Pesticidally active heterocyclic derivatives with sulfoximine-containing substituents

Abstract

To provide heterocyclic derivatives that are pesticidally active, in particular insecticidally active, as well as methods for exterminating and controlling insects, mites, nematodes, or mollusks.SOLUTION: The present invention provides a compound of formula (I) (where A is CH or N, and Q is a nitrogen-containing heterocyclic ring).SELECTED DRAWING: None

Description

[Technical field]

[0001] The present invention relates to pesticidally active, in particular insecticidally active, heterocyclic derivatives containing a sulfoximine substituent, processes for their preparation, compositions containing these compounds and their use for controlling arthropods, in particular insects or animal pests, including representatives of the order Acarina. [Background technology]

[0002] Pesticidal active hetero-bicyclic substituted cyclopropyl derivatives having sulfur-containing substituents are known and are described, for example, in WO 2018 / 077565, WO 2018 / 070502, WO 2017 / 146226, WO 2017 / 089190, WO 2017 / 084879, WO 2016 / 121997, WO 201 Pesticidal active heterocyclic sulfoximine derivatives have been described previously in the literature, for example in WO 2015 / 071180. [Prior art documents] [Patent documents]

[0003] [Patent Document 1] International Publication No. 2018 / 077565 [Patent Document 2] International Publication No. 2016 / 039441 [Patent Document 3] International Publication No. 2016 / 104746 [Patent Document 4] International Publication No. 2016 / 121997 Summary of the Invention [Means for solving the problem]

[0004] Surprisingly, it has now been found that certain novel bicyclic sulfoximine-containing substituted cyclopropyl derivatives have favorable properties as pesticides. The present invention therefore relates to a compound of formula I [ka] (In the formula, A is CH or N; R1 is a C1-C4 alkyl group; R2 is hydrogen, cyano, -C(O)R7, -C(O)OR8, C1-C6 alkyl, or -CONR9R 10 , SO2R 11 where: R7 is hydrogen, C1-C6 alkyl or C1-C6 haloalkyl, and R8 is C1-C6 alkyl or C1-C6 haloalkyl; R9, R 10 are each independently hydrogen or C1-C6 alkyl; R 11 is C1-C6 alkyl; R3 is hydrogen, C1-C3 alkyl, C1-C3 haloalkyl, cyano, -CO2H, -CO2NH2, C1-C4 alkoxycarbonyl, C1-C4 alkylaminocarbonyl, or C1-C4 dialkylaminocarbonyl; n is 0 or 1; Q is a group of the formulas Q1, Q2, Q3, Q4 and Q5 [ka] where the arrow indicates the point of attachment to the ring incorporating radical A; R4 is halogen, C1-C6 haloalkyl, C1-C4 haloalkylsulfanyl, C1-C4 haloalkylsulfinyl, C1-C4 haloalkylsulfonyl or C1-C6 haloalkoxy; X1 is O or NR5; R5 is C1-C4 alkyl; R6 is C1-C4 alkyl, C1-C4 haloalkyl, C1-C4 alkoxy or C3-C6 cycloalkyl; G1 and G2 are each independently N or CH. is a radical selected from the group consisting of or an agrochemically acceptable salt, stereoisomer, enantiomer, tautomer or N-oxide of a compound of formula I. DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS

[0005] The compounds of formula I which have at least one basic centre can, for example, form acid addition salts, for example with strong inorganic acids, such as mineral acids, for example perchloric acid, sulfuric acid, nitric acid, nitrous acid, phosphoric acid or hydrohalic acids, with strong organic carboxylic acids, for example C1-C4 alkane carboxylic acids which are unsubstituted or substituted, for example by halogens, for example acetic acid, with saturated or unsaturated dicarboxylic acids, for example oxalic acid, malonic acid, succinic acid, maleic acid, fumaric acid or phthalic acid, with hydroxycarboxylic acids, for example ascorbic acid, lactic acid, malic acid, tartaric acid or citric acid, or for example benzoic acid, or with organic sulfonic acids, for example C1-C4 alkane- or arylsulfonic acids which are unsubstituted or substituted, for example by halogens, for example methane- or p-toluenesulfonic acid. The compounds of formula I which have at least one acidic group can, for example, form salts with bases, for example inorganic salts, for example alkali metal or alkaline earth metal salts, for example sodium, potassium or magnesium salts, or ammonia, or salts with organic amines, for example morpholine, piperidine, pyrrolidine, mono-, di- or tri-lower alkylamines, for example ethyl-, diethyl-, triethyl- or dimethylpropylamine, or mono-, di- or trihydroxy-lower alkylamines, for example mono-, di- or triethanolamine.

[0006] As used herein, "C1-C nThe term "alkyl" refers to a saturated straight or branched hydrocarbon radical attached through any carbon atom having 1 to n carbon atoms, such as any one of the radicals methyl, ethyl, n-propyl, isopropyl, n-butyl, sec-butyl, iso-butyl, t-butyl, pentyl, hexyl, and branched isomers thereof. For example, mention may be made of one of the radicals 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. As described below, haloalkyl, haloalkylsulfanyl, haloalkylsulfinyl, haloalkylsulfonyl, alkoxy and haloalkoxy radicals are derived from alkyl radicals.

[0007] Halogen is generally fluorine, chlorine, bromine or iodine. This applies correspondingly to halogen in combination with other meanings, such as haloalkyl.

[0008] As used herein, "C1-C n The term "haloalkyl" refers to a linear or branched saturated C1-C alkyl group having 1 to n carbon atoms (as defined above). nrefers to alkyl radicals, in which some or all of the hydrogen atoms can be replaced by any one of fluorine, chlorine, bromine and / or iodine, i.e. for example chloromethyl, dichloromethyl, trichloromethyl, 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, oropropyl, 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-chlorobutyl, 4-bromobutyl, nonafluorobutyl 1,1-difluoro-2,2,2-trichloroethyl and 2,2,3,3-tetrafluoroethyl; preferably trichloromethyl, difluorochloromethyl, difluoromethyl, trifluoromethyl and dichlorofluoromethyl.

[0009] As used herein, "C1-C n The term "alkoxy" refers to a linear or branched saturated C1-C alkyl group having 1 to n carbon atoms (as defined above) attached via an oxygen atom. nIt refers to alkyl radicals, i.e. for example methoxy, ethoxy, propoxy, i-propoxy, n-butoxy, isobutoxy, sec-butoxy, t-butoxy, 1-methylpropoxy, 2-methylpropoxy and 1,1-dimethylethoxy and also the isomeric pentyloxy and hexyloxy radicals; preferably any one of radicals such as methoxy and ethoxy.

[0010] As used herein, "C1-C n The term "haloalkoxy" refers to any C1-C n Similar to alkoxy, linear or branched saturated C1-C alkoxy groups have 1 to n carbon atoms (as above) bonded through an oxygen atom. n Refers to a haloalkyl radical.

