2-trifluoroethoxy, -NH(CH3), - N(CH3)COCH3 or -N(CH3)COCF3; more preferably Yi is hydrogen, trifluoromethyl, -CF2CH3, cyclopropyl, 1 -cyanocyclopropyl, 1-cyano-1-methyl-ethyl, -NH(CH3), -N(CH3)COCH3 or - N(CH3)COCF3
Preferred definitions of R1, R2, X, R3, R4, G1, G2 are as defined for compounds of formula I (above), and more preferably R2 is Ci-Cefluoroalkyl; more preferably R2 is -CH2CH2CF3, -CH2CF2CHF2 or - CH2CF2CF3; preferably X is S or SO2; more preferably X is SO2; R1 is Ci-C4alkyl or cyclopropyl-Ci- C4alkyl; preferably R1 is ethyl or cyclopropylmethyl; more preferably R1 is ethyl; Y1 is halogen, trifluoromethyl, 1 ,1 -difluoroethyl, cyclopropyl, cyanocyclopropyl, cyanoisopropyl or trifluoroethoxy; more preferably Y1 is cyclopropyl, 1 -cyanocyclopropyl or 1-cyano-1-methyl-ethyl.
One group of compounds according to this embodiment are compounds of formula (1-1 a) which are compounds of formula (1-1) wherein G2 is N and G1 is CH.
Figure imgf000008_0001
wherein R1, R2, X, R3, R4 and Y1 are as defined for compounds of formula I (above), or an agrochemically acceptable salt, stereoisomer, enantiomer, tautomer or N-oxide thereof, and wherein Y1 is preferably hydrogen, halogen, Ci-C4alkyl, Ci-Cehaloalkyl, Cs-Cecycloalkyl, Cs-Cecycloalkyl monosubstituted by cyano, Ci-Cecyanoalkyl, Ci-Cecyanoalkoxy, cyano, Ci-C4alkoxy, Ci-Cehaloalkoxy, -N(R3)2, -N(R3)COR4; and each R3 and R4 are independently from each other, hydrogen, Ci-C4alkyl, Ci-Cehaloalkyl or C3- Cecycloalkyl.
Preferably each R3 is independently hydrogen or Ci-C4alkyl; and
R4 is preferably Ci-Cealkyl or Cs-Cecycloalkyl.
Preferably in compounds of formula (1-1 a), Y1 is hydrogen, chlorine, bromine, trifluoromethyl, -CF2CH3, cyclopropyl, 1 -cyanocyclopropyl, 1-cyano-1-methyl-ethyl, 2,2,2-trifluoroethoxy, -NH(CH3), - N(CH3)COCH3 or -N(CH3)COCF3; more preferably Y1 is hydrogen, trifluoromethyl, -CF2CH3, cyclopropyl, 1 -cyanocyclopropyl, 1-cyano-1-methyl-ethyl, -NH(CH3), -N(CH3)COCH3 or - N(CH3)COCF3
Preferred definitions of R1, R2, X, R3 and R4 are as defined for compounds of formula I (above), and more preferably R2 is Ci-Cefluoroalkyl; more preferably R2 is -CH2CH2CF3, -CH2CF2CHF2 or - CH2CF2CF3; preferably X is S or SO2; more preferably X is SO2; R1 is Ci-C4alkyl or cyclopropyl-Ci- C4alkyl; preferably R1 is ethyl or cyclopropylmethyl; more preferably R1 is ethyl; Y1 is halogen, trifluoromethyl, 1 ,1-difluoroethyl, cyclopropyl, cyanocyclopropyl, cyanoisopropyl or trifluoroethoxy; more preferably Yi is cyclopropyl, 1 -cyanocyclopropyl or 1-cyano-1-methyl-ethyl..
Another group of compounds according to this embodiment are compounds of formula (1-1 b) which are compounds of formula (1-1) wherein G2 and G1 are both CH.
Figure imgf000009_0001
wherein R1, R2, X, R3, R4 and Y1 are as defined for compounds of formula I (above), or an agrochemically acceptable salt, stereoisomer, enantiomer, tautomer or N-oxide thereof, and wherein Y1 is preferably hydrogen, halogen, Ci-C4alkyl, Ci-Cehaloalkyl, Cs-Cecycloalkyl, Cs-Cecycloalkyl monosubstituted by cyano, Ci-Cecyanoalkyl, Ci-Cecyanoalkoxy, cyano, Ci-C4alkoxy, Ci-Cehaloalkoxy, -N(R3)2, -N(R3)COR4; and each R3 and R4 are independently from each other, hydrogen, Ci-C4alkyl, Ci-Cehaloalkyl or C3- Cecycloalkyl.
Preferably each R3 is independently hydrogen or Ci-C4alkyl; and
R4 is preferably Ci-Cealkyl or Cs-Cecycloalkyl.
Preferably in compounds of formula (1-1 b), Y1 is hydrogen, chlorine, bromine, trifluoromethyl, -CF2CH3, cyclopropyl, 1 -cyanocyclopropyl, 1-cyano-1-methyl-ethyl, 2,2,2-trifluoroethoxy, -NH(CH3), - N(CH3)COCH3 or -N(CH3)COCF3; more preferably Y1 is hydrogen, trifluoromethyl, -CF2CH3, cyclopropyl, 1 -cyanocyclopropyl, 1-cyano-1-methyl-ethyl, -NH(CH3), -N(CH3)COCH3 or - N(CH3)COCF3.
Preferred definitions of R1, R2, X, R3 and R4 are as defined for compounds of formula I (above), and more preferably R2 is Ci-Cefluoroalkyl; more preferably R2 is -CH2CH2CF3, -CH2CF2CHF2 or - CH2CF2CF3; preferably X is S or SO2; more preferably X is SO2; R1 is Ci-C4alkyl or cyclopropyl-Ci- C4alkyl; preferably R1 is ethyl or cyclopropylmethyl; more preferably R1 is ethyl; Y1 is halogen, trifluoromethyl, 1 ,1-difluoroethyl, cyclopropyl, cyanocyclopropyl, cyanoisopropyl or trifluoroethoxy; more preferably Y1 is cyclopropyl, 1 -cyanocyclopropyl or 1-cyano-1-methyl-ethyl..
Another group of compounds according to this embodiment are compounds of formula (1-1 c) which are compounds of formula (1-1) wherein G2 is CH and G1 is N.
Figure imgf000010_0002
wherein Ri, R2, X, R3, R4 and Y1 are as defined for compounds of formula I (above), or an agrochemically acceptable salt, stereoisomer, enantiomer, tautomer or N-oxide thereof, and wherein Y1 is preferably hydrogen, halogen, Ci-C4alkyl, Ci-Cehaloalkyl, Cs-Cecycloalkyl, Cs-Cecycloalkyl monosubstituted by cyano, Ci-Cecyanoalkyl, Ci-Cecyanoalkoxy, cyano, Ci-C4alkoxy, Ci-Cehaloalkoxy, -N(R3)2, -N(R3)COR4; and each R3 and R4 are independently from each other, hydrogen, Ci-C4alkyl, Ci-Cehaloalkyl or C3- Cecycloalkyl.
Preferably each R3 is independently hydrogen or Ci-C4alkyl; and
R4 is preferably Ci-Cealkyl or Cs-Cecycloalkyl.
Preferably in compounds of formula (1-1 c), Y1 is hydrogen, chlorine, bromine, trifluoromethyl, -CF2CH3, cyclopropyl, 1 -cyanocyclopropyl, 1-cyano-1-methyl-ethyl, 2,2,2-trifluoroethoxy, -NH(CH3), - N(CH3)COCH3 or -N(CH3)COCF3; more preferably Y1 is hydrogen, trifluoromethyl, -CF2CH3, cyclopropyl, 1 -cyanocyclopropyl, 1-cyano-1-methyl-ethyl, -NH(CH3), -N(CH3)COCH3 or - N(CH3)COCF3.
Preferred definitions of R1, R2, X, R3 and R4 are as defined for compounds of formula I (above), and more preferably R2 is Ci-Cefluoroalkyl; more preferably R2 is -CH2CH2CF3, -CH2CF2CHF2 or - CH2CF2CF3; preferably X is S or SO2; more preferably X is SO2; R1 is Ci-C4alkyl or cyclopropyl-Ci- C4alkyl; preferably R1 is ethyl or cyclopropylmethyl; more preferably R1 is ethyl; Y1 is halogen, trifluoromethyl, 1 ,1-difluoroethyl, cyclopropyl, cyanocyclopropyl, cyanoisopropyl or trifluoroethoxy; more preferably Y1 is cyclopropyl, 1 -cyanocyclopropyl or 1-cyano-1-methyl-ethyl.
Another group of compounds according to the invention are those of formula I-2
Figure imgf000010_0001
wherein R1, R2, X, R3, R4, G1, G2 and Y2 are as defined for compounds of formula I (above), or an agrochemically acceptable salt, stereoisomer, enantiomer, tautomer or N-oxide thereof, and wherein Y2 is preferably hydrogen, halogen, Ci-C4alkyl, Ci-Cehaloalkyl, Cs-Cecycloalkyl, Cs-Cecycloalkyl monosubstituted by cyano, Ci-Cecyanoalkyl, Ci-Cecyanoalkoxy, cyano, Ci-C4alkoxy, Ci-Cehaloalkoxy, -N(R3)2, -N(R3)COR4; and each R3 and R4 are independently from each other, hydrogen, Ci-C4alkyl, Ci-Cehaloalkyl or C3- Cecycloalkyl.
Preferably each R3 is independently hydrogen or Ci-C4alkyl; and R4 is preferably Ci-Cealkyl or Cs-Cecycloalkyl.
Preferably in compounds of formula (I-2), Y2 is hydrogen, chlorine, bromine, trifluoromethyl, -CF2CH3, cyclopropyl, 1 -cyanocyclopropyl, 1-cyano-1-methyl-ethyl, 2,2,2-trifluoroethoxy, -NH(CH3), - N(CH3)COCH3 or -N(CH3)COCF3; more preferably Y2 is hydrogen, trifluoromethyl, -CF2CH3, cyclopropyl, 1 -cyanocyclopropyl, 1-cyano-1-methyl-ethyl, -NH(CH3), -N(CH3)COCH3 or - N(CH3)COCF3.
Preferred definitions of R1, R2, X, R3, R4, G1, G2 are as defined for compounds of formula I (above), and more preferably R2 is Ci-Cefluoroalkyl; more preferably R2 is -CH2CH2CF3, -CH2CF2CHF2 or - CH2CF2CF3; preferably X is S or SO2; more preferably X is SO2; R1 is Ci-C4alkyl or cyclopropyl-Ci- C4alkyl; preferably R1 is ethyl or cyclopropylmethyl; more preferably R1 is ethyl; Y2 is halogen, trifluoromethyl, 1 ,1-difluoroethyl, cyclopropyl, cyanocyclopropyl, cyanoisopropyl or trifluoroethoxy; more preferably Y2 is cyclopropyl, 1 -cyanocyclopropyl or 1-cyano-1-methyl-ethyl..
One group of compounds according to this embodiment are compounds of formula (l-2a) which are compounds of formula (I-2) wherein G2 is N and G1 is CH.
Figure imgf000011_0001
wherein R1, R2, X, R3, R4 and Y2 are as defined for compounds of formula I (above), or an agrochemically acceptable salt, stereoisomer, enantiomer, tautomer or N-oxide thereof, and wherein Y2 is preferably hydrogen, halogen, Ci-C4alkyl, Ci-Cehaloalkyl, Cs-Cecycloalkyl, Cs-Cecycloalkyl monosubstituted by cyano, Ci-Cecyanoalkyl, Ci-Cecyanoalkoxy, cyano, Ci-C4alkoxy, Ci-Cehaloalkoxy, -N(R3)2, -N(R3)COR4; and each R3 and R4 are independently from each other, hydrogen, Ci-C4alkyl, Ci-Cehaloalkyl or C3- Cecycloalkyl.
Preferably each R3 is independently hydrogen or Ci-C4alkyl; and
R4 IS preferably Ci-Cealkyl or Cs-Cecycloalkyl. Preferably in compounds of formula (l-2a), Y2 is hydrogen, chlorine, bromine, trifluoromethyl, -CF2CH3, cyclopropyl, 1 -cyanocyclopropyl, 1-cyano-1-methyl-ethyl, 2,2,2-trifluoroethoxy, -NH(CH3), - N(CH3)COCH3 or -N(CH3)COCF3; more preferably Y2 is hydrogen, trifluoromethyl, -CF2CH3, cyclopropyl, 1 -cyanocyclopropyl, 1-cyano-1-methyl-ethyl, -NH(CH3), -N(CH3)COCH3 or - N(CH3)COCF3.
Preferred definitions of R1, R2, X, R3 and R4 are as defined for compounds of formula I (above), and more preferably R2 is Ci-Cefluoroalkyl; more preferably R2 is -CH2CH2CF3, -CH2CF2CHF2 or - CH2CF2CF3; preferably X is S or SO2; more preferably X is SO2; R1 is Ci-C4alkyl or cyclopropyl-Ci- C4alkyl; preferably R1 is ethyl or cyclopropylmethyl; more preferably R1 is ethyl; Y2 is halogen, trifluoromethyl, 1 ,1-difluoroethyl, cyclopropyl, cyanocyclopropyl, cyanoisopropyl or trifluoroethoxy; more preferably Y2 is cyclopropyl, 1 -cyanocyclopropyl or 1-cyano-1-methyl-ethyl.
Another group of compounds according to this embodiment are compounds of formula (l-2b) which are compounds of formula (I-2) wherein G2 and G1 are both CH.
Figure imgf000012_0001
wherein R1, R2, X, R3, R4 and Y2 are as defined for compounds of formula I (above), or an agrochemically acceptable salt, stereoisomer, enantiomer, tautomer or N-oxide thereof, and wherein Y2 is preferably hydrogen, halogen, Ci-C4alkyl, Ci-Cehaloalkyl, Cs-Cecycloalkyl, Cs-Cecycloalkyl monosubstituted by cyano, Ci-Cecyanoalkyl, Ci-Cecyanoalkoxy, cyano, Ci-C4alkoxy, Ci-Cehaloalkoxy, -N(R3)2, -N(R3)COR4; and each R3 and R4 are independently from each other, hydrogen, Ci-C4alkyl, Ci-Cehaloalkyl or C3- Cecycloalkyl.
Preferably each R3 is independently hydrogen or Ci-C4alkyl; and
R4 is preferably Ci-Cealkyl or Cs-Cecycloalkyl.
Preferably in compounds of formula (l-2b), Y2 is hydrogen, chlorine, bromine, trifluoromethyl, -CF2CH3, cyclopropyl, 1 -cyanocyclopropyl, 1-cyano-1-methyl-ethyl, 2,2,2-trifluoroethoxy, -NH(CH3), - N(CH3)COCH3 or -N(CH3)COCF3; more preferably Y2 is hydrogen, trifluoromethyl, -CF2CH3, cyclopropyl, 1 -cyanocyclopropyl, 1-cyano-1-methyl-ethyl, -NH(CH3), -N(CH3)COCH3 or - N(CH3)COCF3.
Preferred definitions of R1, R2, X, R3 and R4 are as defined for compounds of formula I (above), and more preferably R2 is Ci-Cefluoroalkyl; more preferably R2 is -CH2CH2CF3, -CH2CF2CHF2 or - CH2CF2CF3; preferably X is S or SO2; more preferably X is SO2; R1 is Ci-C4alkyl or cyclopropyl-Ci- C4alkyl; preferably R1 is ethyl or cyclopropylmethyl; more preferably R1 is ethyl; Y2 is halogen, trifluoromethyl, 1 ,1-difluoroethyl, cyclopropyl, cyanocyclopropyl, cyanoisopropyl or trifluoroethoxy; more preferably Y2 is cyclopropyl, 1 -cyanocyclopropyl or 1-cyano-1-methyl-ethyl..
Another group of compounds according to this embodiment are compounds of formula (l-2c) which are compounds of formula (I-2) wherein G2 is CH and G1 is N.
Figure imgf000013_0001
wherein R1, R2, X, R3, R4 and Y2 are as defined for compounds of formula I (above), or an agrochemically acceptable salt, stereoisomer, enantiomer, tautomer or N-oxide thereof, and wherein Y2 is preferably hydrogen, halogen, Ci-C4alkyl, Ci-Cehaloalkyl, Cs-Cecycloalkyl, Cs-Cecycloalkyl monosubstituted by cyano, Ci-Cecyanoalkyl, Ci-Cecyanoalkoxy, cyano, Ci-C4alkoxy, Ci-Cehaloalkoxy, -N(R3)2, -N(R3)COR4; and each R3 and R4 are independently from each other, hydrogen, Ci-C4alkyl, Ci-Cehaloalkyl or C3- Cecycloalkyl.
Preferably each R3 is independently hydrogen or Ci-C4alkyl; and
R4 is preferably Ci-Cealkyl or Cs-Cecycloalkyl.
Preferably in compounds of formula (l-2c), Y2 is hydrogen, chlorine, bromine, trifluoromethyl, -CF2CH3, cyclopropyl, 1 -cyanocyclopropyl, 1-cyano-1-methyl-ethyl, 2,2,2-trifluoroethoxy, -NH(CH3), - N(CH3)COCH3 or -N(CH3)COCF3; more preferably Y2 is hydrogen, trifluoromethyl, -CF2CH3, cyclopropyl, 1 -cyanocyclopropyl, 1-cyano-1-methyl-ethyl, -NH(CH3), -N(CH3)COCH3 or - N(CH3)COCF3.
Preferred definitions of R1, R2, X, R3 and R4 are as defined for compounds of formula I (above), and more preferably R2 is Ci-Cefluoroalkyl; more preferably R2 is -CH2CH2CF3, -CH2CF2CHF2 or - CH2CF2CF3; preferably X is S or SO2; more preferably X is SO2; R1 is Ci-C4alkyl or cyclopropyl-Ci- C4alkyl; preferably R1 is ethyl or cyclopropylmethyl; more preferably R1 is ethyl; Y2 is halogen, trifluoromethyl, 1 ,1-difluoroethyl, cyclopropyl, cyanocyclopropyl, cyanoisopropyl or trifluoroethoxy; more preferably Y2 is cyclopropyl, 1 -cyanocyclopropyl or 1-cyano-1-methyl-ethyl.
Another group of compounds according to the invention are those of formula I-3
Figure imgf000014_0001
wherein R2, R3, R4, G1, G2 and Y1 are as defined for compounds of formula I (above), or an agrochemically acceptable salt, stereoisomer, enantiomer, tautomer or N-oxide thereof, and wherein Y1 is preferably hydrogen, halogen, Ci-C4alkyl, Ci-Cehaloalkyl, Cs-Cecycloalkyl, Cs-Cecycloalkyl monosubstituted by cyano, Ci-Cecyanoalkyl, Ci-Cecyanoalkoxy, cyano, Ci-C4alkoxy, Ci-Cehaloalkoxy, -N(R3)2, -N(R3)COR4; and each R3 and R4 are independently from each other, hydrogen, Ci-C4alkyl, Ci-Cehaloalkyl or C3- Cecycloalkyl.
Preferably each R3 is independently hydrogen or Ci-C4alkyl; and
R4 is preferably Ci-Cealkyl or Cs-Cecycloalkyl.
Preferably in compounds of formula (I-3), Y1 is hydrogen, chlorine, bromine, trifluoromethyl, -CF2CH3, cyclopropyl, 1 -cyanocyclopropyl, 1-cyano-1-methyl-ethyl, 2,2,2-trifluoroethoxy, -NH(CH3), - N(CH3)COCH3 or -N(CH3)COCF3; more preferably Y1 is hydrogen, trifluoromethyl, -CF2CH3, cyclopropyl, 1 -cyanocyclopropyl, 1-cyano-1-methyl-ethyl, -NH(CH3), -N(CH3)COCH3 or - N(CH3)COCF3.
Preferred definitions of R2, R3 and R4 are as defined for compounds of formula I (above), and more preferably R2 is Ci-Cefluoroalkyl; more preferably R2 is -CH2CH2CF3, -CH2CF2CHF2 or -CH2CF2CF3; Y1 is halogen, trifluoromethyl, 1 ,1-difluoroethyl, cyclopropyl, cyanocyclopropyl, cyanoisopropyl or trifluoroethoxy; more preferably Y1 is cyclopropyl, 1 -cyanocyclopropyl or 1-cyano-1-methyl-ethyl.
Another group of compounds according to this embodiment are those of formula l-3a which are compounds of formula (I-3) wherein R1 is ethyl, X is SO2, G2 is N and G1 is CH.
Figure imgf000014_0002
wherein R2, R3, R4 and Y1 are as defined for compounds of formula I (above), or an agrochemically acceptable salt, stereoisomer, enantiomer, tautomer or N-oxide thereof, and wherein Y1 is preferably hydrogen, halogen, Ci-C4alkyl, Ci-Cehaloalkyl, Cs-Cecycloalkyl, Cs-Cecycloalkyl monosubstituted by cyano, Ci-Cecyanoalkyl, Ci-Cecyanoalkoxy, cyano, Ci-C4alkoxy, Ci-Cehaloalkoxy, -N(R3)2, - N(R3)COR4; and each R3 and R4 are independently from each other, hydrogen, Ci-C4alkyl, Ci-Cehaloalkyl or C3- Cecycloalkyl.
Preferably each R3 is independently hydrogen or Ci-C4alkyl; and
R4 is preferably Ci-Cealkyl or C3-C6cycloalkyl.
Preferably in compounds of formula (l-3a), Yi is hydrogen, chlorine, bromine, trifluoromethyl, -CF2CH3, cyclopropyl, 1 -cyanocyclopropyl, 1-cyano-1-methyl-ethyl, 2,2,2-trifluoroethoxy, -NH(CH3), - N(CH3)COCH3 or -N(CH3)COCF3; more preferably Yi is hydrogen, trifluoromethyl, -CF2CH3, cyclopropyl, 1 -cyanocyclopropyl, 1-cyano-1-methyl-ethyl, -NH(CH3), -N(CH3)COCH3 or - N(CH3)COCF3.
Preferred definitions of R2, R3 and R4 are as defined for compounds of formula I (above), and more preferably Yi is halogen, trifluoromethyl, 1 ,1-difluoroethyl, cyclopropyl, cyanocyclopropyl, cyanoisopropyl or trifluoroethoxy.
One group of compounds according to this embodiment are compounds of formula (l-3a-1) which are compounds of formula (l-3a), or of any of the preferred embodiments of the compounds of formula (I- 3a), wherein
R2 is -CH2CH2CF3, -CH2CF2CHF2 or -CH2CF2CF3; preferably -CH2CH2CF3 or -CH2CF2CF3; and
Yi is trifluoromethyl, difluoroethyl, cyclopropyl, cyanocyclopropyl, cyanoisopropyl, -NH(CH3), - N(CH3)COCH3 or -N(CH3)COCF3; preferably -CF3, -CF2CH3, cyclopropyl, 1 -cyanocyclopropyl, 1- cyano-1-methyl-ethyl, -NH(CH3), -N(CH3)COCH3 or -N(CH3)COCF3; more preferably Yi is cyclopropyl, 1 -cyanocyclopropyl or 1-cyano-1-methyl-ethyl.
Another group of compounds according to this embodiment are compounds of formula (l-3b) which are compounds of formula (I-3) wherein R1 is ethyl, X is SO2, G2 is CH and G1 is CH.
Figure imgf000015_0001
wherein R2, R3, R4 and Yi are as defined for compounds of formula I (above), or an agrochemically acceptable salt, stereoisomer, enantiomer, tautomer or N-oxide thereof, and wherein Yi is preferably hydrogen, halogen, Ci-C4alkyl, Ci-Cehaloalkyl, C3-C6cycloalkyl, C3-C6cycloalkyl monosubstituted by cyano, Ci-Cecyanoalkyl, Ci-Cecyanoalkoxy, cyano, Ci-C4alkoxy, Ci-Cehaloalkoxy, -N(R3)2, - N(R3)COR4; and each R3 and R4 are independently from each other, hydrogen, Ci-C4alkyl, Ci-Cehaloalkyl or C3- Cecycloalkyl.
Preferably each R3 is independently hydrogen or Ci-C4alkyl; and
R4 is preferably Ci-Cealkyl or C3-C6cycloalkyl.
Preferably in compounds of formula (l-3b), Y1 is hydrogen, chlorine, bromine, trifluoromethyl, -CF2CH3, cyclopropyl, 1 -cyanocyclopropyl, 1-cyano-1-methyl-ethyl, 2,2,2-trifluoroethoxy, -NH(CH3), - N(CH3)COCH3 or -N(CH3)COCF3; more preferably Y1 is hydrogen, trifluoromethyl, -CF2CH3, cyclopropyl, 1 -cyanocyclopropyl, 1-cyano-1-methyl-ethyl, -NH(CH3), -N(CH3)COCH3 or - N(CH3)COCF3.
Preferred definitions of R2, R3 and R4 are as defined for compounds of formula I (above), and more preferably R2 is Ci-Cefluoroalkyl; more preferably R2 is -CH2CH2CF3, -CH2CF2CHF2 or -CH2CF2CF3; Y1 is halogen, trifluoromethyl, 1 ,1-difluoroethyl, cyclopropyl, cyanocyclopropyl, cyanoisopropyl or trifluoroethoxy; more preferably Y1 is cyclopropyl, 1 -cyanocyclopropyl or 1-cyano-1-methyl-ethyl.
Another group of compounds according to this embodiment are compounds of formula (l-3c) which are compounds of formula (I-3) wherein R1 is ethyl, X is SO2, G2 is CH and G1 is N.
Figure imgf000016_0001
wherein R2, R3, R4 and Y1 are as defined for compounds of formula I (above), or an agrochemically acceptable salt, stereoisomer, enantiomer, tautomer or N-oxide thereof, and wherein Y1 is preferably hydrogen, halogen, Ci-C4alkyl, Ci-Cehaloalkyl, C3-C6cycloalkyl, C3-C6cycloalkyl monosubstituted by cyano, Ci-Cecyanoalkyl, Ci-Cecyanoalkoxy, cyano, Ci-C4alkoxy, Ci-Cehaloalkoxy, -N(R3)2, - N(R3)COR4; and each R3 and R4 are independently from each other, hydrogen, Ci-C4alkyl, Ci-Cehaloalkyl or C3- Cecycloalkyl.
Preferably each R3 is independently hydrogen or Ci-C4alkyl; and
R4 is preferably Ci-Cealkyl or C3-C6cycloalkyl.
Preferably in compounds of formula (l-3c), Y1 is hydrogen, chlorine, bromine, trifluoromethyl, -CF2CH3, cyclopropyl, 1 -cyanocyclopropyl, 1-cyano-1-methyl-ethyl, 2,2,2-trifluoroethoxy, -NH(CH3), - N(CH3)COCH3 or -N(CH3)COCF3; more preferably Y1 is hydrogen, trifluoromethyl, -CF2CH3, cyclopropyl, 1 -cyanocyclopropyl, 1-cyano-1-methyl-ethyl, -NH(CH3), -N(CH3)COCH3 or -
N(CH3)COCF3. Preferred definitions of R2, R3 and R4 are as defined for compounds of formula I (above), and more preferably R2 is Ci-Cefluoroalkyl; more preferably R2 is -CH2CH2CF3, -CH2CF2CHF2 or -CH2CF2CF3; Y1 is halogen, trifluoromethyl, 1 ,1-difluoroethyl, cyclopropyl, cyanocyclopropyl, cyanoisopropyl or trifluoroethoxy; more preferably Y1 is cyclopropyl, 1 -cyanocyclopropyl or 1-cyano-1-methyl-ethyl.
Yet, another group of compounds according to the invention are those of formula I-4
Figure imgf000017_0001
wherein R2, R3, R4, G1, G2 and Y2 are as defined for compounds of formula I (above), or an agrochemically acceptable salt, stereoisomer, enantiomer, tautomer or N-oxide thereof, and wherein Y2 is preferably hydrogen, halogen, Ci-C4alkyl, Ci-Cehaloalkyl, Cs-Cecycloalkyl, Cs-Cecycloalkyl monosubstituted by cyano, Ci-Cecyanoalkyl, Ci-Cecyanoalkoxy, cyano, Ci-C4alkoxy, Ci-Cehaloalkoxy, -N(R3)2, -N(R3)COR4; and each R3 and R4 are independently from each other, hydrogen, Ci-C4alkyl, Ci-Cehaloalkyl or C3- Cecycloalkyl.
Preferably each R3 is independently hydrogen or Ci-C4alkyl; and
R4 is preferably Ci-Cealkyl or Cs-Cecycloalkyl.
Preferably in compounds of formula (I-4), Y2 is hydrogen, chlorine, bromine, trifluoromethyl, -CF2CH3, cyclopropyl, 1 -cyanocyclopropyl, 1-cyano-1-methyl-ethyl, 2,2,2-trifluoroethoxy, -NH(CH3), - N(CH3)COCH3 or -N(CH3)COCF3; more preferably Y2 is hydrogen, trifluoromethyl, -CF2CH3, cyclopropyl, 1 -cyanocyclopropyl, 1-cyano-1-methyl-ethyl, -NH(CH3), -N(CH3)COCH3 or - N(CH3)COCF3.
Preferred definitions of R2, R3 and R4 are as defined for compounds of formula I (above), and more preferably R2 is Ci-Cefluoroalkyl; more preferably R2 is -CH2CH2CF3, -CH2CF2CHF2 or -CH2CF2CF3; Y2 is halogen, trifluoromethyl, 1 ,1-difluoroethyl, cyclopropyl, cyanocyclopropyl, cyanoisopropyl or trifluoroethoxy; more preferably Y2 is cyclopropyl, 1 -cyanocyclopropyl or 1-cyano-1-methyl-ethyl.
Another group of compounds according to this embodiment are those of formula l-4a which are compounds of formula (I-4) wherein R1 is ethyl, X is SO2, G2 is N and G1 is CH.
Figure imgf000018_0001
wherein R2, R3, R4 and Y2 are as defined for compounds of formula I (above), or an agrochemically acceptable salt, stereoisomer, enantiomer, tautomer or N-oxide thereof, and wherein Y2 is preferably hydrogen, halogen, Ci-C4alkyl, Ci-Cehaloalkyl, Cs-Cecycloalkyl, Cs-Cecycloalkyl monosubstituted by cyano, Ci-Cecyanoalkyl, Ci-Cecyanoalkoxy, cyano, Ci-C4alkoxy, Ci-Cehaloalkoxy, -N(Rs)2, - N(R3)COR4; and each R3 and R4 are independently from each other, hydrogen, Ci-C4alkyl, Ci-Cehaloalkyl or C3- Cecycloalkyl.
Preferably each R3 is independently hydrogen or Ci-C4alkyl; and
R4 is preferably Ci-Cealkyl or Cs-Cecycloalkyl.
Preferably in compounds of formula (l-4a), Y2 is hydrogen, chlorine, bromine, trifluoromethyl, -CF2CH3, cyclopropyl, 1 -cyanocyclopropyl, 1-cyano-1-methyl-ethyl, 2,2,2-trifluoroethoxy, -NH(CH3), - N(CH3)COCH3 or -N(CH3)COCF3; more preferably Y2 is hydrogen, trifluoromethyl, -CF2CH3, cyclopropyl, 1 -cyanocyclopropyl, 1-cyano-1-methyl-ethyl, -NH(CH3), -N(CH3)COCH3 or - N(CH3)COCF3.
Preferred definitions of R2, R3 and R4 are as defined for compounds of formula I (above), and more preferably Y2 is halogen, trifluoromethyl, 1 ,1-difluoroethyl, cyclopropyl, cyanocyclopropyl, cyanoisopropyl or trifluoroethoxy.
One group of compounds according to this embodiment are compounds of formula (l-4a-1) which are compounds of formula (l-4a), or of any of the preferred embodiments of the compounds of formula (I- 4a), wherein
R2 is -CH2CH2CF3, -CH2CF2CHF2 or -CH2CF2CF3; preferably -CH2CH2CF3 or -CH2CF2CF3; and
Y2 is trifluoromethyl, difluoroethyl, cyclopropyl, cyanocyclopropyl, cyanoisopropyl, -NH(CH3), - N(CH3)COCH3 or -N(CH3)COCF3; preferably -CF3, -CF2CH3, cyclopropyl, 1 -cyanocyclopropyl, 1- cyano-1-methyl-ethyl, -NH(CH3), -N(CH3)COCH3 or -N(CH3)COCF3; more preferably Y2 is -CF3, - CF2CH3, 1 -cyanocyclopropyl, 1-cyano-1-methyl-ethyl, -NH(CH3), -N(CH3)COCH3 or -N(CH3)COCF3.
Another group of compounds according to this embodiment are compounds of formula (l-4b) which are compounds of formula (I-4) wherein R1 is ethyl, X is SO2, G2 is CH and G1 is CH.
Figure imgf000019_0001
wherein R2, R3, R4 and Y2 are as defined for compounds of formula I (above), or an agrochemically acceptable salt, stereoisomer, enantiomer, tautomer or N-oxide thereof, and wherein Y2 is preferably hydrogen, halogen, Ci-C4alkyl, Ci-Cehaloalkyl, Cs-Cecycloalkyl, Cs-Cecycloalkyl monosubstituted by cyano, Ci-Cecyanoalkyl, Ci-Cecyanoalkoxy, cyano, Ci-C4alkoxy, Ci-Cehaloalkoxy, -N(Rs)2, - N(R3)COR4; and each R3 and R4 are independently from each other, hydrogen, Ci-C4alkyl, Ci-Cehaloalkyl or C3- Cecycloalkyl.
Preferably each R3 is independently hydrogen or Ci-C4alkyl; and R4 is preferably Ci-Cealkyl or Cs-Cecycloalkyl.
Preferably in compounds of formula (l-4b), Y2 is hydrogen, chlorine, bromine, trifluoromethyl, -CF2CH3, cyclopropyl, 1 -cyanocyclopropyl, 1-cyano-1-methyl-ethyl, 2,2,2-trifluoroethoxy, -NH(CH3), - N(CH3)COCH3 or -N(CH3)COCF3; more preferably Y2 is hydrogen, trifluoromethyl, -CF2CH3, cyclopropyl, 1 -cyanocyclopropyl, 1-cyano-1-methyl-ethyl, -NH(CH3), -N(CH3)COCH3 or - N(CH3)COCF3.
Preferred definitions of R2, R3 and R4 are as defined for compounds of formula I (above), and more preferably R2 is Ci-Cefluoroalkyl; more preferably R2 is -CH2CH2CF3, -CH2CF2CHF2 or -CH2CF2CF3; Y2 is halogen, trifluoromethyl, 1 ,1-difluoroethyl, cyclopropyl, cyanocyclopropyl, cyanoisopropyl or trifluoroethoxy; more preferably Y2 is cyclopropyl, 1 -cyanocyclopropyl or 1-cyano-1-methyl-ethyl.
Another group of compounds according to this embodiment are compounds of formula (l-4c) which are compounds of formula (I-4) wherein R1 is ethyl, X is SO2, G2 is CH and G1 is N.
Figure imgf000019_0002
wherein R2, R3, R4 and Y2 are as defined for compounds of formula I (above), or an agrochemically acceptable salt, stereoisomer, enantiomer, tautomer or N-oxide thereof, and wherein Y2 is preferably hydrogen, halogen, Ci-C4alkyl, Ci-Cehaloalkyl, Cs-Cecycloalkyl, Cs-Cecycloalkyl monosubstituted by cyano, Ci-Cecyanoalkyl, Ci-Cecyanoalkoxy, cyano, Ci-C4alkoxy, Ci-Cehaloalkoxy, -N(R3)2, - N(R3)COR4; and each R3 and R4 are independently from each other, hydrogen, Ci-C4alkyl, Ci-Cehaloalkyl or C3- Cecycloalkyl.
Preferably each R3 is independently hydrogen or Ci-C4alkyl; and
R4 is preferably Ci-Cealkyl or C3-C6cycloalkyl.
Preferably in compounds of formula (l-4c), Y2 is hydrogen, chlorine, bromine, trifluoromethyl, -CF2CH3, cyclopropyl, 1 -cyanocyclopropyl, 1-cyano-1-methyl-ethyl, 2,2,2-trifluoroethoxy, -NH(CH3), - N(CH3)COCH3 or -N(CH3)COCF3; more preferably Y2 is hydrogen, trifluoromethyl, -CF2CH3, cyclopropyl, 1 -cyanocyclopropyl, 1-cyano-1-methyl-ethyl, -NH(CH3), -N(CH3)COCH3 or - N(CH3)COCF3.
Preferred definitions of R2, R3 and R4 are as defined for compounds of formula I (above), and more preferably R2 is Ci-Cefluoroalkyl; more preferably R2 is -CH2CH2CF3, -CH2CF2CHF2 or -CH2CF2CF3; Y2 is halogen, trifluoromethyl, 1 ,1-difluoroethyl, cyclopropyl, cyanocyclopropyl, cyanoisopropyl or trifluoroethoxy; more preferably Y2 is cyclopropyl, 1 -cyanocyclopropyl or 1-cyano-1-methyl-ethyl.
Compounds according to the invention may possess any number of benefits including, inter alia, advantageous levels of biological activity for protecting plants against insects or superior properties for use as agrochemical active ingredients (for example, greater biological activity, an advantageous spectrum of activity, an increased safety profile, improved physico-chemical properties, or increased biodegradability or environmental profile). In particular, it has been surprisingly found that certain compounds of formula (I) may show an advantageous safety profile with respect to non-target arthropods, in particular pollinators such as honey bees, solitary bees, and bumble bees. Most particularly, Apis mellifera.
In another aspect the present invention provides a composition comprising an insecticidally, acaricidally, nematicidally or molluscicidally effective amount of a compound of formula (I), or an agrochemically acceptable salt, stereoisomer, enantiomer, tautomer or N-oxide thereof, as defined in any of the embodiments under compounds of formula (I), (1-1), (I-2), (I-3) or (I-4) (above), and, optionally, an auxiliary or diluent.
In a further aspect the present invention provides a method of combating and controlling insects, acarines, nematodes or molluscs which comprises applying to a pest, to a locus of a pest, or to a plant susceptible to attack by a pest an insecticidally, acaricidally, nematicidally or molluscicidally effective amount of a compound of formula (I), or an agrochemically acceptable salt, stereoisomer, enantiomer, tautomer or N-oxide thereof, as defined in any of the embodiments under compounds of formula (I), (I- 1), (I-2), (I-3) or (I-4) (above) or a composition as defined above. In a yet further aspect, the present invention provides a method for the protection of plant propagation material from the attack by insects, acarines, nematodes or molluscs, which comprises treating the propagation material or the site, where the propagation material is planted, with a composition as defined above.
The process according to the invention for preparing compounds of formula I is carried out in principle by methods known to those skilled in the art as depicted in scheme 1 . More specifically, the subgroup of compounds of formula I, wherein X is SO (sulfoxide) and/or SO2 (sulfone), may be obtained by means of an oxidation reaction of the corresponding sulfide compounds of formula II defined as compounds of formula I, wherein X is S, involving reagents such as, for example, m-chloroperoxy- benzoic acid (mCPBA), hydrogen peroxide, oxone, sodium periodate, sodium hypochlorite or tert-butyl hypochlorite amongst other oxidants. The oxidation reaction is generally conducted in the presence of a solvent. Examples of the solvent to be used in the reaction include aliphatic halogenated hydrocarbons such as dichloromethane and chloroform; alcohols such as methanol and ethanol; acetic acid; water; and mixtures thereof. The amount of the oxidant to be used in the reaction is generally 1 to 3 moles, preferably 1 to 1.2 moles, relative to 1 mole of the sulfide compounds I to produce the sulfoxide compounds I, and preferably 2 to 2.2 moles of oxidant, relative to 1 mole of of the sulfide compounds I to produce the sulfone compounds I. Such oxidation reactions are disclosed, for example, in WO 2013/018928.
Scheme 1
Figure imgf000021_0001
The compounds of formula II, wherein Gi, G2, R1, R2, Y1 and Y2 are as defined for compounds of formula I (above), may be prepared as described in scheme 2.
Scheme 2
Figure imgf000021_0002
Compounds of formula II can be obtained by reacting a compound of formula III, or a compound of formula Illa, wherein Ri is as defined in formula I and M is a cationic species, for example a metal cation, with a compound of formula IV wherein Gi, G2, R2, Y1 and Y2 are as defined in formula I and Xa is a leaving group. When the reaction is performed with a compound of formula III, Xa is preferentially chlorine, bromine or iodine, more preferentially bromine or iodine and the reaction is performed with a base, for example a tertiary amine or a mineral base, as for example an alkali metal carbonate, in a non-participating solvent, like dimethoxyethane or acetonitrile, at a temperature between 0°C and the boiling point of the reaction mixture. This coupling is most efficiently performed in presence of a catalyst, preferable a palladium-based catalyst. When the reaction is performed with compounds of formula Illa, Xa is preferably a halogen, preferably chlorine, bromine or iodine and the solvent is preferably a polar aprotic solvent, as for example dimethylformamide. The reaction can be performed preferably between -20°C and 100°C, most preferably between 0°C and 80°C. An excess of reagent III or Illa maybe used for a good conversion.
Compounds of formula IV maybe conveniently obtained by treating compounds of formula V, wherein G1, G2, R2, Y1 and Y2 are as defined in formula I with an electrophilic halogenating reagent, as for example N-chlorosuccinimide, N-bromosuccinimide, N-iodosuccinimide or a molecular halogen, like bromine, just to cite a few.
Compounds of formula IV-a
Figure imgf000022_0001
wherein
R2, Y1 and Y2 are as defined in formula I above; and
Xa is a halogen, are novel, especially developed for the preparation of the compounds of formula I according to the invention and therefore represent a further object of the invention. The preferences and preferred embodiments of the substituents of the compounds of formula I are also valid for the compounds of formula IV-a. Xa preferably is chlorine, bromine or iodine; even more preferably bromine or iodine.
Compounds of formula V can be obtained by cyclization of compounds of formula VI, wherein G1, G2, R2, Y1 and Y2 are as defined in formula I. The reaction can be performed with a large range of reducing agents. Trialkylphosphines, for example tributylphosphine, are convenient reagents for this purpose. The reaction can be performed in a inert solvent, like acetonitrile or dimethoxyethane, at temperatures between -30°C and 100°C. Compounds of formula V-a
Figure imgf000023_0001
(V-a), wherein
R2, Y1 and Y2 are as defined in formula I above, are novel, especially developed for the preparation of the compounds of formula I according to the invention and therefore represent a further object of the invention. The preferences and preferred embodiments of the substituents of the compounds of formula I are also valid for the compounds of formula V-a.
Compounds of formula VI can be prepared by condensing an amino compound of formula VIII, wherein G1, G2 and R2 are as defined in formula I and an aldehyde of formula VII, wherein Y1 and Y2 are as defined in formula I. The dehydration can be preferably performed in an inert solvent, like toluene, at a temperature between 20°C and the boiling point of the solvent. It is convenient to use a dehydrating agent, like molecular sieves.
Compounds of formula Vl-a
Figure imgf000023_0002
wherein
R2, Y1 and Y2 are as defined in formula I above, are novel, especially developed for the preparation of the compounds of formula I according to the invention and therefore represent a further object of the invention. The preferences and preferred embodiments of the substituents of the compounds of formula I are also valid for the compounds of formula Vl-a.
Many examples of compounds of formula VII are described in the literature or are even commercially available. Those who are not, can be prepared by a person skilled in the art, by analogy to known compounds. Some examples described in the preparation examples hereafter can illustrate this task.
Compounds of formula VIII, wherein G1, G2 and R2 are as defined in formula I, can be accessed to through various ways, as depicted in scheme 3.