[0011] As used herein, "C1-C n The term "alkylsulfanyl" refers to a straight or branched saturated alkyl radical having 1 to n carbon atoms (as defined above) attached through a sulfur atom, i.e., any one of methylthio, ethylthio, n-propylthio, 1-methylethylthio, butylthio, 1-methylpropylthio, 2-methylpropylthio, or 1,1-dimethylethylthio.

[0012] As used herein, "C1-C n The term "haloalkylsulfanyl" refers to any of the above C1-C alkyl groups partially or fully substituted with fluorine, chlorine, bromine and / or iodine. nalkylsulfanyl radicals, i.e. for example fluoromethylthio, difluoromethylthio, trifluoromethylthio, chlorodifluoromethylthio, bromodifluoromethylthio, 2-fluoroethylthio, 2-chloroethylthio, 2-bromoethylthio, 2-iodoethylthio, 2,2-difluoroethylthio, 2,2,2-trifluoroethylthio, 2,2,2-trichloroethylthio, 2-chloro-2-fluoroethylthio, 2-chloro-2,2-difluoroethylthio, 2,2-dichloro-2-fluoroethylthio, pentafluoroethylthio, 2-fluoropropylthio, 3-fluoropropylthio, 2 -chloropropylthio, 3-chloropropylthio, 2-bromopropylthio, 3-bromopropylthio, 2,2-difluoropropylthio, 2,3-difluoropropylthio, 2,3-dichloropropylthio, 3,3,3-trifluoropropylthio, 3,3,3-trichloropropylthio, 2,2,3,3,3-pentafluoropropylthio, heptafluoropropylthio, 1-(fluoromethyl)-2-fluoroethylthio, 1-(chloromethyl)-2-chloroethylthio, 1-(bromomethyl)-2-bromoethylthio, 4-fluorobutylthio, 4-chlorobutylthio, or 4-bromobutylthio.

[0013] Similar considerations apply to C1~C n It refers to haloalkylsulfanyl (as above), but with different oxidation states of sulfur, e.g., sulfoxide -S(O)C1-C n Haloalkyl or sulfone-S(O)2C1~C n Haloalkyl refers to "C1-C n Haloalkylsulfinyl" and "C1-C n The term "haloalkylsulfonyl" also applies to the term "haloalkylsulfonyl". Thus, for example, groups such as trifluoromethylsulfinyl, trifluoromethylsulfonyl or 2,2,2-trifluoroethylsulfonyl.

[0014] As used herein, the term "C3-C6 cycloalkyl" refers to a 3- to 6-membered cycloalkyl group, such as cyclopropane, cyclobutane, cyclopropane, cyclopentane, and cyclohexane.

[0015] "C1~C n The term "alkoxycarbonyl" refers to a linear or branched saturated C1-C alkyl group having 1 to n carbon atoms (as defined above) attached via a carbonyl group. n Refers to alkoxy radicals.

[0016] "C1~C n The term "alkylaminocarbonyl" refers to a linear or branched saturated C1-C alkyl group having 1 to n carbon atoms (as defined above) attached through the nitrogen atom of the aminocarbonyl group. n Refers to alkyl radicals.

[0017] "C1~C n The term "dialkylaminocarbonyl" refers to two identical or different linear or branched saturated C1-C alkyl groups having 1-n carbon atoms (as defined above) bonded through the nitrogen atom of the aminocarbonyl group. n Refers to alkyl radicals.

[0018] A terminal single bond (free radical) represents a methyl group in the context of a given molecular structure, or represents the point of attachment in the context of a variable group definition.

[0019] The compounds of formula I according to the present invention also include the hydrates which may be formed during salt formation.

[0020] The embodiments of the present invention are as follows.

[0021] Embodiment 1 provides a compound of formula I as defined above, or an agrochemically acceptable salt, stereoisomer, enantiomer, tautomer, or N-oxide thereof.

[0022] Embodiment 2 provides a compound according to embodiment 1 or an agrochemically acceptable salt, stereoisomer, enantiomer, tautomer, or N-oxide thereof, wherein: A is CH or N; R1 is ethyl, propyl or isopropyl; R2 is hydrogen, cyano, C1-C3 alkyl, C1-C3 alkylcarbonyl, C1-C3 alkoxycarbonyl, C1-C3 haloalkylcarbonyl; R3 is hydrogen, C1-C3 haloalkyl, cyano, -CO2H, -CO2NH2, C1-C4 dialkylaminocarbonyl; and n is 1.

[0023] Embodiment 3 provides a compound according to embodiment 1 or an agrochemically acceptable salt, stereoisomer, enantiomer, tautomer, or N-oxide thereof, wherein: A is CH or N; R1 is ethyl; R2 is hydrogen; R3 is hydrogen, C1-C2 haloalkyl, cyano, -CO2NH2, C1-C2 dialkylaminocarbonyl; and n is 1.

[0024] Embodiment 4 provides a compound according to embodiment 1 or an agrochemically acceptable salt, stereoisomer, enantiomer, tautomer, or N-oxide thereof, wherein: A is CH or N; R1 is ethyl; R2 is hydrogen; R3 is hydrogen, cyano or CO2NH2; and n is 1.

[0025] Embodiment 5 provides a compound according to embodiment 1 or an agrochemically acceptable salt, stereoisomer, enantiomer, tautomer, or N-oxide thereof, wherein: A is CH or N; R1 is ethyl; R2 is hydrogen; R3 is hydrogen or cyano; and n is 1.

[0026] Embodiment 6 provides a compound according to embodiment 1 or an agrochemically acceptable salt, stereoisomer, enantiomer, tautomer, or N-oxide thereof, wherein: Q is Q1, Q2, Q4 and Q5 [ka] where the arrow indicates the point of attachment to the ring incorporating radical A; R4 is C1-C2 haloalkyl, C1-C2 haloalkylsulfanyl, C1-C2 haloalkylsulfinyl or C1-C2 haloalkylsulfonyl; X1 is oxygen or NCH3; R6 is C1-C2 alkyl, C1-C2 haloalkyl, C1-C2 alkoxy or cyclopropyl; and G1 and G2 are each independently N or CH. is a radical selected from

[0027] Embodiment 7 provides a compound according to embodiment 1 or an agrochemically acceptable salt, stereoisomer, enantiomer, tautomer, or N-oxide thereof, wherein: Q1, Q2 and Q5 [ka] where the arrow indicates the point of attachment to the ring incorporating radical A; R4 is C1-C2 fluoroalkyl, trifluoromethylsulfanyl, trifluoromethylsulfinyl, trifluoromethylsulfonyl, difluoromethylsulfanyl, difluoromethylsulfinyl, or difluoromethylsulfonyl; X1 is NCH3; R6 is methyl, ethyl, 2,2,2-trifluoroethyl, methoxy or cyclopropyl; and G1 and G2 are each independently N or CH. is a radical selected from

[0028] Embodiment 8 provides a compound according to embodiment 1 or an agrochemically acceptable salt, stereoisomer, enantiomer, tautomer, or N-oxide thereof, wherein: Q is Q1 and Q5 [ka] where the arrow indicates the point of attachment to the ring incorporating radical A; R4 is trifluoromethyl, pentafluoroethyl, trifluoromethylsulfanyl, trifluoromethylsulfinyl or trifluoromethylsulfonyl; X1 is NCH3; R6 is ethyl, methoxy or cyclopropyl; and G1 is N and G2 is CH, or G1 is CH and G2 is N, or G1 and G2 are N, or G1 and G2 are CH. is a radical selected from

[0029] Embodiment 9 provides a compound according to embodiment 1 or an agrochemically acceptable salt, stereoisomer, enantiomer, tautomer, or N-oxide thereof, wherein: Q is the radical Q1 [ka] where the arrow indicates the point of attachment to the ring incorporating radical A; R4 is trifluoromethyl; X1 is NCH3; and G1 is N and G2 is CH, G1 is CH and G2 is N, or G1 and G2 are N. It is.