Scheme 3
Figure imgf000024_0001
Compounds of formula VIII can be obtained by deprotection of the amine function of compounds of formula IX, wherein Gi, G2 and R2 are as defined in formula I. This is a standard operation frequently described in the literature. Usually, acid conditions are employed, preferably, trifluoroacetic acid or HCI. The reaction can be performed in an inert solvent, for example dichloromethane, ethyl acetate or dimethoxyethane, or in an excess of the acid, between 0°C and 60°C.
Compounds of formula IX can be prepared from compounds of formula X, wherein G1, G2 and R2 are as defined in formula I and Rr is a Ci-C4alkyl group, preferably methyl or ethyl. The first step of this transformation consists of the hydrolysis of the ester function to the carboxylic acid, which is standardwise performed under aqueous alkaline conditions followed by acidification, leading to an intermediate of formula X wherein Rr is H. This intermediate can then be treated with an azidocontaining reagent, for example diphenylphosphoryl azide, and heated in presence of t-butyl alcohol to effect the Curtius rearrangement to lead to the BOC-protected amine.
Compounds of formula X can be obtained from compounds of formula XI, wherein G1, G2 and R2 are as defined in formula I, and Xb is a leaving group, like a trifluoro methanesulfonate or a halogen, preferentially chloro, bromo or iodo, most preferably bromo. The transformation can best be carried out under pressure of carbon monoxide, in an autoclave, in presence of an lower alcohol Rr-OH, wherein Rr is C1-C4 alkyl, preferably methanol or ethanol. The reaction is best catalyzed by a palladium-based catalyst. Alkoxycarbonylation reactions are standard reactions very often encountered in the chemical literature and are known to the person skilled in the art.
Alternatively, compounds of formula VIII can be prepared directly from compounds of formula XI (same definition as above) by treatment with ammonia. The reaction is preferably performed with a large excess of ammonia, in a solvent that could be a lower alcohol or water, eventually mixed with another organic solvent. The reaction mixture may need to be heated so, because of the volatility of ammonia, an autoclave should be used. Copper salts can be added to facilitate the reaction. Another preparation method of compounds of formula VIII from compounds of formula XI, consists of coupling with te/Y-butyl carbamate, in presence of a base and with a palladium-based catalyst. This type of reaction is also well described in the literature. The coupling product is a compound of formula IX, which conversion to compound of formula VIII has been described hereabove.
Compounds of formula XI, as described hereabove, can be prepared by reacting compounds of formula XII, wherein Gi and G2 are as defined in formula I, and Xb is a halogen (or a pseudo-halogen leaving group, such as a triflate), preferably chloro, bromo or iodo, most preferably bromo with a compound R2-LG, wherein R2 is as defined in formula I and LG is a halogen, preferably iodo, bromo or chloro or a pseudo-halogen leaving group, such as a (halo)alkyl or aryl sulfonate ester, for example triflate, in the presence of a base, such as sodium hydride or an alkali metal hydride, carbonate (e.g. sodium carbonate, potassium carbonate or cesium carbonate) or hydroxide, in an inert solvent such as tetra hydrofuran, dioxane, N,N-dimethylformamide DMF, N,N-dimethylacetamide or acetonitrile and the like, at temperatures between 0 and 120°C, by procedures well known to those skilled in the art.
Many compounds of formula XII, wherein G1 and G2 are as defined in formula I, and Xb is a halogen (or a pseudo-halogen leaving group, such as a triflate), and especially the compounds where Xb is bromo, are described in the literature and are commercially available.
Compounds of formula Vlll-a
Figure imgf000025_0001
(Vlll-a), wherein
R2 is as defined in formula I, are novel, especially developed for the preparation of the compounds of formula I according to the invention and therefore represent a further object of the invention. The preferences and preferred embodiments of the substituents of the compounds of formula I are also valid for the compounds of formula Vlll-a.
The reactants can be reacted in the presence of a base. Examples of suitable bases are alkali metal or alkaline earth metal hydroxides, alkali metal or alkaline earth metal hydrides, alkali metal or alkaline earth metal amides, alkali metal or alkaline earth metal alkoxides, alkali metal or alkaline earth metal acetates, alkali metal or alkaline earth metal carbonates, alkali metal or alkaline earth metal dialkylamides or alkali metal or alkaline earth metal alkylsilylamides, alkylamines, alkylenediamines, free or N-alkylated saturated or unsaturated cycloalkylamines, basic heterocycles, ammonium hydroxides and carbocyclic amines. Examples which may be mentioned are sodium hydroxide, sodium hydride, sodium amide, sodium methoxide, sodium acetate, sodium carbonate, potassium tert- butoxide, potassium hydroxide, potassium carbonate, potassium hydride, lithium diisopropylamide, potassium bis(trimethylsilyl)amide, calcium hydride, triethylamine, diisopropylethylamine, triethylenediamine, cyclohexylamine, N-cyclohexyl-N,N-dimethylamine, N,N-diethylaniline, pyridine, 4- (N,N-dimethylamino)pyridine, quinuclidine, N-methylmorpholine, benzyltrimethylammonium hydroxide and 1 ,8-diazabicyclo[5.4.0]undec-7-ene (DBU).
The reactants can be reacted with each other as such, i.e. without adding a solvent or diluent. In most cases, however, it is advantageous to add an inert solvent or diluent or a mixture of these. If the reaction is carried out in the presence of a base, bases which are employed in excess, such as triethylamine, pyridine, N-methylmorpholine or N , N-diethylaniline , may also act as solvents or diluents.
The reactions are advantageously carried out in a temperature range from approximately -80°C to approximately +140°C, preferably from approximately -30°C to approximately +100°C, in many cases in the range between ambient temperature and approximately +80°C.
A compound of formula I can be converted in a manner known per se into another compound of formula I by replacing one or more substituents of the starting compound of formula I in the customary manner by (an)other substituent(s) according to the invention, and by post modification of compounds of with reactions such as oxidation, alkylation, reduction, acylation and other methods known by those skilled in the art.
Depending on the choice of the reaction conditions and starting materials which are suitable in each case, it is possible, for example, in one reaction step only to replace one substituent by another substituent according to the invention, or a plurality of substituents can be replaced by other substituents according to the invention in the same reaction step.
Salts of compounds of formula I can be prepared in a manner known per se. Thus, for example, acid addition salts of compounds of formula I are obtained by treatment with a suitable acid or a suitable ion exchanger reagent and salts with bases are obtained by treatment with a suitable base or with a suitable ion exchanger reagent.
Salts of compounds of formula I can be converted in the customary manner into the free compounds I, acid addition salts, for example, by treatment with a suitable basic compound or with a suitable ion exchanger reagent and salts with bases, for example, by treatment with a suitable acid or with a suitable ion exchanger reagent.
Salts of compounds of formula I can be converted in a manner known per se into other salts of compounds of formula I, acid addition salts, for example, into other acid addition salts, for example by treatment of a salt of inorganic acid such as hydrochloride with a suitable metal salt such as a sodium, barium or silver salt, of an acid, for example with silver acetate, in a suitable solvent in which an inorganic salt which forms, for example silver chloride, is insoluble and thus precipitates from the reaction mixture.
Depending on the procedure or the reaction conditions, the compounds of formula I, which have saltforming properties can be obtained in free form or in the form of salts.
The compounds of formula I and, where appropriate, the tautomers thereof, in each case in free form or in salt form, can be present in the form of one of the isomers which are possible or as a mixture of these, for example in the form of pure isomers, such as antipodes and/or diastereomers, or as isomer mixtures, such as enantiomer mixtures, for example racemates, diastereomer mixtures or racemate mixtures, depending on the number, absolute and relative configuration of asymmetric carbon atoms which occur in the molecule and/or depending on the configuration of non-aromatic double bonds which occur in the molecule; the invention relates to the pure isomers and also to all isomer mixtures which are possible and is to be understood in each case in this sense hereinabove and hereinbelow, even when stereochemical details are not mentioned specifically in each case.
Diastereomer mixtures or racemate mixtures of compounds of formula I, in free form or in salt form, which can be obtained depending on which starting materials and procedures have been chosen can be separated in a known manner into the pure diasteromers or racemates on the basis of the physicochemical differences of the components, for example by fractional crystallization, distillation and/or chromatography.
Enantiomer mixtures, such as racemates, which can be obtained in a similar manner can be resolved into the optical antipodes by known methods, for example by recrystallization from an optically active solvent, by chromatography on chiral adsorbents, for example high-performance liquid chromatography (HPLC) on acetyl celulose, with the aid of suitable microorganisms, by cleavage with specific, immobilized enzymes, via the formation of inclusion compounds, for example using chiral crown ethers, where only one enantiomer is complexed, or by conversion into diastereomeric salts, for example by reacting a basic end-product racemate with an optically active acid, such as a carboxylic acid, for example camphor, tartaric or malic acid, or sulfonic acid, for example camphorsulfonic acid, and separating the diastereomer mixture which can be obtained in this manner, for example by fractional crystallization based on their differing solubilities, to give the diastereomers, from which the desired enantiomer can be set free by the action of suitable agents, for example basic agents.
Pure diastereomers or enantiomers can be obtained according to the invention not only by separating suitable isomer mixtures, but also by generally known methods of diastereoselective or enantioselective synthesis, for example by carrying out the process according to the invention with starting materials of a suitable stereochemistry. N-oxides can be prepared by reacting a compound of the formula I with a suitable oxidizing agent, for example the H2C>2/urea adduct in the presence of an acid anhydride, e.g. trifluoroacetic anhydride. Such oxidations are known from the literature, for example from J. Med. Chem., 32 (12), 2561-73, 1989 or WO 2000/15615.
It is advantageous to isolate or synthesize in each case the biologically more effective isomer, for example enantiomer or diastereomer, or isomer mixture, for example enantiomer mixture or diastereomer mixture, if the individual components have a different biological activity.
The compounds of formula I and, where appropriate, the tautomers thereof, in each case in free form or in salt form, can, if appropriate, also be obtained in the form of hydrates and/or include other solvents, for example those which may have been used for the crystallization of compounds which are present in solid form.
The compounds according to the following Tables A-1 to A-12 and Tables B-1 to B-12 below can be prepared according to the methods described above. The examples which follow are intended to illustrate the invention and show preferred compounds of formula I.
The tables A-1 to A-6 below illustrate specific compounds of the invention.
Figure imgf000028_0001
Table Y: Substituent definitions of Y
Figure imgf000028_0002
Figure imgf000029_0001
Table A-1 provides 18 compounds A-1 .001 to A-1 .018 of formula l-la wherein Ri is CH2CH3, R2 is CH2CF2CF3, X is S and Y1 is Y as defined in table Y.
Table A-2 provides 18 compounds A-2.001 to A-2.018 of formula l-la wherein R1 is CH2CH3, R2 is CH2CF2CF3, X is SO and Y1 is Y as defined in table Y.
Table A-3 provides 18 compounds A-3.001 to A-3.018 of formula l-la wherein R1 is CH2CH3, R2 is CH2CF2CF3, X is SO2 and Y1 is Y as defined in table Y.
Table A-4 provides 18 compounds A-4.001 to A-4.018 of formula l-la wherein R1 is CH2CH3, R2 is CH2CF2CHF2, X is S and Y1 is Y as defined in table Y.
Table A-5 provides 18 compounds A-5.001 to A-5.018 of formula l-la wherein R1 is CH2CH3, R2 is CH2CF2CHF2, X is SO and Y1 is Y as defined in table Y.
Table A-6 provides 18 compounds A-6.001 to A-6.018 of formula l-la wherein R1 is CH2CH3, R2 is CH2CF2CHF2, X is SO2 and Y1 is Y as defined in table Y.
The tables B-1 to B-6 below further illustrate specific compounds of the invention.
Table B-1 provides 18 compounds B-1 .001 to B-1.018 of formula l-la wherein R1 is CH2CH3, R2 is CH2CH2CF3, X is S and Y1 is Y as defined in table Y.
Table B-2 provides 18 compounds B-2.001 to B-2.018 of formula l-la wherein R1 is CH2CH3, R2 is CH2CH2CF3, X is SO and Y1 is Y as defined in table Y.
Table B-3 provides 18 compounds B-3.001 to B-3.018 of formula l-la wherein R1 is CH2CH3, R2 is CH2CH2CF3, X is SO2 and Y1 is Y as defined in table Y.
Table B-4 provides 18 compounds B-4.001 to B-4.018 of formula l-la wherein R1 is CH2CH3, R2 is CH2CF3, X is S and Y1 is Y as defined in table Y.
Table B-5 provides 18 compounds B-5.001 to B-5.018 of formula l-la wherein R1 is CH2CH3, R2 is CH2CF3, X is SO and Y1 is Y as defined in table Y.
Table B-6 provides 18 compounds B-6.001 to B-6.018 of formula l-la wherein R1 is CH2CH3, R2 is CH2CF3, X is SO2 and Y1 is Y as defined in table Y.
The tables A- 7 to A-12 below illustrate specific compounds of the invention.
Figure imgf000030_0001
Table A- 7 provides 18 compounds A-7.001 to A-7.018 of formula l-2a wherein Ri is CH2CH3, R2 is CH2CF2CF3, X is S and Y2 is Y as defined in table Y.
Table A-8 provides 18 compounds A-8.001 to A-8.018 of formula l-2a wherein R1 is CH2CH3, R2 is CH2CF2CF3, X is SO and Y2 is Y as defined in table Y.
Table A-9 provides 18 compounds A-9.001 to A-9.018 of formula l-2a wherein R1 is CH2CH3, R2 is CH2CF2CF3, X is SO2 and Y2 is Y as defined in table Y.
Table A-10 provides 18 compounds A-10.001 to A-10.018 of formula l-2a wherein R1 is CH2CH3, R2 is CH2CF2CHF2, X is S and Y2 is Y as defined in table Y.
Table A-11 provides 18 compounds A-11 .001 to A-11 .018 of formula l-2a wherein R1 is CH2CH3, R2 is CH2CF2CHF2, X is SO and Y2 is Y as defined in table Y.
Table A-12 provides 18 compounds A-12.001 to A-12.018 of formula l-2a wherein R1 is CH2CH3, R2 is CH2CF2CHF2, X is SO2 and Y2 is Y as defined in table Y.
The tables B-7 to B-12 below further illustrate specific compounds of the invention.
Table B-7 provides 18 compounds B-7.001 to B-7.018 of formula l-2a wherein R1 is CH2CH3, R2 is CH2CH2CF3, X is S and Y2 is Y as defined in table Y.
Table B-8 provides 18 compounds B-8.001 to B-8.018 of formula l-2a wherein R1 is CH2CH3, R2 is CH2CH2CF3, X is SO and Y2 is Y as defined in table Y.
Table B-9 provides 18 compounds B-9.001 to B-9.018 of formula l-2a wherein R1 is CH2CH3, R2 is CH2CH2CF3, X is SO2 and Y2 is Y as defined in table Y.
Table B-10 provides 18 compounds B-10.001 to B-10.018 of formula l-2a wherein R1 is CH2CH3, R2 is CH2CF3, X is S and Y2 is Y as defined in table Y.
Table B-11 provides 18 compounds B-11.001 to B-11.018 of formula l-2a wherein R1 is CH2CH3, R2 is CH2CF3, X is SO and Y2 is Y as defined in table Y.
Table B-12 provides 18 compounds B-12.001 to B-12.018 of formula l-2a wherein R1 is CH2CH3, R2 is CH2CF3, X is SO2 and Y2 is Y as defined in table Y. The compounds of formula I according to the invention are preventively and/or curatively valuable active ingredients in the field of pest control, even at low rates of application, which have a very favorable biocidal spectrum and are well tolerated by warm-blooded species, fish and plants. The active ingredients according to the invention act against all or individual developmental stages of normally sensitive, but also resistant, animal pests, such as insects or representatives of the order Acarina. The insecticidal or acaricidal activity of the active ingredients according to the invention can manifest itself directly, i. e. in destruction of the pests, which takes place either immediately or only after some time has elapsed, for example during ecdysis, or indirectly, for example in a reduced oviposition and/or hatching rate, a good activity corresponding to a destruction rate (mortality) of at least 50 to 60%.
Examples of the above mentioned animal pests are: from the order Acarina, for example,
Acalitus spp, Aculus spp, Acaricalus spp, Aceria spp, Acarus siro, Amblyomma spp., Argas spp., Boophilus spp., Brevipalpus spp., Bryobia spp, Calipitrimerus spp., Chorioptes spp., Dermanyssus gallinae, Dermatophagoides spp, Eotetranychus spp, Eriophyes spp., Hemitarsonemus spp, Hyalomma spp., Ixodes spp., Olygonychus spp, Ornithodoros spp., Polyphagotarsone latus, Panonychus spp., Phyllocoptruta oleivora, Phytonemus spp, Polyphagotarsonemus spp, Psoroptes spp., Rhipicephalus spp., Rhizoglyphus spp., Sarcoptes spp., Steneotarsonemus spp, Tarsonemus spp. and Tetranychus spp.; from the order Anoplura, for example, Haematopinus spp., Linognathus spp., Pediculus spp., Pemphigus spp. and Phylloxera spp.; from the order Coleoptera, for example,
Agriotes spp., Amphimallon majale, Anomala orientalis, Anthonomus spp., Aphodius spp, Astylus atromaculatus, Ataenius spp, Atomaria linearis, Chaetocnema tibialis, Cerotoma spp, Conoderus spp, Cosmopolites spp., Cotinis nitida, Curculio spp., Cyclocephala spp, Dermestes spp., Diabrotica spp., Diloboderus abderus, Epilachna spp., Eremnus spp., Heteronychus arator, Hypothenemus hampei, Lagria vilosa, Leptinotarsa decemLineata, Lissorhoptrus spp., Liogenys spp, Maecolaspis spp, Maladera castanea, Megascelis spp, Melighetes aeneus, Melolontha spp., Myochrous armatus, Orycaephilus spp., Otiorhynchus spp., Phyllophaga spp, Phlyctinus spp., Popillia spp., Psylliodes spp., Rhyssomatus aubtilis, Rhizopertha spp., Scarabeidae, Sitophilus spp., Sitotroga spp., Somaticus spp, Sphenophorus spp, Sternechus subsignatus, Tenebrio spp., Tribolium spp. and Trogoderma spp.; from the order Diptera, for example,
Aedes spp., Anopheles spp, Antherigona soccata.Bactrocea oleae, Bibio hortulanus, Bradysia spp, Calliphora erythrocephala, Ceratitis spp., Chrysomyia spp., Culex spp., Cuterebra spp., Dacus spp., Delia spp, Drosophila melanogaster, Fannia spp., Gastrophilus spp., Geomyza tripunctata, Glossina spp., Hypoderma spp., Hyppobosca spp., Liriomyza spp., Lucilia spp., Melanagromyza spp., Musca spp., Oestrus spp., Orseolia spp., Oscinella frit, Pegomyia hyoscyami, Phorbia spp., Rhagoletis spp, Rivelia quadrifasciata, Scatella spp, Sciara spp., Stomoxys spp., Tabanus spp., Tannia spp. and Tipula spp.; from the order Hemiptera, for example, Acanthocoris scabrator, Acrosternum spp, Adelphocoris lineolatus, Amblypelta nitida, Bathycoelia thalassina, Blissus spp, Cimex spp., Clavigralla tomentosicollis, Creontiades spp, Distantiella theobroma, Dichelops furcatus, Dysdercus spp., Edessa spp, Euschistus spp., Eurydema pulchrum, Eurygaster spp., Halyomorpha halys, Horcias nobilellus, Leptocorisa spp., Lygus spp, Margarodes spp, Murgantia histrionic, Neomegalotomus spp, Nesidiocoris tenuis, Nezara spp., Nysius simulans, Oebalus insularis, Piesma spp., Piezodorus spp, Rhodnius spp., Sahlbergella singularis, Scaptocoris castanea, Scotinophara spp. , Thyanta spp , Triatoma spp., Vatiga illudens;
Acyrthosium pisum, Adalges spp, Agalliana ensigera, Agonoscena targionii, Aleurodicus spp, Aleurocanthus spp, Aleurolobus barodensis, Aleurothrixus floccosus, Aleyrodes brassicae, Amarasca biguttula, Amritodus atkinsoni, Aonidiella spp., Aphididae, Aphis spp., Aspidiotus spp., Aulacorthum solani, Bactericera cockerelli, Bemisia spp, Brachycaudus spp, Brevicoryne brassicae, Cacopsylla spp, Cavariella aegopodii Scop., Ceroplaster spp., Chrysomphalus aonidium, Chrysomphalus dictyospermi, Cicadella spp, Cofana spectra, Cryptomyzus spp, Cicadulina spp, Coccus hesperidum, Dalbulus maidis, Dialeurodes spp, Diaphorina citri, Diuraphis noxia, Dysaphis spp, Empoasca spp., Eriosoma larigerum, Erythroneura spp., Gascardia spp., Glycaspis brimblecombei, Hyadaphis pseudobrassicae, Hyalopterus spp, Hyperomyzus pallidus, Idioscopus clypealis, Jacobiasca lybica, Laodelphax spp., Lecanium corni, Lepidosaphes spp., Lopaphis erysimi, Lyogenys maidis, Macrosiphum spp., Mahanarva spp, Metcalfa pruinosa, Metopolophium dirhodum, Myndus crudus, Myzus spp., Neotoxoptera sp, Nephotettix spp., Nilaparvata spp., Nippolachnus piri Mats, Odonaspis ruthae, Oregma lanigera Zehnter, Parabemisia myricae, Paratrioza cockerelli, Parlatoria spp., Pemphigus spp., Peregrinus maidis, Perkinsiella spp, Phorodon humuli, Phylloxera spp, Pianococcus spp., Pseudaulacaspis spp., Pseudococcus spp., Pseudatomoscelis seriatus, Psylla spp., Pulvinaria aethiopica, Quadraspidiotus spp., Quesada gigas, Recilia dorsalis, Rhopalosiphum spp., Saissetia spp., Scaphoideus spp., Schizaphis spp., Sitobion spp., Sogatella furcifera, Spissistilus festinus, Tarophagus Proserpina, Toxoptera spp, Trialeurodes spp, Tridiscus sporoboli, Trionymus spp, Trioza erytreae , Unaspis citri, Zygina flammigera, Zyginidia scutellaris, ; from the order Hymenoptera, for example, Acromyrmex, Arge spp, Atta spp., Cephus spp., Diprion spp., Diprionidae, Gilpinia polytoma, Hoplo- campa spp., Lasius spp., Monomorium pharaonis, Neodiprion spp., Pogonomyrmex spp, Slenopsis invicta, Solenopsis spp. and Vespa spp.; from the order Isoptera, for example, Coptotermes spp, Corniternes cumulans, Incisitermes spp, Macrotermes spp, Mastotermes spp, Microtermes spp, Reticulitermes spp.; Solenopsis geminate from the order Lepidoptera, for example,
Acleris spp., Adoxophyes spp., Aegeria spp., Agrotis spp., Alabama argillaceae, Amylois spp., Anticarsia gemmatalis, Archips spp., Argyresthia spp, Argyrotaenia spp., Autographa spp., Bucculatrix thurberiella, Busseola fusca, Cadra cautella, Carposina nipponensis, Chilo spp., Choristoneura spp., Chrysoteuchia topiaria, Clysia ambiguella, Cnaphalocrocis spp., Cnephasia spp., Cochylis spp., Coleophora spp., Colias lesbia, Cosmophila flava, Crambus spp, Crocidolomia binotalis, Cryptophlebia leucotreta, Cydalima perspectalis, Cydia spp., Diaphania perspectalis, Diatraea spp., Diparopsis castanea, Earias spp., Eldana saccharina, Ephestia spp., Epinotia spp, Estigmene acrea, Etiella zinckinella, Eucosma spp., Eupoecilia ambiguella, Euproctis spp., Euxoa spp., Feltia jaculiferia, Grapholita spp., Hedya nubiferana, Heliothis spp., Hellula undalis, Herpetogramma spp, Hyphantria cunea, Keiferia lycopersicella, Lasmopalpus lignosellus, Leucoptera scitella, Lithocollethis spp., Lobesia botrana, Loxostege bifidalis, Lymantria spp., Lyonetia spp., Malacosoma spp., Mamestra brassicae, Manduca sexta, Mythimna spp, Noctua spp, Operophtera spp., Orniodes indica, Ostrinia nubilalis, Pammene spp., Pandemis spp., Panolis flammea, Papaipema nebris, Pectinophora gossypi- ela, Perileucoptera coffeella, Pseudaletia unipuncta, Phthorimaea operculella, Pieris rapae, Pieris spp., Plutella xylostella, Prays spp., Pseudoplusia spp, Rachiplusia nu, Richia albicosta, Scirpophaga spp., Sesamia spp., Sparganothis spp., Spodoptera spp., Sylepta derogate, Synanthedon spp., Thaumetopoea spp., Tortrix spp., Trichoplusia ni, Tuta absoluta, and Yponomeuta spp.; from the order Mallophaga, for example, Damalinea spp. and Trichodectes spp.; from the order Orthoptera, for example, Blatta spp., Blattella spp., Gryllotalpa spp., Leucophaea maderae, Locusta spp., Neocurtilla hexadactyla, Periplaneta spp. , Scapteriscus spp, and Schistocerca spp.; from the order Psocoptera, for example, Liposcelis spp.; from the order Siphonaptera, for example, Ceratophyllus spp., Ctenocephalides spp. and Xenopsylla cheopis; from the order Thysanoptera, for example, Calliothrips phaseoli, Frankliniella spp., Heliothrips spp, Hercinothrips spp., Parthenothrips spp, Scirtothrips aurantii, Sericothrips variabilis, Taeniothrips spp., Thrips spp; from the order Thysanura, for example, Lepisma saccharina.
The active ingredients according to the invention can be used for controlling, i. e. containing or destroying, pests of the abovementioned type which occur in particular on plants, especially on useful plants and ornamentals in agriculture, in horticulture and in forests, or on organs, such as fruits, flowers, foliage, stalks, tubers or roots, of such plants, and in some cases even plant organs which are formed at a later point in time remain protected against these pests.
Suitable target crops are, in particular, cereals, such as wheat, barley, rye, oats, rice, maize or sorghum; beet, such as sugar or fodder beet; fruit, for example pomaceous fruit, stone fruit or soft fruit, such as apples, pears, plums, peaches, almonds, cherries or berries, for example strawberries, raspberries or blackberries; leguminous crops, such as beans, lentils, peas or soya; oil crops, such as oilseed rape, mustard, poppies, olives, sunflowers, coconut, castor, cocoa or ground nuts; cucurbits, such as pumpkins, cucumbers or melons; fibre plants, such as cotton, flax, hemp or jute; citrus fruit, such as oranges, lemons, grapefruit or tangerines; vegetables, such as spinach, lettuce, asparagus, cabbages, carrots, onions, tomatoes, potatoes or bell peppers; Lauraceae, such as avocado, Cinnamonium or camphor; and also tobacco, nuts, coffee, eggplants, sugarcane, tea, pepper, grapevines, hops, the plantain family and latex plants.
The compositions and/or methods of the present invention may be also used on any ornamental and/or vegetable crops, including flowers, shrubs, broad-leaved trees and evergreens.
For example the invention may be used on any of the following ornamental species: Ageratum spp., Alonsoa spp., Anemone spp., Anisodontea capsenisis, Anthemis spp., Antirrhinum spp., Aster spp., Begonia spp. (e.g. B. elatior, B. semperflorens, B. tubereux), Bougainvillea spp., Brachycome spp., Brassica spp. (ornamental), Calceolaria spp., Capsicum annuum, Catharanthus roseus, Canna spp., Centaurea spp., Chrysanthemum spp., Cineraria spp. (C. maritime), Coreopsis spp., Crassula coccinea, Cuphea ignea, Dahlia spp., Delphinium spp., Dicentra spectabilis, Dorotheantus spp., Eustoma grandiflorum, Forsythia spp., Fuchsia spp., Geranium gnaphalium, Gerbera spp., Gomphrena globosa, Heliotropium spp., Helianthus spp., Hibiscus spp., Hortensia spp., Hydrangea spp., Hypoestes phyllostachya, I mpatiens spp. (/. Walleriana), Iresines spp., Kalanchoe spp., Lantana camara, Lavatera trimestris, Leonotis leonurus, Lilium spp., Mesembryanthemum spp., Mimulus spp., Monarda spp., Nemesia spp., Tagetes spp., Dianthus spp. (carnation), Canna spp., Oxalis spp., Bellis spp., Pelargonium spp. (P. peltatum, P. Zonale), Viola spp. (pansy), Petunia spp., Phlox spp., Plecthranthus spp., Poinsettia spp., Parthenocissus spp. (P. quinquefolia, P. tricuspidata), Primula spp., Ranunculus spp., Rhododendron spp., Rosa spp. (rose), Rudbeckia spp., Saintpaulia spp., Salvia spp., Scaevola aemola, Schizanthus wisetonensis, Sedum spp., Solanum spp., Surfinia spp., Tagetes spp., Nicotinia spp., Verbena spp., Zinnia spp. and other bedding plants.
For example the invention may be used on any of the following vegetable species: Allium spp. (A sativum, A., cepa, A. oschaninii, A. Porrum, A. ascalonicum, A. fistulosum), Anthriscus cerefolium, Apium graveolus, Asparagus officinalis, Beta vulgarus, Brassica spp. (B. Oleracea, B. Pekinensis, B. rapa), Capsicum annuum, Cicer arietinum, Cichorium endivia, Cichorum spp. (C. intybus, C. endivia), Citrillus lanatus, Cucumis spp. (C. sativus, C. meld), Cucurbita spp. (C. pepo, C. maxima), Cyanara spp. (C. scolymus, C. cardunculus), Daucus carota, Foeniculum vulgare, Hypericum spp., Lactuca sativa, Lycopersicon spp. (L esculentum, L. lycopersicum), Mentha spp., Ocimum basilicum, Petroselinum crispum, Phaseolus spp. (P. vulgaris, P. coccineus), Pisum sativum, Raphanus sativus, Rheum rhaponticum, Rosemarinus spp., Salvia spp., Scorzonera hispanica, Solanum melongena, Spinacea oleracea, Valerianella spp. (IZ. locusta, V. eriocarpa) and Vicia faba.
Preferred ornamental species include African violet, Begonia, Dahlia, Gerbera, Hydrangea, Verbena, Rosa, Kalanchoe, Poinsettia, Aster, Centaurea, Coreopsis, Delphinium, Monarda, Phlox, Rudbeckia, Sedum, Petunia, Viola, Impatiens, Geranium, Chrysanthemum, Ranunculus, Fuchsia, Salvia, Hortensia, rosemary, sage, St. Johnswort, mint, sweet pepper, tomato and cucumber.
The active ingredients according to the invention are especially suitable for controlling Aphis craccivora, Diabrotica balteata, Heliothis virescens, Myzus persicae, Plutella xylostella and Spodoptera littoralis in cotton, vegetable, maize, rice and soya crops. The active ingredients according to the invention are further especially suitable for controlling Mamestra (preferably in vegetables), Cydia pomonella (preferably in apples), Empoasca(preferably in vegetables, vineyards), Leptinotarsa (preferably in potatos) and Chilo supressalis (preferably in rice).
The active ingredients according to the invention are especially suitable for controlling Aphis craccivora, Diabrotica balteata, Heliothis virescens, Myzus persicae, Plutella xylostella and Spodoptera littoralis in cotton, vegetable, maize, rice and soya crops. The active ingredients according to the invention are further especially suitable for controlling Mamestra (preferably in vegetables), Cydia pomonella (preferably in apples), Empoasca(preferably in vegetables, vineyards), Leptinotarsa (preferably in potatos) and Chilo supressalis (preferably in rice).
In a further aspect, the invention may also relate to a method of controlling damage to plant and parts thereof by plant parasitic nematodes (Endoparasitic-, Semiendoparasitic- and Ectoparasitic nematodes), especially plant parasitic nematodes such as root knot nematodes, Meloidogyne hapla, Meloidogyne incognita, Meloidogyne javanica, Meloidogyne arenaria and other Meloidogyne species; cyst-forming nematodes, Globodera rostochiensis and other Globodera species; Heterodera avenae, Heterodera glycines, Heterodera schachtii, Heterodera trifolii, and other Heterodera species; Seed gall nematodes, Anguina species; Stem and foliar nematodes, Aphelenchoides species; Sting nematodes, Belonolaimus longicaudatus and other Belonolaimus species; Pine nematodes, Bursaphelenchus xylophilus and other Bursaphelenchus species; Ring nematodes, Criconema species, Criconemella species, Criconemoides species, Mesocriconema species; Stem and bulb nematodes, Ditylenchus destructor, Ditylenchus dipsaci and other Ditylenchus species; Awl nematodes, Dolichodorus species; Spiral nematodes, Heliocotylenchus multicinctus and other Helicotylenchus species; Sheath and sheathoid nematodes, Hemicycliophora species and Hemicriconemoides species; Hirshmanniella species; Lance nematodes, Hoploaimus species; false rootknot nematodes, Nacobbus species;
Needle nematodes, Longidorus elongatus and other Longidorus species; Pin nematodes, Pratylenchus species; Lesion nematodes, Pratylenchus neglectus, Pratylenchus penetrans, Pratylenchus curvitatus, Pratylenchus goodeyi and other Pratylenchus species; Burrowing nematodes, Radopholus similis and other Radopholus species; Reniform nematodes, Rotylenchus robustus, Rotylenchus reniformis and other Rotylenchus species; Scutellonema species; Stubby root nematodes, Trichodorus primitivus and other Trichodorus species, Paratrichodorus species; Stunt nematodes, Tylenchorhynchus claytoni, Tylenchorhynchus dubius and other Tylenchorhynchus species; Citrus nematodes, Tylenchulus species; Dagger nematodes, Xiphinema species; and other plant parasitic nematode species, such as Subanguina spp., Hypsoperine spp., Macroposthonia spp., Melinius spp., Punctodera spp., and Quinisulcius spp..
The compounds of the invention may also have activity against the molluscs. Examples of which include, for example, Ampullariidae; Arion (A. ater, A. circumscriptus, A. hortensis, A. rufus); Bradybaenidae (Bradybaena fruticum); Cepaea (C. hortensis, C. Nemoralis); ochlodina; Deroceras (D. agrestis, D. empiricorum, D. laeve, D. reticulatum); Discus (D. rotundatus); Euomphalia; Galba (G. trunculata); Helicelia (H. itala, H. obvia); Helicidae Helicigona arbustorum); Helicodiscus; Helix (H. aperta); Limax (L. cinereoniger, L. flavus, L. marginatus, L. maximus, L. tenellus); Lymnaea; Milax (M. gagates, M. marginatus, M. sowerbyi); Opeas; Pomacea (P. canaticulata); Vallonia and Zanitoides.
The term "crops" is to be understood as including also crop plants which have been so transformed by the use of recombinant DNA techniques that they are capable of synthesising one or more selectively acting toxins, such as are known, for example, from toxin-producing bacteria, especially those of the genus Bacillus.
Toxins that can be expressed by such transgenic plants include, for example, insecticidal proteins, for example insecticidal proteins from Bacillus cereus or Bacillus popilliae; or insecticidal proteins from Bacillus thuringiensis, such as 8-endotoxins, e.g. CrylAb, CrylAc, Cry1 F, Cry1 Fa2, Cry2Ab, Cry3A, Cry3Bb1 or Cry9C, or vegetative insecticidal proteins (Vip), e.g. Vip1 , Vip2, Vip3 or Vip3A; or insecticidal proteins of bacteria colonising nematodes, for example Photorhabdus spp. or Xenorhabdus spp., such as Photorhabdus luminescens, Xenorhabdus nematophilus; toxins produced by animals, such as scorpion toxins, arachnid toxins, wasp toxins and other insect-specific neurotoxins; toxins produced by fungi, such as Streptomycetes toxins, plant lectins, such as pea lectins, barley lectins or snowdrop lectins; agglutinins; proteinase inhibitors, such as trypsin inhibitors, serine protease inhibitors, patatin, cystatin, papain inhibitors; ribosome-inactivating proteins (RIP), such as ricin, maize-RIP, abrin, luffin, saporin or bryodin; steroid metabolism enzymes, such as 3-hydroxysteroidoxidase, ecdysteroid-UDP-glycosyl-transferase, cholesterol oxidases, ecdysone inhibitors, HMG-COA-reductase, ion channel blockers, such as blockers of sodium or calcium channels, juvenile hormone esterase, diuretic hormone receptors, stilbene synthase, bibenzyl synthase, chitinases and glucanases.
In the context of the present invention there are to be understood by 8-endotoxins, for example CrylAb, CrylAc, Cry1 F, Cry1 Fa2, Cry2Ab, Cry3A, Cry3Bb1 or Cry9C, or vegetative insecticidal proteins (Vip), for example Vip1 , Vip2, Vip3 or Vip3A, expressly also hybrid toxins, truncated toxins and modified toxins. Hybrid toxins are produced recombinantly by a new combination of different domains of those proteins (see, for example, WO 02/15701). Truncated toxins, for example a truncated CrylAb, are known. In the case of modified toxins, one or more amino acids of the naturally occurring toxin are replaced. In such amino acid replacements, preferably non-naturally present protease recognition sequences are inserted into the toxin, such as, for example, in the case of Cry3A055, a cathepsin-G-recognition sequence is inserted into a Cry3A toxin (see WO 03/018810). Examples of such toxins or transgenic plants capable of synthesising such toxins are disclosed, for example, in EP-A-0 374 753, WO 93/07278, WO 95/34656, EP-A-0 427 529, EP-A-451 878 and WO 03/052073.
The processes for the preparation of such transgenic plants are generally known to the person skilled in the art and are described, for example, in the publications mentioned above. Cryl-type deoxyribonucleic acids and their preparation are known, for example, from WO 95/34656, EP-A-0 367 474, EP-A-0 401 979 and WO 90/13651.
The toxin contained in the transgenic plants imparts to the plants tolerance to harmful insects. Such insects can occur in any taxonomic group of insects, but are especially commonly found in the beetles (Coleoptera), two-winged insects (Diptera) and moths (Lepidoptera).
Transgenic plants containing one or more genes that code for an insecticidal resistance and express one or more toxins are known and some of them are commercially available. Examples of such plants are: YieldGard® (maize variety that expresses a Cry1 Ab toxin); YieldGard Rootworm® (maize variety that expresses a Cry3Bb1 toxin); YieldGard Plus® (maize variety that expresses a Cry1 Ab and a Cry3Bb1 toxin); Starlink® (maize variety that expresses a Cry9C toxin); Herculex I® (maize variety that expresses a Cry1 Fa2 toxin and the enzyme phosphinothricine N-acetyltransferase (PAT) to achieve tolerance to the herbicide glufosinate ammonium); NuCOTN 33B® (cotton variety that expresses a Cry1 Ac toxin); Bollgard I® (cotton variety that expresses a Cry1 Ac toxin); Bollgard II® (cotton variety that expresses a Cry1 Ac and a Cry2Ab toxin); VipCot® (cotton variety that expresses a Vip3A and a Cry1 Ab toxin); NewLeaf® (potato variety that expresses a Cry3A toxin); NatureGard®, Agrisure® GT Advantage (GA21 glyphosate-tolerant trait), Agrisure® CB Advantage (Bt11 corn borer (CB) trait) and Protecta®.
Further examples of such transgenic crops are:
1. Bt11 Maize from Syngenta Seeds SAS, Chemin de I'Hobit 27, F-31 790 St. Sauveur, France, registration number C/FR/96/05/10. Genetically modified Zea mays which has been rendered resistant to attack by the European corn borer (Ostrinia nubilalis and Sesamia nonagrioides) by transgenic expression of a truncated Cry1 Ab toxin. Bt11 maize also transgenically expresses the enzyme PAT to achieve tolerance to the herbicide glufosinate ammonium.
2. Bt176 Maize from Syngenta Seeds SAS, Chemin de I'Hobit 27, F-31 790 St. Sauveur, France, registration number C/FR/96/05/10. Genetically modified Zea mays which has been rendered resistant to attack by the European corn borer (Ostrinia nubilalis and Sesamia nonagrioides) by transgenic expression of a CrylAb toxin. Bt176 maize also transgenically expresses the enzyme PAT to achieve tolerance to the herbicide glufosinate ammonium.
3. MIR604 Maize from Syngenta Seeds SAS, Chemin de I'Hobit 27, F-31 790 St. Sauveur, France, registration number C/FR/96/05/10. Maize which has been rendered insect-resistant by transgenic expression of a modified Cry3A toxin. This toxin is Cry3A055 modified by insertion of a cathepsin-G- protease recognition sequence. The preparation of such transgenic maize plants is described in WO 03/018810.
4. MON 863 Maize from Monsanto Europe S.A. 270-272 Avenue de Tervuren, B-1150 Brussels, Belgium, registration number C/DE/02/9. MON 863 expresses a Cry3Bb1 toxin and has resistance to certain Coleoptera insects.
5. IPC 531 Cotton from Monsanto Europe S.A. 270-272 Avenue de Tervuren, B-1150 Brussels, Belgium, registration number C/ES/96/02.
6. 1507 Maize from Pioneer Overseas Corporation, Avenue Tedesco, 7 B-1160 Brussels, Belgium, registration number C/NL/00/10. Genetically modified maize for the expression of the protein Cry1 F for achieving resistance to certain Lepidoptera insects and of the PAT protein for achieving tolerance to the herbicide glufosinate ammonium.
7. NK603 x MON 810 Maize from Monsanto Europe S.A. 270-272 Avenue de Tervuren, B-1150 Brussels, Belgium, registration number C/GB/02/M3/03. Consists of conventionally bred hybrid maize varieties by crossing the genetically modified varieties NK603 and MON 810. NK603 x MON 810 Maize transgenically expresses the protein CP4 EPSPS, obtained from Agrobacterium sp. strain CP4, which imparts tolerance to the herbicide Roundup® (contains glyphosate), and also a Cry1 Ab toxin obtained from Bacillus thuringiensis subsp. kurstaki which brings about tolerance to certain Lepidoptera, include the European corn borer.
Transgenic crops of insect-resistant plants are also described in BATS (Zentrum fur Biosicherheit und Nachhaltigkeit, Zentrum BATS, Clarastrasse 13, 4058 Basel, Switzerland) Report 2003, (http://bats.ch).
The term "crops" is to be understood as including also crop plants which have been so transformed by the use of recombinant DNA techniques that they are capable of synthesising antipathogenic substances having a selective action, such as, for example, the so-called "pathogenesis-related proteins" (PRPs, see e.g. EP-A-0 392 225). Examples of such antipathogenic substances and transgenic plants capable of synthesising such antipathogenic substances are known, for example, from EP-A-0 392225, WO 95/33818 and EP-A-0 353 191. The methods of producing such transgenic plants are generally known to the person skilled in the art and are described, for example, in the publications mentioned above.
Crops may also be modified for enhanced resistance to fungal (for example Fusarium, Anthracnose, or Phytophthora), bacterial (for example Pseudomonas) or viral (for example potato leafroll virus, tomato spotted wilt virus, cucumber mosaic virus) pathogens.
Crops also include those that have enhanced resistance to nematodes, such as the soybean cyst nematode.
Crops that are tolerance to abiotic stress include those that have enhanced tolerance to drought, high salt, high temperature, chill, frost, or light radiation, for example through expression of NF-YB or other proteins known in the art. Antipathogenic substances which can be expressed by such transgenic plants include, for example, ion channel blockers, such as blockers for sodium and calcium channels, for example the viral KP1 , KP4 or KP6 toxins; stilbene synthases; bibenzyl synthases; chitinases; glucanases; the so-called "pathogenesis-related proteins" (PRPs; see e.g. EP-A-0 392 225); antipathogenic substances produced by microorganisms, for example peptide antibiotics or heterocyclic antibiotics (see e.g.
WO 95/33818) or protein or polypeptide factors involved in plant pathogen defence (so-called "plant disease resistance genes", as described in WO 03/000906).
Further areas of use of the compositions according to the invention are the protection of stored goods and store rooms and the protection of raw materials, such as wood, textiles, floor coverings or buildings, and also in the hygiene sector, especially the protection of humans, domestic animals and productive livestock against pests of the mentioned type.