[0030] Embodiment 10 provides a compound according to embodiment 1 or an agrochemically acceptable salt, stereoisomer, enantiomer, tautomer, or N-oxide thereof, wherein: A is CH or N; R1 is ethyl, propyl or isopropyl; R2 is hydrogen, cyano, C1-C3 alkyl, C1-C3 alkylcarbonyl, C1-C3 alkoxycarbonyl, C1-C3 haloalkylcarbonyl; R3 is hydrogen, C1-C3 haloalkyl, cyano, CO2H, CO2NH2, C1-C4 dialkylaminocarbonyl; n is 1; Q is Q1, Q2, Q4 and Q5 [ka] where the arrow indicates the point of attachment to the ring incorporating radical A; R4 is C1-C2 haloalkyl, C1-C2 haloalkylsulfanyl, C1-C2 haloalkylsulfinyl or C1-C2 haloalkylsulfonyl; X1 is oxygen or NCH3; R6 is C1-C2 alkyl, C1-C2 haloalkyl, C1-C2 alkoxy or cyclopropyl; and G1 and G2 are each independently N or CH. is a radical selected from

[0031] Embodiment 11 provides a compound according to embodiment 1 or an agrochemically acceptable salt, stereoisomer, enantiomer, tautomer, or N-oxide thereof, wherein: A is CH or N; R1 is ethyl; R2 is hydrogen; R3 is hydrogen, C1-C2 haloalkyl, cyano, CO2NH2, C1-C2 dialkylaminocarbonyl; n is 1; Q is Q1, Q2 and Q5 [ka] where the arrow indicates the point of attachment to the ring incorporating radical A; R4 is C1-C2 fluoroalkyl, trifluoromethylsulfanyl, trifluoromethylsulfinyl, trifluoromethylsulfonyl, difluoromethylsulfanyl, difluoromethylsulfinyl, or difluoromethylsulfonyl; X1 is NCH3; R6 is methyl, ethyl, 2,2,2-trifluoroethyl, methoxy or cyclopropyl; and G1 and G2 are each independently N or CH. is a radical selected from

[0032] Embodiment 12 provides a compound according to embodiment 1 or an agrochemically acceptable salt, stereoisomer, enantiomer, tautomer, or N-oxide thereof, wherein: A is CH or N; R1 is ethyl; R2 is hydrogen; R3 is hydrogen, cyano or CO2NH2; n is 1; Q is Q1 and Q5 [ka] where the arrow indicates the point of attachment to the ring incorporating radical A; R4 is trifluoromethyl, pentafluoroethyl, trifluoromethylsulfanyl, trifluoromethylsulfinyl or trifluoromethylsulfonyl; X1 is NCH3; R6 is ethyl, methoxy or cyclopropyl; and G1 is N and G2 is CH, or G1 is CH and G2 is N, or G1 and G2 are N, or G1 and G2 are CH. is a radical selected from

[0033] Embodiment 13 provides a compound according to embodiment 1 or an agrochemically acceptable salt, stereoisomer, enantiomer, tautomer, or N-oxide thereof, wherein: A is CH or N; R1 is ethyl; R2 is hydrogen; R3 is hydrogen or cyano; n is 1; Q is the radical Q1 [ka] where the arrow indicates the point of attachment to the ring incorporating radical A; R4 is trifluoromethyl; X1 is NCH3; and G1 is N and G2 is CH, G1 is CH and G2 is N, or G1 and G2 are N. It is.

[0034] Embodiment 14 provides a compound according to embodiment 1, 2, 3, 4 or 5, or an agrochemically acceptable salt, stereoisomer, enantiomer, tautomer, or N-oxide thereof, wherein Q is Q 1-1 , Q 1-2 , Q 1-3 , Q 1-4 and Q 1-5 [ka] where the arrow indicates the point of attachment to the ring incorporating radical A; and R4 is trifluoromethyl, trifluoromethylsulfanyl or trifluoromethylsulfonyl. is a radical selected from

[0035] Embodiment 15 provides a compound according to embodiment 14 or an agrochemically acceptable salt, stereoisomer, enantiomer, tautomer, or N-oxide thereof, wherein Q is Q 1-2 , Q 1-3 , Q 1-4 and Q 1-5 is a radical selected from

[0036] Embodiment 16 provides a compound according to embodiment 1, 2, 3, 4 or 5, or an agrochemically acceptable salt, stereoisomer, enantiomer, tautomer, or N-oxide thereof, wherein Q is for Q5 [ka] where the arrow indicates the point of attachment to the ring incorporating radical A; R4 is trifluoromethyl, trifluoromethylsulfanyl or trifluoromethylsulfonyl; and R6 is OCH3, CH2CH3 or cyclopropyl. is a radical selected from

[0037] Embodiment 17 provides a compound according to embodiment 1, 2, 3, 4 or 5, or an agrochemically acceptable salt, stereoisomer, enantiomer, tautomer, or N-oxide thereof, wherein Q is the radical Q2 [ka] where the arrow indicates the point of attachment to the ring incorporating radical A; R4 is trifluoromethyl, trifluoromethylsulfanyl or trifluoromethylsulfonyl; and G2 is N or CH. It is.

[0038] Embodiment 18 provides a compound according to embodiment 1, 2, 3, 4 or 5, or an agrochemically acceptable salt, stereoisomer, enantiomer, tautomer, or N-oxide thereof, wherein Q is Q3; and R4 is trifluoromethyl, trifluoromethylsulfanyl or trifluoromethylsulfonyl.

[0039] Embodiment 19 provides a compound according to embodiment 1, 2, 3, 4 or 5, or an agrochemically acceptable salt, stereoisomer, enantiomer, tautomer, or N-oxide thereof, wherein Q is Q4 [ka] where the arrow indicates the point of attachment to the ring incorporating radical A; R4 is trifluoromethyl, trifluoromethylsulfanyl or trifluoromethylsulfonyl; and G1 is N and G2 is CH, G1 is CH and G2 is N, G1 and G2 are CH, or G1 and G2 are N; preferably, G1 is CH and G2 is N. It is.

[0040] In another aspect, the present invention provides a composition comprising an insecticidally, acaricidally, nematicidally or molluscicidally effective amount of a compound of formula (I) as defined in any of the preceding embodiments 1 to 19, or an agrochemically acceptable salt, stereoisomer, enantiomer, tautomer or N-oxide thereof, and optionally an auxiliary or diluent.

[0041] In a further aspect, the present invention provides a method for combating and controlling insects, acaridae, nematodes or molluscs, which comprises the step of applying to the pest, the pest's habitat or a plant susceptible to attack by the pest an insecticidally, acaricidally, nematicidally or molluscicidally effective amount of a compound of formula (I) as defined in any of the preceding embodiments 1 to 19 or an agrochemically acceptable salt, stereoisomer, enantiomer, tautomer or N-oxide thereof or a composition as defined above.

[0042] In a further aspect, the present invention provides a method for protecting plant propagation material from attack by insects, acaridae, nematodes or mollusks, which comprises the step of treating the propagation material or the site where the propagation material is planted with a composition as defined above.

[0043] 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. The subgroup of compounds of formula I where n is 0, i.e. sulfilimines Ia, where R1, R2, R3, A and Q are as defined above, can be prepared by reacting the corresponding sulfides of formula II, where R1, R2, R3, A and Q are as defined above, under iminization reaction conditions (Step A, Scheme 1). The specific subgroup of compounds of formula I where n is 1, defined as sulfoximines I, where R1, R2, R3, A and Q are as defined above, can be obtained by oxidation of sulfilimine compounds of formula Ia, where R1, R2, R3, A and Q are as defined above (Step B). Scheme 1 [ka]

[0044] Conversely, the order of the two steps may be reversed, whereby a sulfoximine compound of formula I, in which R1, R2, R3, A and Q are as defined above, may be prepared under suitable imination reaction conditions from a sulfoxide of formula III, in which R1, R2, R3, A and Q are as defined above (Step A').

[0045] Typical preparation methods and reaction conditions for obtaining compounds of formula I, either towards sulfilimine Ia (step A) or towards sulfoximine I (step A'), can be found, for example, in H. Okamura, C. Bolm, Org. Lett., 2004, 6, 1305-1307; H. Okamura, C. Bolm, Chem. Lett., 2004, 33, 482-487; D. Leca, K. Song, M. Amatore, L. Fensterbank, E. Lacote, M. Malacria, Chem. Eur. J., 2004, 10, 906-916; or M. Reggelin, C. Zur, Synthesis, 2000, 1-64. Typical iminization reagents / conditions can be defined as R2-N3 / FeCl2, R2-NH2 / Fe(acac)3 / PhI=O, PhI=N-R2 / Fe(OTf)2, PhI=N-R2 / CuOTf, PhI=N-R2 / Cu(OTf)2, PhI=N-R2 / CuPF6, PhI(OAc)2 / R2-NH2 / MgO / Rh2(OAc)4 or oxaziridines (e.g. 3-(4-cyano-phenyl)-oxaziridine-2-carboxylic acid t-butyl ester), NaN3 / H2SO4, O-mesitylenesulfonyl-hydroxylamine (MSH) or metal-catalyzed methods [see OG Mancheno, C. Bolm, Chem. Eur. J., 2007, 13, 6674-6681].

[0046] Of particular interest is a metal-free method for the iminization of sulfides of formula II and / or sulfoxides of formula III to prepare sulfilimines of formula Ia (step A) and / or sulfoximines of formula I (step A'). Such iminization reactions use R2-NH2 and an oxidizing agent, such as PhI(OAc)2 / R2-NH2, as described in GY Cho, C. Bolm, Tetrahedron Lett., 2005, 46, 8007-8008; or N-bromosuccinimide (NBS) / R2-NH2 and a base, such as sodium or potassium t-butoxide, as described in C. Bolm et al., Synthesis, 2010, No 17, 2922-2925. Oxidizing agents such as N-iodosuccinimide (NIS) or iodine may alternatively be used, for example as described in OG Mancheno, C. Bolm, Org. Lett. 2007, 9, 3809-3811. An example of a hypochlorite salt used as an oxidizing agent, such as sodium hypochlorite NaOCl or calcium hypochlorite Ca(OCl)2, is described in WO 2008 / 106006.

[0047] For the conversion of sulfilimine Ia to sulfoximine I (step B), classical oxidation reagents may be included, such as, for example, KMnO4, NaMnO4, mCPBA, NaIO4 / RuO2, NaIO4 / RuCl3, H2O2, oxone, etc. In particular, the use of ruthenium salts in combination with alkali metal periodates or the use of alkali metal permanganates is described in WO 2008 / 097235 and WO 2008 / 106006.

[0048] Detailed preparative conditions useful for the synthesis of such sulfilimine and / or sulfoximine compounds of formula Ia and I, respectively, are also described, for example, in WO 2006 / 061200 or WO 2007 / 080131.

[0049] Alternatively, the subgroup of sulfoximine compounds comprising formula I, in which R2 is hydrogen and n is 1, and R1, R3, A and Q are as defined in formula I, Scheme 1a [ka] Sulfide compounds of formula II, where R1, R3, A and Q are as defined in formula I, can be prepared by reacting them with a suitable nitrogen source, such as, for example, ammonia, ammonium carbamate or ammonium acetate (preferably ammonium carbamate), in the presence of a hypervalent iodine reagent, such as diacetoxyiodobenzene, in a solvent such as toluene, acetonitrile or methanol, at a temperature between 0 and 100° C., preferably at about room temperature, for example, as described in Chem. Commun. 53, 348-351; 2017 (and references cited therein) (Scheme 1a).

[0050] Compounds of formula Ib, where R1, R3, A and Q are as defined above, n is 1 and R2 is CN, can be converted to compounds of formula Ic, where R1, R3, A and Q are as defined above, n is 1 and R2 is C(O)CF3, by treatment with trifluoroacetic anhydride in a solvent such as dichloromethane, as described, for example, in OG Mancheno, C. Bolm, Org. Lett. 2007, 9, 3809-3811. Compounds of formula Ic, where R1, R3, A and Q are as defined above, n is 1 and R2 is C(O)CF3, can be converted to compounds of formula I, where R1, R3, A and Q are as defined above, n is 1 and R2 is hydrogen, by treatment with a base such as sodium carbonate or potassium carbonate in a polar protic solvent such as methanol or ethanol, as described, for example, in H. Okamura, C. Bolm, Org. Lett. 2004, 6, 1305-1307. Compounds of formula Id, where R1, R3, A and Q are as defined above, n is 1 and R2 is C(O)NH2, can be prepared from compounds of formula Ib, where R1, R3, A and Q are as defined above, n is 1 and R2 is CN, by treatment with a strong acid, such as concentrated sulfuric acid, in an organic solvent, such as acetonitrile, as described, for example, in WO 09 / 111309. The chemistry is outlined in Scheme 2. Scheme 2 [ka]