The present invention also provides a method for controlling pests (such as mosquitoes and other disease vectors; see also http://www.who.int/malaria/vector_control/irs/en/). In one embodiment, the method for controlling pests comprises applying the compositions of the invention to the target pests, to their locus or to a surface or substrate by brushing, rolling, spraying, spreading or dipping. By way of example, an IRS (indoor residual spraying) application of a surface such as a wall, ceiling or floor surface is contemplated by the method of the invention. In another embodiment, it is contemplated to apply such compositions to a substrate such as non-woven or a fabric material in the form of (or which can be used in the manufacture of) netting, clothing, bedding, curtains and tents.
In one embodiment, the method for controlling such pests comprises applying a pesticidally effective amount of the compositions of the invention to the target pests, to their locus, or to a surface or substrate so as to provide effective residual pesticidal activity on the surface or substrate. Such application may be made by brushing, rolling, spraying, spreading or dipping the pesticidal composition of the invention. By way of example, an IRS application of a surface such as a wall, ceiling or floor surface is contemplated by the method of the invention so as to provide effective residual pesticidal activity on the surface. In another embodiment, it is contemplated to apply such compositions for residual control of pests on a substrate such as a fabric material in the form of (or which can be used in the manufacture of) netting, clothing, bedding, curtains and tents.
Substrates including non-woven, fabrics or netting to be treated may be made of natural fibres such as cotton, raffia, jute, flax, sisal, hessian, or wool, or synthetic fibres such as polyamide, polyester, polypropylene, polyacrylonitrile or the like. The polyesters are particularly suitable. The methods of textile treatment are known, e.g. WO 2008/151984, WO 2003/034823, US 5631072, WO 2005/64072, W02006/128870, EP 1724392, WO 2005113886 or WO 2007/090739. Further areas of use of the compositions according to the invention are the field of tree injection/trunk treatment for all ornamental trees as well all sort of fruit and nut trees.
In the field of tree injection/trunk treatment, the compounds according to the present invention are especially suitable against wood-boring insects from the order Lepidoptera as mentioned above and from the order Coleoptera, especially against woodborers listed in the following tables A and B:
Table A. Examples of exotic woodborers of economic importance.
Figure imgf000040_0001
Table B. Examples of native woodborers of economic importance.
Figure imgf000040_0002
Figure imgf000041_0001
Figure imgf000042_0001
The present invention may be also used to control any insect pests that may be present in turfgrass, including for example beetles, caterpillars, fire ants, ground pearls, millipedes, sow bugs, mites, mole crickets, scales, mealybugs ticks, spittlebugs, southern chinch bugs and white grubs. The present invention may be used to control insect pests at various stages of their life cycle, including eggs, larvae, nymphs and adults.
In particular, the present invention may be used to control insect pests that feed on the roots of turfgrass including white grubs (such as Cyclocephala spp. (e.g. masked chafer, C. lurida), Rhizotrogus spp. (e.g. European chafer, R. majalis), Cotinus spp. (e.g. Green June beetle, C. nitida), Popillia spp. (e.g. Japanese beetle, P. japonica), Phyllophaga spp. (e.g. May/June beetle), Ataenius spp. (e.g. Black turfgrass ataenius, A. spretulus), Maladera spp. (e.g. Asiatic garden beetle, M. castanea) and Tomarus spp.), ground pearls (Margarodes spp.), mole crickets (tawny, southern, and short-winged; Scapteriscus spp., Gryllotalpa africana) and leatherjackets (European crane fly, Tipula spp.).
The present invention may also be used to control insect pests of turfgrass that are thatch dwelling, including armyworms (such as fall armyworm Spodoptera frugiperda, and common armyworm Pseudaletia unipuncta), cutworms, billbugs (Sphenophorus spp., such as S. venatus verstitus and S. parvulus), and sod webworms (such as Crambus spp. and the tropical sod webworm, Herpetogramma phaeopteralis).
The present invention may also be used to control insect pests of turfgrass that live above the ground and feed on the turfgrass leaves, including chinch bugs (such as southern chinch bugs, B/issus insularis), Bermudagrass mite (Eriophyes cynodoniensis), rhodesgrass mealybug (Antonina graminis), two-lined spittlebug (Propsapia bicincta), leafhoppers, cutworms (Noctuidae family), and greenbugs. The present invention may also be used to control other pests of turfgrass such as red imported fire ants (Solenopsis invicta) that create ant mounds in turf.
In the hygiene sector, the compositions according to the invention are active against ectoparasites such as hard ticks, soft ticks, mange mites, harvest mites, flies (biting and licking), parasitic fly larvae, lice, hair lice, bird lice and fleas.
Examples of such parasites are:
Of the order Anoplurida: Haematopinus spp., Linognathus spp., Pediculus spp. and Phtirus spp., Solenopotes spp..
Of the order Mallophagida: Trimenopon spp., Menopon spp., Trinoton spp., Bovicola spp., Werneckiella spp., Lepikentron spp., Damalina spp., Trichodectes spp. and Felicola spp..
Of the order Diptera and the suborders Nematocerina and Brachycerina, for example Aedes spp., Anopheles spp., Culex spp., Simulium spp., Eusimulium spp., Phlebotomus spp., Lutzomyia spp., Culicoides spp., Chrysops spp., Hybomitra spp., Atylotus spp., Tabanus spp., Haematopota spp., Philipomyia spp., Braula spp., Musca spp., Hydrotaea spp., Stomoxys spp., Haematobia spp., Morellia spp., Fannia spp., Glossina spp., Calliphora spp., Lucilia spp., Chrysomyia spp., Wohlfahrtia spp., Sarcophaga spp., Oestrus spp., Hypoderma spp., Gasterophilus spp., Hippobosca spp., Lipoptena spp. and Melophagus spp..
Of the order Siphonapterida, for example Pulex spp., Ctenocephalides spp., Xenopsylla spp., Ceratophyllus spp..
Of the order Heteropterida, for example Cimex spp., Triatoma spp., Rhodnius spp., Panstrongylus spp..
Of the order Blattarida, for example Blatta orientalis, Periplaneta americana, Blattelagermanica and Supella spp..
Of the subclass Acaria (Acarida) and the orders Meta- and Meso-stigmata, for example Argas spp., Ornithodorus spp., Otobius spp., Ixodes spp., Amblyomma spp., Boophilus spp., Dermacentor spp., Haemophysalis spp., Hyalomma spp., Rhipicephalus spp., Dermanyssus spp., Raillietia spp., Pneumonyssus spp., Sternostoma spp. and Varroa spp..
Of the orders Actinedida (Prostigmata) and Acaridida (Astigmata), for example Acarapis spp., Cheyletiella spp., Ornithocheyletia spp., Myobia spp., Psorergatesspp., Demodex spp., Trombicula spp., Listrophorus spp., Acarus spp., Tyrophagus spp., Caloglyphus spp., Hypodectes spp., Pterolichus spp., Psoroptes spp., Chorioptes spp., Otodectes spp., Sarcoptes spp., Notoedres spp., Knemidocoptes spp., Cytodites spp. and Laminosioptes spp..
The compositions according to the invention are also suitable for protecting against insect infestation in the case of materials such as wood, textiles, plastics, adhesives, glues, paints, paper and card, leather, floor coverings and buildings.
The compositions according to the invention can be used, for example, against the following pests: beetles such as Hylotrupes bajulus, Chlorophorus pilosis, Anobium punctatum, Xestobium rufovillosum, Ptilinuspecticornis, Dendrobium pertinex, Ernobius mollis, Priobium carpini, Lyctus brunneus, Lyctus africanus, Lyctus planicollis, Lyctus linearis, Lyctus pubescens, Trogoxylon aequale, Minthesrugicollis, Xyleborus spec.,Tryptodendron spec., Apate monachus, Bostrychus capucins, Heterobostrychus brunneus, Sinoxylon spec, and Dinoderus minutus, and also hymenopterans such as Sirex juvencus, Urocerus gigas, Urocerus gigas taignus and Urocerus augur, and termites such as Kalotermes flavicollis, Cryptotermes brevis, Heterotermes indicola, Reticulitermes flavipes, Reticulitermes santonensis, Reticulitermes lucifugus, Mastotermes darwiniensis, Zootermopsis nevadensis and Coptotermes formosanus, and bristletails such as Lepisma saccharina.
The compounds according to the invention can be used as pesticidal agents in unmodified form, but they are generally formulated into compositions in various ways using formulation adjuvants, such as carriers, solvents and surface-active substances. The formulations can be in various physical forms, e.g. in the form of dusting powders, gels, wettable powders, water-dispersible granules, water- dispersible tablets, effervescent pellets, emulsifiable concentrates, microemulsifiable concentrates, oil- in-water emulsions, oil-flowables, aqueous dispersions, oily dispersions, suspo-emulsions, capsule suspensions, emulsifiable granules, soluble liquids, water-soluble concentrates (with water or a water- miscible organic solvent as carrier), impregnated polymer films or in other forms known e.g. from the Manual on Development and Use of FAO and WHO Specifications for Pesticides, United Nations, First Edition, Second Revision (2010). Such formulations can either be used directly or diluted prior to use. The dilutions can be made, for example, with water, liquid fertilisers, micronutrients, biological organisms, oil or solvents.
The formulations can be prepared e.g. by mixing the active ingredient with the formulation adjuvants in order to obtain compositions in the form of finely divided solids, granules, solutions, dispersions or emulsions. The active ingredients can also be formulated with other adjuvants, such as finely divided solids, mineral oils, oils of vegetable or animal origin, modified oils of vegetable or animal origin, organic solvents, water, surface-active substances or combinations thereof.
The active ingredients can also be contained in very fine microcapsules. Microcapsules contain the active ingredients in a porous carrier. This enables the active ingredients to be released into the environment in controlled amounts (e.g. slow-release). Microcapsules usually have a diameter of from 0.1 to 500 microns. They contain active ingredients in an amount of about from 25 to 95 % by weight of the capsule weight. The active ingredients can be in the form of a monolithic solid, in the form of fine particles in solid or liquid dispersion or in the form of a suitable solution. The encapsulating membranes can comprise, for example, natural or synthetic rubbers, cellulose, styrene/butadiene copolymers, polyacrylonitrile, polyacrylate, polyesters, polyamides, polyureas, polyurethane or chemically modified polymers and starch xanthates or other polymers that are known to the person skilled in the art. Alternatively, very fine microcapsules can be formed in which the active ingredient is contained in the form of finely divided particles in a solid matrix of base substance, but the microcapsules are not themselves encapsulated.
The formulation adjuvants that are suitable for the preparation of the compositions according to the invention are known perse. As liquid carriers there may be used: water, toluene, xylene, petroleum ether, vegetable oils, acetone, methyl ethyl ketone, cyclohexanone, acid anhydrides, acetonitrile, acetophenone, amyl acetate, 2-butanone, butylene carbonate, chlorobenzene, cyclohexane, cyclohexanol, alkyl esters of acetic acid, diacetone alcohol, 1 ,2-dichloropropane, diethanolamine, p- diethylbenzene, diethylene glycol, diethylene glycol abietate, diethylene glycol butyl ether, diethylene glycol ethyl ether, diethylene glycol methyl ether, A/,A/-dimethylformamide, dimethyl sulfoxide, 1 ,4- dioxane, dipropylene glycol, dipropylene glycol methyl ether, dipropylene glycol dibenzoate, diproxitol, alkylpyrrolidone, ethyl acetate, 2-ethylhexanol, ethylene carbonate, 1 ,1 ,1-trichloroethane, 2- heptanone, alpha-pinene, d-limonene, ethyl lactate, ethylene glycol, ethylene glycol butyl ether, ethylene glycol methyl ether, gamma-butyrolactone, glycerol, glycerol acetate, glycerol diacetate, glycerol triacetate, hexadecane, hexylene glycol, isoamyl acetate, isobornyl acetate, isooctane, isophorone, isopropylbenzene, isopropyl myristate, lactic acid, laurylamine, mesityl oxide, methoxypropanol, methyl isoamyl ketone, methyl isobutyl ketone, methyl laurate, methyl octanoate, methyl oleate, methylene chloride, m-xylene, n-hexane, n-octylamine, octadecanoic acid, octylamine acetate, oleic acid, oleylamine, o-xylene, phenol, polyethylene glycol, propionic acid, propyl lactate, propylene carbonate, propylene glycol, propylene glycol methyl ether, p-xylene, toluene, triethyl phosphate, triethylene glycol, xylenesulfonic acid, paraffin, mineral oil, trichloroethylene, perchloroethylene, ethyl acetate, amyl acetate, butyl acetate, propylene glycol methyl ether, diethylene glycol methyl ether, methanol, ethanol, isopropanol, and alcohols of higher molecular weight, such as amyl alcohol, tetra hydrofurfuryl alcohol, hexanol, octanol, ethylene glycol, propylene glycol, glycerol, A/-methyl-2- pyrrolidone and the like.
Suitable solid carriers are, for example, talc, titanium dioxide, pyrophyllite clay, silica, attapulgite clay, kieselguhr, limestone, calcium carbonate, bentonite, calcium montmorillonite, cottonseed husks, wheat flour, soybean flour, pumice, wood flour, ground walnut shells, lignin and similar substances.
A large number of surface-active substances can advantageously be used in both solid and liquid formulations, especially in those formulations which can be diluted with a carrier prior to use. Surfaceactive substances may be anionic, cationic, non-ionic or polymeric and they can be used as emulsifiers, wetting agents or suspending agents or for other purposes. Typical surface-active substances include, for example, salts of alkyl sulfates, such as diethanolammonium lauryl sulfate; salts of alkylarylsulfonates, such as calcium dodecylbenzenesulfonate; alkylphenol/alkylene oxide addition products, such as nonylphenol ethoxylate; alcohol/alkylene oxide addition products, such as tridecylalcohol ethoxylate; soaps, such as sodium stearate; salts of alkylnaphthalenesulfonates, such as sodium dibutylnaphthalenesulfonate; dialkyl esters of sulfosuccinate salts, such as sodium di(2- ethylhexyl)sulfosuccinate; sorbitol esters, such as sorbitol oleate; quaternary amines, such as lauryltrimethylammonium chloride, polyethylene glycol esters of fatty acids, such as polyethylene glycol stearate; block copolymers of ethylene oxide and propylene oxide; and salts of mono- and dialkylphosphate esters; and also further substances described e.g. in McCutcheon's Detergents and Emulsifiers Annual, MC Publishing Corp., Ridgewood New Jersey (1981).
Further adjuvants that can be used in pesticidal formulations include crystallisation inhibitors, viscosity modifiers, suspending agents, dyes, anti-oxidants, foaming agents, light absorbers, mixing auxiliaries, antifoams, complexing agents, neutralising or pH-modifying substances and buffers, corrosion inhibitors, fragrances, wetting agents, take-up enhancers, micronutrients, plasticisers, glidants, lubricants, dispersants, thickeners, antifreezes, microbicides, and liquid and solid fertilisers. The compositions according to the invention can include an additive comprising an oil of vegetable or animal origin, a mineral oil, alkyl esters of such oils or mixtures of such oils and oil derivatives. The amount of oil additive in the composition according to the invention is generally from 0.01 to 10 %, based on the mixture to be applied. For example, the oil additive can be added to a spray tank in the desired concentration after a spray mixture has been prepared. Preferred oil additives comprise mineral oils or an oil of vegetable origin, for example rapeseed oil, olive oil or sunflower oil, emulsified vegetable oil, alkyl esters of oils of vegetable origin, for example the methyl derivatives, or an oil of animal origin, such as fish oil or beef tallow. Preferred oil additives comprise alkyl esters of C8-C22 fatty acids, especially the methyl derivatives of C12-C18 fatty acids, for example the methyl esters of lauric acid, palmitic acid and oleic acid (methyl laurate, methyl palmitate and methyl oleate, respectively). Many oil derivatives are known from the Compendium of Herbicide Adjuvants, 10th Edition, Southern Illinois University, 2010.
The inventive compositions generally comprise from 0.1 to 99 % by weight, especially from 0.1 to 95 % by weight, of compounds of the present invention and from 1 to 99.9 % by weight of a formulation adjuvant which preferably includes from 0 to 25 % by weight of a surface-active substance. Whereas commercial products may preferably be formulated as concentrates, the end user will normally employ dilute formulations.
The rates of application vary within wide limits and depend on the nature of the soil, the method of application, the crop plant, the pest to be controlled, the prevailing climatic conditions, and other factors governed by the method of application, the time of application and the target crop. As a general guideline compounds may be applied at a rate of from 1 to 2000 l/ha, especially from 10 to 1000 l/ha.
Preferred formulations can have the following compositions (weight %):
Emulsifiable concentrates: active ingredient: 1 to 95 %, preferably 60 to 90 % surface-active agent: 1 to 30 %, preferably 5 to 20 % liquid carrier: 1 to 80 %, preferably 1 to 35 %
Dusts: active ingredient: 0.1 to 10 %, preferably 0.1 to 5 % solid carrier: 99.9 to 90 %, preferably 99.9 to 99 %
Suspension concentrates: active ingredient: 5 to 75 %, preferably 10 to 50 % water: 94 to 24 %, preferably 88 to 30 % surface-active agent: 1 to 40 %, preferably 2 to 30 %
Wettable powders: active ingredient: 0.5 to 90 %, preferably 1 to 80 % surface-active agent: 0.5 to 20 %, preferably 1 to 15 % solid carrier: 5 to 95 %, preferably 15 to 90 %
Granules: active ingredient: 0.1 to 30 %, preferably 0.1 to 15 % solid carrier: 99.5 to 70 %, preferably 97 to 85 %
The following Examples further illustrate, but do not limit, the invention.
Figure imgf000048_0001
The combination is thoroughly mixed with the adjuvants and the mixture is thoroughly ground in a suitable mill, affording wettable powders that can be diluted with water to give suspensions of the desired concentration.
Figure imgf000048_0002
The combination is thoroughly mixed with the adjuvants and the mixture is thoroughly ground in a suitable mill, affording powders that can be used directly for seed treatment.
Figure imgf000048_0003
Figure imgf000049_0001
Emulsions of any required dilution, which can be used in plant protection, can be obtained from this concentrate by dilution with water.
Figure imgf000049_0002
Ready-for-use dusts are obtained by mixing the combination with the carrier and grinding the mixture in a suitable mill. Such powders can also be used for dry dressings for seed.
Figure imgf000049_0003
The combination is mixed and ground with the adjuvants, and the mixture is moistened with water.
The mixture is extruded and then dried in a stream of air.
Figure imgf000049_0004
The finely ground combination is uniformly applied, in a mixer, to the kaolin moistened with polyethylene glycol. Non-dusty coated granules are obtained in this manner.
Suspension concentrate
Figure imgf000049_0005
Figure imgf000050_0001
The finely ground combination is intimately mixed with the adjuvants, giving a suspension concentrate from which suspensions of any desired dilution can be obtained by dilution with water. Using such dilutions, living plants as well as plant propagation material can be treated and protected against infestation by microorganisms, by spraying, pouring or immersion.
Flowable concentrate for seed treatment
Figure imgf000050_0002
The finely ground combination is intimately mixed with the adjuvants, giving a suspension concentrate from which suspensions of any desired dilution can be obtained by dilution with water. Using such dilutions, living plants as well as plant propagation material can be treated and protected against infestation by microorganisms, by spraying, pouring or immersion.
Slow Release Capsule Suspension
28 parts of the combination are mixed with 2 parts of an aromatic solvent and 7 parts of toluene diisocyanate/polymethylene-polyphenylisocyanate-mixture (8:1). This mixture is emulsified in a mixture of 1 .2 parts of polyvinylalcohol, 0.05 parts of a defoamer and 51 .6 parts of water until the desired particle size is achieved. To this emulsion a mixture of 2.8 parts 1 ,6-diaminohexane in 5.3 parts of water is added. The mixture is agitated until the polymerization reaction is completed. The obtained capsule suspension is stabilized by adding 0.25 parts of a thickener and 3 parts of a dispersing agent. The capsule suspension formulation contains 28% of the active ingredients. The medium capsule diameter is 8-15 microns. The resulting formulation is applied to seeds as an aqueous suspension in an apparatus suitable forthat purpose.
Formulation types include an emulsion concentrate (EC), a suspension concentrate (SC), a suspo- emulsion (SE), a capsule suspension (CS), a water dispersible granule (WG), an emulsifiable granule (EG), an emulsion, water in oil (EG), an emulsion, oil in water (EW), a micro-emulsion (ME), an oil dispersion (OD), an oil miscible flowable (OF), an oil miscible liquid (OL), a soluble concentrate (SL), an ultra-low volume suspension (SU), an ultra-low volume liquid (UL), a technical concentrate (TK), a dispersible concentrate (DC), a wettable powder (WP), a soluble granule (SG) or any technically feasible formulation in combination with agriculturally acceptable adjuvants.
Figure imgf000051_0001
“Mp” means melting point in °C. Free radicals represent methyl groups. 1 H NMR measurements were recorded on a Brucker 400MHz spectrometer, chemical shifts are given in ppm relevant to a TMS standard. Spectra measured in deuterated solvents as indicated. Either one of the LCMS methods below was used to characterize the compounds. The characteristic LCMS values obtained for each compound were the retention time (“Rt”, recorded in minutes) and the measured molecular ion (M+H)H or (M-H)-.
LCMS Methods:
STANDARD:
Spectra were recorded on a Mass Spectrometer from Waters Corporation (SQD, SQDII or QDA Single quadrupole mass spectrometer) equipped with an electrospray source (Polarity: positive and negative ions), Capillary: 0.8-3.00 kV, Cone: 5-30 V, Source Temperature: 120-150°C, Desolvation Temperature: 350-600°C, Cone Gas Flow: 50-150 l/h, Desolvation Gas Flow: 650-1000 l/h, Mass range: 50 to 900 Da and an Acquity UPLC from Waters Corporation: Binary pump, heated column compartment , diode-array detector and ELSD. Column: Waters UPLC HSS T3, 1 .8 pm, 30 x 2.1 mm, Temp: 60 °C, DAD Wavelength range (nm): 210 to 400, Runtime: 1 .5 min; Solvents: A = water + 5% MeOH + 0.05 % HCOOH, B= Acetonitrile + 0.05 % HCOOH; Flow (ml/min) 0.85, Gradient: 10% B isocratic for 0.2 min, then 10-100% B in 1.0 min, 100% B isocratic for 0.2min, 100-10% B in 0.05min, 10% B isocratic for 0.05 min.
STANDARD LONG:
Spectra were recorded on a Mass Spectrometer from Waters Corporation (SQD, SQDII or QDA Single quadrupole mass spectrometer) equipped with an electrospray source (Polarity: positive and negative ions), Capillary: 0.8-3.00 kV, Cone: 5-30 V, Source Temperature: 120-150°C, Desolvation Temperature: 350-600°C, Cone Gas Flow: 50-150 l/h, Desolvation Gas Flow: 650-1000 l/h, Mass range: 50 to 900 Da and an Acquity UPLC from Waters Corporation: Binary pump, heated column compartment , diode-array detector and ELSD. Column: Waters UPLC HSS T3, 1 .8 pm, 30 x 2.1 mm, Temp: 60 °C, DAD Wavelength range (nm): 210 to 400, Runtime: 3.0 min; Solvents: A = water + 5% MeOH + 0.05 % HCOOH, B= Acetonitrile + 0.05 % HCOOH; Flow (ml/min) 0.85, Gradient: 10% B isocratic for 0.2 min, then 10-100% B in 2.5 min, 100% B isocratic for 0.3min.
Figure imgf000051_0002
Figure imgf000052_0001
Preparation example P1 Preparation example P2
Step 1 : Preparation of 5-bromo-1-(2,2,3,3,3-pentafluoropropyl)pyrazolo[3,4-clpyridine
Figure imgf000052_0002
Potassium carbonate (237 mg, 1.72 mmol, 2.0 eq.) and 2,2,3,3,3-pentafluoropropyl trifluoromethanesulfonate (CAS 6401-00-9) (315 mg, 1.12 mmol, 1.30 eq.) were added to a solution of 5-bromo-1 H- pyrazolo[3,4-c]pyridine (CAS 929617-35-6) (170 mg, 0.86 mmol) in N,N-dimethylformamide (4.30 ml_). After stirring for 2 hours at room temperature, the reaction mixture was poured over water. The aqueous phase was thoroughly extracted with ethyl acetate, the combined organic phases were dried over sodium sulfate, filtered and concentrated. Purification of the crude material by flash chromatography over silica gel (ethyl acetate in cyclohexane) afforded the desired product as a white solid (150 mg). LCMS (standard): m/z=330/332 (M+H)+, RT 0.97 min.
Step 2: Preparation of methyl 1-(2,2,3,3,3-pentafluoropropyl)pyrazolo[3,4-clpyridine-5-carboxylate
Figure imgf000052_0003
5-bromo-1-(2,2,3,3,3-pentafluoropropyl)pyrazolo[3,4-c]pyridine (10.00 g, 30.30 mmol, 1.0 eq.) was dissolved in methanol (140 mL) in an autoclave and triethylamine (6.45 mL, 45.45 mmol, 1.5 eq.) was added, followed by xanthphos (0.37 g, 0.61 mmol, 0.02 eq.) and palladium acetate (0.07 g, 0.30 mmol, 0.01 eq.). The reaction mixture was let react under 5 bar of carbon monoxide at 90°C overnight. The mixture was filtered through celite/hyflo and washed well with methanol. The filtrate was evaporated
SUBSTITUTE SHEET (RULE 26) aqueous half-saturated NH4CI solution. The combined organic layers were dried over MgSO4, filtered and evaporated under vacuo to give the desired product methyl 1 -(2, 2, 3,3,3- pentafluoropropyl)pyrazolo[3,4-c]pyridine-5-carboxylate as a beige solid.
LCMS (standard): RT=0.86 min, m/z=310 (M+H)+ and 373 (M+CH3CN+Na)+
Step 3: Preparation of 1-(2,2,3,3,3-pentafluoropropyl)pyrazolo[3,4-clpyridine-5-carboxylic acid
Figure imgf000053_0001
Methyl 1-(2,2,3,3,3-pentafluoropropyl)pyrazolo[3,4-c]pyridine-5-carboxylate (3.68 g, 11.90 mmol, 1.0 eq.) (synthesis described hereabove) was dissolved in tetrahydrofuran (35.7 mL) and diluted with water (35.7 mL). The mixture was cooled to 0-5°C. Lithium hydroxide monohydrate (0.76 g, 17.90 mmol, 1 .5 eq.) was added. The orange mixture was stirred at 0-5°C. After 1 .5 hours the reaction mixture was carefully poured onto HC1 1 M (50ml). The pH was 1-2. The mixture was extracted 2x between ethyl acetate and HC1 1 M : NH4CI sat. 1 :1. The combined organic layers were dried over MgSO4, filtered and evaporated under vacuo to leave a bright yellow solid. The crude compound was suspended in around 10 mL diisopropylether. The beige suspension was stirred at room temperature for 30 minutes, filtered and the solid was washed with 1x 10 mL diisopropylether and 2x 10ml pentane. The solid was dried on vacuum to give 1-(2,2,3,3,3-pentafluoropropyl)pyrazolo[3,4-c]pyridine-5- carboxylic acid as yellow-beige solid.
LCMS (standard): RT=0.75 min, m/z=296 (M+H)+, 294 (M-H)’ and 589 (2M-H)’
Step 4: Preparation of tert-butyl N-[1-(2, 2,3,3, 3-pentafluoropropyl)pyrazolo[3,4-clpyridin-5- yllcarbamate
Figure imgf000053_0002
1-(2,2,3,3,3-pentafluoropropyl)pyrazolo[3,4-c]pyridine-5-carboxylic acid (3.00 g, 10.00 mmol, 1 .0 eq.) was suspended in tert-butanol (41 mL). Triethylamine (1 .4 mL, 10.00 mmol, 1 .0 eq.) was added, followed by dropwise addition of diphenylphosphoryl azide (2.90 g, 10.00 mmol, 1.0 eq.). The yellow- brown reaction mixture was heated to reflux. After 4 hours the heating was stopped and the mixture was cooled to room temperature. The mixture was extracted twice between ethyl acetate I NaCI sat. The combined organic layers were dried over MgSC>4, filtered and evaporated to give a brown amorphous residue. The crude compound was suspended in diisopropylether, methanol and dichloromethane and the suspension was stirred for 15 minutes. The solid was filtered off, washed with small amount of dichloromethane and methanol, then DIPE and twice with 20 ml pentane. The solid was dried under vacuum to give the title compound as a pale rose solid. The wash solutions were evaporated and the residue which was purified by chromatography with 0- 30% ethyl acetate in cyclohexane to give another portion of the title compound.
LCMS (standard): RT=1.08 min, m/z=367 (M+H)+
Step 5: Preparation of 1-(2, 2,3,3, 3-pentafluoropropyl)pyrazolo[3,4-clpyridin-5-amine
Figure imgf000054_0001
A solution of terf-butyl N-[1-(2,2,3,3,3-pentafluoropropyl)pyrazolo[3,4-c]pyridin-5-yl]carbamate (1.89 g, 5.16 mmol, 1 .0 eq.) dissolved in dichloromethane (48.9 mL) was cooled to 0-5°C and trifluoroacetic acid (8.11 mL, 103.00 mmol, 20.0 eq.) was added and the reaction mixture was stirred at 0-5°C. The clear, bright yellow solution was stirred at room temperature overnight. The reaction mixture was carefully poured onto 200 mL NaHCO3 sat. solution and the mixture was extracted twice with ethyl acetate. The combined organic layers were dried over Na2SO4, filtered and evaporated to give the brown amorphous title compound.
LCMS (standard): RT=0.66 min, m/z=267 (M+H)+
Step 6: Preparation of (E)-1-[2-nitro-4-(trifluoromethyl)phenyl1-N-[1-(2,2,3,3,3- pentafluoropropyl)pyrazolo[3,4-clpyridin-5-yl1methanimine
Figure imgf000054_0002
A mixture of 1-(2, 2,3,3, 3-pentafluoropropyl)pyrazolo[3,4-c]pyridin-5-amine (0.60 g, 2.30 mmol, 1 .0 eq.) and 2-Nitro-4-(trifluoromethyl)benzaldehyde (0.57 g, 2.50 mmol, 1 .1 eq.) were suspended in 2- propanol (6.8 mL) and about 1 g molecular sieve 4A was added. The mixture was heated to reflux for 3 hours. No work-up done. The reaction mixture was kept at reflux and used directly for next step.
Step 7: Preparation of 1-(2,2,3,3,3-pentafluoropropyl)-5-[6-(trifluoromethyl)indazol-2-yllpyrazolo[3,4- clpyridine
Figure imgf000054_0003
To the reaction mixture of step 6, tributylphosphine (1 .60 g, 6.9 mmol, 3.0 eq.) was added and the mixture stirred at reflux for around 2 hours. Heating was stopped and the reaction mixture was cooled to room temperature. Then the mixture was extracted twice between ethyl acetate and brine. The combined organic layers were dried over Na2SO4, filtered and evaporated under vacuo to give 3.05 g crude of a black oil which was purified by chromatography with 0-70% ethyl acetate in cyclohexane using combiflash to get the title compound as a beige solid.
LCMS (standard): RT=1.25 min, m/z=436 (M+H)+ and 480 (M+HCOO')'
Step 8: Preparation of 5-[3-iodo-6-(trifluoromethyl)indazol-2-yl1-1-(2,2,3,3,3- pentafluoropropyl)pyrazolo[3,4-clpyridine
Figure imgf000055_0001
1-(2,2,3,3,3-pentafluoropropyl)-5-[6-(trifluoromethyl)indazol-2-yl]pyrazolo[3,4-c]pyridine (0.175 g, 0.40 mmol, 1 .0 eq.) was suspended in acetonitrile (4.0 mL) and N-iodosuccinimide (0.11 g, 0.44 mmol, 1.1 eq.) was added, followed by p-toluenesulfonic acid monohydrate (0.007 g, 0.04 mmol, 0.1 eq.). The white suspension was stirred at room temperature for 4 days and turned into an orange. The mixture was extracted twice between ethyl acetate and HCI 0.5 M. The combined organic layers were dried over MgSO4, filtered and evaporated under vacuo to give a yellow solid which was suspended in 3 mL diisopropylether / pentane 1 :5. The resulting yellow suspension was stirred at room temperature, filtered and the solid washed with 1 mL diisopropylether / pentane 1 :5, dried under vacuum to give the title compound as a yellow-green powder.
LCMS (standard): RT=1.24 min, m/z=562 (M+H)+ and 606 (M+HCOO') '
Step 9: Preparation of example P1 : 5-[3-ethylsulfanyl-6-(trifluoromethyl)indazol-2-yl1-1-(2,2,3,3,3- pentafluoropropyl)pyrazolo[3,4-clpyridine (compound P1)
Figure imgf000055_0002
5-[3-iodo-6-(trifluoromethyl)indazol-2-yl]-1-(2,2,3,3,3-pentafluoropropyl)pyrazolo[3,4-c]pyridine (0.05 g, 0.09 mmol, 1 .0 eq.) was dissolved in 1 ,4-dioxane (1 .0 mL) and N,N-diisopropylethylamine (0.04 mL, 0.23 mmol, 2.6 eq.) was added. To the green-yellow solution Xantphos (0.003 g, 0.005 mmol, 0.05 eq.) and Pd2(dba)3 (0.003 g, 0.004 mmol, 0.04 eq.) were added and the brown solution was degassed with argon for 10 minutes. Ethanethiol (0.008 mL, 0.098 mmol, 1.1 eq.) was added and the mixture was heated to 100°C for around 6 hours. The resulting dark brown solution was extracted twice between ethyl acetate and brine. The combined organic layers were dried over MgSO4, filtered and evaporated under vacuo to give 48 mg brown oil. The crude was absorbed on “isolute” and purified by chromatography with 0-100% ethyl acetate in cyclohexane using the rf-machine combiflash to give the title compound as a bright-yellow solid.
LCMS (standard): RT=1.26 min, m/z=496 (M+H)+ and 495 (M+HCOO') ' Step 10: Preparation of example P2: 5-[3-ethylsulfonyl-6-(trifluoromethyl)indazol-2-yl1-1-(2,2,3,3,3- pentafluoropropyl)pyrazolo[3,4-clpyridine (compound P2)
Figure imgf000056_0001
5-[3-ethylsulfanyl-6-(trifluoromethyl)indazol-2-yl]-1-(2,2,3,3,3-pentafluoropropyl)pyrazolo[3,4-c]pyridine (0.24 g, 0.49 mmol, 1 .0 eq.) dissolved in dichloromethane (7.39 mL) was cooled to 0-5°C. 3- chloroperbenzoic acid (0.23 g, 0.99 mmol, 2.0 eq.) was added. The orange-brown suspension stirred at 0-5°C, then the ice bath was removed and the reaction mixture was further stirred at room temperature. After 1 hour , more 3-chloroperbenzoic acid (0.03 g, 0.15 mmol, 0.3 eq.) was added. After another 2 hours the mixture was poured onto around 50 mL NaHCO3 sat. solution, diluted with ethylacetate and stirred for 15 minutes at room temperature. The mixture was extracted twice between ethyl acetate and NaHCO3 sat. solution. Organic phases were washed with NaHS03-sol. (20%). The combined organic layers were dried over MgSO4, filtered and evaporated to give 0.31 g brown amourphous crude. The crude product was absorbed on “isolute” and purified by chromatography with 0-100% ethyl acetate in cyclohexane using the rf-machine (Chromabond Flash RS 15 Sphere SiOH 15um - column used) to get light beige solid which was suspended in around 1 .5 mL diisopropylether and the suspension stirred for 10 minutes. The solid was filtered off, washed with 1 mL diisopropylether and twice with 1 mL pentane, then dried on vacuum to give the title compound. LCMS (standard): RT=1.20 min, m/z=528 (M+H)+ and 572 (M+HCOO')'
Example H2: Preparation of 2-[3-ethylsulfonyl-2-[1-(2,2,3,3,3-pentafluoropropyl)-pyrazolo[3,4-clpyridin-
5-yl1indazol-6-yl1-2-methyl-propanenitrile (compound P4)
Figure imgf000056_0002
SUBSTITUTE SHEET (RULE 26) Step 1 : Preparation of 2-(4-bromo-2-nitro-phenyD-1 ,3-dioxolane
Figure imgf000057_0001
4-bromo-2-nitrobenzaldehyde (5.00 g, 21 .30 mmol, 1 .00 eq.) was dissolved in toluene (53 mL) and p- toluenesulfonic acid (0.11 g, 0.64 mmol, 0.03 eq.) was added. Ethylene glycol (6.96 g, 6.25 mL, 106.51 mmol, 5.00 eq.) was added and the reaction mixture was heated to strong reflux (bath 135°C) with a Dean-Stark overnight. The oil bath was removed and reaction was allowed to cool down for 10 minutes. The mixture was poured onto NaHCO3 sat. solution and then extracted 2x between ethyl acetate and brine. The combined organic layers were dried over Na2SO4, filtered and evaporated to give 6.18 g crude as a dark orange liquid. The crude product was absorbed on “isolute” and purified by chromatography with 0-100% ethyl acetate in cyclohexane using combiflash to yield the title compound as a yellow liquid. 1H NMR (400 MHz, CDCb) 6 ppm: 8.04 (s, 1 H), 7.75 (d, 1 H), 7.67 (d, 1 H), 6.43 (s, 1 H), 4.08 - 3.96 (m. 4 H).
Step 2: Preparation of 2-[4-(1 ,3-dioxolan-2-yl)-3-nitro-phenyl1-2-methyl-propanenitrile
Figure imgf000057_0002
2-(4-bromo-2-nitro-phenyl)-1 ,3-dioxolane (preparation described hereabove) (0.32 g, 1.20 mmol, 1.0eq.) and potassium 2-cyano-2-methyl-propanoate (0.26 g, 1.80 mmol, 1.5 eq. ) were suspended in mesitylene (9 mL) and the suspension was degassed with argon for 15 minutes. [XantPhos Pd(allyl)]CI (0.044 g, 0.06 mmol, 0.05 eq.) was added and the suspension was heated to 130°C. The reaction mixture was extracted 2xwith ethyl acetate and brine. The combined organic layers were dried over sodium sulfate, filtered and evaporated. The brown solution was absorbed on “isolute” and purified by chromatography with 0-50% ethyl acetae in cyclohexane using the combiflash. To remove mesitylene the first 2 minutes of the separation only cyclohexane was used. The title compound was isolated as a orange oil. LCMS (standard): RT=0.91 min, m/z=263 (M+H)+.
Step 3: Preparation of 2-(4-formyl-3-nitro-phenyl)-2-methyl-propanenitrile
Figure imgf000058_0001
To a clear, bright yellow solution of 2-[4-(1 ,3-dioxolan-2-yl)-3-nitro-phenyl]-2-methyl-propanenitrile (0.67 g, 2.55 mmol, 1 .00 eq.) dissolved in acetone (38 mL) and water (9 mL) was added hydrochloric acid 32% (1 .46 g, 1 .25 mL, 12.8 mmol, 5.00 eq.). The solution was warmed up to 50°C and stirred overnight. The reaction mixture was carefully poured on NaHCO3 sat. solution, so that the pH was neutral. Then the mixture was extracted 2x with ethyl acetate and NaHCO3 sat. solution. The combined organic layers were evaporated to give 0.66 g of a yellow oil. The crude was purified by a reverse phase column to give the title compound as yellow crystals.
1H NMR (400 MHz, CDCb) 6 ppm: 10.44 (s, 1 H), 8.22 (s, 1 H), 8.05 (d, 1 H), 7.97 (d, 1 H).
Step 4: Preparation of 2-methyl-2-[3-nitro-4-[(E)-[1-(2,2,3,3,3-pentafluoropropyl)-pyrazolo[3,4-clpyridin- 5-ylliminomethyllphenyllpropanenitrile
Figure imgf000058_0002
To a suspension of 2-(4-formyl-3-nitro-phenyl)-2-methyl-propanenitrile (0.33 g, 1.24 mmol, 1.00 eq.) and 1-(2,2,3,3,3-pentafluoropropyl)pyrazolo[3,4-c]pyridin-5-amine (0.30 g, 1.36 mmol, 1 .10 eq.) (described in the example H1 step 5) in 2-propanol (6 mL) around 1 g molecular sieve 4A was added and the mixture was heated up to reflux for 1 hour. The resulting reaction mixture was kept at reflux and used directly for the next step.
Step 5: Preparation of 2-methyl-2-[2-[1-(2,2,3,3,3-pentafluoropropyl)pyrazolo[3,4-clpyridin-5-yl1indazol- 6-yllpropanenitrile
Figure imgf000058_0003
To the refluxing reaction mixture of step 5 tributylphosphine (0.89 g, 1.08 mL, 3.72 mmol, 3.00 eq.) was added and the mixture was stirred further at reflux. After 75 minutes the suspension was diluted with ethyl acetate and water and the molecular sieves were filtered off. The mixture was extracted twice with ethyl acetate and brine and the combined organic layers were dried over sodium sulfate, filtered and evaporated to give 0.81 g crude. The solid residue was treated with small amounts of ethyl acetate, methanol and dichloromethane, then filtered and washed with diisopropylether. The wash solution was evaporated and purified by chromatography over silica gel eluting with a gradient of 0- 70% ethyl acetate in cyclohexane using combiflash. The title compound was isolated as a beige solid. LCMS (standard): RT=1.16 min, m/z=435 (M+H)+.
Step 6: Preparation of 2-[3-iodo-2-[1-(2,2,3,3,3-pentafluoropropyl)pyrazolo[3,4-clpyridin-5-yl1indazol-6- yll-2-methyl-propanenitrile
Figure imgf000059_0001
To a white suspension of 2-methyl-2-[2-[1-(2, 2,3,3, 3-pentafluoropropyl)pyrazolo[3,4-c]pyridin-5- yl]indazol-6-yl]propanenitrile (prepared as described above) (0.31 g, 0.70 mmol, 1.00 eq.) in acetonitrile (7 mL) was added first N-iodosuccinimide (0.18 g, 0.77 mmol, 1 .10 eq.) and then p- toluenesulfonic acid monohydrate (0.01 g, 0.07 mmol, 0.10 eq.). The beige suspension was stirred at room temperature. The resulting clear orange solution was stirred at room temperature overnight. The mixture was extracted 3x between ethyl acetate and HCI 0.5 M (2x) and NaOH 0.5 M (1x). The combined organic layers were dried over magnesium sulfate, filtered and evaporated to give 0.43 g crude as a brown foam. The crude product was absorbed on “isolute” and purified by chromatography with 0-100% EtOAc in cyclohexane using combiflash to give the title compound as a beige solid. LCMS (standard): RT=1.15 min, m/z=561 (M+H)+ and 605 (M+HCOO')'.