[0051] Compounds of formula Ie, where R1, R3, A and Q are as defined above, n is 1 and R2 is C1-C6 alkyl, can be prepared by reacting with an alkylating agent of formula LG-R2, where LG is a halogen (especially bromine or iodine), a sulfonate OSO2R 12 (especially mesylate or tosylate) (wherein R 12is a leaving group such as C1-C6 alkyl, C1-C6 halo-alkyl, or phenyl optionally substituted with nitro or C1-C3 alkyl, or a sulfate (such as dimethyl sulfate)), preferably in the presence of a suitable base such as an alkali metal carbonate, for example sodium carbonate or potassium carbonate, or an alkali metal hydride, for example sodium hydride, or an alkali metal hydroxide, for example sodium hydroxide and potassium hydroxide, in an inert solvent at a temperature between -20 and 150°C, preferably 0 to 80°C. Examples of solvents used include ethers such as tetrahydrofuran, ethylene glycol dimethyl ether (1,2-dimethoxyethane), t-butyl methyl ether and 1,4-dioxane, aromatic hydrocarbons such as toluene and xylene, nitriles such as acetonitrile or polar aprotic solvents such as N,N-dimethylformamide, N,N-dimethylacetamide, N-methyl-2-pyrrolidone or dimethylsulfoxide.

[0052] Compounds of formula If, where R1, R3, A and Q are as defined above, n is 1 and R2 is C(O)R7 and R7 is C1-C6 alkyl or C1-C6 haloalkyl, can be prepared from compounds of formula I, where R1, R3, A and Q are as defined above, n is 1 and R2 is hydrogen, by treatment with a reagent of formula LG1-C(O)R7 or an anhydride reagent of formula R7C(O)-OC(O)R7, where R7 is as defined above and LG1 is a leaving group such as a halogen, especially chlorine, in an inert solvent, optionally in the presence of an acylation catalyst such as 4-dimethylaminopyridine (DMAP), preferably in the presence of a base such as triethylamine, diisopropylethylamine or pyridine, at a temperature of 0-50°C. Examples of solvents used include ethers such as tetrahydrofuran, ethylene glycol dimethyl ether, tert-butyl methyl ether and 1,4-dioxane, aromatic hydrocarbons such as toluene and xylene, halogenated hydrocarbons such as dichloromethane and chloroform, nitriles such as acetonitrile or polar aprotic solvents such as N,N-dimethylformamide, N,N-dimethylacetamide, N-methyl-2-pyrrolidone or dimethylsulfoxide. The reaction can also be carried out in the presence of an excess of a base, which can also act as a solvent or diluent.

[0053] Compounds of formula Ig, where R1, R3, A and Q are as defined above, n is 1 and R2 is C(O)OR8 and R8 is C1-C6 alkyl, C1-C6 haloalkyl, can be prepared from compounds of formula I, where R1, R3, A and Q are as defined above, n is 1 and R2 is hydrogen, by treatment with a reagent of formula LG2-C(O)OR8, where R8 is as defined above and LG2 is a leaving group such as halogen (especially chlorine), in an inert solvent, optionally in the presence of an acylation catalyst such as 4-dimethylaminopyridine (DMAP), preferably in the presence of a base such as triethylamine, diisopropylethylamine or pyridine, at a temperature of 0-50°C. Examples of solvents used include ethers such as tetrahydrofuran, ethylene glycol dimethyl ether, t-butyl methyl ether and 1,4-dioxane, aromatic hydrocarbons such as toluene and xylene, halogenated hydrocarbons such as dichloromethane and chloroform, nitriles such as acetonitrile or polar aprotic solvents such as N,N-dimethylformamide, N,N-dimethylacetamide, N-methyl-2-pyrrolidone or dimethylsulfoxide. The reaction can also be carried out in the presence of an excess of a base, which can also act as a solvent or diluent.

[0054] Compounds of formula Ih, where R1, R3, A and Q are as defined above, n is 1, and R2 is CONR9R 10 and R9, R 10 are each independently hydrogen or C1-C6 alkyl) optionally in the presence of an acylation catalyst such as 4-dimethylaminopyridine (DMAP), preferably in the presence of a base such as triethylamine, diisopropylethylamine or pyridine, in an inert solvent at a temperature between 0 and 50° C., with a compound of the formula LG3-C(O)NR9R 10 Reagent (where R9 and R 10can be prepared from compounds of formula I (wherein R1, R3, A and Q are as defined above, n is 1 and R2 is hydrogen) by treatment with LG3 (wherein R1, R3, A and Q are as defined above, n is 1 and R2 is hydrogen) (wherein R1, R3, A and Q are as defined above, n is 1 and R2 is hydrogen) (wherein R1, R3, A and Q are as defined above, n is 1 and R2 is hydrogen)). Examples of solvents used include ethers such as tetrahydrofuran, ethylene glycol dimethyl ether, t-butyl methyl ether and 1,4-dioxane, aromatic hydrocarbons such as toluene and xylene, halogenated hydrocarbons such as dichloromethane and chloroform, nitriles such as acetonitrile or polar aprotic solvents such as N,N-dimethylformamide, N,N-dimethylacetamide, N-methyl-2-pyrrolidone or dimethylsulfoxide. The reaction can also be carried out in the presence of an excess of base, which can also act as a solvent or diluent.

[0055] Compounds of formula Ii, where R, R, A and Q are as defined above, n is 1, and R is SO2R 11 and R 11 is C1-C6 alkyl) optionally in the presence of an acylation catalyst such as 4-dimethyl-aminopyridine (DMAP), preferably in the presence of a base such as triethylamine, diisopropylethylamine or pyridine, in an inert solvent at a temperature of 0-50° C. 11 of reagent (where R 11can be prepared from compounds of formula I (wherein R1, R3, A and Q are as defined above, n is 1 and R2 is hydrogen) by treatment with LG4 (wherein R1, R3, A and Q are as defined above, n is 1 and R2 is hydrogen) (wherein R1, R3, A and Q are as defined above, n is 1 and R2 is hydrogen) (wherein R1, R3, A and Q are as defined above, n is 1 and R2 is hydrogen)). Examples of solvents used include ethers such as tetrahydrofuran, ethylene glycol dimethyl ether, tert-butyl methyl ether and 1,4-dioxane, aromatic hydrocarbons such as toluene and xylene, halogenated hydrocarbons such as dichloromethane and chloroform, nitriles such as acetonitrile or polar aprotic solvents such as N,N-dimethylformamide, N,N-dimethylacetamide, N-methyl-2-pyrrolidone or dimethylsulfoxide. The reaction can also be carried out in the presence of an excess of base, which can also act as a solvent or diluent. Compounds of formula Ij, where R1, R2, R3 and Q are as defined above, n is 1, R2 is C(O)R7 and R7 is hydrogen, can be prepared from compounds of formula I, where R1, R3, A and Q are as defined above, n is 1 and R2 is hydrogen, by treatment with a trialkyl orthoformate, such as trimethyl orthoformate, at a temperature between 0 and 180° C., optionally in the presence of an acid activator, such as p-toluenesulfonic acid, and optionally in the presence of an inert organic solvent. This reaction can also be carried out in the presence of an excess of a trialkyl orthoformate, which can also act as a solvent or diluent. Such processes are exemplified, for example, in WO 2006 / 037945. The above transformation is illustrated in Scheme 3. Scheme 3 [ka]

[0056] Compounds of formula II in which R3 is hydrogen are known in some cases, for example: 2-(5-cyclopropyl-3-ethylsulfanyl-2-pyridyl)-5-(trifluoromethoxy)-1,3-benzoxazole, CAS[2128705-99-5], WO 2017146226; 2-(5-cyclopropyl-3-ethylsulfanyl-2-pyridyl)-5-(difluoromethylsulfanyl)-1,3-benzoxazole, CAS[2128706-06-7], WO 2017146226; 2-( 5-Cyclopropyl-3-ethylsulfanyl-2-pyridyl)-5-(difluoromethoxy)-1,3-benzoxazole, CAS[2128706-01-2], WO 2017146226;5-Cyclopropyl-2-(5-cyclopropyl-3-ethylsulfanyl-2-pyridyl)-3-methyl-6-(trifluoromethyl)imidazo[4,5-c]pyridin-4-one, CAS[2098699-63-7], WO 2017089190;5-Cyclopropyl-2-(4-cyclopropyl-2-ethylsulfani 2-(5-cyclopropyl-3-ethylsulfanyl-2-pyridyl)-5-(1,1,2,2,2-pentafluoroethyl)-1,3-benzoxazole, CAS[1975147-97-7], WO2016121997;2-(5-cyclopropyl-3-ethylsulfanyl-2-pyridyl)-5-(trifluoromethylsulfanyl)- 1,3-Benzoxazole, CAS[1975147-94-4], WO 2017146226;2-(5-Cyclopropyl-3-ethylsulfanyl-2-pyridyl)-1-methyl-5-(trifluoromethyl)benzimidazole, CAS[1975147-91-1], WO 2016121997;2-(5-Cyclopropyl-3-ethylsulfanyl-2-pyridyl)-6-(trifluoromethyl)oxazolo[5,4-b]pyridine, CAS[1975147-87-5], WO 2016121997;2-(5-cyclopropyl-3-ethylsulfanyl-2-pyridyl)-3-methyl-6-(1,1,2,2,2-pentafluoroethyl)imidazo[4,5-b]pyridine, CAS[1975147-85-3], WO 2016121997; 6-(5-cyclopropyl-3-ethylsulfanyl-2-pyridyl)-7-methyl-3-(2,2,2-trifluoroethoxy)imidazo[4,5-c]pyridine RIDAZINE, CAS[1957168-99-8], WO2016104746;2-(5-cyclopropyl-3-ethylsulfanyl-2-pyridyl)-3-methyl-6-(trifluoromethyl)imidazo[4,5-b]pyridine, CAS[1951416-89-9], WO2016096584;2-(4-cyclopropyl-2-ethylsulfanyl-phenyl)-7-(trifluoromethyl )imidazo[1,2-c]pyrimidine, CAS[1923785-41-4], WO 2016071214;2-(5-cyclopropyl-3-ethylsulfanyl-2-pyridyl)-7-(trifluoromethyl)imidazo[1,2-c]pyrimidine, CAS[1923784-36-4], WO 2016071214;2-(4-cyclopropyl-2-ethylsulfanyl-phenyl)-5-ethyl 2-(4-cyclopropyl-2-ethylsulfanyl-phenyl)-3,5-dimethyl-6-(trifluoromethyl)imidazo[4,5-c]pyridin-4-one, CAS[1879051-89-4], WO 2016023954; 2-(4-cyclopropyl-2-ethylsulfanyl-phenyl)-3,5-dimethyl-6-(trifluoromethyl)imidazo[4,5-c]pyridin-4-one, CAS[1879051-88-3], WO 2016023954;

[0057] Compounds of formula II where R3 is H, i.e., formula IIa [ka] Compounds of formula (IV) can generally be prepared by reacting a compound of formula (IV) (wherein A, Q and R1 are as defined above in formula I) with a compound of formula V, as shown in Scheme 4. Scheme 4 [ka]

[0058] More specifically, the compound of formula IIa can be prepared by reacting a compound of formula IIa with a compound of formula V (wherein X b1 may be a halogen, preferably chlorine, bromine or iodine, and Y b1 is a boron-derived functional group such as, for example, B(OH)2 or a B(OR) such as, for example, a boronic acid pinacol ester. b1 )2(where R b1 can be a C1-C6 alkyl group, or two OR b1 The group can be taken together with the boron atom to form a 5- or 6-membered ring) (Suzuki cross-coupling, see e.g. Tetrahedron Letters, 43(39), 6987-6990; 2002). In formula IIa, A, R1 and Q are as described in formula I. This reaction can be carried out using a palladium-based catalyst such as tetrakis(triphenylphosphine)palladium(0), bis(triphenylphosphine)palladium(II) dichloride, chloro(2-dicyclohexylphosphino-2',4',6'-triisopropyl-1,1'-biphenyl)[2-(2'-amino-1,1'-biphenyl)]palladium(II) (XPhos palladacycle), (1,1'bis(diphenylphosphino)-ferrocene)dichloropalladium-dichloromethane (1:1 complex) or It can be catalyzed by palladium acetate plus phosphine ligands (such as triphenylphosphine or tricyclohexylphosphine) in the presence of a base such as sodium carbonate, tripotassium phosphate or cesium fluoride in a solvent (such as toluene, 1,2-dimethoxy-ethane DME, tetrahydrofuran or dioxane) or in a mixture of solvents such as a mixture of 1,2-dimethoxyethane (or dioxane, toluene or tetrahydrofuran) with water, preferably under an inert atmosphere. The reaction temperature can preferably range from ambient temperature to the boiling point of the reaction mixture, or alternatively, heating can be performed under microwave irradiation.

[0059] Alternatively, a compound of formula IV, where X b1 may be a halogen, preferably chlorine, bromine or iodine) to a compound of formula V, b1 can be reacted with a magnesium halide group such as -MgBr (Kumada cross-coupling), optionally in the presence of an additive such as a zinc halide (Journal of Organic Chemistry, 75(19), 6677-6680; 2010). This reaction can be catalyzed by a palladium-based catalyst or can include a nickel-based catalyst such as 1,3-bis(diphenylphosphino)propanenickeldichloride (dppp)NiCl2.

[0060] For example, as illustrated in Synthetic Communications, 28(2), 225-232; 1998, a compound of formula IV and a compound of formula V (wherein Y b1 is also known to react with zinc halide groups such as -ZnBr (Negishi cross-coupling). This reaction can be catalyzed by a palladium-based catalyst containing, for example, (1,1'bis(diphenylphosphino)-ferrocene)dichloropalladium Pd(dppf)Cl2 or bis(triphenylphosphine)palladium(II) dichloride, optionally in the presence of a phosphine additive (such as 2-dicyclohexyl-phosphino-2',6'-dimethoxy-biphenyl S-PHOS), in a solvent such as 1,2-dimethoxyethane, dioxane, toluene or tetrahydrofuran, preferably under an inert atmosphere. The reaction temperature can preferably range from ambient temperature to the boiling point of the reaction mixture.