Step 7: Preparation of example P3: 2-[3-ethylsulfanyl-2-[1-(2,2,3,3,3-pentafluoro-propyl)pyrazolo[3,4- clpyridin-5-yl1indazol-6-yl1-2-methyl-propanenitrile
Figure imgf000059_0002
In a vial closed with a septum, 2-[3-iodo-2-[1-(2,2,3,3,3-pentafluoropropyl)-pyrazolo[3,4-c]pyridin-5- yl]indazol-6-yl]-2-methyl-propanenitrile (preparation described hereabove) (0.19 g, 0.33 mmol, 1.00eq.) was dissolved in 1 ,4-dioxane (4 mL) and N,N-diisopropylethylamine (0.11 g, 0.15 mL, 0.86 mmol, 2.60 eq.) was added. The bright yellow solution was degassed with argon and xantphos (0.01 g, 0.02 mmol, 0.05 eq.) and Pd2(dba)3 (0.01 g, 0.01 mmol, 0.04 eq.) were added. The dark reaction mixture was further degassed with argon for another 5 minutes. Ethanethiol (0.02 g, 0.03 mL, 0.36 mmol, 1 .10 eq.) was added and the reaction mixture was heated to 100°C overnight. The heating was then stopped and the reaction mixture was extracted twice between ethyl acetate and brine. The combined organic layers were dried over sodium sulfate, filtered and evaporated to give 0.21 g crude as a yellow-brown oil. The crude product was absorbed on “isolute” and purified by chromatography with 0-100% EtOAc in cyclohexane using combiflash to yield the title compound as a beige solid. LCMS (standard): RT=1.18 min, m/z = 495 (M+H)+ and 539 (M+HCOO')'
Step 8: Preparation of example P4: 2-[3-ethylsulfonyl-2-[1-(2,2,3,3,3-pentafluoro-propyl)pyrazolo[3,4- clpyridin-5-yl1indazol-6-yl1-2-methyl-propanenitrile
Figure imgf000060_0001
2-[3-ethylsulfanyl-2-[1-(2,2,3,3,3-pentafluoropropyl)pyrazolo[3,4-c]pyridin-5-yl]indazol -6-yl]-2-methyl- propanenitrile (0.12 g, 0.24 mmol, 1 .00 eq.) was dissolved in dichloromethane (3.5 mL) and the yellow solution was cooled to 0-5°C. 3-Chloro-perbenzoic acid (0.12 g, 0.47 mmol, 2 eq.) was added and the orange-brown suspension was stirred at 0-5°C. The resulting beige suspension was stirred 2 hours at 0-5°C and 2 hours at room temperature. The mixture was poured onto 50 ml NaHCO3 sat. solution and diluted with ethylacetate and the mixture stirred for 15 minutes at room temperature. The mixture was extracted between ethyl acetate and NaHCO3 sat. solution. The organic layer was washed twice with aqueous NaHSO3 solution (20% w/v). The aqueous layer was back-extracted again with ethyl acetate. The combined organic layers were dried over MgSO4, filtered and evaporated to give 0.13 g crude as a white foam which was purified by chromatography with 0-100% EtOAc in cyclohexane using combiflash to yield the title compound as a colorless solid.
LCMS (standard): RT=1.12 min, m/z=527 (M+H)+ and 571 (M+HCOO')' LCMS (standard long): RT=1.86 min.
Example H3: Preparation of 1-[3-ethylsulfonyl-2-[1-(2,2,3,3,3-pentafluoropropyl)-pyrazolo[3,4-clpyridin-
5-yl1indazol-6-yl1cyclopropanecarbonitrile (compound P6)
Figure imgf000060_0002
Step 1 : Preparation of 2-[4-(1 ,3-dioxolan-2-yl)-3-nitro-phenyl1acetonitrile
SUBSTITUTE SHEET (RULE 26)
Figure imgf000061_0001
2-(4-Bromo-2-nitro-phenyl)-1 ,3-dioxolane (prepared as described above, in step 1 of example H2) (3.00 g, 11.00 mmol, 1.00 equiv.) and potassium cyanoacetate (2.10 g, 16.00 mmol 1 .50 equiv.) were suspended in mesitylene (55 mL). The reaction mixture was stirred and degassed with argon via bubbling trough the mixture for 5 minutes. (Pd(allyl)CI)2 (0.20 g, 0.55 mmol, 0.05 equiv.) and SPhos (0.47 g, 1.10 mmol, 0.10 equiv.) were added. The reaction mixture was stirred and degassed with argon for further 5 minutes. The suspension was stirred and heated to 130°C. After 4.5 hours the mixture was extracted twice with ethyl acetate and brine. The combined organic layers were dried over MgSO4, filtered and evaporated using high vacuum to remove mesitylene to give 3.70 g crude as a black oil which was absorbed on “isolute” and purified by chromatography with 0-100% EtOAc in cyclohexane using combiflash to give the title product as a dark orange oil.
1H NMR (400 MHz, CDCb) 6 ppm: 7.90 (d, 1 H), 7.87 (d, 1 H), 7.65 (dd, 1 H), 6.50 (s, 1 H), 4.13-4.01 (m, 4 H), 3.88 (s, 2 H).
Step 2: Preparation of 1-[4-(1 ,3-dioxolan-2-yl)-3-nitro-phenyl1cyclopropanecarbonitrile
Figure imgf000061_0002
2-[4-(1 ,3-Dioxolan-2-yl)-3-nitro-phenyl]acetonitrile (preparation described hereabove) (1.10 g, 4.70 mmol, 1 .00 equiv.) and potassium carbonate (1 .97 g, 14.1 mmol, 3.00 equiv.) were suspended in dimethylsulfoxide (29 mL). To the dark brown suspension was added 1 ,2-dibromoethane (1 .34 g, 0.61 mL, 7.04 mmol, 1 .50 equiv.). The resulting dark purple suspension was warmed up to 50°C for 6 hours. The mixture was extracted 2x between ethyl acetate and aqueous NaCI sat. solution. The combined organic layers were dried over Na2SO4, filtered and evaporated to give 1 .62 g crude as a dark-red oil. The crude product was absorbed on “isolute” and purified by chromatography with 0- 100% EtOAc in cyclohexane using combiflash to yield the title compound as an orange solid.
1H NMR (400 MHz, CDCb) 6 ppm: 7.82 (d, 1 H), 7.73 (d, 1 H), 7.65 (dd, 1 H), 6.47 (s, 1 H), 4.12-4.00 (m, 4 H), 1 .90-1 .85 (m, 2 H), 1 .54-1 .49 (m, 2 H).
Figure imgf000061_0003
Figure imgf000062_0001
To a bright yellow solution of 1-[4-(1 ,3-dioxolan-2-yl)-3-nitro-phenyl]cyclopropanecarbonitrile (preparation hereabove) (1.04 g, 4.00 mmol, 1.00 equiv.) dissolved in acetone (60 mL) and water (15 mL), was added hydrochloric acid (32%) (2.28 g, 1.96 mL, 20.00 mmol, 5.00 equiv.). The solution was warmed up to 50°C and stirred overnight. The reaction mixture was carefully poured on 40 mL NaHCO3 sat. solution. Then the mixture was extracted 2x with ethyl acetate and NaHCO3 sat. solution. The combined organic layers were evaporated to give 1 .60 g crude. The crude was absorbed on “isolute” and purified by chromatography with 0-100% EtOAc in cyclohexane using combiflash. After evaporation of the selected fractions, the residue was suspended in 10 mL diisopropylether and 0.1 mL ethanol and this suspension was stirred for 20 minutes. The solid was filtered off, washed twice with 5 mL diisopropylether and twice with 5 mL pentane, then dried on vacuum to yield the title compound as a beige solid.
1H NMR (400 MHz, CDCb) 6 ppm: 10.41 (s, 1 H), 8.00 (d, 1 H), 7.95 (s, 1 H), 7.77 (d, 1 H), 2.00 (t, 2 H), 1.62 (t, 2 H).
Step 4: Preparation of 1-[3-nitro-4-[(E)-[1-(2,2,3,3,3-pentafluoropropyl)pyrazolo[3,4-clpyridin-5- ylliminomethyllphenyllcyclopropanecarbonitrile
Figure imgf000062_0002
To a suspension of 1-(4-formyl-3-nitro-phenyl)cyclopropanecarbonitrile (preparation described hereabove) (0.45 g, 2.10 mmol, 1.10 equiv.) and 1-(2, 2,3,3, 3-pentafluoropropyl)pyrazolo[3,4-c]pyridin- 5-amine (0.50 g, 1.90 mmol, 1.00 equiv.) (described in the example H1 step 5) in 2-propanol (9 mL) about 1 g molecular sieve 4A were added and the mixture was heated up to reflux for 3 hours. The resulting reaction mixture was kept at reflux and used directly for the next step.
Step 5: Preparation of 1-[2-[1-(2,2,3,3,3-pentafluoropropyl)pyrazolo[3,4-clpyridin-5-yl1indazol-6- yllcyclopropanecarbonitrile
Figure imgf000062_0003
To the refluxing reaction mixture of step 4, tributylphosphine (1 .40 g, 1 .7 mL, 5.70 mmol, 3.00 equiv.) was added and the mixture was stirred further at reflux. After 95 minutes, the heating was stopped and the suspension was stirred at room temperature overnight. The mixture was diluted with ethyl acetate and water. After filtration, the crude solution was extracted twice with ethyl acetate and brine and the combined organic layers were dried over sodium sulfate, filtered and evaporated to give a black oil. This was absorbed on “isolute” and purified by chromatography with 0-70% ethyl acetate in cyclohexane using combiflash to yield the title compound as a yellow powder.
LCMS (standard): RT=1.13 min, m/z=433 (M+H)+ and 477 (M+HCOO') '
Step 6: Preparation of 1-[3-iodo-2-[1-(2,2,3,3,3-pentafluoropropyl)pyrazolo[3,4-clpyridin-5-yl1indazol-6- yllcyclopropanecarbonitrile
Figure imgf000063_0001
To a suspension of 1-[2-[1-(2, 2,3,3, 3-pentafluoropropyl)pyrazolo[3,4-c]pyridin-5-yl]indazol-6- yl]cyclopropanecarbonitrile (0.58 g, 1.30 mmol, 1.00 equiv.) in acetonitrile (14 mL) were added N- iodosuccinimide (0.35 g, 1.55 mmol, 1.10 equiv.) and p-toluenesulfonic acid monohydrate (0.02 g, 0.13 mmol, 0.10 equiv.). The beige suspension was stirred at room temperature overnight. The mixture was extracted 2x between ethyl acetate and brine and the combined organic layers were dried over sodium sulfate, filtered and evaporated to give 0.84 g of an orange-brown residue. After trituration with EtOAc, dichloromethane and methanol, it was filtered and washed with dichloromethane and diisopropylether. The washings were evaporated and chromatographed over silica gel, eluting with a gradient of 0-100% EtOAc in cyclohexane. After evaporation of the selected fractions, the residue was washed with diisopropylether, then pentane to deliver the title compound. LCMS (standard long): RT=1.87 min, m/z=559 (M+H)+ and 603 (M+HCOO')'
Step 7: Preparation of example P5: 1-[3-ethylsulfanyl-2-[1-(2,2,3,3,3-pentafluoropropyl)pyrazolo[3,4- clpyridin-5-yl1indazol-6-yl1cyclopropanecarbonitrile
Figure imgf000063_0002
1-[3-iodo-2-[1-(2,2,3,3,3-pentafluoropropyl)pyrazolo[3,4-c]pyridin-5-yl]indazol-6- yl]cyclopropanecarbonitrile (0.30 g, 0.54 mmol, 1.00 eq.) was dissolved in 1 ,4-dioxane (6 mL) and N,N-diisopropylethylamine (0.21 g, 0.28 mL, 1.60 mmol, 3.00 equiv.) was added. The yellow suspension was degassed with argon for 10 minutes and xantphos (0.02 g, 0.03 mmol, 0.05 equiv.) and Pd2(dba)3 (0.02 g, 0.02 mmol, 0.04 equiv.) were added. The reaction mixture was degassed with argon for another 5 minutes. Ethanethiol (0.05 g, 0.05 mL, 0.70 mmol, 1 .30 equiv.) was added and the reaction mixture was heated to 100°C overnight. The heating was stopped and the reaction mixture was extracted twice between ethyl acetate and brine. The combined organic layers were dried over sodium sulfate, filtered and evaporated to give 0.38 g crude. The crude product was absorbed on “isolute” and purified by chromatography with 0-100% EtOAc in cyclohexane using combiflash to yield the title compound as a beige solid.
LCMS (standard): RT=1.15 min, m/z = 493 (M+H)+ and 537 (M+HCOO')'
LCMS (standard long): RT=1.93 min.
Step 8: Preparation of example P6: 1-[3-ethylsulfonyl-2-[1-(2,2,3,3,3-pentafluoropropyl)pyrazolo[3,4- clpyridin-5-yl1indazol-6-yl1cyclopropanecarbonitrile
Figure imgf000064_0001
1-[3-Ethylsulfanyl-2-[1-(2,2,3,3,3-pentafluoropropyl)pyrazolo[3,4-c]pyridin-5-yl]indazol-6- yl]cyclopropanecarbonitrile (preparation described above) (0.19 g, 0.38 mmol, 1.00 equiv.) was dissolved in dichloromethane (5.6 mL) and the colourless solution was cooled to 0-5°C. 3- Chloroperbenzoic acid (0.18 g, 0.78 mmol, 2.10 equiv.) was added and the cloudy suspension was stirred at 0-5°C. The resulting beige suspension was stirred 1 hour at 0-5°C, then for 1 .5 hour at 20°C. The mixture was poured onto 50 ml NaHCO3 sat. solution and diluted with ethylacetate and stirred for 15 min at 20°C. After extraction with ethyl acetate, the organic layer was washed twice with aqueous NaHS03-solution (20%). The aqueous layer was back-extracted with ethyl acetate. The combined organic layers were dried over MgSO4, filtered and evaporated to give 0.20 g residue that was purified by chromatography with 0-100% EtOAc in cyclohexane using combiflash to yield the title compound. LCMS (standard): RT=1.09 min, m/z=525 (M+H)+ and 569 (M+HCOO') ' LCMS (standard long): RT=1.80 min.
Example H4: Preparation of 2-[3-ethylsulfonyl-2-[1-(2,2,3,3,3-pentafluoropropyl)-pyrazolo[3,4-clpyridin-
5-yl1indazol-5-yl1-2-methyl-propanenitrile (compound P8)
Figure imgf000065_0001
Preparation example P7 Preparation example P8
Step 1 : Preparation of 2-(5-bromo-2-nitro-phenyl)-1 ,3-dioxolane
Figure imgf000065_0002
To a solution of 5-bromo-2-nitro-benzaldehyde (2.50 g, 10.70 mmol, 1 .00 equiv.) in toluene (27 mL) and p-toluenesulfonic acid monohydrate (0.06 g, 0.32 mmol, 0.03 equiv.) was added ethylene glycol (3.48 g, 3.13 mL, 53.30 mmol, 5.00 equiv.). The mixture was heated to reflux overnight under a Dean- Stark trap. After cooling down, the mixture was extracted 2x between ethyl acetate and brine. The combined organic layers were dried over MgSO4, filtered and evaporated to give 2.98 g yellow solid which was suspended in 5 mL diisopropylether and the suspension stirred for 1 hour. The solid was filtered off, washed with 1 .5 mL diisopropylether and 2x 5 mL pentane, then dried under vacuum to yield the title compound as a beige solid. 1H NMR (400 MHz, CDCh) 5 ppm: 7.97 (d, 1 H), 7.82 (d, 1 H), 7.66 (dd, 1 H), 6.50 (s, 1 H), 4.12-4.02 (m, 4 H). Step 2: Preparation of 2-[3-(1 ,3-dioxolan-2-yl)-4-nitro-phenyl1-2-methyl-propanenitrile
Figure imgf000065_0003
SUBSTITUTE SHEET (RULE 26) A suspension of 2-(5-bromo-2-nitro-phenyl)-1 ,3-dioxolane (preparation described above) (0.50 g, 1.80 mmol, 1 .00 equiv.) and potassium 2-cyano-2-methyl-propanoate (0.41 g, 2.70 mmol, 1 .50 equiv.) in mesitylene (15 mL) was degassed with argon for 5 minutes. [XantPhos Pd(allyl)]CI (0.07 g, 0.09 mmol, 0.05 equiv.) was added and the suspension was heated up to 130°C. After 2 hours the heating was stopped and the reaction mixture was allowed to cool to room temperature. The reaction mixture was absorbed on “isolute” and purified by chromatography with 0-50% EtOAc in cyclohexane using combiflash. The title compound was isolated as a yellow-orange oil. 1H NMR (400 MHz, CDCh) 5 ppm: 7.98 (d, 1 H), 7.94 (d, 1 H), 7.64 (dd, 1 H), 6.49 (s, 1 H), 4.12-4.05 (m, 4 H).
Step 3: Preparation of 2-(3-formyl-4-nitro-phenyl)-2-methyl-propanenitrile
Figure imgf000066_0001
A solution of 2-[3-(1 ,3-dioxolan-2-yl)-4-nitro-phenyl]-2-methyl-propanenitrile (preparation described above) (0.352 g, 1 .34 mmol, 1 .00 equiv.) in acetone (20 mL) and water (5 mL) was treated with concentrated aqueous hydrochloric acid (0.66 mL, 6.71 mmol, 5.00 equiv.). The mixture was heated and stirred at 50°C overnight. After cooling, the reaction mixture was cautiously poured onto 60 mL NaHCO3 sat. solution. The mixture was diluted with ethylacetate and extracted 2x with ethyl acetate. The combined organic layers were dried over sodium sulfate, filtered and evaporated to give 0.32 g residue, which was dissolved in 1 .5 mL in DMSO and injected into the preparative reversed-phase combiflash-machine (solvent: H20/ACN 20 to 70%). The product was obtained as a bright yellow oil. 1H NMR (400 MHz, CDCh) 6 ppm: 10.48 (s, 1 H), 8.20 (d, 1 H), 8.02 (d, 1 H), 7.96 (dd, 1 H), 1.82 (s, 6 H).
Step 4: Preparation of 2-methyl-2-[4-nitro-3-[(E)-[1-(2,2,3,3,3-pentafluoropropyl)-pyrazolo[3,4-clpyridin-
5-ylliminomethyllphenyllpropanenitrile
Figure imgf000066_0002
1-(2,2,3,3,3-Pentafluoropropyl)pyrazolo[3,4-c]pyridin-5-amine (preparation described in preparation example H1) (0.20 g, 0.75 mmol, 1 .00 equiv.) and 2-(3-formyl-4-nitro-phenyl)-2-methyl-propanenitrile (0.18 g, 0.83 mmol, 1.10 equiv.) were suspended in 2-propanol (4 mL) and 1 g molecular sieves 4A were added. The reaction mixture was heated up to reflux. The reaction mixture changed to a beige suspension after 45 minutes. The suspension was kept stirring on reflux and used directly for the next step. Step 5: Preparation of 2-methyl-2-[2-[1-(2,2,3,3,3-pentafluoropropyl)pyrazolo[3,4-clpyridin-5-yl1indazol-
5-yllpropanenitrile
Figure imgf000067_0001
To the hot reaction mixture of step 5 was added tributylphosphine (0.54 g, 0.65 mL, 2.30 mmol, 3.00 equiv.) and the mixture stirred further at reflux for 30 minutes and then at room temperature overnight. Some more tributylphosphine (0.18 g, 0.22 mL, 0.75 mmol, 1 .00 equiv.) was added and the suspension was heated again to reflux for 90 minutes. After cooling down, the yellow-beige suspension was diluted with EtOAc and water and the molecular sieves were filtered off. The mixture was extracted 2x with ethyl acetate. The combined organic layers were dried over sodium sulfate, filtered and evaporated to give 1 .29 g brown oil. The crude product was absorbed on “isolute” and purified by chromatography with 0-70% EtOAc in cyclohexane using the rf-machine. The isolated yellow amorphous residue was suspended in 2 mL diisopropylether and the suspension stirred for 10 minutes. The solid was filtered off, washed with 2x 1 .5 mL diisopropylether and 2x 2 mL pentane, then dried on vacuum to give the title compound as a white solid.
LCMS (standard): RT=1.15 min, m/z = 435 (M+H)+ and 479 (M+HCOO') '
Step 6: Preparation of 2-[3-iodo-2-[1-(2,2,3,3,3-pentafluoropropyl)pyrazolo[3,4-clpyridin-5-yl1indazol-5- yll-2-methyl-propanenitrile
Figure imgf000067_0002
To a suspension of 2-methyl-2-[2-[1-(2,2,3,3,3-pentafluoropropyl)pyrazolo[3,4-c]pyridin-5-yl]indazol-5- yl]propanenitrile (0.160 g, 0.37 mmol, 1.00 equiv.) in acetonitrile (4 mL), was added N-iodosuccinimide (0.10 g, 0.41 mmol, 1.10 equiv.) and para-toluenesulfonic acid monohydrate (0.007 g, 0.04 mmol, 0.10 equiv.). The mixture was stirred at room temperature over the weekend. The mixture was extracted 3x with ethyl acetate, then washed with HCI 0.5 M (2x) and NaOH 0.5 M (1x). The combined organic layers were dried over MgSO4, filtered and evaporated to give 0.21 g beige solid. The crude product was absorbed on “isolute” and purified by chromatography with 0-100% EtOAc in cyclohexane using the rf-machine. The title compound was isolated as a beige solid.
LCMS (standard): RT=1.14 min, m/z = 561 (M+H)+ and 605 (M+HCOO')'
Step 7: Preparation of example P7: 2-[3-ethylsulfanyl-2-[1-(2,2,3,3,3-pentafluoro-propyl)pyrazolo[3,4- clpyridin-5-yl1indazol-5-yl1-2-methyl-propanenitrile
Figure imgf000068_0001
To a solution of 2-[3-iodo-2-[1-(2,2,3,3,3-pentafluoropropyl)pyrazolo[3,4-c]pyridin-5-yl]indazol-5-yl]-2- methyl-propanenitrile (preparation described above) (0.17 g, 0.29 mmol, 1.00 equiv.) in 1 ,4-dioxane (3 mL) and N,N-diisopropylethylamine (0.10 g, 0.13 mL, 0.77 mmol, 2.60 equiv.) were added Xantphos (0.009 g, 0.015 mmol, 0.05 equiv.) and Pd2(dba)3 (0.011 g, 0.012 mmol, 0.04 equiv.). The brown solution was degassed with argon for 10 minutes. Ethanethiol (0.02 g, 0.02 mL, 0.32 mmol, 1.10 equiv.) was added and the reaction mixture was heated up to 100°C and stirred overnight. The heating was stopped and the reaction mixture was cooled to room temperature. The mixture was extracted 2x between ethyl acetate and brine. The combined organic layers were dried over MgSO4, filtered and evaporated to give 0.21 g brown oil. The crude product was absorbed on “isolute” and purified by chromatography with 0-100% EtOAc in cyclohexane using the rf-machine. The title compound was isolated as a yellow foam.
LCMS (standard): RT=1.16 min, m/z=495 (M+H)+ and 539 (M+HCOO')' LCMS (standard long): RT=1.95 min.
Step 8: Preparation of P8: 2-[3-ethylsulfonyl-2-[1-(2,2,3,3,3-pentafluoropropyl)-pyrazolo[3,4-clpyridin-
5-yl1indazol-5-yl1-2-methyl-propanenitrile
Figure imgf000068_0002
A solution of 2-[3-ethylsulfanyl-2-[1-(2,2,3,3,3-pentafluoropropyl)pyrazolo[3,4-c]pyridin-5-yl]indazol-5- yl]-2-methyl-propanenitrile (0.05 g, 0.11 mmol, 1.00 equiv.) in dichloromethane (2 mL) was cooled to 0-5°C. 3-Chloroperbenzoic acid (0.05 g, 0.21 mmol, 2.00 equiv.) were added and the suspension stirred at 0-5°C for 1 hour. The ice bath was removed and the reaction mixture was stirred at room temperature for 2.5 hours. The mixture was poured onto 50 mL NaHCO3 sat. solution, diluted with ethylacetate and stirred for 15 minutes at room temperature. The phases were separated and the aqueous phase was extracted with ethyl acetate. The organic layer was washed with an aqueous solution of NaHSO3 (20%) followed by NaHCO3 sat. solution. The inorganic layer was back-extracted with ethyl acetate. The combined organic layers were dried over MgSO4, filtered and evaporated to give 0.06 g beige yellow-foam. The crude product was dissolved in 1 .5 mL DMSO and injected into the prep, reversed-phase Combiflash- machine (solvent: H20 / ACN 20 to 70%) to yield the title compound as a bright yellow foam.
LCMS (standard): RT=1.12 min, m/z=527 (M+H)+ and 571 (M+HCOO')' Example H5: Preparation of 1-[3-ethylsulfonyl-2-[1-(2,2,3,3,3-pentafluoropropyl)-pyrazolo[3,4-clpyridin-
5-yl1indazol-5-yl1cyclopropanecarbonitrile (compound P10)
Figure imgf000069_0001
Step 1 : Preparation of 2-[3-(1 ,3-dioxolan-2-yl)-4-nitro-phenyl1acetonitrile
Figure imgf000069_0002
A suspension of 2-(5-bromo-2-nitro-phenyl)-1 ,3-dioxolane (1.00 g, 3.60 mmol, 1.00 equiv.) and potassium cyanoacetate (0.71 g, 5.50 mmol, 1.50 eq.) in mesitylene (26 mL) was stirred and degassed by bubbling argon through the mixture for 5 minutes. (Pd(allyl)CI)2 (0.07 g, 0.18 mmol, 0.05 equiv.) and SPhos (0.16 g, 0.36 mmol, 0.10 equiv.) were added. The mixture was stirred and degassed with argon for another 5 minutes. The vial was closed and the mixture was heated to 130°C for 2.5 hours. Then the mixture was extracted 2x between ethyl acetate and brine. The combined organic layers were dried over MgSO4, filtered and evaporated to give 30 ml of a dark-green oil. The crude oil was absorbed on “isolute” and purified by chromatography with 0-100% EtOAc in cyclohexane using the rf-machine. The title compound was obtained as a dark-green amorphous substance. 1H NMR (400 MHz, CDCb) 6 ppm: 7.98 (d, 1 H), 7.81 (s, 1 H), 7.53 (d, 1 H), 6.49 (s, 1 H), 4.15-4.00 (m, 4 H), 3.89 (s, 2 H).
Step 2: Preparation of 1-[3-(1 ,3-dioxolan-2-yl)-4-nitro-phenyl1cyclopropanecarbonitrile
Figure imgf000070_0001
To a suspension of 2-[3-(1 ,3-dioxolan-2-yl)-4-nitro-phenyl]acetonitrile (preparation described above) (1 .0 g, 4.30 mmol, 1 .00 equiv.) and potassium carbonate (1 .80 g, 13.00 mmol, 3.0 equiv.) in dimethylsulfoxide (26 mL) was added 1 ,2-dibromoethane (1 .20 g, 0.56 mL, 6.40 mmol, 1 .50 equiv.). The dark purple mixture was stirred at room temperature for 5 minutes and then warmed up to 50°C for 4 hours. The heating was stopped and the mixture was stirred at room temperature overnight. The reaction mixture was extracted twice between ethyl acetate and brine. The combined organic layers were dried over sodium sulfate, filtered and evaporated to give 1 .42 g black oily residue, which was. absorbed on “isolute” and purified by chromatography with 0-100% EtOAc in cyclohexane using the rf- machine. The title compound was isolated as a green solid. 1H NMR (400 MHz, CDCh) 5 ppm: 7.95 (d, 1 H), 7.69 (d, 1 H), 7.46 (dd, 1 H), 6.48 (s, 1 H), 4.14-4.00 (m, 4 H), 1.93-1.88 (m, 2 H), 1.60-1.53 (m, 2 H).
Step 3: Preparation of 1-(3-formyl-4-nitro-phenyl)cyclopropanecarbonitrile
Figure imgf000070_0002
A solution of 1-[3-(1 ,3-dioxolan-2-yl)-4-nitro-phenyl]cyclopropanecarbonitrile (preparation described above) (0.57 g, 2.18 mmol, 1 .00 equiv.) in acetone (33 mL) and water (8 mL) was treated with concentrated aqueous hydrochloric acid (1 .24 g, 1 .07 mL, 10.90 mmol, 5.00 equiv.). The reaction mixture turned yellow. It was stirred at room temperature for 5 minutes and then warmed up to 50°C and stirred at this temperature overnight. After concentration under reduced pressure, the reaction mixture was cautiously poured on 40 mL aqueous NaHCO3 sat. solution and diluted with ethyl acetate. The phases were separated and the aqueous phase was extracted twice with ethyl acetate. The combined organic layers were dried over sodium sulfate, filtered and evaporated to give 0.48 g residue, which was absorbed on “isolute” and purified by chromatography with 0-100% EtOAc in cyclohexane using the rf-machine. The title compound was isolated as an orange solid.
1H NMR (400 MHz, CDCh) 6 ppm: 10.45 (s, 1 H), 8.18 (d, 1 H), 7.82 (d, 1 H), 7.67 (s, 1 H), 2.01-1.95 (m, 2 H), 1.66-1.55 (m, 2 H).
Step 4: Preparation of 1-[4-nitro-3-[(E)-[1-(2,2,3,3,3-pentafluoropropyl)pyrazolo[3,4-clpyridin-5- ylliminomethyllphenyllcyclopropanecarbonitrile
Figure imgf000071_0001
A suspension of 1-(2,2,3,3,3-pentafluoropropyl)pyrazolo[3,4-c]pyridin-5-amine (preparation described in preparation example H1) (0.50 g, 1.90 mmol, 1 .00 equiv.) and 1-(3-formyl-4-nitro- phenyl)cyclopropanecarbonitrile (0.45 g, 2.10 mmol, 1.10 equiv.) in 2-propanol (9 mL) and 1 g molecular sieves 4A was heated to for 4 hours and kept on reflux for the following step.
Step 5: Preparation of 1-[2-[1-(2,2,3,3,3-pentafluoropropyl)pyrazolo[3,4-clpyridin-5-yl1indazol-5- yllcyclopropanecarbonitrile
Figure imgf000071_0002
To the refluxing reaction mixture of step 4 was added tributylphosphine (0.45 g, 0.55 mL, 1 .90 mmol, 1 .00 equiv.) and stirring at this temperature was continued for 1 hour, then overnight, at room temperature. More tributylphosphine (0.45 g, 0.55 mL, 1 .90 mmol, 1 .00 equiv.) was added and the mixture was heated again at reflux for 6 hours. After cooling down, the suspension was diluted with EtOAc and water and molecular sieve was filtered off. The phases were separated and the aqueous phase was extracted twice with ethyl acetate. The combined organic layers were dried over sodium sulfate, filtered and evaporated to give 2.2 g of a black residue which was purified by chromatography on silica gel with 0-70% EtOAc in cyclohexane using the rf-machine. After evaporation of the selected fractions, the residue was suspended in 7 mL diisopropylether and the suspension stirred for 20 minutes. The solid was filtered off, washed twice with 5 mL diisopropylether and twice with 5 mL pentane. The title compound was isolated as a colorless solid.
LCMS (standard): RT=1.13 min, m/z = 433 (M+H)+ and 477 (M+HCOO')'
Step 6: Preparation of 1-[3-iodo-2-[1-(2,2,3,3,3-pentafluoropropyl)pyrazolo[3,4-clpyridin-5-yl1indazol-5- yllcyclopropanecarbonitrile
Figure imgf000071_0003
To a suspension of 1-[2-[1-(2, 2,3,3, 3-pentafluoropropyl)pyrazolo[3,4-c]pyridin-5-yl]indazol-5- yl]cyclopropanecarbonitrile (preparation described above) (0.25 g, 0.58 mmol, 1.00 equiv.) in acetonitrile (6 mL), was added N-iodosuccinimide (0.15 g, 0.64 mmol, 1.10 equiv.) and p- oluenesulfonic acid monohydrate (0.01 g, 0.06 mmol, 0.10 equiv.). The beige suspension was stirred at room temperature for 4 hours. The mixture was extracted 3x between ethyl acetate and HCI 0.5 M (2x) and NaOH 0.5 M (1x). The combined organic layers were dried over MgSO4, filtered and evaporated to give 0.32 g of an orange-brown oil. The residue was absorbed on “isolute” and purified by chromatography with 0-100% EtOAc in cyclohexane using the rf-machine. The title compound was isolated as a beige solid.
LCMS (standard): RT=1.11 min, m/z = 559 (M+H)+ and 603 (M+HCOO')'
LCMS (standard long): RT=1.83 min.
Step 7: Preparation of example P9: 1-[3-ethylsulfanyl-2-[1-(2,2,3,3,3-pentafluoro-propyl)pyrazolo[3,4- clpyridin-5-yl1indazol-5-yl1cyclopropanecarbonitrile
Figure imgf000072_0001
In a vial, a solution of 1-[3-iodo-2-[1-(2, 2,3,3, 3-pentafluoropropyl)pyrazolo[3,4-c]pyridin-5-yl]indazol-5- yl]cyclopropanecarbonitrile (preparation described above) (0.28 g, 0.50 mmol, 1.00 equiv.) in 1 ,4- dioxane (6 mL) and N,N-diisopropylethylamine (0.17 g, 0.23 mL, 1.30 mmol, 2.60 equiv.) was degassed with argon, then xantphos (0.02 g, 0.03 mmol, 0.05 equiv.) and Pd2(dba)3 (0.02 g, 0.02 mmol, 0.04 equiv.) were added. The dark mixture was further degassed by bubbling argon for another 5 minutes and then ethanethiol (0.04 g, 0.05 mL, 0.65 mmol, 1.30 equiv.) was added. The reaction mixture was heated to 100°C and stirred at this temperature overnight. The next day, the reaction mixture was cooled down and N,N-diisopropylethylamine (0.17 g, 0.23 mL, 1.30 mmol, 2.60 equiv.), xantphos (0.02 g, 0.03 mmol, 0.05 equiv.), Pd2(dba)3 (0.02 g, 0.02 mmol, 0.04 equiv.) and ethanethiol (0.04 g, 0.05 mL, 0.65 mmol, 1 .30 equiv.) were added and the reaction mixture was heated again to 100°C for another 5 hours. The heating was stopped and the mixture was extracted twice between ethyl acetate and brine. The combined organic layers were dried over sodium sulfate, filtered and evaporated to give 0.35 g green-brown residue, which was absorbed on “isolute” and purified by chromatography with 0-100% EtOAc in cyclohexane using the rf-machine. The title product was isolated as a white foam.
LCMS (standard): RT=1.14 min, m/z = 493 (M+H)+ and 537 (M+HCOO')' LCMS (standard long): RT= 1.90 min.
Step 8: Preparation of example P10: 1-[3-ethylsulfonyl-2-[1-(2,2,3,3,3-pentafluoro-propyl)pyrazolo[3,4- clpyridin-5-yl1indazol-5-yl1cyclopropanecarbonitrile
Figure imgf000072_0002
A solution of 1-[3-ethylsulfanyl-2-[1-(2,2,3,3,3-pentafluoropropyl)pyrazolo[3,4-c]pyridin-5-yl]indazol-5- yl]cyclopropanecarbonitrile (preparation described above) (0.130 g, 0.26 mmol, 1.00 equiv.) in dichloromethane (4 mL) was cooled to 0-5°C and 3-chloroperbenzoic acid (0.13 g, 0.55 mmol, 2.10 equiv.) was added. The cloudy mixture was stirred at 0-5°C and after 40 minutes a beige suspension was formed. After 2 hours the ice-bath was removed and the mixture was stirred for another 2 hours. More 3-chloroperbenzoic acid (0.015 g, 0.07 mmol, 0.25 equiv.) was added. After another 1.5 hours the mixture was poured onto 50 mL NaHCO3 sat. solution, diluted with ethylacetate and the resulting mixture was stirred for 15 minutes at room temperature. The mixture was extracted between ethyl acetate and NaHCO3 sat. solution. The organic layer was washed with aqueous NaHS03-solution (20%) and one more time with NaHCO3 sat. solution. The inorganic layer was back-extracted with ethyl acetate. The combined organic layers were dried over MgSO4, filtered and evaporated to give 0.19 g of a residue that was absorbed on “isolute” and purified by chromatography with 0-100% EtOAc in cyclohexane using the rf-machine. The title compound was isolated as a white solid.
LCMS (standard): 1.09 min, m/z=525 (M+H)+ and 569 (M+HCOO')' LCMS (standard long): 1.80 min.
Example H6: Preparation of 5-[6-(1 ,1-difluoroethyl)-3-ethylsulfonyl-indazol-2-yl1-1-(2,2,3,3,3-penta- fluoropropyl)pyrazolo[3,4-clpyridine (compound P12)
Figure imgf000073_0001
Preparation example P11 Preparation example P12
Step 1 : Preparation of 4-isopropenyl-2-nitro-benzaldehyde
Figure imgf000073_0002
To a solution of 4-bromo-2-nitro-benzaldehyde (7.5 g, 32 mmol, 1.0 equiv.) and isopropenylboronic acid pinacol ester (7.4 mL, 64 mmol, 2.0 equiv.) in tetrahydrofuran (96 mL) and water (24 mL) was added tripotassium phosphate monohydrate (14 g, 64 mmol, 2.0 equiv.). The 2-layer mixture was
SUBSTITUTE SHEET (RULE 26) degassed with argon. Then SPhos (1 .3 g, 3.2 mmol, 0.10 equiv.) followed by palladium (II) acetate (0.37 g, 1 .6 mmol, 0.050 equiv.) were added at room temperature. The reaction mixture was degassed for 10 minutes with Argon then heated at 50°C for 3 hours. The mixture was extracted twice with ethyl acetate, the combined organic layers were washed with brine, dried over sodium sulfate, filtered and evaporated to give 12.4 g dark brown oil, which was absorbed on “isolute” and purified by chromatography on silica gel, eluting with 0-100% ethyl acetate in cyclohexane. The selected fractions were evaporated under reduced pressure to yield the title compound as a dark red-brown solid.
LCMS (standard): RT=0.97 min, m/z = 192 (M+H)+ and 190 (M-H)’. 1H NMR (400 MHz, CDCb) 6 ppm: 10.41 (s, 1 H) 8.15 (d, J=1 .47 Hz, 1 H) 7.95 (d, J=8.07 Hz, 1 H) 7.84 (d, J=7.84 Hz, 1 H) 5.61 - 5.64 (m, 1 H) 5.37 - 5.41 (m, 1 H) 2.23 (dd, J=1.47, 0.73 Hz, 3 H).
Step 2: Preparation of 2-(4-isopropenyl-2-nitro-phenyD-1 ,3-dioxolane
Figure imgf000074_0001
The title compound, 2-(4-isopropenyl-2-nitro-phenyl)-1 ,3-dioxolane, was prepared in an analogous way as step 1 in example H4, starting from 4-isopropenyl-2-nitro-benzaldehyde.
LCMS (standard): RT=1.02 min, m/z = 236 (M+H)+. 1H NMR (400 MHz, CDCI3) 6 ppm: 7.97 (d, J=1.83 Hz, 1 H) 7.75 (d, J=7.91 Hz, 1 H) 7.69 (d, J=8.23 Hz, 1 H) 6.48 (s, 1 H) 5.44 - 5.54 (m, 1 H) 5.23 - 5.27 (m, 1 H) 3.98 - 4.12 (m, 4 H) 2.13 - 2.23 (m, 3 H).
Step 3: Preparation of 1-[4-(1 ,3-dioxolan-2-yl)-3-nitro-phenyl1ethanone
Figure imgf000074_0002
In a 100 ml three necked round bottomed flask, equipped with a thermometer, a magnetic stirring bar, a glass stopper, a gas inlet tube ended with sintered glass and connected to an ozone generator, was placed a solution of 2-(4-isopropenyl-2-nitro-phenyl)-1 ,3-dioxolane (preparation describe above) (3.18 g, 13.5 mmol, 1.00equiv.) in dichloromethane (65 ml). The flask was cooled down in a dry ice-acetone bath and a mixture of 03 in 02 was bubbled through. at an average rate of 0.83 mmole 03 per minute. After 20 minutes, the color turned blue. The ozone generation was stopped, and excess ozone was stripped away by bubbling oxygen through the reaction mixture. An excess of dimethyl sulfide was then added and the reaction mixture was stirred overnight, while warming up. The next day, the reaction mixture was checked for the presence of peroxides (Kl-starch paper) and was carefully evaporated under reduced pressure and without heating to yield a yellow oil that was submitted to chromatography on silica gel eluting with 0-40% EtOAc in cyclohexane. The title compound was isolated as a white solid. LCMS (standard): RT=0.81 min, m/z = 238 (M+H)+. 1H NMR (400 MHz, CDCB) 6 ppm: 8.44 (d, J=1 .83 Hz, 1 H) 8.18 (dd, J=8.07, 1.47 Hz, 1 H) 7.93 (d, J=8.07 Hz, 1 H) 6.52 (s, 1 H) 3.96 - 4.16 (m, 4 H) 2.67 (s, 3 H)
Step 4: Preparation of 2-[4-(1 ,1-difluoroethyl)-2-nitro-phenyl1-1 ,3-dioxolane
Figure imgf000075_0001
A solution of 1-[4-(1 ,3-dioxolan-2-yl)-3-nitro-phenyl]ethenone (preparation described above) (1 .50 g, 6.32 mmol, 1.0 equiv.) in Deoxo-Fluor solution (50% in THF, 26.9 mL, 10.0 equiv.) under argon, was stirred at 60°C overnight. The solution was then added dropwise onto a well stirred aqueous saturated solution of NaHCO3. The mixture was extracted twice with ethyl acetate and the combined organic layers were washed with sat. aq. NaHCO3, dried over sodium sulfate, filtered, and evaporated to give 2.83 g of dark brown oil which was absorbed on “isolute” and purified by chromatography on silica gel, eluting with 0-100% ethyl acetate in cyclohexane. The title compound was isolated as a yellow oil. LCMS (standard): RT=1.00 min. 1H NMR (400 MHz, CDCb) 6 ppm: 8.05 (s, 1 H) 7.89 (d, J=8.07 Hz, 1 H) 7.76 (dd, J=8.07, 1.47 Hz, 1 H) 6.51 (s, 1 H) 3.97 - 4.14 (m, 4 H) 1.96 (t, J=18.16 Hz, 3 H).
Step 5: Preparation of 4-(1 ,1-difluoroethyl)-2-nitro-benzaldehyde
Figure imgf000075_0002
The title compound was prepared from 2-[4-(1 , 1 -difluoroethyl)-2-nitro-phenyl]-1 ,3-dioxolane (preparation described above) in an analogous way as 2-(4-formyl-3-nitro-phenyl)-2-methyl- propanenitrile (example H2, step 3). LCMS (standard): RT=0.89 min, m/z = 214 (M-H)-.
1H NMR (400 MHz, CDCb) 6 ppm: 10.46 (d, J=0.73 Hz, 1 H) 8.27 (s, 1 H) 8.04 (d, J=8.07 Hz, 1 H) 7.93 (d, J=7.93 Hz, 1 H) 2.00 (t, J=18.34 Hz, 3 H). Step 6: Preparation of (E)-1-[4-(1 ,1-difluoroethyl)-2-nitro-phenyl1-N-[1-(2, 2,3,3, 3-pentafluoropropyl)- pyrazolo[3,4-clpyridin-5-yl1methanimine
Figure imgf000076_0001
The title compound, (E)-1-[4-(1 ,1-difluoroethyl)-2-nitro-phenyl]-N-[1-(2,2,3,3,3-pentafluoropropyl)pyra- zolo[3,4-c]pyridin-5-yl]methanimine was prepared from 4-(1 ,1-difluoroethyl)-2-nitro-benzaldehyde and 1-(2,2,3,3,3-pentafluoropropyl)pyrazolo[3,4-c]pyridin-5-amine (described in the example H1 step 5) in an analogous way 2-methyl-2-[3-nitro-4-[(E)-[1-(2,2,3,3,3-pentafluoropropyl)-pyrazolo[3,4-c]pyridin-5- yl]iminomethyl]phenyl]propanenitrile (example H2, step 4). The product was used directly in the following step without purification.