[0061] Compounds of formula II in which R3 is cyano are known in several cases, for example: 1-[5-ethylsulfanyl-6-[5-methoxy-3-methyl-4-oxo-6-(trifluoromethyl)imidazo[4,5-c]pyridin-2-yl]-3-pyridyl]cyclopropanecarbonitrile, CAS[2225113-68-6], WO 2018 / 077565; 1-[3-ethylsulfanyl-4-[5-methoxy-3-methyl-4-oxo-6-(trifluoromethyl)imidazo[4,5-c]pyridin-2-yl]-3-pyridyl]cyclopropanecarbonitrile, CAS[2225113-68-6], WO 2018 / 077565; 1-[4-[5-Cyclopropyl-3-methyl-4-oxo-6-(trifluoromethyl)imidazo[4,5-c]pyridin-2-yl]-3-ethylsulfanyl-phenyl]cyclopropanecarbonitrile, CAS[CAS[2225113-73-3], WO 2018 / 077565;1-[4-[5-Cyclopropyl-3-methyl-4-oxo-6-(trifluoromethyl)imidazo[4,5-c]pyridin-2-yl]-3-ethylsulfanyl-phenyl]cyclopropanecarbonitrile, CAS[2098699-74-0], WO 2017 / 089190;1-[6-[5-Cyclopropyl- 3-Methyl-4-oxo-6-(trifluoromethyl)imidazo[4,5-c]pyridin-2-yl]-5-ethylsulfanyl-3-pyridyl]cyclopropanecarbonitrile, CAS[2098699-59-1], WO 2017 / 089190; 1-[5-ethylsulfanyl-6-[5-(trifluoromethylsulfanyl)-1,3-benzoxazol-2-yl]-3-pyridyl]cyclopropanecarbonitrile, CAS[1975148-53-8], WO 2016 / 12 1997; 1-[3-ethylsulfanyl-4-[7-(trifluoromethyl)imidazo[1,2-c]pyrimidin-2-yl]phenyl]cyclopropanecarbonitrile, CAS[1923785-47-0], WO 2016 / 071214; 1-[5-ethylsulfanyl-6-[7-(trifluoromethyl)imidazo[1,2-c]pyrimidin-2-yl]-3-pyridyl]cyclopropanecarbonitrile, CAS[1923784-42-2], WO 2016 / 071214.

[0062] Other compounds of formula II, wherein R3 is cyano and R1, A and Q are as defined in formula I, i.e., compounds of formula IIb [ka] The compound of Scheme 5: Scheme 5 [ka] It can be prepared as shown in

[0063] As shown in Scheme 5, treatment of a compound of formula IV (wherein R1, Q and A are as described in formula I, and Xb1 is preferably a halogen (even more preferably chlorine, bromine or iodine)) with trimethylsilyl-acetonitrile TMSCN in the presence of zinc(II) fluoride and a palladium(0) catalyst, such as tris(dibenzylideneacetone)dipalladium(0)-chloroform adduct (Pd2(dba)3), a ligand, such as Xantphos, in an inert solvent, such as DMF, at a temperature between 100-160° C., optionally with microwave heating, provides a compound of formula VI. Such chemistry is described in the literature, for example in Org. Lett., 16(24), 6314-6317; 2014. Compounds of formula IIb can be obtained by treating compounds of formula IV with compounds of formula VII, where Xb1 is as above, in the presence of a base such as sodium hydride, K2CO3 or Cs2CO3 in an inert solvent such as DMF, acetone or acetonitrile. Alternatively, compounds of formula IIb can be prepared directly from compounds of formula IV by treatment with compounds of formula VIII, with a ligand such as Pd2(dba)3, BINAP, a strong base such as LiHMDS, in an inert solvent such as THF at temperatures between 40 and 70°C. Such chemistry is described, for example, in J.Am.Chem.Soc.,127(45),15824-15832;2005.

[0064] Other processes to compounds of formula IIb include reaction of compounds of formula IV (wherein A, R1 and Q are as described in formula I and Xb1 is halogen, preferably chlorine, bromine, iodine) with 4-isoxazoleboronic acid or 4-isoxazoleboronic acid pinacol ester (compound of formula IX) in the presence of palladium catalyst such as potassium fluoride KF and bis(triphenylphosphine)palladium(II) dichloride Pd(PPh3)2Cl2 in an inert solvent such as dimethylsulfoxide DMSO, optionally in a mixture with water, at a temperature between 40-150°C, optionally under microwave heating to give compounds of formula IX, where Q, R1 and A are as described in formula I above. Reaction of a compound of formula IX with aqueous potassium fluoride KF (concentration 0.5-3M, preferably 1M) in an inert solvent such as dimethylsulfoxide DMSO or methanol at a temperature of 20-150° C., optionally with microwave heating, leads to a compound of formula VI, where A, R1 and Q are as described above in formula I. Conversion of a compound of formula V to a compound of formula IIb is as described above. Such chemistry is described in the literature, for example in J Am Chem Soc 2011, 133, 6948-6951.

[0065] The compound of formula IIb can be further utilized to prepare the compound of formula II (Scheme 6) in which R3 is further functionalized. In practice, the compound of formula IIb, in which A, R1, X1 and R2 are as defined above in formula I, can be partially hydrolyzed to the compound of formula IIc under acidic or basic conditions known to those skilled in the art, or can be completely hydrolyzed to the compound of formula IId. Optionally, the treatment of the compound of formula IIc with a reagent such as SF4 or Fluolead (4-t-butyl-2,6-dimethylphenylsulfur trifluoride) in the presence of HF leads to the compound of formula IIe (for example, as described in Organic Letters, 16, 6314-6317; 2014).