Step 7: Preparation of 5-[6-(1 ,1-difluoroethyr)indazol-2-yl1-1-(2,2,3,3,3-pentafluoropropyDpyrazolo[3,4- clpyridine
Figure imgf000076_0002
The title compound 5-[6-(1 ,1-difluoroethyl)indazol-2-yl]-1-(2,2,3,3,3-pentafluoropropyl)pyrazolo[3,4- c]pyridine was prepared from crude (E)-1-[4-(1 ,1-difluoroethyl)-2-nitro-phenyl]-N-[1-(2,2,3,3,3- pentafluoropropyl)pyrazolo[3,4-c]pyridin-5-yl]methanimine (preparation described above) under the conditions described for the preparation of 2-methyl-2-[2-[1-(2,2,3,3,3-pentafluoropropyl)pyrazolo[3,4- c]pyridin-5-yl]indazol-6-yl]propanenitrile (example H2, step 5). LCMS (standard): RT=1.18 min, m/z = 432 (M+H)+. 1H NMR (400 MHz, CDCb) 6 ppm 9.15 (d, J=0.73 Hz, 1 H) 8.87 (s, 1 H) 8.63 (d, J=1 .10 Hz, 1 H) 8.28 (s, 1 H) 7.95 (d, J=1 .10 Hz, 1 H) 7.82 (d, J=9.18 Hz, 1 H) 7.24 (dd, J=8.80, 1.47 Hz, 1 H) 5.15 (t, J=13.94 Hz, 2 H) 1.94 - 2.08 (m, 3 H).
Step 8: Preparation of S-fG-d .l-difluoroethyD-S-iodo-indazol^-yll-l-^^.S.S.S-pentafluoropropyD- pyrazolofS^-clpyridine
Figure imgf000077_0001
The title compound 5-[6-(1 ,1-difluoroethyl)-3-iodo-indazol-2-yl]-1-(2,2,3,3,3-pentafluoropropyl)pyra- zolo[3,4-c]pyridine was prepared from 5-[6-(1 ,1-difluoroethyl)indazol-2-yl]-1-(2, 2,3,3, 3-penta- fluoropropyl)pyrazolo[3,4-c]pyridine (preparation described above) in an analogous way as for 2-[3- iodo-2-[1-(2,2,3,3,3-pentafluoropropyl)pyrazolo[3,4-c]pyridin-5-yl]indazol-6-yl]-2-methyl-propanenitrile (example H2, step 6). LCMS (standard): RT=1 .19 min, m/z = 558 (M+H)+.
1H NMR (400 MHz, CDCb) 6 ppm: 9.02 (s, 1 H) 8.34 (s, 1 H) 8.24 (d, J=1 .10 Hz, 1 H) 7.94 - 7.97 (m, 1 H) 7.63 (dd, J=8.80, 0.73 Hz, 1 H) 7.32 (dd, J=8.80, 1.47 Hz, 1 H) 5.21 (t, J=13.75 Hz, 2 H) 2.03 (t, J=18.16 Hz, 3 H) 1.58 (s, 3 H).
Step 9: Preparation of example P11 : 5-[6-(1 ,1-difluoroethyl)-3-ethylsulfanyl-indazol-2-yl1-1-(2,2,3,3,3- pentafluoropropyl)pyrazolo[3,4-clpyridine
Figure imgf000077_0002
The title compound 5-[6-(1 ,1-difluoroethyl)-3-ethylsulfanyl-indazol-2-yl]-1-(2,2,3,3,3-pentafluoropropyl)- pyrazolo[3,4-c]pyridine was prepared from 5-[6-(1 ,1-difluoroethyl)-3-iodo-indazol-2-yl]-1-(2,2,3,3,3- pentafluoropropyl)pyrazolo[3,4-c]pyridine (preparation described above) under analogous conditions as described for 2-[3-ethylsulfanyl-2-[1-(2,2,3,3,3-pentafluoro-propyl)pyrazolo[3,4-c]pyridin-5- yl]indazol-6-yl]-2-methyl-propanenitrile (example H2, step 7).
LCMS (standard): RT=1.21 min, m/z = 493 (M+H)+. 1H NMR (400 MHz, CDCI3) 6 ppm: 9.03 (s, 1 H) 8.30 - 8.35 (m, 1 H) 8.15 (d, J=1 .10 Hz, 1 H) 7.96 - 8.00 (m, 1 H) 7.90 (dd, J=8.80, 0.73 Hz, 1 H) 7.34 (dd, J=8.80, 1 .47 Hz, 1 H) 5.20 (t, J=13.76 Hz, 2 H) 2.94 (q, J=7.34 Hz, 2 H) 1 .94 - 2.09 (m, 3 H) 1 .17 (t, J=7.34 Hz, 3 H).
Step 10: Preparation of example P12: 5-[6-(1 ,1-difluoroethyl)-3-ethylsulfonyl-indazol-2-yl1-1-(2,2,3,3,3- pentafluoropropyl)pyrazolo[3,4-clpyridine
Figure imgf000078_0001
The title compound, 5-[6-(1 ,1-difluoroethyl)-3-ethylsulfonyl-indazol-2-yl]-1-(2,2,3,3,3- pentafluoropropyl)-pyrazolo[3,4-c]pyridine, was prepared from 5-[6-(1 , 1 -difluoroethyl)-3-ethylsulfanyl- indazol-2-yl]-1-(2,2,3,3,3-pentafluoropropyl)pyrazolo[3,4-c]pyridine using the conditions described for 2-[3-ethylsulfonyl-2-[1-(2,2,3,3,3-pentafluoro-propyl)pyrazolo[3,4-c]pyridin-5-yl]indazol-6-yl]-2-methyl- propanenitrile (compound P4, example H2, step 8). LCMS (standard): RT=1.94 min, m/z = 524 (M+H)+. 1H NMR (400 MHz, CDCb) 6 ppm 8.93 (s, 1 H) 8.35 (s, 1 H) 8.27 (d, J=8.36 Hz, 1 H) 8.24 (d, J=0.73 Hz, 1 H) 8.06 (s, 1 H) 7.50 (dd, J=9.08, 1.45 Hz, 1 H) 5.19 (t, J=13.81 Hz, 2 H) 3.95 (d, J=7.27 Hz, 1 H) 3.91 - 3.99 (m, 1 H) 1 .96 - 2.10 (m, 4 H) 1.49 (t, J=7.45 Hz, 4 H).
Example H7: Preparation of 5-(5-cyclopropyl-3-ethylsulfonyl-indazol-2-yl)-1-(2,2,3,3,3-pentafluoro- propyl)pyrazolo[3,4-clpyridine (compound P14)
Figure imgf000078_0002
Under argon, to a solution of 5-bromo-2-nitro-benzaldehyde (3.35 g, 14.3 mmol, 1 .0 equiv.) and cyclopropylboronic acid (1 .52 g, 17.1 mmol, 1 .2 equiv.) in toluene (42.8 mL) was added palladium (II) acetate (0.163 g, 0.714 mmol, 0.05 equiv.), tripotassium phosphate monohydrate (6.18 g, 28.5 mmol, 2.0 equiv.), water (10.7 mL) and SPhos (0.598 g, 1 .43 mmol, 0.1 equiv.). The reaction was stirred at 80°C for 5 days. The mixture was diluted with ethyl acetate, then washed with water. The aqueous
SUBSTITUTE SHEET (RULE 26) layer was extracted with ethyl acetate. The combined organic layers were dried over sodium sulfate, filtered and evaporated to give 2.78 g of brown oil which was absorbed on “isolute” and purified by chromatography, eluting with 0-10% ethyl acetate in cyclohexane. Evaporation of the selected fractions under reduced pressure yielded the title compound. LCMS (standard): RT= 0.93 min, m/z = 190 (M-H)-. 1H NMR (400 MHz, CDCb) 6 ppm 10.45 (d, J=1.47 Hz, 1 H) 8.04 (d, J=8.01 Hz, 1 H) 7.54 (s, 1 H) 7.39 (d, J=8.61 Hz, 1 H) 2.01 - 2.11 (m, 1 H) 1 .08 - 1 .31 (m, 2 H) 0.83 - 0.94 (m, 2 H).
Step 2: Preparation of (E)-1-(5-cyclopropyl-2-nitro-phenyl)-N-[1-(2,2,3,3,3-pentafluoropropyl)pyra- zolo[3,4-clpyridin-5-yl1methanimine
Figure imgf000079_0001
The title compound, (E)-1-(5-cyclopropyl-2-nitro-phenyl)-N-[1-(2,2,3,3,3-pentafluoropropyl)pyrazolo [3,4-c]pyridin-5-yl]methanimine, was prepared from 5-cyclopropyl-2-nitro-benzaldehyde (preparation described hereabove) and 1-(2,2,3,3,3-pentafluoropropyl)pyrazolo[3,4-c]pyridin-5-amine (described in the example H1 step 5) in an analogous way as for 2-methyl-2-[3-nitro-4-[(E)-[1-(2,2,3,3,3- pentafluoropropyl)-pyrazolo[3,4-c]pyridin-5-yl]iminomethyl]phenyl]propanenitrile (example H2, step 4). LCMS (standard): RT= 0.94 min, m/z = 438 (M-H)’.
Step 3: Preparation of 5-(5-cyclopropylindazol-2-yl)-1-(2,2,3,3,3-pentafluoropropyl)pyrazolo[3,4- clpyridine
Figure imgf000079_0002
The title compound, 5-(5-cyclopropylindazol-2-yl)-1-(2,2,3,3,3-pentafluoropropyl)pyrazolo[3,4-c]- pyridine, was prepared from (E)-1-(5-cyclopropyl-2-nitro-phenyl)-N-[1-(2,2,3,3,3-pentafluoro- propyl)pyrazolo[3,4-c]pyridin-5-yl]methanimine (preparation described hereabove) in an analogous way as for 2-methyl-2-[2-[1-(2,2,3,3,3-pentafluoropropyl)pyrazolo[3,4-c]pyridin-5-yl]indazol-6- yl]propane-nitrile (example H2, step 5). LCMS (standard): RT=1 .23 min, m/z = 408 (M+H)+.
1H NMR (400 MHz, CDCb) 6 ppm 9.00 (s, 1 H) 8.86 (s, 1 H) 8.59 (s, 1 H) 8.25 (s, 1 H) 7.69 (d, J=9.17 Hz, 1 H) 7.44 (s, 1 H) 7.12 (d, J=8.80 Hz, 1 H) 5.13 (t, J=13.94 Hz, 2 H) 1 .97 - 2.08 (m, 1 H) 0.94 - 1 .03 (m, 2 H) 0.72 - 0.80 (m, 2 H). Step 4: Preparation of 5-(5-cyclopropyl-3-iodo-indazol-2-yl)-1-(2,2,3,3,3- pentafluoropropyl)pyrazolo[3,4-clpyridine
Figure imgf000080_0001
The title compound, 5-(5-cyclopropyl-3-iodo-indazol-2-yl)-1-(2,2,3,3,3-pentafluoropropyl)pyrazolo[3,4- c]pyridine, was prepared from 5-(5-cyclopropylindazol-2-yl)-1-(2,2,3,3,3- pentafluoropropyl)pyrazolo[3,4-c]pyridine (preparation described above) in an analogous way as for 2- [3-iodo-2-[1-(2,2,3,3,3-pentafluoropropyl)pyrazolo[3,4-c]pyridin-5-yl]indazol-6-yl]-2-methyl- propanenitrile (example H2, step 6). LCMS (standard): RT=1.22 min, m/z = 534 (M+H)+.
1H NMR (400 MHz, CDCb) 6 ppm 9.01 (s, 1 H) 8.29 - 8.34 (m, 1 H) 8.20 (d, J=1 .10 Hz, 1 H) 7.67 (dd, J=8.80, 0.73 Hz, 1 H) 7.22 (s, 1 H) 7.15 - 7.19 (m, 1 H) 5.19 (t, J=13.75 Hz, 2 H) 2.03 - 2.11 (m, 1 H) 0.94 - 1 .06 (m, 2 H) 0.76 - 0.92 (m, 2 H).
Step 5: Preparation of example P13: 5-(5-cyclopropyl-3-ethylsulfanyl-indazol-2-yl)-1-(2,2,3,3,3- pentafluoropropyl)pyrazolo[3,4-clpyridine
Figure imgf000080_0002
Under argon atmosphere, to a solution of 5-(5-cyclopropyl-3-iodo-indazol-2-yl)-1-(2,2,3,3,3- pentafluoropropyl)pyrazolo[3,4-c]pyridine (0.130 g, 0.244 mmol, 1.0 equiv.) in toluene (15 mL) was added copper (I) iodide (0.000827 mL, 0.0244 mmol, 0.1 equiv.), neocuproine (0.0051 g, 0.0244 mmol, 0.1 equiv.) and ethanethiol sodium salt (0.077 g, 0.734 mmol, 3.0 equiv.). The reaction mixture was stirred at 110°C for 1 hour. Then, it was filtered over celite and the filtrate was evaporated to give 0.114 g of orange oil, which was absorbed on “isolute” and purified by chromatography with 0-10% ethyl acetate in cyclohexane. The title compound /example P13) was isolated as a yellow oil.
LCMS (standard): RT=1.22 min, m/z = 534 (M+H)+. 1H NMR (400 MHz.CDCb) 6 ppm: 9.00 (s, 1 H) 8.29 (d, J=0.73 Hz, 1 H) 8.10 (d, J=1 .09 Hz, 1 H) 7.69 - 7.73 (m, 1 H) 7.51 (d, J=0.73 Hz, 1 H) 7.10 - 7.18 (m, 1 H) 5.13 - 5.23 (m, 2 H) 2.85 - 2.93 (m, 2 H) 2.00 - 2.12 (m, 1 H) 1.12 - 1.17 (m, 3 H) 0.99 - 1 .05 (m, 2 H) 0.78 - 0.84 (m, 2 H). Step 6: Preparation of example P14: 5-(5-cyclopropyl-3-ethylsulfonyl-indazol-2-yl)-1-(2, 2,3,3, 3-penta- fluoropropyl)pyrazolo[3,4-clpyridine
Figure imgf000081_0001
The example P14, 5-(5-cyclopropyl-3-ethylsulfonyl-indazol-2-yl)-1 -(2,2,3,3,3-pentafluoropropyl)pyra- zolo[3,4-c]pyridine, was prepared from 5-(5-cyclopropyl-3-ethylsulfanyl-indazol-2-yl)-1-(2,2,3,3,3- pentafluoropropyl)pyrazolo[3,4-c]pyridine (preparation described hereabove) in a similar way as for 2- [3-ethylsulfonyl-2-[1-(2,2,3,3,3-pentafluoro-propyl)pyrazolo[3,4-c]pyridin-5-yl]indazol-6-yl]-2-methyl- propanenitrile (Preparation example H2, step 8). LCMS (standard): RT=1.18 min, m/z = 500 (M+H)+. 1H NMR (400 MHz, CDCb) 6 ppm 8.85 - 8.93 (m, 1 H) 8.29 (s, 1 H) 8.15 - 8.19 (m, 1 H) 7.87 (s, 1 H) 7.71 - 7.80 (m, 1 H) 7.11 - 7.20 (m, 1 H) 5.07 - 5.25 (m, 3 H) 3.89 (q, J=7.63 Hz, 2 H) 1 .98 - 2.16 (m, 1
H) 1 .39 - 1 .51 (m, 3 H) 0.93 - 1 .12 (m, 3 H) 0.74 - 0.89 (m, 3 H).
Example H8: Preparation of 1-[3-ethylsulfonyl-2-[1-(3,3,3-trifluoropropyl)pyrazolo[3,4-clpyridin-5-yl1- indazol-6-yllcyclopropanecarbonitrile (compound P16)
Figure imgf000081_0002
Step 1 : Preparation of 2-(4-bromo-2-nitro-phenyl)-1 ,3-dioxolane
SUBSTITUTE SHEET (RULE 26)
Figure imgf000082_0001
The title compound, 2-(4-bromo-2-nitro-phenyl)-1 ,3-dioxolane, was prepared from 4-bromo-2-nitro- benzaldehyde under the conditions described for 2-(5-bromo-2-nitro-phenyl)-1 ,3-dioxolane (example H4, step 1). LCMS (standard): RT=0.98 min, m/z = 275 (M+H)+. 1H NMR (400 MHz, CDCb) 6 ppm 8.07 (d, J=1.83 Hz, 1 H) 7.77 (d, J=8.10 Hz, 1 H) 7.70 (d, J=8.16 Hz, 1 H) 6.45 (s, 1 H) 3.99 - 4.24 (m, 4 H).
Step 2: Preparation of 2-[4-(1 ,3-dioxolan-2-yl)-3-nitro-phenyl1acetonitrile
Figure imgf000082_0002
A suspension of 2-(4-bromo-2-nitro-phenyl)-1 ,3-dioxolane (6.0 g, 22 mmol, 1.0 equiv.) and potassium cyanoacetate (4.3 g, 33 mmol, 1 .5 equiv.) in mesitylene (110 mL) was stirred and degassed with argon for 5 minutes. Then Bis(allyl)dichloropalladium (0.41 g, 1.1 mmol, 0.05 equiv.) and SPhos (0.95 g, 2.2 mmol, 0.1 equiv.) were added and the reaction mixture was degassed with argon for 5 minutes, then heated at 130°C overnight. Additional potassium cyanoacetate (1.4 g, 11 mmol, 0.5 equiv.) was added and the mixture was stirred at 130°C for 2 more hours. The reaction mixture was cooled to room temperature, then extracted between ethyl acetate and water. The combined organic layers were washed with brine, dried over magnesium sulfate, filtered, and evaporated to give 8.70 g of dark brown oil which was absorbed on “isolute” and purified by chromatography, eluting with a gradient of 0-100% ethyl acetate in cyclohexane. The title compound was isolated as an orange oil.
LCMS (standard): RT=0.76 min, m/z = 233 (M-H)’. 1H NMR (400 MHz, CDCb) 6 ppm 7.85 - 7.96 (m, 2 H) 7.62 - 7.70 (m, 1 H) 6.45 - 6.51 (m, 1 H) 4.00 - 4.15 (m, 4 H) 3.88 (s, 2 H).
Step 3: Preparation of 1-[4-(1 ,3-dioxolan-2-yl)-3-nitro-phenyl1cyclopropanecarbonitrile
Figure imgf000083_0001
To a suspension of 2-[4-(1 ,3-dioxolan-2-yl)-3-nitro-phenyl]acetonitrile (preparation described above) (1.10 g, 4.70 mmol, 1 .00 equiv.) and potassium carbonate (1 .97 g, 14.1 mmol, 3.0 equiv.) in dimethylsulfoxide (28.6 mL) was added 1 ,2-dibromoethane (0.613 mL, 7.04 mmol, 1.50 equiv.). The reaction mixture was heated at 50°C overnight. After addition of water, the mixture was extracted twice with ethyl acetate, the combined organic layers were washed with brine, dried over sodium sulfate, filtered, and evaporated to give 1 .62 g of dark red oily residue, which was absorbed on “isolute” and purified by chromatography, eluting with a gradient of 0-100% ethyl acetate in cyclohexane. The title compound was isolated as an orange solid. LCMS (standard): RT=0.88 min, m/z = 261 (M+H)+.
1H NMR (400 MHz, CDCb) 6 ppm 7.83 (d, J=8.07 Hz, 1 H) 7.74 (d, J=1.83 Hz, 1 H) 7.62 - 7.68 (m, 1 H) 6.47 (s, 1 H) 4.00 - 4.11 (m, 4 H) 1 .82 - 1 .94 (m, 2 H) 1 .48 - 1 .54 (m, 2 H).
Step 4: Preparation of 1-(4-formyl-3-nitro-phenyl)cyclopropanecarbonitrile
Figure imgf000083_0002
The title compound, 1-(4-formyl-3-nitro-phenyl)cyclopropanecarbonitrile, was prepared 1-[4-(1 ,3- dioxolan-2-yl)-3-nitro-phenyl]cyclopropanecarbonitrile (preparation described above), using analogous conditions as for the preparation of 2-(4-formyl-3-nitro-phenyl)-2-methyl-propanenitrile (example H2, step 3). LCMS (standard): RT=0.81 min, m/z = 215 (M-H)’. 1H NMR (400 MHz, CDCb) 6 ppm 10.40 - 10.46 (m, 1 H) 8.00 (d, J=7.99 Hz, 1 H) 7.95 (d, J=1.82 Hz, 1 H) 7.76 (dd, J=7.99, 1.45 Hz, 1 H) 1.94 - 2.02 (m, 2 H) 1.56 - 1.68 (m, 2 H).
Step 5: Preparation of 5-bromo-1-(3,3,3-trifluoropropyl)pyrazolo[3,4-clpyridine
Figure imgf000083_0003
To a suspension of 5-bromo-1 H-pyrazolo[3,4-c]pyridine (CAS 929617-35-6) (1.50 g, 7.35 mmol, 1.0 equiv.) in acetonitrile (15 mL) was added potassium carbonate (2.63 g, 11.0 mmol, 1.50 equiv.) and the mixture was stirred at room temperature for 30 minutes. Then, 1 ,1 ,1-Trifluoro-3-iodo-propane (1 .32 mL, 11 .0 mmol, 1 .5 equiv.) was slowly added at room temperature, and the mixture was stirred at 60°C overnight. More 1 ,1 ,1-trifluoro-3-iodo-propane (1 .32 mL, 11 .0 mmol, 1 .5 equiv.) was slowly added and the reaction mixture was stirred at 60°C for 7 hours. Potassium carbonate (2.63 g, 11 .0 mmol, 1 .50 equiv.) was added and the mixture was stirred at 60°C overnight. Another portion of 1 ,1 ,1- trifluoro-3-iodo-propane (1 .32 mL, 11 .0 mmol, 1 .5 equiv.) was added and reaction mixture was stirred at 60°C for 24 more hours. Finally, a last portion of 1 ,1 ,1-trifluoro-3-iodo-propane (1.32 mL, 11.0 mmol, 1 .5 equiv.) and potassium carbonate (2.63 g, 11 .0 mmol, 1 .50 equiv.) were added and the reaction mixture was stirred at 60°C for 6.5 hours. The mixture was cooled down to room temperature, diluted with water and extracted twice with ethyl acetate. The combined organic layers were washed with brine, dried over sodium sulfate, filtered, and evaporated to give 2.15 g of brown amorphous residue, which was absorbed on “isolute” and purified by chromatography, eluting with a gradient of 0- 100% ethyl acetate in cyclohexane. The title compound was isolated as a beige solid. LCMS (standard): RT=0.92 min, m/z = 295 (M+H)+. 1H NMR (400 MHz, CDCb) 6 ppm: 8.76 (s, 1 H) 8.06 (d, J=0.73 Hz, 1 H) 7.85 (d, J=1 .09 Hz, 1 H) 4.72 (t, J=7.08 Hz, 2 H) 2.86 (qt, J=10.29, 7.08 Hz, 2 H).
Step 6: Preparation of tert-butyl N-[1-(3,3,3-trifluoropropyl)pyrazolo[3,4-clpyridin-5-yl1carbamate
Figure imgf000084_0001
To a solution of 5-bromo-1-(3,3,3-trifluoropropyl)pyrazolo[3,4-c]pyridine (0.150 g, 0.510 mmol, 1.0 equiv.) and tert-butyl carbamate (0.091 g, 0.765 mmol, 1 .5 equiv.) in 1 ,4- dioxane (3 mL) was added cesium carbonate (0.509 g, 1 .53 mmol, 3.0 equiv.). The suspension was degassed with argon for 5 minutes. Xantphos (0.0487 g, 0.0816 mmol, 0.16 equiv.) and tris(dibenzylideneacetone)dipalladium(0) (0.0385 g, 0.041 mmol, 0.08 equiv.) were added and the mixture was heated at 90°C for 2 hours. After cooling down to room temperature, water was added and the resulting mixture was extracted twice with ethyl acetate. The combined organic layers were washed with sat.aq. NaHCC , dried over sodium sulfate, filtered and evaporated to give 1 ,44g of orange amorphous residue, which was absorbed on “isolute” and purified by chromatography with 0-100% ethyl acetate in cyclohexane. The title compound was isolated as a beige solid. LCMS (standard): RT=1 .02 min, m/z = 331 (M+H)+. 1H NMR (400 MHz, CDCb) 6 ppm: 8.63 (s, 1 H) 8.24 (s, 1 H) 8.01 (s, 1 H) 7.67 (br s, 1 H) 4.67 (t, J=7.08 Hz, 2 H) 4.39 (br s, 1 H) 2.82 (qt, J=10.29, 7.27 Hz, 2 H) 1.56 (s, 10 H). Step 7: Preparation of 1-(3,3,3-trifluoropropyl)pyrazolo[3,4-clpyridin-5-amine
Figure imgf000085_0001
tert-Butyl N-[1-(3,3,3-trifluoropropyl)pyrazolo[3,4-c]pyridin-5-yl]carbamate (1.06 g, 3.21 mmol, 1.0 equiv.) was suspended in HCI (4M in dioxane, 16mL, 64 mmol, 20.0 equiv.) and the reaction mixture was stirred at room temperature overnight. The suspension was filtered and solid was washed three times with diisopropylether. The solid was dissolved in water and the aqueous layer was extracted twice with ethyl acetate. The combined organic layers were washed with sat. aq. NaHCO3, dried over sodium sulfate, filtered, and evaporated to give the title compound as a brown solid. LCMS (standard): RT=0.46 min, m/z = 231 (M+H)+. 1H NMR (400 MHz, CDCb) 6 ppm 8.54 (s, 2 H) 7.86 (s, 2 H) 6.76 (s, 2 H) 4.63 (t, J=7.27 Hz, 5 H) 2.73 - 2.89 (m, 5 H).
Step 8: Preparation of 1-[3-nitro-4-[(E)-[1-(3,3,3-trifluoropropyl)pyrazolo[3,4-clpyridin-5-yl1iminomethyl1- phenyllcyclopropanecarbonitrile
Figure imgf000085_0002
1-[3-nitro-4-[(E)-[1-(3,3,3-trifluoropropyl)pyrazolo[3,4-c]pyridin-5-yl]iminomethyl]phenyl]cyclopropane- carbonitrile was prepared from 1-(3,3,3-trifluoropropyl)pyrazolo[3,4-c]pyridin-5-amine (preparation described hereabove) and 1-(4-formyl-3-nitro-phenyl)cyclopropanecarbonitrile (preparation described in example H8 step 4) under analogous conditions as described for 2-methyl-2-[3-nitro-4-[(E)-[1- (2,2,3,3,3-pentafluoropropyl)-pyrazolo[3,4-c]pyridin-5-yl]iminomethyl]phenyl]propanenitrile (example H2, step 4). The compound was not purified and was used directly for the following step.
Step 9: Preparation of 1-[2-[1-(3,3,3-trifluoropropyl)pyrazolo[3,4-clpyridin-5-yl1indazol-6-yl1cyclopro- panecarbonitrile
Figure imgf000086_0001
The title compound, 1-[2-[1-(3,3,3-trifluoropropyl)pyrazolo[3,4-c]pyridin-5-yl]indazol-6-yl]cyclopropane- carbonitrile was prepared from 1-[3-nitro-4-[(E)-[1-(3,3,3-trifluoropropyl)pyrazolo[3,4-c]pyridin-5- yl]iminomethyl]phenyl]cyclopropanecarbonitrile and the conditions described for 2-methyl-2-[2-[1- (2,2,3,3,3-pentafluoropropyl)pyrazolo[3,4-c]pyridin-5-yl]indazol-6-yl]propanenitrile (example H2, step 5). LCMS (standard): RT=1.11 min, m/z = 397 (M+H)+. 1H NMR (400 MHz, CDCb) 6 ppm: 9.13 (d, J=1 .09 Hz, 1 H) 8.86 (s, 1 H) 8.58 - 8.61 (m, 1 H) 8.23 (d, J=0.73 Hz, 1 H) 7.77 (d, J=8.81 Hz, 1 H) 7.70 - 7.74 (m, 1 H) 7.10 (d, J=8.71 Hz, 1 H) 4.79 (t, J=7.08 Hz, 2 H) 2.91 (qt, J=10.29, 7.08 Hz, 2 H) 1 .76 - 1 .82 (m, 2 H) 1 .49 - 1 .57 (m, 2 H).
Step 10: Preparation of 1-[3-iodo-2-[1-(3,3,3-trifluoropropyl)pyrazolo[3,4-clpyridin-5-yl1indazol-6-yl1- cyclopropanecarbonitrile
Figure imgf000086_0002
The title compound, 1-[3-iodo-2-[1-(3,3,3-trifluoropropyl)pyrazolo[3,4-c]pyridin-5-yl]indazol-6- yl]cyclopropanecarbonitrile, was prepared from 1-[2-[1-(3,3,3-trifluoropropyl)pyrazolo[3,4-c]pyridin-5- yl]indazol-6-yl]cyclopropanecarbonitrile analogously to the preparation of 2-[3-iodo-2-[1-(2,2,3,3,3- pentafluoropropyl)pyrazolo[3,4-c]pyridin-5-yl]indazol-6-yl]-2-methyl-propanenitrile (example H2, step 6). LCMS (standard): RT=1.07 min, m/z = 523 (M+H)+. 1H NMR (400 MHz, CDCb) 6 ppm 9.00 (s, 1 H) 8.24 - 8.31 (m, 1 H) 8.17 (d, J=1.09 Hz, 1 H) 7.70 (dd, J=1 .45, 0.73 Hz, 1 H) 7.54 - 7.58 (m, 1 H) 7.18 (dd, J=8.90, 1 .63 Hz, 1 H) 4.83 (t, J=7.08 Hz, 2 H) 2.94 (qt, J=10.29, 7.08 Hz, 2 H) 1 .75 - 1 .83 (m, 2 H) 1.50 - 1.57 (m, 2 H).
Step 11 : Preparation of example P15: 1-[3-ethylsulfanyl-2-[1-(3,3,3-trifluoropropyl)pyrazolo[3,4-c1- pyridin-5-yl1indazol-6-yl1cyclopropanecarbonitrile
Figure imgf000087_0001
The title compound, 1-[3-ethylsulfanyl-2-[1-(3,3,3-trifluoropropyl)pyrazolo[3,4-c]pyridin-5-yl]indazol-6- yl]cyclopropanecarbonitrile, was prepared from 1-[3-iodo-2-[1-(3,3,3-trifluoropropyl)pyrazolo[3,4- c]pyridin-5-yl]indazol-6-yl]cyclopropanecarbonitrile (preparation described hereabove) under analogous conditions as for 2-[3-ethylsulfanyl-2-[1-(2,2,3,3,3-pentafluoro-propyl)pyrazolo[3,4-c]pyridin- 5-yl]indazol-6-yl]-2-methyl-propanenitrile (example H2, step 7).
LCMS (standard): RT=1.11 min, m/z = 457 (M+H)+.
Step 12: Preparation of example P16: 1-[3-ethylsulfonyl-2-[1-(3,3,3-trifluoropropyl)pyrazolo[3,4-c1 pyridin-5-yl1indazol-6-yl1cyclopropanecarbonitrile
Figure imgf000087_0002
The title compound, 1-[3-ethylsulfonyl-2-[1-(3,3,3-trifluoropropyl)pyrazolo[3,4-c]pyridin-5-yl]indazol-6- yl]-cyclopropanecarbonitrile, was prepared from 1 -[3-ethylsulfanyl-2-[1 -(3,3,3-trifluoropropyl)- pyrazolo[3,4-c]pyridin-5-yl]indazol-6-yl]cyclopropanecarbonitrile (preparation described hereabove) under analogous conditions as for 2-[3-ethylsulfonyl-2-[1 -(2,2,3,3,3-pentafluoro-propyl)pyrazolo[3,4- c]pyridin-5-yl]indazol-6-yl]-2-methyl-propanenitrile (example H2, step 8). LCMS (standard): RT=1.04 min, m/z = 489 (M+H)+. 1H NMR (400 MHz, CDCb) 6 ppm 8.89 (s, 1 H) 8.28 (s, 1 H) 8.21 (br dd, J=9.08, 0.73 Hz, 1 H) 8.19 (d, J=1.09 Hz, 1 H) 7.85 (s, 1 H) 7.29 - 7.31 (m, 1 H) 4.80 (t, J=7.27 Hz, 2 H) 3.95 (q, J=7.63 Hz, 2 H) 2.88 - 3.01 (m, 2 H) 1 .79 - 1 .89 (m, 2 H) 1 .52 - 1 .62 (m, 2 H) 1 .48 (t, J=7.45 Hz, 3 H).
Example H9: Preparation of N-[3-ethylsulfonyl-2-[1-(2,2,3,3,3-pentafluoropropyl) pyrazolo[3,4- clpyridin-5-yl1indazol-6-yl1-N-methyl-acetamide (compound P20)
Figure imgf000088_0001
Step 1 : Preparation of 2-(4-fluoro-2-nitro-phenyl)-1 ,3-dioxolane
Figure imgf000088_0002
The title compound, 2-(4-fluoro-2-nitro-phenyl)-1 ,3-dioxolane, was prepared from 4-fluoro-2-nitro- benzaldehyde under the conditions described for 2-(5-bromo-2-nitro-phenyl)-1 ,3-dioxolane (example H4, step 1). LCMS (standard): RT=0.86 min, m/z = 214 (M+H)+. 1H NMR (400 MHz, CDCb) 6 ppm 7.76 (dd, J=8.72, 5.45 Hz, 1 H) 7.56 (dd, J=8.17, 2.72 Hz, 1 H) 7.28 (ddd, J=8.72, 7.63, 2.54 Hz, 1 H) 6.31 - 6.36 (m, 1 H) 3.90 - 4.03 (m, 4 H). Step 2: Preparation of 4-(1 ,3-dioxolan-2-yl)-N-methyl-3-nitro-aniline
Figure imgf000088_0003
To a biphasic solution of 2-(4-fluoro-2-nitro-phenyl)-1 ,3-dioxolane (preparation described hereabove) (27 g, 126.67 mmol, 1 .0 equiv.) in methylamine (40 mass% in water, 110 mL, 1266.7 mmol, 10.0
SUBSTITUTE SHEET (RULE 26) equiv.) was added 1 ,2-dimethoxyethane (110 mL, 1013.3 mmol, 8.0 equiv.). The reaction was heated in microwave at 120°C for 6 hours. The product was extracted three times with ethyl acetate. The combined organic layers were combined, washed with brine, dried over sodium sulfate, filtered, and evaporated to give 31 g of brown oil. The crude was used as such in the following step.
LCMS (standard): RT=0.80 min, m/z = 225 (M+H)+. 1H NMR (400 MHz, CDCb) 6 ppm 7.55 (d, J=8.72 Hz, 1 H) 7.02 - 7.08 (m, 1 H) 6.77 (dd, J=8.54, 2.36 Hz, 1 H) 6.31 (s, 1 H) 4.18 - 4.27 (m, 1 H) 3.96 - 4.10 (m, 4 H) 2.88 (d, J=5.09 Hz, 3 H).
Step 3: Preparation of N-[4-(1 ,3-dioxolan-2-yl)-3-nitro-phenyl1-N-methyl-acetamide
Figure imgf000089_0001
A solution of 4-(1 ,3-dioxolan-2-yl)-N-methyl-3-nitro-aniline (preparation described above) (31 g, 138 mmol, 1 .0 equiv.) in 1 ,2-dimethoxyethane (553 mL) was cooled down to -20°C. Then, acetyl chloride (20 mL, 276 mmol, 2.0 equiv.) followed by triethylamine (194 mL, 1382 mmol, 10.0 equiv.) were added. The mixture was allowed to reach room temperature and was stirred at that temperature for 1 .5 hours. The suspension was then filtered and the residue rinsed with ethyl acetate. The filtrate was concentrated, then diluted with water. The aqueous layer was extracted three times with ethyl acetate. The combined organic layers were washed with brine, dried over sodium sulfate, filtered, and evaporated to give 33.5 g of brown oil residue which was absorbed on “isolute” and purified by chromatography, eluting with a gradient of 0-100% ethyl acetate in cyclohexane. Evaportion of the selected fractions yielded the title compound. LCMS (standard): RT=0.71 min, m/z = 267 (M+H)+. 1H NMR (400 MHz, CDCb) 6 ppm 7.84 (br d, J=8.36 Hz, 1 H) 7.73 - 7.80 (m, 1 H) 7.48 (br d, J=7.27 Hz, 1 H) 6.43 (s, 1 H) 3.99 - 4.06 (m, 4 H) 3.29 (br s, 3 H) 1 .96 (br s, 3 H).
Step 4: Preparation of N-(4-formyl-3-nitro-phenyl)-N-methyl-acetamide
Figure imgf000089_0002
To a solution of N-[4-(1 ,3-dioxolan-2-yl)-3-nitro-phenyl]-N-methyl-acetamide (preparation described hereabove) (19.3 g, 72.5 mmol, 1 .0 equiv.) in acetone (123 mL) and water (40.6 mL) was added concentrated aqueous hydrochloric acid (7.12 mL, 72.5 mmol, 1.0 equiv.). The reaction mixture was stirred at 50°C for 4 hours. The, reaction mixture was then neutralized by addition of sodium hydroxide (2M, 30 mL) followed by addition of sat.aqueous NaHCOs at 0°C. The aqueous layer was extracted three times with ethyl acetate. The combined organic layers were washed with brine, dried over sodium sulfate, filtered, and evaporated to yield the title compound as an orange solid. The crude was used in the next step without further purification. LCMS (standard): RT=0.64 min, m/z = 223 (M+H)+. 1H NMR (400 MHz, CDCb) 6 ppm 10.41 (s, 1 H) 8.01 - 8.05 (m, 2 H) 7.68 (dd, J=8.36, 1 .82 Hz, 1 H) 3.42 (s, 3 H) 2.14 (s, 3 H).
Step 5: Preparation of N-methyl-N-[3-nitro-4-[(E)-[1-(2,2,3,3,3-pentafluoropropyl)pyrazolo[3,4-clpyridin- 5-ylliminomethyllphenyllacetamide
Figure imgf000090_0001
The title compound, N-methyl-N-[3-nitro-4-[(E)-[1-(2,2,3,3,3-pentafluoropropyl)pyrazolo[3,4-c]pyridin-5- yl]iminomethyl]phenyl]acetamide, was prepared from N-(4-formyl-3-nitro-phenyl)-N-methyl-acetamide (preparation described hereabove) and 1-(2,2,3,3,3-pentafluoropropyl)pyrazolo[3,4-c]pyridin-5-amine (described in the example H1 step 5) in an analogous way as for 2-methyl-2-[3-nitro-4-[(E)-[1- (2,2,3,3,3-pentafluoropropyl)-pyrazolo[3,4-c]pyridin-5-yl]iminomethyl]phenyl]propanenitrile (example H2, step 4).
Step 6: Preparation of N-methyl-N-[2-[1-(2, 2,3,3, 3-pentafluoropropyl)pyrazolo[3,4-clpyridin-5- yllindazol-6-yllacetamide
Figure imgf000090_0002
The title compound N-methyl-N-[2-[1-(2,2,3,3,3-pentafluoropropyl)pyrazolo[3,4-c]pyridin-5-yl]indazol-6- yl]acetamide was prepared from N-methyl-N-[3-nitro-4-[(E)-[1-(2,2,3,3,3-pentafluoropropyl)- pyrazolo[3,4-c]pyridin-5-yl]iminomethyl]phenyl]acetamide in an analogous way as for 2-methyl-2-[2-[1- (2,2,3,3,3-pentafluoropropyl)pyrazolo[3,4-c]pyridin-5-yl]indazol-6-yl]propanenitrile (example H2, step 5). LCMS (standard): RT=1.00 min, m/z = 440 (M+H)+. 1H NMR (400 MHz, CDCb) 6 ppm 9.19 (s, 1 H) 8.90 (s, 1 H) 8.63 (d, J=1.09 Hz, 1 H) 8.29 (s, 1 H) 7.83 (d, J=8.72 Hz, 1 H) 7.60 (s, 1 H) 6.96 (br d, J=8.72 Hz, 1 H) 5.05 - 5.22 (m, 2 H) 3.37 (s, 3 H) 2.01 (s, 3 H).
Step 7: Preparation of N-methyl-2-[1-(2,2,3,3,3-pentafluoropropyl)pyrazolo[3,4-clpyridin-5-yl1indazol-6- amine
Figure imgf000091_0001
To a solution of N-methyl-N-[2-[1-(2, 2,3,3, 3-pentafluoropropyl)pyrazolo[3,4-c]pyridin-5-yl]indazol-6- yl]acetamide (0.40 g, 0.912 mmol, 1 .0 equiv.) in 1 ,2-dimethoxyethane (8.7 mL) was added hydrochloric acid (4M in water, 2.3 mL, 9.12 mmol, 10.0 equiv.). The reaction mixture was stirred at reflux over two days, after what, it was quenched by addition of sat. aq. NaHCOs. The phases were separated and the aqueous layer was extracted three times with ethyl acetate. The combined organic layers were washed with brine, dried over sodium sulfate, filtered and evaporated to yield the title compound as a yellow solid. The crude product was used as such without further purification.
LCMS (standard): RT=1.02 min, m/z = 397 (M+H)+. 1H NMR (400 MHz, CDCb) 6 ppm 8.93 (d, J=0.73 Hz, 1 H) 8.83 (s, 1 H) 8.52 (d, J=1.45 Hz, 1 H) 8.23 (d, J=0.73 Hz, 1 H) 7.49 - 7.53 (m, 1 H) 6.63 (s, 1 H) 6.57 (dd, J=8.90, 2.00 Hz, 1 H) 5.13 (t, J=13.81 Hz, 2 H) 3.97 (br s, 1 H) 2.96 (s, 3 H).
Step 8: Preparation of 2,2,2-trifluoro-N-methyl-N-[2-[1-(2,2,3,3,3-pentafluoropropyl)pyrazolo[3,4- clpyridin-5-yl1indazol-6-yl1acetamide
Figure imgf000091_0002
To a solution of N-methyl-2-[1-(2,2,3,3,3-pentafluoropropyl)pyrazolo[3,4-c]pyridin-5-yl]indazol-6-amine (preparation described above) (0.35 g, 0.883 mmol, 1.0 equiv.) in THF (15 mL) was added triethylamine (0.249 mL, 1.76 mmol, 2.0 equiv.) and pyridine (0.072 mL, 0.883 mmol, 1.0 equiv.).
Trifluoroacetic anhydride (0.248 mL, 1 .76 mmol, 2.0 equiv.) was added dropwise at 0°C. The reaction mixture was stirred at room temperature for 30 minutes, then evaporated. The residue was diluted with sat. aq. NaHCC (5 mL) and extracted with ethyl acetate. The organic layer was washed with brine, dried over sodium sulfate, filtered, and evaporated to give the title compound in form of a brown solid. The crude was used as such in the following step. LCMS (standard): RT=1 .14 min, m/z = 493 (M+H)+. 1H NMR (400 MHz, CDCb) 6 ppm 9.20 (s, 1 H) 8.90 (s, 1 H) 8.63 (s, 1 H) 8.28 (s, 1 H) 7.84 (d, J=8.72 Hz, 1 H) 7.67 (s, 1 H) 6.93 - 7.01 (m, 1 H) 5.07 - 5.23 (m, 2 H) 3.46 (s, 3 H).
Step 9: Preparation of 2,2,2-trifluoro-N-[3-iodo-2-[1-(2,2,3,3,3-pentafluoropropyl)pyrazolo[3,4-clpyridin-
5-yl1indazol-6-yl1-N-methyl-acetamide
Figure imgf000092_0001
The title compound, 2,2,2-trifluoro-N-[3-iodo-2-[1-(2,2,3,3,3-pentafluoropropyl)pyrazolo[3,4-c]pyridin-5- yl]indazol-6-yl]-N-methyl-acetamide was prepared from 2,2,2-trifluoro-N-methyl-N-[2-[1-(2,2,3,3,3- pentafluoropropyl)pyrazolo[3,4-c]pyridin-5-yl]indazol-6-yl]acetamide in an analogous way as for 2-[3- iodo-2-[1-(2,2,3,3,3-pentafluoropropyl)pyrazolo[3,4-c]pyridin-5-yl]indazol-6-yl]-2-methyl-propanenitrile (example H2, step 6). LCMS (standard): RT=1 .14 min, m/z = 619 (M+H)+. 1H NMR (400 MHz, CDCb) 6 ppm 9.03 (s, 1 H) 8.30 - 8.38 (m, 1 H) 8.23 - 8.26 (m, 1 H) 7.68 (s, 1 H) 7.66 (d, J=9.08 Hz, 1 H) 7.02 - 7.08 (m, 1 H) 5.21 (t, J=13.81 Hz, 2 H) 3.46 (s, 3 H).
Step 10: Preparation of example P17: N-[3-ethylsulfanyl-2-[1-(2,2,3,3,3- pentafluoropropyl)pyrazolo[3,4-clpyridin-5-yl1indazol-6-yl1-2,2,2-trifluoro-N-methyl-acetamide
Figure imgf000092_0002
The title compound, N-[3-ethylsulfanyl-2-[1-(2,2,3,3,3-pentafluoropropyl)pyrazolo[3,4-c]pyridin-5- yl]indazol-6-yl]-2,2,2-trifluoro-N-methyl-acetamide was prepared from 2,2,2-trifluoro-N-[3-iodo-2-[1- (2,2,3,3,3-pentafluoropropyl)pyrazolo[3,4-c]pyridin-5-yl]indazol-6-yl]-N-methyl-acetamide (preparation described above) in an analogous way as for 5-(5-cyclopropyl-3-ethylsulfanyl-indazol-2-yl)-1- (2,2,3,3,3-pentafluoropropyl)pyrazolo[3,4-c]pyridine (example H7, step 5). LCMS (standard): RT=1.17 min, m/z = 553 (M+H)+. 1H NMR (400 MHz, CDCb) 6 ppm 9.03 (s, 1 H) 8.30 - 8.35 (m, 1 H) 8.15 (s, 1 H) 7.91 (d, J=8.72 Hz, 1 H) 7.70 (s, 1 H) 7.06 (br d, J=8.72 Hz, 1 H) 5.21 (t, J=13.81 Hz, 2 H) 3.45 (s, 3 H) 2.95 (q, J=7.51 Hz, 2 H) 1.19 (t, J=7.45 Hz, 3 H). Step 1 1 : Preparation of example P18: N-[3-ethylsulfonyl-2-[1-(2,2,3,3,3- pentafluoropropyl)pyrazolo[3,4-clpyridin-5-yl1indazol-6-yl1-2,2,2-trifluoro-N-methyl-acetamide
Figure imgf000093_0001
The title compound, N-[3-ethylsulfonyl-2-[1-(2,2,3,3,3-pentafluoropropyl)pyrazolo[3,4-c]pyridin-5-yl]- indazol-6-yl]-2,2,2-trifluoro-N-methyl-acetamide was prepared from N-[3-ethylsulfanyl-2-[1-(2,2,3,3,3- pentafluoropropyl)pyrazolo[3,4-c]pyridin-5-yl]indazol-6-yl]-2,2,2-trifluoro-N-methyl-acetamide (preparation described above) under similar conditions as described for 2-[3-ethylsulfonyl-2-[1- (2,2,3,3,3-pentafluoro-propyl)pyrazolo[3,4-c]pyridin-5-yl]indazol-6-yl]-2-methyl-propanenitrile (example H2, step 8). LCMS (standard): RT=1.10 min, m/z = 585 (M+H)+. 1H NMR (400 MHz, CDCb) 6 ppm 8.94 (s, 1 H) 8.35 (s, 1 H) 8.30 (d, J=9.08 Hz, 1 H) 8.25 (s, 1 H) 7.79 (s, 1 H) 7.25 (br d, J=9.08 Hz, 1 H) 5.20 (t, J=13.99 Hz, 2 H) 3.97 (q, J=7.27 Hz, 2 H) 3.47 (s, 3 H) 1.51 (t, J=7.45 Hz, 3 H).
Step 12: Preparation of example P19: 3-ethylsulfonyl-N-methyl-2-[1-(2,2,3,3,3-pentafluoropropyl)- pyrazolo[3,4-clpyridin-5-yl1indazol-6-amine
Figure imgf000093_0002
To a solution of N-[3-ethylsulfonyl-2-[1-(2, 2,3,3, 3-pentafluoropropyl)pyrazolo[3, 4-c]pyridin-5-yl]indazol- 6-yl]-2,2,2-trifluoro-N-methyl-acetamide (0.075 g, 0.128 mmol, 1 .0 equiv.) in methanol (2 mL) was added potassium carbonate (0.054 g, 0.385 mmol, 3.0 equiv.). The reaction mixture was stirred at room temperature for 2 hours, then, water was added, and the aqueous layer was extracted with ethyl acetate. The organic layer was dried over sodium sulfate, filtered, and evaporated to give the title compound as a yellow solid. The crude was used in the next step without further purification.
LCMS (standard): RT=1.02 min, m/z = 489 (M+H)+. 1H NMR (400 MHz, CDCb) 6 ppm 8.88 (s, 1 H) 8.28 (s, 1 H) 8.18 (d, J=1.09 Hz, 1 H) 7.93 (d, J=9.45 Hz, 1 H) 6.79 (dd, J=9.26, 2.00 Hz, 1 H) 6.63 (d, J=1 .45 Hz, 1 H) 5.15 (t, J=13.99 Hz, 2 H) 3.86 - 3.99 (m, 2 H) 2.91 - 3.04 (m, 3 H) 1 .38 - 1 .51 (m, 3 H) 1.25 - 1.31 (m, 1 H).
Step 13: Preparation of example P20: N-[3-ethylsulfonyl-2-[1-(2,2,3,3,3- pentafluoropropyl)pyrazolo[3,4-clpyridin-5-yl1indazol-6-yl1-N-methyl-acetamide
Figure imgf000094_0001
To a solution of 3-ethylsulfonyl-N-methyl-2-[1-(2, 2,3,3, 3-pentafluoropropyl)pyrazolo[3,4-c]pyridin-5- yl]indazol-6-amine (preparation described above) (0.048 g, 0.0983 mmol, 1.0 equiv.) in 1 ,2- dimethoxyethane (1.1 mL) was added acetyl chloride (0.0142 mL, 0.197 mmol, 2.0 equiv.) at -20°C followed by triethylamine (0.0413 mL, 0.295 mmol, 3.0 equiv.). The orange suspension was allowed to reach room temperature over 1 .5 hours. The mixture was concentrated, and the residue taken up in water. The aqueous layer was extracted three times with ethyl acetate. The combined organic layers were washed with brine, dried over sodium sulfate, filtered, and evaporated to yield the title compound as a yellow oil. LCMS (standard): RT=0.97 min, m/z = 531 (M+H)+. 1H NMR (400 MHz, CDCb) 6 ppm 8.95 (s, 1 H) 8.35 (s, 1 H) 8.20 - 8.31 (m, 2 H) 7.71 (s, 1 H) 7.24 (br d, J=9.08 Hz, 1 H) 5.21 (br t,
J=13.81 Hz, 2 H) 3.96 (q, J=7.39 Hz, 2 H) 3.39 (br s, 3 H) 2.02 (br s, 3 H) 1 .51 (br t, J=7.45 Hz, 3 H).
Table P: Examples of compounds of formula (I)
Figure imgf000094_0002
Figure imgf000095_0001
Figure imgf000096_0001
The activity of the compositions according to the invention can be broadened considerably, and adapted to prevailing circumstances, by adding other insecticidally, acaricidally and/or fungicidally active ingredients. The mixtures of the compounds of formula I with other insecticidally, acaricidally and/or fungicidally active ingredients may also have further surprising advantages which can also be described, in a wider sense, as synergistic activity. For example, better tolerance by plants, reduced phytotoxicity, insects can be controlled in their different development stages or better behaviour during their production, for example during grinding or mixing, during their storage or during their use. Suitable additions to active ingredients here are, for example, representatives of the following classes of active ingredients: organophosphorus compounds, nitrophenol derivatives, thioureas, juvenile hormones, formamidines, benzophenone derivatives, ureas, pyrrole derivatives, carbamates, pyrethroids, chlorinated hydrocarbons, acylureas, pyridylmethyleneamino derivatives, macrolides, neonicotinoids and Bacillus thuringiensis preparations.
The following mixtures of the compounds of formula I with active ingredients are preferred (the abbreviation “TX” means “one compound selected from the group consisting of the compounds described in Tables A-1 to A-12 and Tables B-1 to B-12 and Table P of the present invention): an adjuvant selected from the group of substances consisting of petroleum oils (alternative name) (628) + TX; an insect control active substance selected from abamectin + TX, acequinocyl + TX, acetamiprid + TX, acetoprole + TX, acrinathrin + TX, acynonapyr + TX, afidopyropen + TX, afoxolaner + TX, alanycarb + TX, allethrin + TX, alpha-cypermethrin + TX, alphamethrin + TX, amidoflumet + TX, aminocarb + TX, azocyclotin + TX, bensultap + TX, benzoximate + TX, benzpyrimoxan + TX, betacyfluthrin + TX, beta- cypermethrin + TX, bifenazate + TX, bifenthrin + TX, binapacryl + TX, bioallethrin + TX, S-bioallethrin + TX, bioresmethrin + TX, bistrifluron + TX, broflanilide + TX, brofluthrinate + TX, bromophos-ethyl + TX, buprofezine + TX, butocarboxim + TX, cadusafos + TX, carbaryl + TX, carbosulfan + TX, cartap + TX, CAS number: 1632218-00-8 + TX, CAS number: 1808115-49-2 + TX, CAS number: 2032403-97-5 + TX, CAS number: 2044701-44-0 + TX, CAS number: 2128706-05-6 + TX, CAS number: 2095470- 94-1 + TX, CAS number: 2377084-09-6 + TX, CAS number: 1445683-71-5 + TX, CAS number: 2408220-94-8 + TX, CAS number: 2408220-91-5 + TX, CAS number: 1365070-72-9 + TX, CAS number: 2171099-09-3 + TX, CAS number: 2396747-83-2 + TX, CAS number: 2133042-31-4 + TX, CAS number: 2133042-44-9 + TX, CAS number: 1445684-82-1 + TX, CAS number: 1445684-82-1 + TX, CAS number: 1922957-45-6 + TX, CAS number: 1922957-46-7 + TX, CAS number: 1922957-47- 8 + TX, CAS number: 1922957-48-9 + TX, CAS number: 2415706-16-8 + TX, CAS number: 1594624-87-9 + TX, CAS number: 1594637-65-6 + TX, CAS number: 1594626-19-3 + TX, CAS number: 1990457-52-7 + TX, CAS number: 1990457-55-0 + TX, CAS number: 1990457-57-2 + TX, CAS number: 1990457-77-6 + TX, CAS number: 1990457-66-3 + TX, CAS number: 1990457-85-6 + TX, CAS number: 2220132-55-6 + TX, CAS number: 1255091-74-7 + TX, chlorantraniliprole + TX, chlordane + TX, chlorfenapyr + TX, chloroprallethrin + TX, chromafenozide + TX, clenpirin + TX, cloethocarb + TX, clothianidin + TX, 2-chlorophenyl N-methylcarbamate (CPMC) + TX, cyanofenphos + TX, cyantraniliprole + TX, cyclaniliprole + TX, cyclobutrifluram + TX, cycloprothrin + TX, cycloxaprid + TX, cyenopyrafen + TX, cyetpyrafen + TX, cyflumetofen + TX, cyfluthrin + TX, cyhalodiamide + TX, cyhalothrin + TX, cypermethrin + TX, cyphenothrin + TX, cyproflanilide + TX, cyromazine + TX, deltamethrin + TX, diafenthiuron + TX, dialifos + TX, dibrom + TX, dicloromezotiaz + TX, diflovidazine + TX, diflubenzuron + TX, dimpropyridaz + TX, dinactin + TX, dinocap + TX, dinotefuran + TX, dioxabenzofos + TX, emamectin (or emamectin benzoate) + TX, empenthrin + TX, epsilon - momfluorothrin + TX, epsilon-metofluthrin + TX, esfenvalerate + TX, ethion + TX, ethiprole + TX, etofenprox + TX, etoxazole + TX, famphur + TX, fenazaquin + TX, fenfluthrin + TX, fenmezoditiaz + TX, fenitrothion + TX, fenobucarb + TX, fenothiocarb + TX, fenoxycarb + TX, fenpropathrin + TX, fenpyroximate + TX, fensulfothion + TX, fenthion + TX, fentinacetate + TX, fenvalerate + TX, fipronil + TX, flometoquin + TX, flonicamid + TX, fluacrypyrim + TX, fluazaindolizine + TX, fluazuron + TX, flubendiamide + TX, flubenzimine + TX, fluchlordiniliprole + TX, flucitrinate + TX, flucycloxuron + TX, flucythrinate + TX, fluensulfone + TX, flufenerim + TX, flufenprox + TX, flufiprole + TX, fluhexafon + TX, flumethrin + TX, fluopyram + TX, flupentiofenox + TX, flu pyradifu rone + TX, flupyrimin + TX, fluralaner + TX, fluvalinate + TX, fluxametamide + TX, fosthiazate + TX, gamma-cyhalothrin + TX, Gossyplure™ + TX, guadipyr + TX, halofenozide + TX, halfenprox + TX, heptafluthrin + TX, hexythiazox + TX, hydramethylnon + TX, imicyafos + TX, imidacloprid + TX, imiprothrin + TX, indazapyroxamet + TX, indoxacarb + TX, iodomethane + TX, iprodione + TX, isocycloseram + TX, isothioate + TX, ivermectin + TX, kappa-bifenthrin + TX, kappa-tefluthrin + TX, lambda-cyhalothrin + TX, lepimectin + TX, lotilaner + TX, lufenuron + TX, metaflumizone + TX, metaldehyde + TX, metam + TX, methomyl + TX, methoxyfenozide + TX, metofluthrin + TX, metolcarb + TX, mexacarbate + TX, milbemectin + TX, momfluorothrin + TX, niclosamide + TX, nicofluprole + TX; nitenpyram + TX, nithiazine + TX, omethoate + TX, oxamyl + TX, oxazosulfyl + TX, parathion-ethyl + TX, permethrin + TX, phenothrin + TX, phosphocarb + TX, piperonylbutoxide + TX, pirimicarb + TX, pirimiphos-ethyl + TX, pirimiphos-methyl + TX, Polyhedrosis virus + TX, pralleth rin + TX, profenofos + TX, profluthrin + TX, propargite + TX, propetamphos + TX, propoxur + TX, prothiophos + TX, protrifenbute + TX, pyflubumide + TX, pymetrozine + TX, pyraclofos + TX, pyrafluprole + TX, pyridaben + TX, pyridalyl + TX, pyrifluquinazon + TX, pyrimidifen + TX, pyriminostrobin + TX, pyriprole + TX, pyriproxyfen + TX, resmethrin + TX, sarolaner + TX, selamectin + TX, silafluofen + TX, spinetoram + TX, spinosad + TX, spirodiclofen + TX, spiromesifen + TX, spiropidion + TX, spirotetramat + TX, spidoxamat + TX, sulfoxaflor + TX, tebufenozide + TX, tebufenpyrad + TX, tebupirimiphos + TX, tefluth rin + TX, temephos + TX, tetrachlorantraniliprole + TX, tetradiphon + TX, tetramethrin + TX, tetramethylfluthrin + TX, tetranactin + TX, tetraniliprole + TX, theta-cypermethrin + TX, thiacloprid + TX, thiamethoxam + TX, thiocyclam + TX, thiodicarb + TX, thiofanox + TX, thiometon + TX, thiosultap + TX, tigolaner + TX, tioxazafen + TX, tolfenpyrad + TX, toxaphene + TX, tralomethrin + TX, transfluthrin + TX, triazamate + TX, triazophos + TX, trichlorfon + TX, trichloronate + TX, trichlorphon + TX, triflu mezopyrim + TX, tyclopyrazoflor + TX, zeta-cypermethrin + TX, Extract of seaweed and fermentation product derived from melasse + TX, Extract of seaweed and fermentation product derived from melasse comprising urea + TX, amino acids + TX, potassium and molybdenum and EDTA-chelated manganese + TX, Extract of seaweed and fermented plant products + TX, Extract of seaweed and fermented plant products comprising phytohormones + TX, vitamins + TX, EDTA-chelated copper + TX, zinc + TX, and iron + TX, azadirachtin + TX, Bacillus aizawai + TX, Bacillus chitinosporus AQ746 (NRRL Accession No B-21 618) + TX, Bacillus firmus + TX, Bacillus kurstaki + TX, Bacillus mycoides AQ726 (NRRL Accession No. B-21664) + TX, Bacillus pumilus (NRRL Accession No B-30087) + TX, Bacillus pumilus AQ717 (NRRL Accession No. B-21662) + TX, Bacillus sp. AQ178 (ATCC Accession No. 53522) + TX, Bacillus sp. AQ175 (ATCC Accession No. 55608) + TX, Bacillus sp. AQ177 (ATCC Accession No. 55609) + TX, Bacillus subtilis unspecified + TX, Bacillus subtilis AQ153 (ATCC Accession No. 55614) + TX, Bacillus subtilis AQ30002 (NRRL Accession No. B-50421) + TX, Bacillus subtilis AQ30004 (NRRL Accession No. B- 50455) + TX, Bacillus subtilis AQ713 (NRRL Accession No. B-21661) + TX, Bacillus subtilis AQ743 (NRRL Accession No. B-21665) + TX, Bacillus thuringiensis AQ52 (NRRL Accession No. B-21619) + TX, Bacillus thuringiensis BD#32 (NRRL Accession No B-21530) + TX, Bacillus thuringiensis subspec. kurstaki BMP 123 + TX, Beauveria bassiana + TX, D-limonene + TX, Granulovirus + TX, Harpin + TX, Helicoverpa armigera Nucleopolyhedrovirus + TX, Helicoverpa zea Nucleopolyhedrovirus + TX, Heliothis virescens Nucleopolyhedrovirus + TX, Heliothis punctigera Nucleopolyhedrovirus + TX, Metarhizium spp. + TX, Muscodor albus 620 (NRRL Accession No. 30547) + TX, Muscodor roseus A3-5 (NRRL Accession No. 30548) + TX, Neem tree based products + TX, Paecilomyces fumosoroseus + TX, Paecilomyces lilacinus + TX, Pasteuria nishizawae + TX, Pasteuria penetrans + TX, Pasteuria ramosa + TX, Pasteuria thornei + TX, Pasteuria usgae + TX, P- cymene + TX, Plutella xylostella Granulosis virus + TX, Plutella xylostella Nucleopolyhedrovirus + TX, Polyhedrosis virus + TX, pyrethrum + TX, QRD 420 (a terpenoid blend) + TX, QRD 452 (a terpenoid blend) + TX, QRD 460 (a terpenoid blend) + TX, Quillaja saponaria + TX, Rhodococcus globerulus AQ719 (NRRL Accession No B-21663) + TX, Spodoptera frugiperda Nucleopolyhedrovirus + TX, Streptomyces galbus (NRRL Accession No. 30232) + TX, Streptomyces sp. (NRRL Accession No. B- 30145) + TX, Terpenoid blend + TX, and Verticillium spp.; an algicide selected from the group of substances consisting of bethoxazin [CON] + TX, copper dioctanoate (IUPAC name) (170) + TX, copper sulfate (172) + TX, cybutryne [CON] + TX, dichlone (1052) + TX, dichlorophen (232) + TX, endothal (295) + TX, fentin (347) + TX, hydrated lime [CON] + TX, nabam (566) + TX, quinoclamine (714) + TX, quinonamid (1379) + TX, simazine (730) + TX, triphenyltin acetate (IUPAC name) (347) and triphenyltin hydroxide (IUPAC name) (347) + TX; an anthelmintic selected from the group of substances consisting of abamectin (1) + TX, crufomate (1011) + TX, cyclobutrifluram + TX, doramectin (alternative name) [CCN] + TX, emamectin (291) + TX, emamectin benzoate (291) + TX, eprinomectin (alternative name) [CCN] + TX, ivermectin (alternative name) [CCN] + TX, milbemycin oxime (alternative name) [CCN] + TX, moxidectin (alternative name) [CCN] + TX, piperazine [CCN] + TX, selamectin (alternative name) [CCN] + TX, spinosad (737) and thiophanate (1435) + TX; an avicide selected from the group of substances consisting of chloralose (127) + TX, endrin (1122) + TX, fenthion (346) + TX, pyridin-4-amine (IUPAC name) (23) and strychnine (745) + TX; a bactericide selected from the group of substances consisting of 1 -hydroxy-1 /7-pyridine-2-thione (IUPAC name) (1222) + TX, 4-(quinoxalin-2-ylamino)benzenesulfonamide (IUPAC name) (748) + TX, 8-hydroxyquinoline sulfate (446) + TX, bronopol (97) + TX, copper dioctanoate (IUPAC name) (170) + TX, copper hydroxide (IUPAC name) (169) + TX, cresol [CCN] + TX, dichlorophen (232) + TX, dipyrithione (1105) + TX, dodicin (1112) + TX, fenaminosulf (1144) + TX, formaldehyde (404) + TX, hydrargaphen (alternative name) [CCN] + TX, kasugamycin (483) + TX, kasugamycin hydrochloride hydrate (483) + TX, nickel bis(dimethyldithiocarbamate) (IUPAC name) (1308) + TX, nitrapyrin (580) + TX, octhilinone (590) + TX, oxolinic acid (606) + TX, oxytetracycline (611) + TX, potassium hydroxyquinoline sulfate (446) + TX, probenazole (658) + TX, streptomycin (744) + TX, streptomycin sesquisulfate (744) + TX, tecloftalam (766) + TX, and thiomersal (alternative name) [CCN] + TX; a biological agent selected from the group of substances consisting of Adoxophyes orana GV (alternative name) (12) + TX, Agrobacterium radiobacter (alternative name) (13) + TX, Amblyseius spp. (alternative name) (19) + TX, Anagrapha falcifera NPV (alternative name) (28) + TX, Anagrus atomus (alternative name) (29) + TX, Aphelinus abdominalis (alternative name) (33) + TX, Aphidius colemani (alternative name) (34) + TX, Aphidoletes aphidimyza (alternative name) (35) + TX, Autographa californica NPV (alternative name) (38) + TX, Bacillus firmus (alternative name) (48) + TX, Bacillus sphaericus Neide (scientific name) (49) + TX, Bacillus thuringiensis Berliner (scientific name) (51) + TX, Bacillus thuringiensis subsp. aizawai (scientific name) (51) + TX, Bacillus thuringiensis subsp. israelensis (scientific name) (51) + TX, Bacillus thuringiensis subsp. japonensis (scientific name) (51) + TX, Bacillus thuringiensis subsp. kurstaki (scientific name) (51) + TX, Bacillus thuringiensis subsp. tenebrionis (scientific name) (51) + TX, Beauveria bassiana (alternative name) (53) + TX, Beauveria brongniartii (alternative name) (54) + TX, Chrysoperla carnea (alternative name) (151) + TX, Cryptolaemus montrouzieri (alternative name) (178) + TX, Cydia pomonella GV (alternative name) (191) + TX, Dacnusa sibirica (alternative name) (212) + TX, Diglyphus isaea (alternative name) (254) + TX, Encarsia formosa (scientific name) (293) + TX, Eretmocerus eremicus (alternative name) (300) + TX, Helicoverpa zea NPV (alternative name) (431) + TX, Heterorhabditis bacteriophora and H. megidis (alternative name) (433) + TX, Hippodamia convergens (alternative name) (442) + TX, Leptomastix dactylopii (alternative name) (488) + TX, Macrolophus caliginosus (alternative name) (491) + TX, Mamestra brassicae NPV (alternative name) (494) + TX, Metaphycus helvolus (alternative name) (522) + TX, Metarhizium anisopliae var. acridum (scientific name) (523) + TX, Metarhizium anisopliae var. anisopliae (scientific name) (523) + TX, Neodiprion sertifer NPV and N. lecontei NPV (alternative name) (575) + TX, Orius spp. (alternative name) (596) + TX, Paecilomyces fumosoroseus (alternative name) (613) + TX, Phytoseiulus persimilis (alternative name) (644) + TX, Spodoptera exigua multicapsid nuclear polyhedrosis virus (scientific name) (741) + TX, Steinernema bibionis (alternative name) (742) + TX, Steinernema carpocapsae (alternative name) (742) + TX, Steinernema feltiae (alternative name) (742) + TX, Steinernema glaseri (alternative name) (742) + TX, Steinernema riobrave (alternative name) (742) + TX, Steinernema riobravis (alternative name) (742) + TX, Steinernema scapterisci (alternative name) (742) + TX, Steinernema spp. (alternative name) (742) + TX, Trichogramma spp. (alternative name) (826) + TX, Typhlodromus occidentalis (alternative name) (844) and Verticillium lecanii (alternative name) (848) + TX; a soil sterilant selected from the group of substances consisting of iodomethane (IUPAC name) (542) and methyl bromide (537) + TX; a chemosterilant selected from the group of substances consisting of apholate [CCN] + TX, bisazir (alternative name) [CCN] + TX, busulfan (alternative name) [CCN] + TX, diflubenzuron (250) + TX, dimatif (alternative name) [CCN] + TX, hemel [CCN] + TX, hempa [CCN] + TX, metepa [CCN] + TX, methiotepa [CCN] + TX, methyl apholate [CCN] + TX, morzid [CCN] + TX, penfluron (alternative name) [CCN] + TX, tepa [CCN] + TX, thiohempa (alternative name) [CCN] + TX, thiotepa (alternative name) [CCN] + TX, tretamine (alternative name) [CCN] and uredepa (alternative name) [CCN] + TX; an insect pheromone selected from the group of substances consisting of (E)-dec-5-en-1-yl acetate with (E)-dec-5-en-1-ol (IUPAC name) (222) + TX, (E)-tridec-4-en-1-yl acetate (IUPAC name) (829) + TX, (E)-6-methylhept-2-en-4-ol (IUPAC name) (541) + TX, (E,Z)-tetradeca-4,10-dien-1-yl acetate (IUPAC name) (779) + TX, (Z)-dodec-7-en-1-yl acetate (IUPAC name) (285) + TX, (Z)-hexadec-11- enal (IUPAC name) (436) + TX, (Z)-hexadec-11 -en-1 -yl acetate (IUPAC name) (437) + TX, (Z)- hexadec-13-en-11-yn-1-yl acetate (IUPAC name) (438) + TX, (Z)-icos-13-en-10-one (IUPAC name) (448) + TX, (Z)-tetradec-7-en-1-al (IUPAC name) (782) + TX, (Z)-tetradec-9-en-1-ol (IUPAC name) (783) + TX, (Z)-tetradec-9-en-1-yl acetate (IUPAC name) (784) + TX, (7E,9Z)-dodeca-7,9-dien-1-yl acetate (IUPAC name) (283) + TX, (9Z,11E)-tetradeca-9,11-dien-1 -yl acetate (IUPAC name) (780) + TX, (9Z,12E)-tetradeca-9,12-dien-1-yl acetate (IUPAC name) (781) + TX, 14-methyloctadec-1-ene (IUPAC name) (545) + TX, 4-methylnonan-5-ol with 4-methylnonan-5-one (IUPAC name) (544) + TX, alpha-multistriatin (alternative name) [CCN] + TX, brevicomin (alternative name) [CCN] + TX, codlelure (alternative name) [CCN] + TX, codlemone (alternative name) (167) + TX, cuelure (alternative name) (179) + TX, disparlure (277) + TX, dodec-8-en-1-yl acetate (IUPAC name) (286) + TX, dodec-9-en-1-yl acetate (IUPAC name) (287) + TX, dodeca-8 + TX, 10-dien-1-yl acetate (IUPAC name) (284) + TX, dominicalure (alternative name) [CCN] + TX, ethyl 4-methyloctanoate (IUPAC name) (317) + TX, eugenol (alternative name) [CCN] + TX, frontalin (alternative name) [CCN] + TX, gossyplure (alternative name) (420) + TX, grandlure (421) + TX, grandlure I (alternative name) (421) + TX, grandlure II (alternative name) (421) + TX, grandlure III (alternative name) (421) + TX, grandlure IV (alternative name) (421) + TX, hexalure [CCN] + TX, ipsdienol (alternative name) [CCN] + TX, ipsenol (alternative name) [CCN] + TX, japonilure (alternative name) (481) + TX, lineatin (alternative name) [CCN] + TX, litlure (alternative name) [CCN] + TX, looplure (alternative name) [CCN] + TX, medlure [CCN] + TX, megatomoic acid (alternative name) [CCN] + TX, methyl eugenol (alternative name) (540) + TX, muscalure (563) + TX, octadeca-2,13-dien-1-yl acetate (IUPAC name) (588) + TX, octadeca-3,13-dien-1-yl acetate (IUPAC name) (589) + TX, orfralure (alternative name) [CCN] + TX, oryctalure (alternative name) (317) + TX, ostramone (alternative name) [CCN] + TX, siglure [CCN] + TX, sordidin (alternative name) (736) + TX, sulcatol (alternative name) [CCN] + TX, tetradec-11 -en-1 -yl acetate (IUPAC name) (785) + TX, trimedlure (839) + TX, trimedlure A (alternative name) (839) + TX, trimedlure Bi (alternative name) (839) + TX, trimedlure B2 (alternative name) (839) + TX, trimedlure C (alternative name) (839) and trunc-call (alternative name) [CCN] + TX; an insect repellent selected from the group of substances consisting of 2-(octylthio)ethanol (IUPAC name) (591) + TX, butopyronoxyl (933) + TX, butoxy(polypropylene glycol) (936) + TX, dibutyl adipate (IUPAC name) (1046) + TX, dibutyl phthalate (1047) + TX, dibutyl succinate (IUPAC name) (1048) + TX, diethyltoluamide [CCN] + TX, dimethyl carbate [CCN] + TX, dimethyl phthalate [CCN] + TX, ethyl hexanediol (1137) + TX, hexamide [CCN] + TX, methoquin-butyl (1276) + TX, methylneodecanamide [CCN] + TX, oxamate [CCN] and picaridin [CCN] + TX; a molluscicide selected from the group of substances consisting of bis(tributyltin) oxide (IUPAC name) (913) + TX, bromoacetamide [CCN] + TX, calcium arsenate [CCN] + TX, cloethocarb (999) + TX, copper acetoarsenite [CCN] + TX, copper sulfate (172) + TX, fentin (347) + TX, ferric phosphate (IUPAC name) (352) + TX, metaldehyde (518) + TX, methiocarb (530) + TX, niclosamide (576) + TX, niclosamide-olamine (576) + TX, pentachlorophenol (623) + TX, sodium pentachlorophenoxide (623) + TX, tazimcarb (1412) + TX, thiodicarb (799) + TX, tributyltin oxide (913) + TX, trifenmorph (1454) + TX, trimethacarb (840) + TX, triphenyltin acetate (IUPAC name) (347) and triphenyltin hydroxide (IUPAC name) (347) + TX, pyriprole [394730-71-3] + TX; a nematicide selected from the group of substances consisting of AKD-3088 (compound code) + TX, 1 ,2-dibromo-3-chloropropane (lUPAC/Chemical Abstracts name) (1045) + TX, 1 ,2-dichloropropane (IUPAC/ Chemical Abstracts name) (1062) + TX, 1 ,2-dichloropropane with 1 ,3-dichloropropene (IUPAC name) (1063) + TX, 1 ,3-dichloropropene (233) + TX, 3,4-dichlorotetrahydrothiophene 1 ,1- dioxide (lUPAC/Chemical Abstracts name) (1065) + TX, 3-(4-chlorophenyl)-5-methylrhodanine (IUPAC name) (980) + TX, 5-methyl-6-thioxo-1 ,3,5-thiadiazinan-3-ylacetic acid (IUPAC name) (1286) + TX, 6-isopentenylaminopurine (alternative name) (210) + TX, abamectin (1) + TX, acetoprole [CCN] + TX, alanycarb (15) + TX, aldicarb (16) + TX, aldoxycarb (863) + TX, AZ 60541 (compound code) + TX, benclothiaz [CCN] + TX, benomyl (62) + TX, butylpyridaben (alternative name) + TX, cadusafos (109) + TX, carbofuran (118) + TX, carbon disulfide (945) + TX, carbosulfan (119) + TX, chloropicrin (141) + TX, chlorpyrifos (145) + TX, cloethocarb (999) + TX, cyclobutrifluram + TX, cytokinins (alternative name) (210) + TX, dazomet (216) + TX, DBCP (1045) + TX, DCIP (218) + TX, diamidafos (1044) + TX, dichlofenthion (1051) + TX, dicliphos (alternative name) + TX, dimethoate (262) + TX, doramectin (alternative name) [CCN] + TX, emamectin (291) + TX, emamectin benzoate (291) + TX, eprinomectin (alternative name) [CCN] + TX, ethoprophos (312) + TX, ethylene dibromide (316) + TX, fenamiphos (326) + TX, fen pyrad (alternative name) + TX, fensulfothion (1158) + TX, fosthiazate (408) + TX, fosthietan (1196) + TX, furfural (alternative name) [CCN] + TX, GY-81 (development code) (423) + TX, heterophos [CCN] + TX, iodomethane (IUPAC name) (542) + TX, isamidofos (1230) + TX, isazofos (1231) + TX, ivermectin (alternative name) [CCN] + TX, kinetin (alternative name) (210) + TX, mecarphon (1258) + TX, metam (519) + TX, metam-potassium (alternative name) (519) + TX, metam-sodium (519) + TX, methyl bromide (537) + TX, methyl isothiocyanate (543) + TX, milbemycin oxime (alternative name) [CCN] + TX, moxidectin (alternative name) [CCN] + TX, Myrothecium verrucaria composition (alternative name) (565) + TX, NC-184 (compound code) + TX, oxamyl (602) + TX, phorate (636) + TX, Phosphamidon (639) + TX, phosphocarb [CCN] + TX, sebufos (alternative name) + TX, selamectin (alternative name) [CCN] + TX, spinosad (737) + TX, terbam (alternative name) + TX, terbufos (773) + TX, tetrachlorothiophene (IUPACZ Chemical Abstracts name) (1422) + TX, thiafenox (alternative name) + TX, thionazin (1434) + TX, triazophos (820) + TX, triazuron (alternative name) + TX, xylenols [CCN] + TX, YI-5302 (compound code) and zeatin (alternative name) (210) + TX, fluensulfone [318290-98-1] + TX, fluopyram + TX; a nitrification inhibitor selected from the group of substances consisting of potassium ethylxanthate [CCN] and nitrapyrin (580) + TX; a plant activator selected from the group of substances consisting of acibenzolar (6) + TX, acibenzolar-S-methyl (6) + TX, probenazole (658) and Reynoutria sachalinensis extract (alternative name) (720) + TX; a rodenticide selected from the group of substances consisting of 2-isovalerylindan-1 ,3-dione (IUPAC name) (1246) + TX, 4-(quinoxalin-2-ylamino)benzenesulfonamide (IUPAC name) (748) + TX, alphachlorohydrin [CCN] + TX, aluminium phosphide (640) + TX, antu (880) + TX, arsenous oxide (882) + TX, barium carbonate (891) + TX, bisthiosemi (912) + TX, brodifacoum (89) + TX, bromadiolone (including alpha-bromadiolone) + TX, bromethalin (92) + TX, calcium cyanide (444) + TX, chloralose (127) + TX, chlorophacinone (140) + TX, cholecalciferol (alternative name) (850) + TX, coumachlor (1004) + TX, coumafuryl (1005) + TX, coumatetralyl (175) + TX, crimidine (1009) + TX, difenacoum (246) + TX, difethialone (249) + TX, diphacinone (273) + TX, ergocalciferol (301) + TX, flocoumafen (357) + TX, fluoroacetamide (379) + TX, flupropadine (1183) + TX, flupropadine hydrochloride (1183) + TX, gamma-HCH (430) + TX, HCH (430) + TX, hydrogen cyanide (444) + TX, iodomethane (IUPAC name) (542) + TX, lindane (430) + TX, magnesium phosphide (IUPAC name) (640) + TX, methyl bromide (537) + TX, norbormide (1318) + TX, phosacetim (1336) + TX, phosphine (IUPAC name) (640) + TX, phosphorus [CCN] + TX, pindone (1341) + TX, potassium arsenite [CCN] + TX, pyrinuron (1371) + TX, scilliroside (1390) + TX, sodium arsenite [CCN] + TX, sodium cyanide (444) + TX, sodium fluoroacetate (735) + TX, strychnine (745) + TX, thallium sulfate [CCN] + TX, warfarin (851) and zinc phosphide (640) + TX; a synergist selected from the group of substances consisting of 2-(2-butoxyethoxy)ethyl piperonylate (IUPAC name) (934) + TX, 5-(1 ,3-benzodioxol-5-yl)-3-hexylcyclohex-2-enone (IUPAC name) (903) + TX, farnesol with nerolidol (alternative name) (324) + TX, MB-599 (development code) (498) + TX, MGK 264 (development code) (296) + TX, piperonyl butoxide (649) + TX, piprotal (1343) + TX, propyl isomer (1358) + TX, S421 (development code) (724) + TX, sesamex (1393) + TX, sesasmolin (1394) and sulfoxide (1406) + TX; an animal repellent selected from the group of substances consisting of anthraquinone (32) + TX, chloralose (127) + TX, copper naphthenate [CCN] + TX, copper oxychloride (171) + TX, diazinon (227) + TX, dicyclopentadiene (chemical name) (1069) + TX, guazatine (422) + TX, guazatine acetates (422) + TX, methiocarb (530) + TX, pyridin-4-amine (IUPAC name) (23) + TX, thiram (804) + TX, trimethacarb (840) + TX, zinc naphthenate [CCN] and ziram (856) + TX; a virucide selected from the group of substances consisting of imanin (alternative name) [CCN] and ribavirin (alternative name) [CCN] + TX; a wound protectant selected from the group of substances consisting of mercuric oxide (512) + TX, octhilinone (590) and thiophanate-methyl (802) + TX; a biologically active substance selected from 1 ,1-bis(4-chloro-phenyl)-2-ethoxyethanol + TX, 2,4- dichlorophenyl benzenesulfonate + TX, 2-fluoro-N-methyl-N-1 -naphthylacetamide + TX, 4-chlorophenyl phenyl sulfone + TX, acetoprole + TX, aldoxycarb + TX, amidithion + TX, amidothioate + TX, amiton + TX, amiton hydrogen oxalate + TX, amitraz + TX, aramite + TX, arsenous oxide + TX, azobenzene + TX, azothoate + TX, benomyl + TX, benoxa-fos + TX, benzyl benzoate + TX, bixafen + TX, brofenvalerate + TX, bromo-cyclen + TX, bromophos + TX, bromopropylate + TX, buprofezin + TX, butocarboxim + TX, butoxycarboxim + TX, butylpyridaben + TX, calcium polysulfide + TX, camphechlor + TX, carbanolate + TX, carbophenothion + TX, cymiazole + TX, chino-methionat + TX, chlorbenside + TX, chlordimeform + TX, chlordimeform hydrochloride + TX, chlorfenethol + TX, chlorfenson + TX, chlorfensulfide + TX, chlorobenzilate + TX, chloromebuform + TX, chloromethiuron + TX, chloropropylate + TX, chlorthiophos + TX, cinerin I + TX, cinerin II + TX, cinerins + TX, closantel + TX, coumaphos + TX, crotamiton + TX, crotoxyphos + TX, cufraneb + TX, cyanthoate + TX, DCPM + TX, DDT + TX, demephion + TX, demephion-O + TX, demephion-S + TX, demeton-methyl + TX, demeton- O + TX, demeton-O-methyl + TX, demeton-S + TX, demeton-S-methyl + TX, demeton-S-methylsulfon + TX, dichlofluanid + TX, dichlorvos + TX, dicliphos + TX, dienochlor + TX, dimefox + TX, dinex + TX, dinex-diclexine + TX, dinocap-4 + TX, dinocap-6 + TX, dinocton + TX, dino-penton + TX, dinosulfon + TX, dinoterbon + TX, dioxathion + TX, diphenyl sulfone + TX, disulfiram + TX, DNOC + TX, dofenapyn + TX, doramectin + TX, endothion + TX, eprinomectin + TX, ethoate-methyl + TX, etrimfos + TX, fenazaflor + TX, fenbutatin oxide + TX, fenothiocarb + TX, fenpyrad + TX, fen-pyroximate + TX, fenpyrazamine + TX, fenson + TX, fentrifanil + TX, flubenzimine + TX, flucycloxuron + TX, fluenetil + TX, fluorbenside + TX, FMC 1137 + TX, formetanate + TX, formetanate hydrochloride + TX, formparanate + TX, gamma-HCH + TX, glyodin + TX, halfenprox + TX, hexadecyl cyclopropanecarboxylate + TX, isocarbophos + TX, jasmolin I + TX, jasmolin II + TX, jodfenphos + TX, lindane + TX, malonoben + TX, mecarbam + TX, mephosfolan + TX, mesulfen + TX, methacrifos + TX, methyl bromide + TX, metolcarb + TX, mexacarbate + TX, milbemycin oxime + TX, mipafox + TX, monocrotophos + TX, morphothion + TX, moxidectin + TX, naled + TX, 4-chloro-2-(2-chloro-2-methyl- propyl)-5-[(6-iodo-3-pyridyl)methoxy]pyridazin-3-one + TX, nifluridide + TX, nikkomycins + TX, nitrilacarb + TX, nitrilacarb 1 :1 zinc chloride complex + TX, omethoate + TX, oxydeprofos + TX, oxydisulfoton + TX, pp'-DDT + TX, parathion + TX, permethrin + TX, phenkapton + TX, phosalone + TX, phosfolan + TX, phosphamidon + TX, polychloroterpenes + TX, polynactins + TX, proclonol + TX, promacyl + TX, propoxur + TX, prothidathion + TX, prothoate + TX, pyrethrin I + TX, pyrethrin II + TX, pyrethrins + TX, pyridaphenthion + TX, pyrimitate + TX, quinalphos + TX, quintiofos + TX, R-1492 + TX, phosglycin + TX, rotenone + TX, schradan + TX, sebufos + TX, selamectin + TX, sophamide + TX, SSI- 121 + TX, sulfiram + TX, sulfluramid + TX, sulfotep + TX, sulfur + TX, diflovidazin + TX, tau-fluvalinate + TX, TEPP + TX, terbam + TX, tetradifon + TX, tetrasul + TX, thiafenox + TX, thiocarboxime + TX, thiofanox + TX, thiometon + TX, thioquinox + TX, thuringiensin + TX, triamiphos + TX, triarathene + TX, triazophos + TX, triazuron + TX, trifenofos + TX, trinactin + TX, vamidothion + TX, vaniliprole + TX, bethoxazin + TX, copper dioctanoate + TX, copper sulfate + TX, cybutryne + TX, dichlone + TX, dichlorophen + TX, endothal + TX, fentin + TX, hydrated lime + TX, nabam + TX, quinoclamine + TX, quinonamid + TX, simazine + TX, triphenyltin acetate + TX, triphenyltin hydroxide + TX, crufomate + TX, piperazine + TX, thiophanate + TX, chloralose + TX, fenthion + TX, pyridin-4-amine + TX, strychnine + TX, 1 -hydroxy-1 H-pyridine-2-thione + TX, 4-(quinoxalin-2-ylamino)benzenesulfonamide + TX, 8- hydroxyquinoline sulfate + TX, bronopol + TX, copper hydroxide + TX, cresol + TX, dipyrithione + TX, dodicin + TX, fenaminosulf + TX, formaldehyde + TX, hydrargaphen + TX, kasugamycin + TX, kasugamycin hydrochloride hydrate + TX, nickel bis(dimethyldithiocarbamate) + TX, nitrapyrin + TX, octhilinone + TX, oxolinic acid + TX, oxytetracycline + TX, potassium hydroxyquinoline sulfate + TX, probenazole + TX, streptomycin + TX, streptomycin sesquisulfate + TX, tecloftalam + TX, thiomersal + TX, Adoxophyes orana GV + TX, Agrobacterium radiobacter + TX, Amblyseius spp. + TX, Anagrapha falcifera NPV + TX, Anagrus atomus + TX, Aphelinus abdominalis + TX, Aphidius colemani + TX, Aphidoletes aphidimyza + TX, Autographa californica NPV + TX, Bacillus sphaericus Neide + TX, Beauveria brongniartii + TX, Chrysoperla carnea + TX, Cryptolaemus montrouzieri + TX, Cydia pomonella GV + TX, Dacnusa sibirica + TX, Diglyphus isaea + TX, Encarsia formosa + TX, Eretmocerus eremicus + TX, Heterorhabditis bacteriophora and H. megidis + TX, Hippodamia convergens + TX, Leptomastix dactylopii + TX, Macrolophus caliginosus + TX, Mamestra brassicae NPV + TX, Metaphycus helvolus + TX, Metarhizium anisopliae var. acridum + TX, Metarhizium anisopliae var. anisopliae + TX, Neodiprion sertifer NPV and N. lecontei NPV + TX, Orius spp. + TX, Paecilomyces fumosoroseus + TX, Phytoseiulus persimilis + TX, Steinernema bibionis + TX, Steinernema carpocapsae + TX, Steinernema feltiae + TX, Steinernema glaseri + TX, Steinernema riobrave + TX, Steinernema riobravis + TX, Steinernema scapterisci + TX, Steinernema spp. + TX, Trichogramma spp. + TX, Typhlodromus occidentalis + TX , Verticillium lecanii + TX, apholate + TX, bisazir + TX, busulfan + TX, dimatif + TX, hemel + TX, hempa + TX, metepa + TX, methiotepa + TX, methyl apholate + TX, morzid + TX, penfluron + TX, tepa + TX, thiohempa + TX, thiotepa + TX, tretamine + TX, uredepa + TX, (E)-dec-5-en-1-yl acetate with (E)-dec-5-en-1-ol + TX, (E)-tridec-4-en-1-yl acetate + TX, (E)-6- methylhept-2-en-4-ol + TX, (E,Z)-tetradeca-4,10-dien-1-yl acetate + TX, (Z)-dodec-7-en-1-yl acetate + TX, (Z)-hexadec-11-enal + TX, (Z)-hexadec-l 1-en-1-yl acetate + TX, (Z)-hexadec-13-en-11-yn-1-yl acetate + TX, (Z)-icos-13-en-10-one + TX, (Z)-tetradec-7-en-1-al + TX, (Z)-tetradec-9-en-1-ol + TX, (Z)- tetradec-9-en-1-yl acetate + TX, (7E,9Z)-dodeca-7,9-dien-1-yl acetate + TX, (9Z,11 E)-tetradeca-9,11- dien-1-yl acetate + TX, (9Z,12E)-tetradeca-9,12-dien-1-yl acetate + TX, 14-methyloctadec-1-ene + TX, 4-methylnonan-5-ol with 4-methylnonan-5-one + TX, alpha-multistriatin + TX, brevicomin + TX, codlelure + TX, codlemone + TX, cuelure + TX, disparlure + TX, dodec-8-en-1-yl acetate + TX, dodec-9-en-1-yl acetate + TX, dodeca-8 + TX, 10-dien-1 -yl acetate + TX, dominicalure + TX, ethyl 4-methyloctanoate + TX, eugenol + TX, frontalin + TX, grandlure + TX, grandlure I + TX, grandlure II + TX, grandlure III + TX, grandlure IV + TX, hexalure + TX, ipsdienol + TX, ipsenol + TX, japonilure + TX, lineatin + TX, litlure + TX, looplure + TX, medlure + TX, megatomoic acid + TX, methyl eugenol + TX, muscalure + TX, octadeca-2,13-dien-1-yl acetate + TX, octadeca-3,13-dien-1-yl acetate + TX, orfralure + TX, oryctalure + TX, ostramone + TX, siglure + TX, sordidin + TX, sulcatol + TX, tetradec-11-en-1-yl acetate + TX, trimedlure + TX, trimedlure A + TX, trimedlure Bi + TX, trimedlure B2 + TX, trimedlure C + TX, trunc-call + TX, 2-(octylthio)-ethanol + TX, butopyronoxyl + TX, butoxy(polypropylene glycol) + TX, dibutyl adipate + TX, dibutyl phthalate + TX, dibutyl succinate + TX, diethyltoluamide + TX, dimethyl carbate + TX, dimethyl phthalate + TX, ethyl hexanediol + TX, hexamide + TX, methoquin-butyl + TX, methylneodecanamide + TX, oxamate + TX, picaridin + TX, 1-dichloro-1 -nitroethane + TX, 1 ,1 -dichloro- 2,2-bis(4-ethylphenyl)-ethane + TX, 1 ,2-dichloropropane with 1 ,3-dichloropropene + TX, 1-bromo-2- chloroethane + TX, 2,2,2-trichloro-1-(3,4-dichloro-phenyl)ethyl acetate + TX, 2,2-dichlorovinyl 2- ethylsulfinylethyl methyl phosphate + TX, 2-(1 ,3-dithiolan-2-yl)phenyl dimethylcarbamate + TX, 2-(2- butoxyethoxy)ethyl thiocyanate + TX, 2-(4,5-dimethyl-1 ,3-dioxolan-2-yl)phenyl methylcarbamate + TX, 2-(4-chloro-3,5-xylyloxy)ethanol + TX, 2-chlorovinyl diethyl phosphate + TX, 2-imidazolidone + TX, 2- isovalerylindan-1 ,3-dione + TX, 2-methyl(prop-2-ynyl)aminophenyl methylcarbamate + TX, 2- thiocyanatoethyl laurate + TX, 3-bromo-1 -chloroprop-1 -ene + TX, 3-methyl-1-phenylpyrazol-5-yl dimethyl-carbamate + TX, 4-methyl(prop-2-ynyl)amino-3,5-xylyl methylcarbamate + TX, 5,5-dimethyl-3- oxocyclohex-1-enyl dimethylcarbamate + TX, acethion + TX, acrylonitrile + TX, aldrin + TX, allosamidin + TX, allyxycarb + TX, alpha-ecdysone + TX, aluminium phosphide + TX, aminocarb + TX, anabasine + TX, athidathion + TX, azamethiphos + TX, Bacillus thuringiensis delta endotoxins + TX, barium hexafluorosilicate + TX, barium polysulfide + TX, barthrin + TX, Bayer 22/190 + TX, Bayer 22408 + TX, beta-cyfluthrin + TX, beta-cypermethrin + TX, bioethanomethrin + TX, biopermethrin + TX, bis(2- chloroethyl) ether + TX, borax + TX, bromfenvinfos + TX, bromo-DDT + TX, bufencarb + TX, butacarb + TX, butathiofos + TX, butonate + TX, calcium arsenate + TX, calcium cyanide + TX, carbon disulfide + TX, carbon tetrachloride + TX, cartap hydrochloride + TX, cevadine + TX, chlorbicyclen + TX, chlordane + TX, chlordecone + TX, chloroform + TX, chloropicrin + TX, chlorphoxim + TX, chlorprazophos + TX, cis-resmethrin + TX, cismethrin + TX, clocythrin + TX, copper acetoarsenite + TX, copper arsenate + TX, copper oleate + TX, coumithoate + TX, cryolite + TX, CS 708 + TX, cyanofenphos + TX, cyanophos + TX, cyclethrin + TX, cythioate + TX, d-tetramethrin + TX, DAEP + TX, dazomet + TX, decarbofuran + TX, diamidafos + TX, dicapthon + TX, dichlofenthion + TX, dicresyl + TX, dicyclanil + TX, dieldrin + TX, diethyl 5-methylpyrazol-3-yl phosphate + TX, dilor + TX, dimefluthrin + TX, dimetan + TX, dimethrin + TX, dimethylvinphos + TX, dimetilan + TX, dinoprop + TX, dinosam + TX, dinoseb + TX, diofenolan + TX, dioxabenzofos + TX, dithicrofos + TX, DSP + TX, ecdysterone + TX, El 1642 + TX, EMPC + TX, EPBP + TX, etaphos + TX, ethiofencarb + TX, ethyl formate + TX, ethylene dibromide + TX, ethylene dichloride + TX, ethylene oxide + TX, EXD + TX, fenchlorphos + TX, fenethacarb + TX, fenitrothion + TX, fenoxacrim + TX, fenpirithrin + TX, fensulfothion + TX, fenthion-ethyl + TX, flucofuron + TX, fosmethilan + TX, fospirate + TX, fosthietan + TX, furathiocarb + TX, furethrin + TX, guazatine + TX, guazatine acetates + TX, sodium tetrathiocarbonate + TX, halfenprox + TX, HCH + TX, HEOD + TX, heptachlor + TX, heterophos + TX, HHDN + TX, hydrogen cyanide + TX, hyquincarb + TX, IPSP + TX, isazofos + TX, isobenzan + TX, isodrin + TX, isofenphos + TX, isolane + TX, isoprothiolane + TX, isoxathion + TX, juvenile hormone I + TX, juvenile hormone II + TX, juvenile hormone III + TX, kelevan + TX, kinoprene + TX, lead arsenate + TX, leptophos + TX, lirimfos + TX, lythidathion + TX, m-cumenyl methylcarbamate + TX, magnesium phosphide + TX, mazidox + TX, mecarphon + TX, menazon + TX, mercurous chloride + TX, mesulfenfos + TX, metam + TX, metam-potassium + TX, metam-sodium + TX, methanesulfonyl fluoride + TX, methocrotophos + TX, methoprene + TX, methothrin + TX, methoxychlor + TX, methyl isothiocyanate + TX, methylchloroform + TX, methylene chloride + TX, metoxadiazone + TX, mirex + TX, naftalofos + TX, naphthalene + TX, NC-170 + TX, nicotine + TX, nicotine sulfate + TX, nithiazine + TX, nornicotine + TX, 0-5-dichloro-4-iodophenyl O-ethyl ethylphosphonothioate + TX, O,O-diethyl 0-4-methyl-2-oxo-2H-chromen-7-yl phosphorothioate + TX, O,O-diethyl 0-6-methyl-2-propylpyrimidin-4-yl phosphorothioate + TX, O,O,O',O'-tetrapropyl dithiopyrophosphate + TX, oleic acid + TX, para-dichlorobenzene + TX, parathion-methyl + TX, pentachlorophenol + TX, pentachlorophenyl laurate + TX, PH 60-38 + TX, phenkapton + TX, phosnichlor + TX, phosphine + TX, phoxim-methyl + TX, pirimetaphos + TX, polychlorodicyclopentadiene isomers + TX, potassium arsenite + TX, potassium thiocyanate + TX, precocene I + TX, precocene II + TX, precocene III + TX, primidophos + TX, profluthrin + TX, promecarb + TX, prothiofos + TX, pyrazophos + TX, pyresmethrin + TX, quassia + TX, quinalphos-methyl + TX, quinothion + TX, rafoxanide + TX, resmethrin + TX, rotenone + TX, kadethrin + TX, ryania + TX, ryanodine + TX, sabadilla + TX, schradan + TX, sebufos + TX, SI-0009 + TX, thiapronil + TX, sodium arsenite + TX, sodium cyanide + TX, sodium fluoride + TX, sodium hexafluorosilicate + TX, sodium pentachlorophenoxide + TX, sodium selenate + TX, sodium thiocyanate + TX, sulcofuron + TX, sulcofuron-sodium + TX, sulfuryl fluoride + TX, sulprofos + TX, tar oils + TX, tazimcarb + TX, TDE + TX, tebupirimfos + TX, temephos + TX, terallethrin + TX, tetrachloroethane + TX, thicrofos + TX, thiocyclam + TX, thiocyclam hydrogen oxalate + TX, thionazin + TX, thiosultap + TX, thiosultap-sodium + TX, tralomethrin + TX, transpermethrin + TX, triazamate + TX, trichlormetaphos-3 + TX, trichloronat + TX, trimethacarb + TX, tolprocarb + TX, triclopyricarb + TX, triprene + TX, veratridine + TX, veratrine + TX, XMC + TX, zetamethrin + TX, zinc phosphide + TX, zolaprofos + TX, meperfluthrin + TX, tetramethylfluthrin + TX, bis(tributyltin) oxide + TX, bromoacetamide + TX, ferric phosphate + TX, niclosamide-olamine + TX, tributyltin oxide + TX, pyrimorph + TX, trifenmorph + TX, 1 ,2-dibromo-3-chloropropane + TX, 1 ,3-dichloropropene + TX, 3,4- dichlorotetrahydrothio-phene 1 ,1 -dioxide + TX, 3-(4-chlorophenyl)-5-methylrhodanine + TX, 5-methyl-6- thioxo-1 ,3,5-thiadiazinan-3-ylacetic acid + TX, 6-isopentenylaminopurine + TX, anisiflupurin + TX, benclothiaz + TX, cytokinins + TX, DCIP + TX, furfural + TX, isamidofos + TX, kinetin + TX, Myrothecium verrucaria composition + TX, tetrachlorothiophene + TX, xylenols + TX, zeatin + TX, potassium ethylxanthate + TX .acibenzolar + TX, acibenzolar-S-methyl + TX, Reynoutria sachalinensis extract + TX, alpha-chlorohydrin + TX, antu + TX, barium carbonate + TX, bisthiosemi + TX, brodifacoum + TX, bromadiolone + TX, bromethalin + TX, chlorophacinone + TX, cholecalciferol + TX, coumachlor + TX, coumafuryl + TX, coumatetralyl + TX, crimidine + TX, difenacoum + TX, difethialone + TX, diphacinone + TX, ergocalciferol + TX, flocoumafen + TX, fluoroacetamide + TX, flupropadine + TX, flupropadine hydrochloride + TX, norbormide + TX, phosacetim + TX, phosphorus + TX, pindone + TX, pyrinuron + TX, scilliroside + TX, -sodium fluoroacetate + TX, thallium sulfate + TX, warfarin + TX, -2-(2- butoxyethoxy)ethyl piperonylate + TX, 5-(1 ,3-benzodioxol-5-yl)-3-hexylcyclohex-2-enone + TX, farnesol with nerolidol + TX, verbutin + TX, MGK 264 + TX, piperonyl butoxide + TX, piprotal + TX, propyl isomer + TX, S421 + TX, sesamex + TX, sesasmolin + TX, sulfoxide + TX, anthraquinone + TX, copper naphthenate + TX, copper oxychloride + TX, dicyclopentadiene + TX, thiram + TX, zinc naphthenate + TX, ziram + TX, imanin + TX, ribavirin + TX, chloroinconazide + TX, mercuric oxide + TX, thiophanate- methyl + TX, azaconazole + TX, bitertanol + TX, bromuconazole + TX, cyproconazole + TX, difenoconazole + TX, diniconazole -+ TX, epoxiconazole + TX, fenbuconazole + TX, fluquinconazole + TX, flusilazole + TX, flutriafol + TX, furametpyr + TX, hexaconazole + TX, imazalil- + TX, imiben-conazole + TX, ipconazole + TX, metconazole + TX, myclobutanil + TX, paclobutrazole + TX, pefurazoate + TX, penconazole + TX, prothioconazole + TX, pyrifenox + TX, prochloraz + TX, propiconazole + TX, pyrisoxazole + TX, -simeconazole + TX, tebucon-azole + TX, tetraconazole + TX, triadimefon + TX, triadimenol + TX, triflumizole + TX, triticonazole + TX, ancymidol + TX, fenarimol + TX, nuarimol + TX, bupirimate + TX, dimethirimol + TX, ethirimol + TX, dodemorph + TX, fenpropidin + TX, fenpropimorph + TX, spiroxamine + TX, tridemorph + TX, cyprodinil + TX, mepanipyrim + TX, pyrimethanil + TX, fenpiclonil + TX, fludioxonil + TX, benalaxyl + TX, furalaxyl + TX, -metalaxyl -+ TX, Rmetalaxyl + TX, ofurace + TX, oxadixyl + TX, carbendazim + TX, debacarb + TX, fuberidazole -+ TX, thiabendazole + TX, chlozolinate + TX, dichlozoline + TX, myclozoline- + TX, procymidone + TX, vinclozoline + TX, boscalid + TX, carboxin + TX, fenfuram + TX, flutolanil + TX, mepronil + TX, oxycarboxin + TX, penthiopyrad + TX, thifluzamide + TX, dodine + TX, iminoctadine + TX, azoxystrobin + TX, dimoxystrobin + TX, enestroburin + TX, fenaminstrobin + TX, flufenoxystrobin + TX, fluoxastrobin + TX, kresoxim-methyl + TX, metominostrobin + TX, trifloxystrobin + TX, orysastrobin + TX, picoxystrobin + TX, pyraclostrobin + TX, pyrametostrobin + TX, pyraoxystrobin + TX, ferbam + TX, mancozeb + TX, maneb + TX, metiram + TX, propineb + TX, zineb + TX, captafol + TX, captan + TX, fluoroimide + TX, folpet + TX, tolylfluanid + TX, bordeaux mixture + TX, copper oxide + TX, mancopper + TX, oxine-copper + TX, nitrothal-isopropyl + TX, edifenphos + TX, iprobenphos + TX, phosdiphen + TX, tolclofos-methyl + TX, anilazine + TX, benthiavalicarb + TX, blasticidin-S + TX, chloroneb -+ TX, chloro-tha-lonil + TX, cyflufenamid + TX, cymoxanil + TX, cyclobutrifluram + TX, diclocymet + TX, diclomezine -+ TX, dicloran + TX, diethofencarb + TX, dimethomorph -+ TX, flumorph + TX, dithianon + TX, ethaboxam + TX, etridiazole + TX, famoxadone + TX, fenamidone + TX, fenoxanil + TX, ferimzone + TX, fluazinam + TX, flumetylsulforim + TX, fluopicolide + TX, fluoxytioconazole + TX, flusulfamide + TX, fluxapyroxad + TX, -fenhexamid + TX, fosetyl-aluminium -+ TX, hymexazol + TX, iprovalicarb + TX, cyazofamid + TX, methasulfocarb + TX, metrafenone + TX, pencycuron + TX, phthalide + TX, polyoxins + TX, propamocarb + TX, pyribencarb + TX, proquinazid + TX, pyroquilon + TX, pyriofenone + TX, quinoxyfen + TX, quintozene + TX, tiadinil + TX, triazoxide + TX, tricyclazole + TX, triforine + TX, validamycin + TX, valifenalate + TX, zoxamide + TX, mandipropamid + TX, flubeneteram + TX, isopyrazam + TX, sedaxane + TX, benzovindiflupyr + TX, pydiflumetofen + TX, 3-difluoromethyl-1- methyl-1 H-pyrazole-4-carboxylic acid (3',4',5'-trifluoro-biphenyl-2-yl)-amide + TX, isoflucypram + TX, isotianil + TX, dipymetitrone + TX, 6-ethyl-5,7-dioxo-pyrrolo[4,5][1 ,4]dithiino[1 ,2-c]isothiazole-3- carbonitrile + TX, 2-(difluoromethyl)-N-[3-ethyl-1 ,1-dimethyl-indan-4-yl]pyridine-3-carboxamide + TX, 4- (2,6-difluorophenyl)-6-methyl-5-phenyl-pyridazine-3-carbonitrile + TX, (R)-3-(difluoromethyl)-1-methyl- N-[1 ,1 ,3-trimethylindan-4-yl]pyrazole-4-carboxamide + TX, 4-(2-bromo-4-fluoro-phenyl)-N-(2-chloro-6- fluoro-phenyl)-2,5-dimethyl-pyrazol-3-amine + TX, 4- (2- bromo- 4- fluorophenyl) - N- (2- chloro- 6- fluorophenyl) - 1 , 3- dimethyl- 1 H- pyrazol- 5- amine + TX, fluindapyr + TX, coumethoxystrobin (jiaxiangjunzhi) + TX, Ivbenmixianan + TX, dichlobentiazox + TX, mandestrobin + TX, 3-(4,4-difluoro- 3,4-dihydro-3,3-dimethylisoquinolin-1-yl)quinolone + TX, 2-[2-fluoro-6-[(8-fluoro-2-methyl-3- quinolyl)oxy]phenyl]propan-2-ol + TX, oxathiapiprolin + TX, tert-butyl N-[6-[[[(1-methyltetrazol-5-yl)- phenyl-methylene]amino]oxymethyl]-2-pyridyl]carbamate + TX, pyraziflumid + TX, inpyrfluxam + TX, trolprocarb + TX, mefentrifluconazole + TX, ipfentrifluconazole+ TX, 2-(difluoromethyl)-N-[(3R)-3-ethyl- 1 ,1-dimethyl-indan-4-yl]pyridine-3-carboxamide + TX, N'-(2,5-dimethyl-4-phenoxy-phenyl)-N-ethyl-N- methyl-formamidine + TX, N'-[4-(4,5-dichlorothiazol-2-yl)oxy-2,5-dimethyl-phenyl]-N-ethyl-N-methyl- formamidine + TX, [2-[3-[2-[1-[2-[3,5-bis(difluoromethyl)pyrazol-1-yl]acetyl]-4-piperidyl]thiazol-4-yl]-4,5- dihydroisoxazol-5-yl]-3-chloro-phenyl] methanesulfonate + TX, but-3-ynyl N-[6-[[(Z)-[(1-methyltetrazol- 5-yl)-phenyl-methylene]amino]oxymethyl]-2-pyridyl]carbamate + TX, methyl N-[[5-[4-(2,4- dimethylphenyl)triazol-2-yl]-2-methyl-phenyl]methyl]carbamate + TX, 3-chloro-6-methyl-5-phenyl-4- (2,4,6-trifluorophenyl)pyridazine + TX, pyridachlometyl + TX, 3-(difluoromethyl)-1-methyl-N-[1 ,1 ,3- trimethylindan-4-yl]pyrazole-4-carboxamide + TX, 1 -[2-[[1 -(4-chlorophenyl)pyrazol-3-yl]oxymethyl]-3- methyl-phenyl]-4-methyl-tetrazol-5-one + TX, 1-methyl-4-[3-methyl-2-[[2-methyl-4-(3,4,5- trimethylpyrazol-1-yl)phenoxy]methyl]phenyl]tetrazol-5-one + TX, aminopyrifen + TX, ametoctradin + TX, amisulbrom + TX, penflufen + TX, (Z,2E)-5-[1-(4-chlorophenyl)pyrazol-3-yl]oxy-2-methoxyimino- N,3-dimethyl-pent-3-enamide + TX, florylpicoxamid + TX, fenpicoxamid + TX, metarylpicoxamid + TX, tebufloquin + TX, ipflufenoquin + TX, quinofumelin + TX, isofetamid + TX, N-[2-[2,4-dichloro- phenoxy]phenyl]-3-(difluoromethyl)-1-methyl-pyrazole-4-carboxamide + TX, N-[2-[2-chloro-4- (trifluoromethyl)phenoxy]phenyl]-3-(difluoromethyl)-1 -methyl-pyrazole-4-carboxamide + TX, benzothiostrobin + TX, phenamacril + TX, 5-amino-1 ,3,4-thiadiazole-2-thiol zinc salt (2:1) + TX, fluopyram + TX, flufenoxadiazam + TX, flutianil + TX, fluopimomide + TX, pyrapropoyne + TX, picarbutrazox + TX, 2-(difluoromethyl)-N-(3-ethyl-1 ,1-dimethyl-indan-4-yl)pyridine-3-carboxamide + TX, 2- (difluoromethyl) - N- ((3R) - 1 , 1 , 3- trimethylindan- 4- yl) pyridine- 3- carboxamide + TX, 4-[[6-[2-(2,4- difluorophenyl)-1 ,1-difluoro-2-hydroxy-3-(1 ,2,4-triazol-1-yl)propyl]-3-pyridyl]oxy]benzonitrile + TX, metyltetraprole + TX, 2- (difluoromethyl) - N- ((3R) - 1 , 1 , 3- trimethylindan- 4- yl) pyridine- 3- carboxamide + TX, a- (1 , 1- dimethylethyl) - a- [4'- (trifluoromethoxy) [1 , 1 '- biphenyl] - 4- yl] -5- pyrimidinemethanol + TX, fluoxapiprolin + TX, enoxastrobin + TX, 4-[[6-[2-(2,4-difluorophenyl)-1 ,1- difluoro-2-hydroxy-3-(1 ,2,4-triazol-1-yl)propyl]-3-pyridyl]oxy] benzonitrile + TX, 4-[[6-[2-(2,4- difluorophenyl)-1 ,1-difluoro-2-hydroxy-3-(5-sulfanyl-1 ,2,4-triazol-1-yl)propyl]-3-pyridyl]oxy] benzonitrile + TX, 4-[[6-[2-(2,4-difluorophenyl)-1 ,1-difluoro-2-hydroxy-3-(5-thioxo-4H-1 ,2,4-triazol-1-yl)propyl]-3- pyridyl]oxy]benzonitrile + TX, trinexapac + TX, coumoxystrobin + TX, zhongshengmycin + TX, thiodiazole copper + TX, zinc thiazole + TX, amectotractin + TX, iprodione + TX, seboctylamine + TX; N'-[5-bromo-2-methyl-6-[(1 S)-1-methyl-2-propoxy-ethoxy]-3-pyridyl]-N-ethyl-N-methyl-formamidine + TX, N'-[5-bromo-2-methyl-6-[(1 R)-1-methyl-2-propoxy-ethoxy]-3-pyridyl]-N-ethyl-N-methyl-formamidine + TX, N'-[5-bromo-2-methyl-6-(1-methyl-2-propoxy-ethoxy)-3-pyridyl]-N-ethyl-N-methyl-formamidine + TX, N'-[5-chloro-2-methyl-6-(1-methyl-2-propoxy-ethoxy)-3-pyridyl]-N-ethyl-N-methyl-formamidine + TX, N'-[5-bromo-2-methyl-6-(1-methyl-2-propoxy-ethoxy)-3-pyridyl]-N-isopropyl-N-methyl-formamidine + TX (these compounds may be prepared from the methods described in WO2015/155075); N'-[5- bromo-2-methyl-6-(2-propoxypropoxy)-3-pyridyl]-N-ethyl-N-methyl-formamidine + TX (this compound may be prepared from the methods described in IPCOM000249876D); N-isopropyl-N’-[5-methoxy-2- methyl-4-(2, 2, 2-trifluoro- 1 -hydroxy-1 -phenyl-ethyl)phenyl]-N-methyl-formamidine+ TX, N’-[4-(1 - cyclopropyl-2,2,2-trifluoro-1-hydroxy-ethyl)-5-methoxy-2-methyl-phenyl]-N-isopropyl-N-methyl- formamidine + TX (these compounds may be prepared from the methods described in WO2018/228896); N-ethyl-N’-[5-methoxy-2-methyl-4-[(2-trifluoromethyl)oxetan-2-yl]phenyl]-N-methyl- formamidine + TX, N-ethyl-N’-[5-methoxy-2-methyl-4-[(2-trifuoromethyl)tetrahydrofuran-2-yl]phenyl]-N- methyl-formamidine + TX (these compounds may be prepared from the methods described in WO2019/1 10427); N-[(1 R)-1 -benzyl-3-chloro-1 -methyl-but-3-enyl]-8-fluoro-quinoline-3-carboxamide + TX, N-[(1 S)-1-benzyl-3-chloro-1-methyl-but-3-enyl]-8-fluoro-quinoline-3-carboxamide + TX, N-[(1 R)-1- benzyl-3,3,3-trifluoro-1 -methyl-propyl]-8-fluoro-quinoline-3-carboxamide + TX, N-[(1 S)-1 -benzyl-3,3,3- trifluoro-1-methyl-propyl]-8-fluoro-quinoline-3-carboxamide + TX, N-[(1 R)-1-benzyl-1 ,3-dimethyl-butyl]- 7,8-difluoro-quinoline-3-carboxamide + TX, N-[(1 S)-1 -benzyl- 1 ,3-dimethyl-butyl]-7,8-difluoro-quinoline- 3-carboxamide + TX, 8-fluoro-N-[(1 R)-1-[(3-fluorophenyl)methyl]-1 ,3-dimethyl-butyl]quinoline-3- carboxamide + TX, 8-fluoro-N-[(1 S)-1-[(3-fluorophenyl)methyl]-1 ,3-dimethyl-butyl]quinoline-3- carboxamide + TX, N-[(1 R)-1-benzyl-1 ,3-dimethyl-butyl]-8-fluoro-quinoline-3-carboxamide + TX, N- [(1 S)-1 -benzyl- 1 ,3-dimethyl-butyl]-8-fluoro-quinoline-3-carboxamide + TX, N-((1 R)-1 -benzyl-3-chloro-1 - methyl-but-3-enyl)-8-fluoro-quinoline-3-carboxamide + TX, N-((1 S)-1 -benzyl-3-chloro-1 -methyl-but-3- enyl)-8-fluoro-quinoline-3-carboxamide + TX (these compounds may be prepared from the methods described in WO2017/153380); 1 -(6,7-dimethylpyrazolo[1 ,5-a]pyridin-3-yl)-4,4,5-trifluoro-3,3-dimethyl- isoquinoline + TX, 1-(6,7-dimethylpyrazolo[1 ,5-a]pyridin-3-yl)-4,4,6-trifluoro-3,3-dimethyl-isoquinoline + TX, 4,4-difluoro-3,3-dimethyl-1-(6-methylpyrazolo[1 ,5-a]pyridin-3-yl)isoquinoline + TX, 4,4-difluoro-3,3- dimethyl-1-(7-methylpyrazolo[1 ,5-a]pyridin-3-yl)isoquinoline + TX, 1-(6-chloro-7-methyl-pyrazolo[1 ,5- a]pyridin-3-yl)-4,4-difluoro-3,3-dimethyl-isoquinoline + TX (these compounds may be prepared from the methods described in WO2017/025510); 1-(4,5-dimethylbenzimidazol-1-yl)-4,4,5-trifluoro-3,3-dimethyl- isoquinoline + TX, 1-(4,5-dimethylbenzimidazol-1-yl)-4,4-difluoro-3,3-dimethyl-isoquinoline + TX, 6- chloro-4,4-difluoro-3,3-dimethyl-1 -(4-methylbenzimidazol-1 -y I) isoq u inol i n e + TX, 4,4-difluoro-1 -(5- fluoro-4-methyl-benzimidazol-1 -yl)-3,3-dimethyl-isoquinoline + TX, 3-(4,4-difluoro-3,3-dimethyl-1 - isoquinolyl)-7,8-dihydro-6H-cyclopenta[e]benzimidazole + TX (these compounds may be prepared from the methods described in WO2016/156085); N-methoxy-N-[[4-[5-(trifluoromethyl)-1 ,2,4-oxadiazol-3- yl]phenyl]methyl]cyclopropanecarboxamide + TX, N,2-dimethoxy-N-[[4-[5-(trifluoromethyl)-1 ,2,4- oxadiazol-3-yl]phenyl]methyl]propanamide + TX, N-ethyl-2-methyl-N-[[4-[5-(trifluoromethyl)-1 ,2,4- oxadiazol-3-yl]phenyl]methyl]propanamide + TX, 1-methoxy-3-methyl-1-[[4-[5-(trifluoromethyl)-1 ,2,4- oxadiazol-3-yl]phenyl]methyl]urea + TX, 1 ,3-dimethoxy-1-[[4-[5-(trifluoromethyl)-1 ,2,4-oxadiazol-3- yl]phenyl]methyl]urea + TX, 3-ethyl-1-methoxy-1-[[4-[5-(trifluoromethyl)-1 ,2,4-oxadiazol-3- yl]phenyl]methyl]urea + TX, N-[[4-[5-(trifluoromethyl)-1 ,2,4-oxadiazol-3-yl]phenyl]methyl]propanamide + TX, 4,4-dimethyl-2-[[4-[5-(trifluoromethyl)-1 ,2,4-oxadiazol-3-yl]phenyl]methyl]isoxazolidin-3-one + TX, 5,5-dimethyl-2-[[4-[5-(trifluoromethyl)-1 ,2,4-oxadiazol-3-yl]phenyl]methyl]isoxazolidin-3-one + TX, ethyl 1-[[4-[5-(trifluoromethyl)-1 ,2,4-oxadiazol-3-yl]phenyl]methyl]pyrazole-4-carboxylate + TX, N,N-dimethyl- 1-[[4-[5-(trifluoromethyl)-1 ,2,4-oxadiazol-3-yl]phenyl]methyl]-1 ,2,4-triazol-3-amine + TX. The compounds in this paragraph may be prepared from the methods described in WO 2017/055473, WO 2017/055469, WO 2017/093348 and WO 2017/118689; 2-[6-(4-chlorophenoxy)-2-(trifluoromethyl)-3- pyridyl]-1-(1 ,2,4-triazol-1-yl)propan-2-ol + TX (this compound may be prepared from the methods described in WO 2017/029179); 2-[6-(4-bromophenoxy)-2-(trifluoromethyl)-3-pyridyl]-1-(1 ,2,4-triazol-1- yl)propan-2-ol + TX (this compound may be prepared from the methods described in WO 2017/029179); 3-[2-(1-chlorocyclopropyl)-3-(2-fluorophenyl)-2-hydroxy-propyl]imidazole-4-carbonitrile + TX (this compound may be prepared from the methods described in WO 2016/156290); 3-[2-(1- chlorocyclopropyl)-3-(3-chloro-2-fluoro-phenyl)-2-hydroxy-propyl]imidazole-4-carbonitrile + TX (this compound may be prepared from the methods described in WO 2016/156290); (4- phenoxyphenyl)methyl 2-amino-6-methyl-pyridine-3-carboxylate + TX (this compound may be prepared from the methods described in WO 2014/006945); 2,6-Dimethyl-1 H,5H-[1 ,4]dithiino[2,3-c:5,6- c']dipyrrole-1 ,3,5,7(2H,6H)-tetrone + TX (this compound may be prepared from the methods described in WO 2011/138281); N-methyl-4-[5-(trifluoromethyl)-1 ,2,4-oxadiazol-3-yl]benzenecarbothioamide + TX; N-methyl-4-[5-(trifluoromethyl)-1 ,2,4-oxadiazol-3-yl]benzamide + TX; (Z,2E)-5-[1-(2,4- dichlorophenyl)pyrazol-3-yl]oxy-2-methoxyimino-N,3-dimethyl-pent-3-enamide + TX (this compound may be prepared from the methods described in WO 2018/153707); N'-(2-chloro-5-methyl-4-phenoxy- phenyl)-N-ethyl-N-methyl-formamidine + TX; N'-[2-chloro-4-(2-fluorophenoxy)-5-methyl-phenyl]-N- ethyl-N-methyl-formamidine + TX (this compound may be prepared from the methods described in WO 2016/202742); 2-(difluoromethyl)-N-[(3S)-3-ethyl-1 ,1-dimethyl-indan-4-yl]pyridine-3-carboxamide + TX (this compound may be prepared from the methods described in WO 2014/095675); (5-methyl-2- pyridyl)-[4-[5-(trifluoromethyl)-1 ,2,4-oxadiazol-3-yl]phenyl]methanone + TX, (3-methylisoxazol-5-yl)-[4- [5-(trifluoromethyl)-1 ,2,4-oxadiazol-3-yl]phenyl]methanone + TX (these compounds may be prepared from the methods described in WO 2017/220485); 2-oxo-N-propyl-2-[4-[5-(trifluoromethyl)-1 ,2,4- oxadiazol-3-yl]phenyl]acetamide + TX (this compound may be prepared from the methods described in WO 2018/065414); ethyl 1-[[5-[5-(trifluoromethyl)-1 ,2,4-oxadiazol-3-yl]-2-thienyl]methyl]pyrazole-4- carboxylate + TX (this compound may be prepared from the methods described in WO 2018/158365); 2,2-difluoro-N-methyl-2-[4-[5-(trifluoromethyl)-1 ,2,4-oxadiazol-3-yl]phenyl]acetamide + TX, N-[(E)- methoxyiminomethyl]-4-[5-(trifluoromethyl)-1 ,2,4-oxadiazol-3-yl]benzamide + TX, N-[(Z)- methoxyiminomethyl]-4-[5-(trifluoromethyl)-1 ,2,4-oxadiazol-3-yl]benzamide + TX, N-[N-methoxy-C- methyl-carbonimidoyl]-4-[5-(trifluoromethyl)-1 ,2,4-oxadiazol-3-yl]benzamide + TX (these compounds may be prepared from the methods described in WO 2018/202428); microbials including: Acinetobacter Iwoffii + TX, Acremonium alternatum + TX + TX, Acremonium cephalosporium + TX + TX, Acremonium diospyri + TX, Acremonium obclavatum + TX, Adoxophyes orana granulovirus (AdoxGV) (Capex®) + TX, Agrobacterium radiobacter strain K84 (Galltrol-A®) + TX, Alternaria alternate + TX, Alternaria cassia + TX, Altemaria destruens (Smolder®) + TX, Ampelomyces quisqualis (AQ10®) + TX, Aspergillus flavus AF36 (AF36®) + TX, Aspergillus flavus NRRL 21882 (Aflaguard®) + TX, Aspergillus spp. + TX, Aureobasidium pullulans + TX, Azospirillum + TX, (MicroAZ® + TX, TAZO B®) + TX, Azotobacter + TX, Azotobacter chroocuccum (Azotomeal®) + TX, Azotobacter cysts (Bionatural Blooming Blossoms®) + TX, Bacillus amyloliquefaciens + TX, Bacillus cereus + TX, Bacillus chitinosporus strain CM-1 + TX, Bacillus chitinosporus strain AQ746 + TX, Bacillus licheniformis strain HB-2 (Biostart™ Rhizoboost®) + TX, Bacillus licheniformis strain 3086 (EcoGuard® + TX, Green Releaf®) + TX, Bacillus circulans + TX, Bacillus firmus (BioSafe® + TX, BioNem-WP® + TX, VOTiVO®) + TX, Bacillus firmus strain 1-1582 + TX, Bacillus macerans + TX, Bacillus marismortui + TX, Bacillus megaterium + TX, Bacillus mycoides strain AQ726 + TX, Bacillus papillae (Milky Spore Powder®) + TX, Bacillus pumilus spp. + TX, Bacillus pumilus strain GB34 (Yield Shield®) + TX, Bacillus pumilus strain AQ717 + TX, Bacillus pumilus strain QST 2808 (Sonata® + TX, Ballad Plus®) + TX, Bacillus spahericus (VectoLex®) + TX, Bacillus spp. + TX, Bacillus spp. strain AQ175 + TX, Bacillus spp. strain AQ177 + TX, Bacillus spp. strain AQ178 + TX, Bacillus subtilis strain QST 713 (CEASE® + TX, Serenade® + TX, Rhapsody®) + TX, Bacillus subtilis strain QST 714 (JAZZ®) + TX, Bacillus subtilis strain AQ153 + TX, Bacillus subtilis strain AQ743 + TX, Bacillus subtilis strain QST3002 + TX, Bacillus subtilis strain QST3004 + TX, Bacillus subtilis var. amyloliquefaciens strain FZB24 (Taegro® + TX, Rhizopro®) + TX, Bacillus thuringiensis Cry 2Ae + TX, Bacillus thuringiensis Cry1 Ab + TX, Bacillus thuringiensis aizawai GC 91 (Agree®) + TX, Bacillus thuringiensis israelensis (BMP123® + TX, Aquabac® + TX, VectoBac®) + TX, Bacillus thuringiensis kurstaki (Javelin® + TX, Deliver® + TX, CryMax® + TX, Bonide® + TX, Scutella WP® + TX, Turilav WP ® + TX, Astuto® + TX, Dipel WP® + TX, Biobit® + TX, Foray®) + TX, Bacillus thuringiensis kurstaki BMP 123 (Baritone®) + TX, Bacillus thuringiensis kurstaki HD-1 (Bioprotec-CAF 13P®) + TX, Bacillus thuringiensis strain BD#32 + TX, Bacillus thuringiensis strain AQ52 + TX, Bacillus thuringiensis var. aizawai (XenTari® + TX, DiPei®) + TX, bacteria spp. (GROWMEND® + TX, GROWSWEET® + TX, Shootup®) + TX, bacteriophage of Clavipacter michiganensis (AgriPhage®) + TX, Bakflor® + TX, Beauveria bassiana (Beaugenic® + TX, Brocaril WP®) + TX, Beauveria bassiana GHA (Mycotrol ES® + TX, Mycotrol O® + TX, BotaniGuard®) + TX, Beauveria brongniartii (Engerlingspilz® + TX, Schweizer Beauveria® + TX, Melocont®) + TX, Beauveria spp. + TX, Botrytis cineria + TX, Bradyrhizobium japonicum (TerraMax®) + TX, Brevibacillus brevis + TX, Bacillus thuringiensis tenebrionis (Novodor®) + TX, BtBooster + TX, Burkholderia cepacia (Deny® + TX, Intercept® + TX, Blue Circle®) + TX, Burkholderia gladii + TX, Burkholderia gladioli + TX, Burkholderia spp. + TX, Canadian thistle fungus (CBH Canadian Bioherbicide®) + TX, Candida butyri + TX, Candida famata + TX, Candida fructus + TX, Candida glabrata + TX, Candida guilliermondii + TX, Candida melibiosica + TX, Candida oleophila strain O + TX, Candida parapsilosis + TX, Candida pelliculosa + TX, Candida pulcherrima + TX, Candida reukaufii + TX, Candida saitoana (Bio-Coat® + TX, Biocure®) + TX, Candida sake + TX, Candida spp. + TX, Candida tenius + TX, Cedecea dravisae + TX, Cellulomonas flavigena + TX, Chaetomium cochliodes (Nova-Cide®) + TX, Chaetomium globosum (Nova-Cide®) + TX, Chromobacterium subtsugae strain PRAA4-1T (Grandevo®) + TX, Cladosporium cladosporioides + TX, Cladosporium oxysporum + TX, Cladosporium chlorocephalum + TX, Cladosporium spp. + TX, Cladosporium tenuissimum + TX, Clonostachys rosea (EndoFine®) + TX, Colletotrichum acutatum + TX, Coniothyrium minitans (Cotans WG®) + TX, Coniothyrium spp. + TX, Cryptococcus albidus (YIELDPLUS®) + TX, Cryptococcus humicola + TX, Cryptococcus infirmo- miniatus + TX, Cryptococcus laurentii + TX, Cryptophlebia leucotreta granulovirus (Cryptex®) + TX, Cupriavidus campinensis + TX, Cydia pomonella granulovirus (CYD-X®) + TX, Cydia pomonella granulovirus (Madex® + TX, Madex Plus® + TX, Madex Max/ Carpovirusine®) + TX, Cylindrobasidium laeve (Stumpout®) + TX, Cylindrocladium + TX, Debaryomyces hansenii + TX, Drechslera hawaiinensis + TX, Enterobacter cloacae + TX, Enterobacteriaceae + TX, Entomophtora virulenta (Vektor®) + TX, Epicoccum nigrum + TX, Epicoccum purpurascens + TX, Epicoccum spp. + TX, Filobasidium floriforme + TX, Fusarium acuminatum + TX, Fusarium chlamydosporum + TX, Fusarium oxysporum (Fusaclean® I Biofox C®) + TX, Fusarium proliferatum + TX, Fusarium spp. + TX, Galactomyces geotrichum + TX, Gliocladium catenulatum (Primastop® + TX, Prestop®) + TX, Gliocladium roseum + TX, Gliocladium spp. (SoilGard®) + TX, Gliocladium virens (Soilgard®) + TX, Granulovirus (Granupom®) + TX, Halobacillus halophilus + TX, Halobacillus litoralis + TX, Halobacillus trueperi + TX, Halomonas spp. + TX, Halomonas subglaciescola + TX, Halovibrio variabilis + TX, Hanseniaspora uvarum + TX, Helicoverpa armigera nucleopolyhedrovirus (Helicovex®) + TX, Helicoverpa zea nuclear polyhedrosis virus (Gemstar®) + TX, Isoflavone - formononetin (Myconate®) + TX, Kloeckera apiculata + TX, Kloeckera spp. + TX, Lagenidium giganteum (Laginex®) + TX, Lecanicillium longisporum (Vertiblast®) + TX, Lecanicillium muscarium (Vertikil®) + TX, Lymantria Dispar nucleopolyhedrosis virus (Disparvirus®) + TX, Marinococcus halophilus + TX, Meira geulakonigii + TX, Metarhizium anisopliae (Met52®) + TX, Metarhizium anisopliae (Destruxin WP®) + TX, Metschnikowia fruticola (Shemer®) + TX, Metschnikowia pulcherrima + TX, Microdochium dimerum (Antibot®) + TX, Micromonospora coerulea + TX, Microsphaeropsis ochracea + TX, Muscodor albus 620 (Muscudor®) + TX, Muscodor roseus strain A3-5 + TX, Mycorrhizae spp. (AMykor® + TX, Root Maximizer®) + TX, Myrothecium verrucaria strain AARC-0255 (DiTera®) + TX, BROS PLUS® + TX, Ophiostoma piliferum strain D97 (Sylvanex®) + TX, Paecilomyces farinosus + TX, Paecilomyces fumosoroseus (PFR-97® + TX, PreFeRal®) + TX, Paecilomyces linacinus (Biostat WP®) + TX, Paecilomyces lilacinus strain 251 (MeloCon WG®) + TX, Paenibacillus polymyxa + TX, Pantoea agglomerans (BlightBan C9-1®) + TX, Pantoea spp. + TX, Pasteuria spp. (Econem®) + TX, Pasteuria nishizawae + TX, Penicillium aurantiogriseum + TX, Penicillium billai (Jumpstart® + TX, TagTeam®) + TX, Penicillium brevicompactum + TX, Penicillium frequentans + TX, Penicillium griseofulvum + TX, Penicillium purpurogenum + TX, Penicillium spp. + TX, Penicillium viridicatum + TX, Phlebiopsis gigantean (Rotstop®) + TX, phosphate solubilizing bacteria (Phosphomeal®) + TX, Phytophthora cryptogea + TX, Phytophthora palmivora (Devine®) + TX, Pichia anomala + TX, Pichia guilermondii + TX, Pichia membranaefaciens + TX, Pichia onychis + TX, Pichia stipites + TX, Pseudomonas aeruginosa + TX, Pseudomonas aureofasciens (Spot-Less Biofungicide®) + TX, Pseudomonas cepacia + TX, Pseudomonas chlororaphis (AtEze®) + TX, Pseudomonas corrugate + TX, Pseudomonas fluorescens strain A506 (BlightBan A506®) + TX, Pseudomonas putida + TX, Pseudomonas reactans + TX, Pseudomonas spp. + TX, Pseudomonas syringae (Bio-Save®) + TX, Pseudomonas viridiflava + TX, Pseudomons fluorescens (Zequanox®) + TX, Pseudozyma flocculosa strain PF-A22 UL (Sporodex L®) + TX, Puccinia canaliculata + TX, Puccinia thlaspeos (Wood Warrior®) + TX, Pythium paroecandrum + TX, Pythium oligandrum (Polygandron® + TX, Polyversum®) + TX, Pythium periplocum + TX, Rhanella aquatilis + TX, Rhanella spp. + TX, Rhizobia (Dormal® + TX, Vault®) + TX, Rhizoctonia + TX, Rhodococcus globerulus strain AQ719 + TX, Rhodosporidium diobovatum + TX, Rhodosporidium toruloides + TX, Rhodotorula spp. + TX, Rhodotorula glutinis + TX, Rhodotorula graminis + TX, Rhodotorula mucilagnosa + TX, Rhodotorula rubra + TX, Saccharomyces cerevisiae + TX, Salinococcus roseus + TX, Sclerotinia minor + TX, Sclerotinia minor (SARRITOR®) + TX, Scytalidium spp. + TX, Scytalidium uredinicola + TX, Spodoptera exigua nuclear polyhedrosis virus (Spod-X® + TX, Spexit®) + TX, Serratia marcescens + TX, Serratia plymuthica + TX, Serratia spp. + TX, Sordaria fimicola + TX, Spodoptera littoralis nucleopolyhedrovirus (Littovir®) + TX, Sporobolomyces roseus + TX, Stenotrophomonas maltophilia + TX, Streptomyces ahygroscopicus + TX, Streptomyces albaduncus + TX, Streptomyces exfoliates + TX, Streptomyces galbus + TX, Streptomyces griseoplanus + TX, Streptomyces griseoviridis (Mycostop®) + TX, Streptomyces lydicus (Actinovate®) + TX, Streptomyces lydicus WYEC-108 (ActinoGrow®) + TX, Streptomyces violaceus + TX, Tilletiopsis minor + TX, Tilletiopsis spp. + TX, Trichoderma asperellum (T34 Biocontrol®) + TX, Trichoderma gamsii (Tenet®) + TX, Trichoderma atroviride (Plantmate®) + TX, Trichoderma hamatum TH 382 + TX, Trichoderma harzianum rifai (Mycostar®) + TX, Trichoderma harzianum T-22 (Trianum-P® + TX, Plantshield HC® + TX, Rootshield® + TX, Trianum-G®) + TX, Trichoderma harzianum T-39 (Trichodex®) + TX, Trichoderma inhamatum + TX, Trichoderma koningii + TX, Trichoderma spp. LC 52 (Sentinel®) + TX, Trichoderma lignorum + TX, Trichoderma longibrachiatum + TX, Trichoderma polysporum (Binab T®) + TX, Trichoderma taxi + TX, Trichoderma virens + TX, Trichoderma virens (formerly Gliocladium virens GL-21) (SoilGuard®) + TX, Trichoderma viride + TX, Trichoderma viride strain ICC 080 (Remedier®) + TX, Trichosporon pullulans + TX, Trichosporon spp. + TX, Trichothecium spp. + TX, Trichothecium roseum + TX, Typhula phacorrhiza strain 94670 + TX, Typhula phacorrhiza strain 94671 + TX, Ulocladium atrum + TX, Ulocladium oudemansii (Botry-Zen®) + TX, Ustilago maydis + TX, various bacteria and supplementary micronutrients (Natural II®) + TX, various fungi (Millennium Microbes®) + TX, Verticillium chlamydosporium + TX, Verticillium lecanii (Mycotal® + TX, Vertalec®) + TX, Vip3Aa20 (VIPtera®) + TX, Virgibaclillus marismortui + TX, Xanthomonas campestris pv. Poae (Camperico®) + TX, Xenorhabdus bovienii + TX, Xenorhabdus nematophilus
Plant extracts including: pine oil (Retenol®) + TX, azadirachtin (Plasma Neem Oil® + TX, AzaGuard® + TX, MeemAzal® + TX, Molt-X® + TX, Botanical IGR (Neemazad® + TX, Neemix®) + TX, canola oil (Lilly Miller Vegol®) + TX, Chenopodium ambrosioides near ambrosioides (Requiem®) + TX, Chrysanthemum extract (Crisant®) + TX, extract of neem oil (Trilogy®) + TX, essentials oils of Labiatae (Botania®) + TX, extracts of clove rosemary peppermint and thyme oil (Garden insect killer®) + TX, Glycinebetaine (Greenstim®) + TX, garlic + TX, lemongrass oil (GreenMatch®) + TX, neem oil + TX, Nepeta cataria (Catnip oil) + TX, Nepeta catarina + TX, nicotine + TX, oregano oil (MossBuster®) + TX, Pedaliaceae oil (Nematon®) + TX, pyrethrum + TX, Quillaja saponaria (NemaQ®) + TX, Reynoutria sachalinensis (Regalia® + TX, Sakalia®) + TX, rotenone (Eco Roten®) + TX, Rutaceae plant extract (Soleo®) + TX, soybean oil (Ortho ecosense®) + TX, tea tree oil (Timorex Gold®) + TX, thymus oil + TX, AGNIQUE® MMF + TX, BugOil® + TX, mixture of rosemary sesame pepermint thyme and cinnamon extracts (EF 300®) + TX, mixture of clove rosemary and peppermint extract (EF 400®) + TX, mixture of clove pepermint garlic oil and mint (Soil Shot®) + TX, kaolin (Screen®) + TX, storage glucam of brown algae (Laminarin®); pheromones including: blackheaded fireworm pheromone (3M Sprayable Blackheaded Fireworm Pheromone®) + TX, Codling Moth Pheromone (Paramount dispenser-(CM)/ Isomate C-Plus®) + TX, Grape Berry Moth Pheromone (3M MEC-GBM Sprayable Pheromone®) + TX, Leafroller pheromone (3M MEC - LR Sprayable Pheromone®) + TX, Muscamone (Snip7 Fly Bait® + TX, Starbar Premium Fly Bait®) + TX, Oriental Fruit Moth Pheromone (3M oriental fruit moth sprayable pheromone®) + TX, Peachtree Borer Pheromone (Isomate-P®) + TX, Tomato Pinworm Pheromone (3M Sprayable pheromone®) + TX, Entostat powder (extract from palm tree) (Exosex CM®) + TX, (E + TX,Z + TX,Z)- 3 + TX,8 + TX,11 Tetradecatrienyl acetate + TX, (Z + TX,Z + TX,E)-7 + TX,11 + TX,13- Hexadecatrienal + TX, (E + TX,Z)-7 + TX,9-Dodecadien-1-yl acetate + TX, 2-Methyl-1 -butanol + TX, Calcium acetate + TX, Scenturion® + TX, Biolure® + TX, Check-Mate® + TX, Lavandulyl senecioate; Macrobials including: Aphelinus abdominalis + TX, Aphidius ervi (Aphelinus-System®) + TX, Acerophagus papaya + TX, Adalia bipunctata (Adalia-System®) + TX, Adalia bipunctata (Adaline®) + TX, Adalia bipunctata (Aphidalia®) + TX, Ageniaspis citricola + TX, Ageniaspis fuscicollis + TX, Amblyseius andersoni (Anderline® + TX, Andersoni-System®) + TX, Amblyseius californicus (Amblyline® + TX, Spical®) + TX, Amblyseius cucumeris (Thripex® + TX, Bugline cucumeris®) + TX, Amblyseius fallacis (Fallacis®) + TX, Amblyseius swirskii (Bugline swirskii® + TX, Swirskii-Mite®) + TX, Amblyseius womersleyi (WomerMite®) + TX, Amitus hesperidum + TX, Anagrus atomus + TX, Anagyrus fusciventris + TX, Anagyrus kamali + TX, Anagyrus loecki + TX, Anagyrus pseudococci (Citripar®) + TX, Anicetus benefices + TX, Anisopteromalus calandrae + TX, Anthocoris nemoralis (Anthocoris-System®) + TX, Aphelinus abdominalis (Apheline® + TX, Aphiline®) + TX, Aphelinus asychis + TX, Aphidius colemani (Aphipar®) + TX, Aphidius ervi (Ervipar®) + TX, Aphidius gifuensis + TX, Aphidius matricariae (Aphipar-M®) + TX, Aphidoletes aphidimyza (Aphidend®) + TX, Aphidoletes aphidimyza (Aphidoline®) + TX, Aphytis lingnanensis + TX, Aphytis melinus + TX, Aprostocetus hagenowii + TX, Atheta coriaria (Staphyline®) + TX, Bombus spp. + TX, Bombus terrestris (Natupol Beehive®) + TX, Bombus terrestris (Beeline® + TX, Tripol®) + TX, Cephalonomia stephanoderis + TX, Chilocorus nigritus + TX, Chrysoperla carnea (Chrysoline®) + TX, Chrysoperla carnea (Chrysopa®) + TX, Chrysoperla rufilabris + TX, Cirrospilus ingenuus + TX, Cirrospilus quadristriatus + TX, Citrostichus phyllocnistoides + TX, Closterocerus Chamaeleon + TX, Closterocerus spp. + TX, Coccidoxenoides perminutus (Pianopar®) + TX, Coccophagus cowperi + TX, Coccophagus lycimnia + TX, Cotesia flavipes + TX, Cotesia plutellae + TX, Cryptolaemus montrouzieri (Cryptobug® + TX, Cryptoline®) + TX, Cybocephalus nipponicus + TX, Dacnusa sibirica + TX, Dacnusa sibirica (Minusa®) + TX, Diglyphus isaea (Diminex®) + TX, Delphastus catalinae (Delphastus®) + TX, Delphastus pusillus + TX, Diachasmimorpha krausii + TX, Diachasmimorpha longicaudata + TX, Diaparsis jucunda + TX, Diaphorencyrtus aligarhensis + TX, Diglyphus isaea + TX, Diglyphus isaea (Miglyphus® + TX, Digline®) + TX, Dacnusa sibirica (DacDigline® + TX, Minex®) + TX, Diversinervus spp. + TX, Encarsia citrina + TX, Encarsia formosa (Encarsia max® + TX, Encarline® + TX, En- Strip®) + TX, Eretmocerus eremicus (Enermix®) + TX, Encarsia guadeloupae + TX, Encarsia haitiensis + TX, Episyrphus balteatus (Syrphidend®) + TX, Eretmoceris siphonini + TX, Eretmocerus californicus + TX, Eretmocerus eremicus (Ercal® + TX, Eretline e®) + TX, Eretmocerus eremicus (Bemimix®) + TX, Eretmocerus hayati + TX, Eretmocerus mundus (Bemipar® + TX, Eretline m®) + TX, Eretmocerus siphonini + TX, Exochomus quadripustulatus + TX, Feltiella acarisuga (Spidend®) + TX, Feltiella acarisuga (Feltiline®) + TX, Fopius arisanus + TX, Fopius ceratitivorus + TX, Formononetin (Wirless Beehome®) + TX, Franklinothrips vespiformis (Vespop®) + TX, Galendromus occidentalis + TX, Goniozus legneri + TX, Habrobracon hebetor + TX, Harmonia axyridis (HarmoBeetle®) + TX, Heterorhabditis spp. (Lawn Patrol®) + TX, Heterorhabditis bacteriophora (NemaShield HB® + TX, Nemaseek® + TX, Terranem-Nam® + TX, Terranem® + TX, Larvanem® + TX, B-Green® + TX, NemAttack ® + TX, Nematop®) + TX, Heterorhabditis megidis (Nemasys H® + TX, BioNem H® + TX, Exhibitline hm® + TX, Larvanem-M®) + TX, Hippodamia convergens + TX, Hypoaspis aculeifer (Aculeifer-System® + TX, Entomite-A®) + TX, Hypoaspis miles (Hypoline m® + TX, Entomite-M®) + TX, Lbalia leucospoides + TX, Lecanoideus floccissimus + TX, Lemophagus errabundus + TX, Leptomastidea abnormis + TX, Leptomastix dactylopii (Leptopar®) + TX, Leptomastix epona + TX, Lindorus lophanthae + TX, Lipolexis oregmae + TX, Lucilia caesar (Natufly®) + TX, Lysiphlebus testaceipes + TX, Macrolophus caliginosus (Mirical-N® + TX, Macroline c® + TX, Mirical®) + TX, Mesoseiulus longipes + TX, Metaphycus flavus + TX, Metaphycus lounsburyi + TX, Micromus angulatus (Milacewing®) + TX, Microterys flavus + TX, Muscidifurax raptorellus and Spalangia cameroni (Biopar®) + TX, Neodryinus typhlocybae + TX, Neoseiulus californicus + TX, Neoseiulus cucumeris (THRYPEX®) + TX, Neoseiulus fallacis + TX, Nesideocoris tenuis (NesidioBug® + TX, Nesibug®) + TX, Ophyra aenescens (Biofly®) + TX, Orius insidiosus (Thripor-I® + TX, Online i®) + TX, Orius laevigatus (Thripor-L® + TX, Online I®) + TX, Orius majusculus (Online m®) + TX, Orius strigicollis (Thripor-S®) + TX, Pauesia juniperorum + TX, Pediobius foveolatus + TX, Phasmarhabditis hermaphrodita (Nemaslug®) + TX, Phymastichus coffea + TX, Phytoseiulus macropilus + TX, Phytoseiulus persimilis (Spidex® + TX, Phytoline p®) + TX, Podisus maculiventris (Podisus®) + TX, Pseudacteon curvatus + TX, Pseudacteon obtusus + TX, Pseudacteon tricuspis + TX, Pseudaphycus maculipennis + TX, Pseudleptomastix mexicana + TX, Psyllaephagus pilosus + TX, Psyttalia concolor (complex) + TX, Quadrastichus spp. + TX, Rhyzobius lophanthae + TX, Rodolia cardinalis + TX, Rumina decollate + TX, Semielacher petiolatus + TX, Sitobion avenae (Ervibank®) + TX, Steinernema carpocapsae (Nematac C® + TX, Millenium® + TX, BioNem C® + TX, NemAttack® + TX, Nemastar® + TX, Capsanem®) + TX, Steinernema feltiae (NemaShield® + TX, Nemasys F® + TX, BioNem F® + TX, Steinernema-System® + TX, NemAttack® + TX, Nemaplus® + TX, Exhibitline st® + TX, Scia-rid® + TX, Entonem®) + TX, Steinernema kraussei (Nemasys L® + TX, BioNem L® + TX, Exhibitline srb®) + TX, Steinernema riobrave (BioVector® + TX, BioVektor®) + TX, Steinernema scapterisci (Nematac S®) + TX, Steinernema spp. + TX, Steinemematid spp. (Guardian Nematodes®) + TX, Stethorus punctillum (Stethorus®) + TX, Tamarixia radiate + TX, Tetrastichus setifer + TX, Thripobius semiluteus + TX, Torymus sinensis + TX, Trichogramma brassicae (Tricholine b®) + TX, Trichogramma brassicae (Tricho-Strip®) + TX, Trichogramma evanescens + TX, Trichogramma minutum + TX, Trichogramma ostriniae + TX, Trichogramma platneri + TX, Trichogramma pretiosum + TX, Xanthopimpla stemmator, other biologicals including: abscisic acid + TX, bioSea® + TX, Chondrostereum purpureum (Chontrol Paste®) + TX, Colletotrichum gloeosporioides (Collego®) + TX, Copper Octanoate (Cueva®) + TX, Delta traps (Trapline d®) + TX, Erwinia amylovora (Harpin) (ProAct® + TX, Ni-HI BIT Gold CST®) + TX, Ferri-phosphate (Ferramol®) + TX, Funnel traps (Trapline y®) + TX, Gallex® + TX, Grower's Secret® + TX, Homo-brassonolide + TX, Iron Phosphate (Lilly Miller Worry Free Ferramol Slug & Snail Bait®) + TX, MCP hail trap (Trapline f®) + TX, Microctonus hyperodae + TX, Mycoleptodiscus terrestris (Des-X®) + TX, BioGain® + TX, Aminomite® + TX, Zenox® + TX, Pheromone trap (Thripline ams®) + TX, potassium bicarbonate (MilStop®) + TX, potassium salts of fatty acids (Sanova®) + TX, potassium silicate solution (Sil-Matrix®) + TX, potassium iodide + potassiumthiocyanate (Enzicur®) + TX, SuffOil-X® + TX, Spider venom + TX, Nosema locustae (Semaspore Organic Grasshopper Control®) + TX, Sticky traps (Trapline YF® + TX, Rebell Amarillo®) + TX and Traps (Takitrapline y + b®) + TX; and a safener, such as benoxacor + TX, cloquintocet (including cloquintocet-mexyl) + TX, cyprosulfamide + TX, dichlormid + TX, fenchlorazole (including fenchlorazole-ethyl) + TX, fenclorim + TX, fluxofenim + TX, furilazole + TX, isoxadifen (including isoxadifen-ethyl) + TX, mefenpyr (including mefenpyr-diethyl) + TX, metcamifen + TX and oxabetrinil + TX.
The references in brackets behind the active ingredients, e.g. [3878-19-1] refer to the Chemical Abstracts Registry number. The above described mixing partners are known. Where the active ingredients are included in "The Pesticide Manual" [The Pesticide Manual - A World Compendium; Thirteenth Edition; Editor: C. D. S. TomLin; The British Crop Protection Council], they are described therein under the entry number given in round brackets hereinabove for the particular compound; for example, the compound "abamectin" is described under entry number (1). Where "[CCN]" is added hereinabove to the particular compound, the compound in question is included in the "Compendium of Pesticide Common Names", which is accessible on the internet [A. Wood; Compendium of Pesticide Common Names, Copyright © 1995-2004]; for example, the compound "acetoprole" is described under the internet address http://www.alanwood.net/pesticides/acetoprole.html.
Most of the active ingredients described above are referred to hereinabove by a so-called "common name", the relevant "ISO common name" or another "common name" being used in individual cases. If the designation is not a "common name", the nature of the designation used instead is given in round brackets for the particular compound; in that case, the IUPAC name, the lUPAC/Chemical Abstracts name, a "chemical name", a "traditional name", a "compound name" or a "develoment code" is used or, if neither one of those designations nor a "common name" is used, an "alternative name" is employed. “CAS Reg. No” means the Chemical Abstracts Registry Number.
The active ingredient mixture of the compounds of formula I selected from Tables A-1 to A-12 and Tables B-1 to B-12 and Table P with active ingredients described above comprises a compound selected from Tables A-1 to A-12 and Tables B-1 to B-12 and Table P and an active ingredient as described above preferably in a mixing ratio of from 100:1 to 1 :6000, especially from 50:1 to 1 :50, more especially in a ratio of from 20:1 to 1 :20, even more especially from 10:1 to 1 :10, very especially from 5:1 and 1 :5, special preference being given to a ratio of from 2:1 to 1 :2, and a ratio of from 4:1 to 2:1 being likewise preferred, above all in a ratio of 1 :1 , or 5:1 , or 5:2, or 5:3, or 5:4, or 4:1 , or 4:2, or 4:3, or 3:1 , or 3:2, or 2:1 , or 1 :5, or 2:5, or 3:5, or 4:5, or 1 :4, or 2:4, or 3:4, or 1 :3, or 2:3, or 1 :2, or 1 :600, or 1 :300, or 1 :150, or 1 :35, or 2:35, or 4:35, or 1 :75, or 2:75, or 4:75, or 1 :6000, or 1 :3000, or 1 :1500, or 1 :350, or 2:350, or 4:350, or 1 :750, or 2:750, or 4:750. Those mixing ratios are by weight.
The mixtures as described above can be used in a method for controlling pests, which comprises applying a composition comprising a mixture as described above to the pests or their environment, with the exception of a method for treatment of the human or animal body by surgery or therapy and diagnostic methods practised on the human or animal body.
The mixtures comprising a compound of formula I selected from Tables A-1 to A-12 and Tables B-1 to B-12 and Table P and one or more active ingredients as described above can be applied, for example, in a single “ready-mix” form, in a combined spray mixture composed from separate formulations of the single active ingredient components, such as a “tank-mix”, and in a combined use of the single active ingredients when applied in a sequential manner, i.e. one after the other with a reasonably short period, such as a few hours or days. The order of applying the compounds of formula I selected from Tables A-1 to A-12 and Tables B-1 to B-12 and Table P and the active ingredients as described above is not essential for working the present invention.
The compositions according to the invention can also comprise further solid or liquid auxiliaries, such as stabilizers, for example unepoxidized or epoxidized vegetable oils (for example epoxidized coconut oil, rapeseed oil or soya oil), antifoams, for example silicone oil, preservatives, viscosity regulators, binders and/or tackifiers, fertilizers or other active ingredients for achieving specific effects, for example bactericides, fungicides, nematocides, plant activators, molluscicides or herbicides.
The compositions according to the invention are prepared in a manner known per se, in the absence of auxiliaries for example by grinding, screening and/or compressing a solid active ingredient and in the presence of at least one auxiliary for example by intimately mixing and/or grinding the active ingredient with the auxiliary (auxiliaries). These processes for the preparation of the compositions and the use of the compounds I for the preparation of these compositions are also a subject of the invention.
The application methods for the compositions, that is the methods of controlling pests of the abovementioned type, such as spraying, atomizing, dusting, brushing on, dressing, scattering or pouring - which are to be selected to suit the intended aims of the prevailing circumstances - and the use of the compositions for controlling pests of the abovementioned type are other subjects of the invention. Typical rates of concentration are between 0.1 and 1000 ppm, preferably between 0.1 and 500 ppm, of active ingredient. The rate of application per hectare is generally 1 to 2000 g of active ingredient per hectare, in particular 10 to 1000 g/ha, preferably 10 to 600 g/ha.
A preferred method of application in the field of crop protection is application to the foliage of the plants (foliar application), it being possible to select frequency and rate of application to match the danger of infestation with the pest in question. Alternatively, the active ingredient can reach the plants via the root system (systemic action), by drenching the locus of the plants with a liquid composition or by incorporating the active ingredient in solid form into the locus of the plants, for example into the soil, for example in the form of granules (soil application). In the case of paddy rice crops, such granules can be metered into the flooded paddy-field.
The compounds of the invention and compositions thereof are also be suitable for the protection of plant propagation material, for example seeds, such as fruit, tubers or kernels, or nursery plants, against pests of the abovementioned type. The propagation material can be treated with the compound prior to planting, for example seed can be treated prior to sowing. Alternatively, the compound can be applied to seed kernels (coating), either by soaking the kernels in a liquid composition or by applying a layer of a solid composition. It is also possible to apply the compositions when the propagation material is planted to the site of application, for example into the seed furrow during drilling. These treatment methods for plant propagation material and the plant propagation material thus treated are further subjects of the invention. Typical treatment rates would depend on the plant and pest/fungi to be controlled and are generally between 1 to 200 grams per 100 kg of seeds, preferably between 5 to 150 grams per 100 kg of seeds, such as between 10 to 100 grams per 100 kg of seeds.
The term seed embraces seeds and plant propagules of all kinds including but not limited to true seeds, seed pieces, suckers, corns, bulbs, fruit, tubers, grains, rhizomes, cuttings, cut shoots and the like and means in a preferred embodiment true seeds.
The present invention also comprises seeds coated or treated with or containing a compound of formula I. The term "coated or treated with and/or containing" generally signifies that the active ingredient is for the most part on the surface of the seed at the time of application, although a greater or lesser part of the ingredient may penetrate into the seed material, depending on the method of application. When the said seed product is (re)planted, it may absorb the active ingredient. In an embodiment, the present invention makes available a plant propagation material adhered thereto with a compound of formula (I). Further, it is hereby made available, a composition comprising a plant propagation material treated with a compound of formula (I).
Seed treatment comprises all suitable seed treatment techniques known in the art, such as seed dressing, seed coating, seed dusting, seed soaking and seed pelleting. The seed treatment application of the compound formula (I) can be carried out by any known methods, such as spraying or by dusting the seeds before sowing or during the sowing/planting of the seeds.
Biological Examples:
The Examples which follow serve to illustrate the invention. Certain compounds of the invention can be distinguished from known compounds by virtue of greater efficacy at low application rates, which can be verified by the person skilled in the art using the experimental procedures outlined in the Examples, using lower application rates if necessary, for example 50 ppm, 12.5 ppm, 6 ppm, 3 ppm, 1 .5 ppm, 0.8 ppm or 0.2 ppm.
Example B1 : Activity against Bemisia tabaci (Cotton white fly): Feedinq/contact activity
Cotton leaf discs were placed on agar in 24-well microtiter plates and sprayed with aqueous test solutions prepared from 10'000 ppm DMSO stock solutions. After drying the leaf discs were infested with adult white flies. The samples were checked for mortality 6 days after incubation.
The following compounds resulted in at least 80% mortality at an application rate of 200 ppm: P5, P6, P10, P16.
Example B2: Activity against Diabrotica balteata (Corn root worm)
Maize sprouts placed onto an agar layer in 24-well microtiter plates were treated with aqueous test solutions prepared from 10'000 ppm DMSO stock solutions by spraying. After drying, the plates were infested with L2 larvae (6 to 10 per well). The samples were assessed for mortality and growth inhibition in comparison to untreated samples 4 days after infestation.
The following compounds gave an effect of at least 80% in at least one of the two categories (mortality or growth inhibition) at an application rate of 200 ppm: P2, P3, P4, P5, P6, P7, P8, P9, P10, P12, P14, P16, P18, P20.
Example B3: Activity against Euschistus heros (Neotropical Brown Stink Bug)
Soybean leaves on agar in 24-well microtiter plates were sprayed with aqueous test solutions prepared from 10'000 ppm DMSO stock solutions. After drying the leaves were infested with N2 nymphs. The samples were assessed for mortality and growth inhibition in comparison to untreated samples 5 days after infestation. The following compounds gave an effect of at least 80% in at least one of the two categories (mortality or growth inhibition) at an application rate of 200 ppm: P2, P5, P6, P9, P10, P12, P16, P17, P18, P20.
Example B4: Activity against Myzus persicae (Green peach aphid) Feedinq/Contact activity Sunflower leaf discs were placed onto agar in a 24-well microtiter plate and sprayed with aqueous test solutions prepared from 10'000 ppm DMSO stock solutions. After drying, the leaf discs were infested with an aphid population of mixed ages. The samples were assessed for mortality 6 days after infestation.
The following compounds resulted in at least 80% mortality at an application rate of 200 ppm: P3, P5, P9, P10, P16, P18, P20.
Example B5: Activity against Plutella xylostella (Diamond back moth) 24-well microtiter plates with artificial diet were treated with aqueous test solutions prepared from 10'000 ppm DMSO stock solutions by pipetting. After drying, Plutella eggs were pipetted through a plastic stencil onto a gel blotting paper and the plate was closed with it. The samples were assessed for mortality and growth inhibition in comparison to untreated samples 8 days after infestation.
The following compounds gave an effect of at least 80% in at least one of the two categories (mortality or growth inhibition) at an application rate of 200 ppm: P2, P3, P4, P5, P6, P7, P8, P9, P10, P12, P14, P16, P17, P18, P19, P20.
Example B6: Activity against Spodoptera litoralis (Egyptian cotton leaf worm)
Cotton leaf discs were placed onto agar in 24-well microtiter plates and sprayed with aqueous test solutions prepared from 10'000 ppm DMSO stock solutions. After drying the leaf discs were infested with five L1 larvae. The samples were assessed for mortality, anti-feeding effect, and growth inhibition in comparison to untreated samples 3 days after infestation. Control of Spodoptera littoralis by a test sample is given when at least one of the categories mortality, anti-feedant effect, and growth inhibition is higher than the untreated sample.
The following compounds resulted in at least 80% control at an application rate of 200 ppm: P2, P3, P4, P5, P6, P8, P9, P10, P12, P14, P16, P17, P18, P19, P20.
Example B7: Activity against Chilo suppressalis (Striped rice stemborer)
24-well microtiter plates with artificial diet were treated with aqueous test solutions prepared from 10'000 ppm DMSO stock solutions by pipetting. After drying, the plates were infested with L2 larvae (6-8 per well). The samples were assessed for mortality, anti-feeding effect, and growth inhibition in comparison to untreated samples 6 days after infestation. Control of Chilo suppressalis by a test sample is given when at least one of the categories mortality, anti-feedant effect, and growth inhibition is higher than the untreated sample.
The following compounds resulted in at least 80% control at an application rate of 200 ppm: P12, P14, P16, P18, P19, P20. Example B8: Activity against Myzus persicae (Green peach aphid) Systemic activity
Roots of pea seedlings infested with an aphid population of mixed ages were placed directly into aqueous test solutions prepared from 10'000 DMSO stock solutions. The samples were assessed for mortality 6 days after placing seedlings into test solutions.
The following compound resulted in at least 80% mortality at a test rate of 24 ppm: P20
Example B9: Activity against Carpocapsa (Cydia) pomonella (Codling moth)
Diet cubes coated with paraffin were sprayed with diluted test solutions in an application chamber. After drying off the treated cubes (10 replicates) were infested with 1 L1 larvae. Samples were incubated at 26-27°C and checked 14 days after infestation for mortality and growth inhibition. The following compounds gave an effect of at least 80% in at least one of the two categories (mortality or growth inhibition) at an application rate of 12.5 ppm: P2, P4, P6, P10, P12, P16, P20.

Claims

CLAIMS:
1 . A compound of formula
Figure imgf000123_0001
wherein
Gi and G2 are, independently from each other, CH or N;
R2 is Ci-Cehaloalkyl;
X is S, SO, or SO2 and
R1 is Ci-C4alkyl or C3-C6cycloalkyl-Ci-C4alkyl;
Y1 and Y2 are, independently from each other, hydrogen, halogen, Ci-C4alkyl, Ci-Cehaloalkyl, C3- Cecycloalkyl, Cs-Cecycloalkyl monosubstituted by cyano, Ci-Cecyanoalkyl, Ci-Cecyanoalkoxy, cyano, Ci-C4alkoxy, Ci-Cehaloalkoxy, -N(R3)2, -N(R3)COR4; and each R3 and R4 are independently from each other, hydrogen, Ci-C4alkyl, Ci-Cehaloalkyl or C3- Cecycloalkyl; or an agrochemically acceptable salt, stereoisomer, enantiomer, tautomer or N-oxide thereof.
2. A compound of formula I according to claim 1 , represented by the compounds of formula 1-1 :
Figure imgf000123_0002
wherein R1 , R2, X, R3, R4, G1 , G2 and Y1 are as defined under formula I in claim 1 , or an agrochemically acceptable salt, stereoisomer, enantiomer, tautomer or N-oxide thereof, and wherein Y1 is hydrogen, halogen, Ci-C4alkyl, Ci-Cehaloalkyl, Cs-Cecycloalkyl, Cs-Cecycloalkyl monosubstituted by cyano, Ci-Cecyanoalkyl, Ci-Cecyanoalkoxy, cyano, Ci-C4alkoxy, Ci-Cehaloalkoxy, -N(R3)2, - N(R3)COR4; and each R3 and R4 are independently from each other, hydrogen, Ci-C4alkyl, Ci-Cehaloalkyl or C3- Cecycloalkyl.
3. A compound of formula I according to claim 1 , represented by the compounds of formula I-2:
Figure imgf000124_0001
wherein Ri , R2, X, R3, R4, G1 , G2 and Y2 are as defined under formula I in claim 1 , or an agrochemically acceptable salt, stereoisomer, enantiomer, tautomer or N-oxide thereof, and wherein Y2 is hydrogen, halogen, Ci-C4alkyl, Ci-Cehaloalkyl, Cs-Cecycloalkyl, Cs-Cecycloalkyl monosubstituted by cyano, Ci-Cecyanoalkyl, Ci-Cecyanoalkoxy, cyano, Ci-C4alkoxy, Ci-Cehaloalkoxy, -N(R3)2, - N(R3)COR4; and each R3 and R4 are independently from each other, hydrogen, Ci-C4alkyl, Ci-Cehaloalkyl or C3- Cecycloalkyl.
4. A compound according to any one of the previous claims, wherein: R1 is ethyl or cyclopropylmethyl; preferably R1 is ethyl.
5. A compound according to any one of the previous claims, wherein: X is S or SO2; preferably X is SO2.
6. A compound of formula I according to claim 1 , represented by the compounds of formula I-3:
Figure imgf000124_0002
wherein R2, R3, R4, G1, G2 and Y1 are as defined under formula I in claim 1 , or an agrochemically acceptable salt, stereoisomer, enantiomer, tautomer or N-oxide thereof, and wherein
Y1 is hydrogen, halogen, Ci-C4alkyl, Ci-Cehaloalkyl, Cs-Cecycloalkyl, Cs-Cecycloalkyl monosubstituted by cyano, Ci-Cecyanoalkyl, Ci-Cecyanoalkoxy, cyano, Ci-C4alkoxy, Ci-Cehaloalkoxy, -N(R3)2, - N(R3)COR4; and each R3 and R4 are independently from each other, hydrogen, Ci-C4alkyl, Ci-Cehaloalkyl or C3- Cecycloalkyl.
7. A compound of formula I according to claim 1 , represented by the compounds of formula I-4:
Figure imgf000125_0001
wherein R2, R3, R4, G1, G2 and Y2 are as defined under formula I in claim 1 , or an agrochemically acceptable salt, stereoisomer, enantiomer, tautomer or N-oxide thereof, and wherein
Y2 is hydrogen, halogen, Ci-C4alkyl, Ci-Cehaloalkyl, Cs-Cecycloalkyl, Cs-Cecycloalkyl monosubstituted by cyano, Ci-Cecyanoalkyl, Ci-Cecyanoalkoxy, cyano, Ci-C4alkoxy, Ci-Cehaloalkoxy, -N(Rs)2, - N(R3)COR4; and each R3 and R4 are independently from each other, hydrogen, Ci-C4alkyl, Ci-Cehaloalkyl or C3- Cecycloalkyl.
8. A compound according to any one of the previous claims, wherein: R2 is Ci-Cefluoroalkyl; preferably R2 is -CH2CF2CHF2, -CH2CF2CF3. or -CH2CH2CF3.
9. A compound according to any one of claims 1 , 2, 4, 5, 6 and 8, wherein Y1 is halogen, trifluoromethyl, 1 ,1-difluoroethyl, cyclopropyl, cyanocyclopropyl, cyanoisopropyl or trifluoroethoxy; preferably Y1 is -CF3, 1 -cyanocyclopropyl or 1-cyano-1-methyl-ethyl.
10. A compound according to any one of claims 1 , 2, 4, 5, 6 and 8, wherein Y1 is hydrogen, trifluoromethyl, -CF2CH3, cyclopropyl, 1 -cyanocyclopropyl, 1-cyano-1-methyl-ethyl, -NH(CH3), - N(CH3)COCH3 or -N(CH3)COCF3.
11 . A compound according to any one of claims 1 , 3, 4, 5, 7 and 8 wherein Y2 is halogen, trifluoromethyl, 1 ,1-difluoroethyl, cyclopropyl, cyanocyclopropyl, cyanoisopropyl or trifluoroethoxy; preferably Y2 is -CF3, 1 -cyanocyclopropyl or 1-cyano-1-methyl-ethyl.
12. A compound according to any one of claims 1 , 2, 4, 5, 6 and 8, wherein Y2 is hydrogen, trifluoromethyl, -CF2CH3, cyclopropyl, 1 -cyanocyclopropyl, 1-cyano-1-methyl-ethyl, -NH(CH3), - N(CH3)COCH3 or -N(CH3)COCF3.
13. A compound according to any one of claims 1-12, wherein: G2 is N and G1 is CH.
14. A compound according to any one of claims 1-12, wherein: G2 and G1 are both CH.
15. A compound according to any one of claims 1-12, wherein: G2 is CH and G1 is N. -125-
16. A compound of formula I according to claim 1 , selected from the group consisting of: 5-[3-ethylsulfanyl-6-(trifluoromethyl)indazol-2-yl]-1-(2,2,3,3,3-pentafluoropropyl)pyrazolo[3,4-c]pyridine (compound P1 ); 5-[3-ethylsulfonyl-6-(trifluoromethyl)indazol-2-yl]-1 -(2, 2, 3,3,3- pentafluoropropyl)pyrazolo[3,4-c]pyridine (compound P2); 2-[3-ethylsulfanyl-2-[1-(2,2,3,3,3- pentafluoropropyl)pyrazolo[3,4-c]pyridin-5-yl]indazol-6-yl]-2-methyl-propanenitrile (compound P3); 2- [3-ethylsulfonyl-2-[1-(2,2,3,3,3-pentafluoropropyl)pyrazolo[3,4-c]pyridin-5-yl]indazol-6-yl]-2-methyl- propanenitrile (compound P4); 1-[3-ethylsulfanyl-2-[1-(2,2,3,3,3-pentafluoropropyl)pyrazolo[3,4- c]pyridin-5-yl]indazol-6-yl]cyclopropanecarbonitrile (compound P5); 1-[3-ethylsulfonyl-2-[1-(2,2,3,3,3- pentafluoropropyl)pyrazolo[3,4-c]pyridin-5-yl]indazol-6-yl]cyclopropanecarbonitrile (compound P6); 2- [3-ethylsulfanyl-2-[1-(2,2,3,3,3-pentafluoropropyl)pyrazolo[3,4-c]pyridin-5-yl]indazol-5-yl]-2-methyl- propanenitrile (compound P7); 2-[3-ethylsulfonyl-2-[1-(2,2,3,3,3-pentafluoropropyl)pyrazolo[3,4- c]pyridin-5-yl]indazol-5-yl]-2-methyl-propanenitrile (compound P8); 1-[3-ethylsulfanyl-2-[1-(2,2,3,3,3- pentafluoropropyl)pyrazolo[3,4-c]pyridin-5-yl]indazol-5-yl]cyclopropanecarbonitrile (compound P9); an 1-[3-ethylsulfonyl-2-[1-(2,2,3,3,3-pentafluoropropyl)pyrazolo[3,4-c]pyridin-5-yl]indazol-5- yl]cyclopropanecarbonitrile (compound P10); 5-[6-(1 , 1 -difluoroethyl)-3-ethylsulfanyl-indazol-2-yl]-1 - (2,2,3,3,3-pentafluoro propyl)pyrazolo[3,4-c] pyridine (compound P11); 5-[6-(1 , 1 -difluoroethyl)-3- ethylsulfonyl-indazol-2-yl]-1-(2,2,3,3,3-pentafluoro propyl)pyrazolo[3,4-c] pyridine (compound P12); 5- (5-cyclopropyl-3-ethyl sulfanyl-indazol-2-yl)-1 -(2,2,3,3,3-pentafluoro propyl)pyrazolo[3,4-c] pyridine (compound P13); 5-(5-cyclopropyl-3-ethyl sulfonyl-indazol-2-yl)-1 -(2,2,3,3,3-pentafluoro propyl)pyrazolo[3,4-c] pyridine (compound P14); 1 -[3-ethylsulfanyl-2-[1 -(3,3,3-trifluoropropyl) pyrazolo[3,4-c]pyridin-5-yl]indazol-6-yl]cyclo propanecarbonitrile (compound P15); 1-[3-ethylsulfonyl-2- [1 -(3,3,3-trifluoropropyl) pyrazolo[3,4-c]pyridin-5-yl]indazol-6-yl]cyclo propanecarbonitrile (compound P16); N-[3-ethylsulfanyl-2-[1 -(2,2,3,3,3-pentafluoro propyl)pyrazolo[3,4-c]pyridin-5-yl]indazol-6-yl]- 2,2,2-trifluoro-N-methyl-acetamide (compound P17); N-[3-ethylsulfonyl-2-[1 -(2,2,3,3,3-pentafluoro propyl)pyrazolo[3,4-c] pyridin-5-yl]indazol-6-yl]-2,2,2-trifluoro-N-methyl-acetamide (compound P18); 3- ethylsulfonyl-N-methyl-2-[1 -(2,2,3,3,3-pentafluoro propyl)pyrazolo[3,4-c] pyridin-5-yl]indazol-6-amine (compound P19) and N-[3-ethylsulfonyl-2-[1 -(2,2,3,3,3-pentafluoro propyl)pyrazolo[3,4-c]pyridin-5- yl]indazol-6-yl]-N-methyl-acetamide (compound P20).
17. A composition comprising an insecticidally, acaricidally, nematicidally or molluscicidally effective amount of a compound of formula (I), or an agrochemically acceptable salt, stereoisomer, enantiomer, tautomer or N-oxide thereof, as defined in any of claims 1 - 16 and, optionally, an auxiliary or diluent.
18. A method of combating and controlling insects, acarines, nematodes or molluscs which comprises applying to a pest, to a locus of a pest, or to a plant susceptible to attack by a pest an insecticidally, acaricidally, nematicidally or molluscicidally effective amount of a compound of formula (I), or an agrochemically acceptable salt, stereoisomer, enantiomer, tautomer or N-oxide thereof, as defined in any of claims 1 - 16 or a composition as defined claim 17. -126-
19. A method for the protection of plant propagation material from the attack by insects, acarines, nematodes or molluscs, which comprises treating the propagation material or the site, where the propagation material is planted, with a composition according to claim 17.
20. A compound of formula Vlll-a
Figure imgf000127_0001
(Vlll-a), wherein R2 is Ci-Cehaloalkyl.
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