[0066] Activation of a compound of formula (IId), where R1, Q and A are as defined in formula I, by a method known to the skilled artisan and described, for example, in Tetrahedron, 2005, 61(46), 10827-10852, results in the formation of an activated species (IIf), where Q, R1 and A are as defined in formula I and X0 is a halogen, preferably chlorine. For example, compound (IIf), where X0 is a halogen, preferably chlorine, is formed by treatment of (IId) with, for example, oxalyl chloride (COCl)2 or thionyl chloride SOCl2 in an inert solvent, such as methylene chloride CH2Cl2 or tetrahydrofuran THF, in the presence of a catalytic amount of N,N-dimethylformamide DMF, at a temperature between 20 and 100°C, preferably 25°C. Alternatively, treatment of compounds of formula (IId) with, for example, 1-ethyl-3-(3-dimethylaminopropyl)carbodiimide EDC or dicyclohexylcarbodiimide DCC in an inert solvent such as pyridine or tetrahydrofuran THF, optionally in the presence of a base such as triethylamine, at temperatures between 50 and 180° C., affords the activated species (XII), where X0 is X 01 Or X 02 such activated intermediates of formula Iif can be converted to compounds of formula HNR in an inert solvent such as CH2Cl2, THF or acetonitrile, optionally in the presence of a base such as triethylamine, pyridine or DMAP; 101 R 012 of amine (where R 101 and R 102 is hydrogen or C1-C6 alkyl) or HOR 103 (wherein R103 is C1-C6 alkyl) to give compounds of formula Iig and Iih, respectively. Such reactions are well known to those skilled in the art. Post-conversion of cyanocyclopropyl is illustrated in Scheme 6. Scheme 6 [ka]

[0067] Formula II-Q1 [ka] (wherein R1, R3, R4, X1, G1 and G2 are as defined in formula I). Compounds of formula II, which defines compounds of the formula (wherein Q is Q1), can be prepared as shown in Scheme 7. Scheme 7 [ka]

[0068] As shown in Scheme 7, compounds of formula II-Q1 can be prepared by cyclizing compounds of formula (XIV), where R1, R3, R4, A, X1, G1 and G2 are as defined in formula I, by heating in, for example, acetic acid or trifluoroacetic acid (preferably, when X1 is NR5, where R5 is C1-C4 alkyl) at temperatures between 0 and 180°C, preferably between 20 and 150°C, optionally under microwave irradiation. Cyclization of compounds of formula (XIV) can also be achieved in the presence of an acid catalyst, for example, methanesulfonic acid or p-toluenesulfonic acid p-TsOH, in an inert solvent, such as N-methylpyrrolidone, toluene or xylene, at temperatures between 25 and 180°C, preferably between 100 and 170°C. Such processes have been previously described, for example, in WO2016096584. Alternatively, compounds of formula (XIV) can be converted to compounds of formula II-Q1 (preferably when X1 is O) using triphenylphosphine, di-isopropyl azodicarboxylate (or di-ethyl azodicarboxylate) in an inert solvent such as tetrahydrofuran THF at temperatures between 20-50° C. Such Mitsunobu conditions have been previously described for these transformations (see WO 2009 / 131237 and WO 2016 / 121997).

[0069] The compound of formula (XIV), wherein R1, R3, R4, A, X1, G1 and G2 are as defined in formula I, may be prepared via acylation by: i) activation of compounds of formula (XIII) where R1, R3 and A are as defined in formula I, by methods known to those skilled in the art and described for example in Tetrahedron, 2005, 61(46), 10827-10852, whereby activated species (XII) is formed, where R1, R3 and A are as defined in formula I and X0 is a halogen, preferably chlorine. For example, compounds (XII) where X0 is a halogen, preferably chlorine, are formed by treatment of (XIII) with, for example, oxalyl chloride (COCl)2 or thionyl chloride SOCl2 in an inert solvent, such as methylene chloride CH2Cl2 or tetrahydrofuran THF, in the presence of a catalytic amount of N,N-dimethylformamide DMF, at a temperature between 20 and 100°C, preferably 25°C. Alternatively, the treatment of compounds of formula (XIII) with, for example, 1-ethyl-3-(3-dimethylaminopropyl)carbodiimide EDC or dicyclohexylcarbodiimide DCC in an inert solvent such as pyridine or tetrahydrofuran THF, optionally in the presence of a base such as triethylamine, at temperatures between 50 and 180° C., gives the activated species (XII), where X0 is, respectively, X 01 Or X 02 ), followed by ii) Treatment of the activated species (XII) with a compound of formula (XI), wherein X1, G1, G2 and R4 are as defined in formula I, in the presence of a base such as triethylamine, N,N-diisopropyl-ethyl-amine or pyridine, in an inert solvent such as dichloromethane, tetrahydrofuran, dioxane, N,N-dimethylformamide, N,N-dimethylacetamide, acetonitrile, ethyl acetate or toluene, at a temperature of 0-50° C., resulting in the formation of a compound of formula (XIV). Compounds of formula XIII where R3 is H, i.e., where R1 is ethyl, R3 is H, and A is N or CH, are known and are described in WO2017146226 or WO2016121997 (5-cyclopropyl-3-ethylsulfanyl-pyridine-2-carboxylic acid, CAS[1975148-58-3]) and WO2016023954 (4-cyclopropyl-2-ethylsulfanyl-benzoic acid, CAS[1879052-58-0]). The compound of formula XIII (wherein R3 is cyano, R1 is ethyl, and A is CH) (4-(1-cyanocyclopropyl)-2-ethylsulfanyl-benzoic acid, CAS[2225113-79-9]) and the compound of formula XIII (wherein R3 is cyano, R1 is ethyl, and A is N) (5-(1-cyanocyclopropyl)-3-ethylsulfanyl-pyridine-2-carboxylic acid, CAS[2225113-77-7]) are known and are described in WO 2018 / 077565.

[0070] Compounds of formula (XI), in which X1, G1, G2 and R2 are as defined in formula I, have been described, for example, in WO 2012 / 086848, WO 2015 / 000715 and WO 2016 / 116338.

[0071] Compounds of formula II-Q2, where R1, R3, R4, A and G2 are as defined in formula I. Scheme 8 [ka] Compounds of formula II, where Q is Q2, may be prepared, for example, by condensing a compound of formula (XVI), where R1, R3, A are as defined in formula I, and Xc is a leaving group, such as, for example, chlorine, bromine or iodine (preferably chlorine or bromine), with a compound of formula (XVI), where G2 and R2 are as defined in formula I, in an inert solvent, such as ethanol or acetonitrile, optionally in the presence of a suitable base, such as sodium carbonate, potassium carbonate or cesium carbonate or magnesium oxide, at a temperature of 80 to 150° C., optionally under microwave heating conditions (Scheme 8). Such processes have been previously described, for example, in WO 2012 / 49280 or WO 2003 / 031587. Compounds of formula (XV), where G2 and R2 are as defined in formula I, are known compounds that are commercially available or can be prepared by methods known to those skilled in the art.

[0072] A compound of formula (XVI) where R1, R3 and A are as defined in formula I and Xc is a leaving group such as, for example, chlorine, bromine or iodine (preferably chlorine or bromine). Scheme 9 [ka] is acetic acid, PhNMe3 + Br3 - , typically in a solvent such as methanol, acetonitrile, tetrahydrofuran, ethyl acetate, chloroform or dichloromethane or a mixture thereof, at a temperature between 0° C. and 150° C., preferably between room temperature and 120° C., optionally under microwave heating conditions, with a halogenating agent such as, for example, N-bromosuccinimide, N-iodosuccinimide, N-chlorosuccinimide, I2, CuBr2, Br2 ("Xc +" source) (Scheme 9). Such a process has been previously described, for example, in WO 2016 / 071214.

[0073] Compounds of formula (XVIII), in which R1, R3 and A are as defined in formula I, can be prepared by reacting compounds of formula (XVII), in which R1 and A are as defined in formula I and Xa is a leaving group such as, for example, chlorine, bromine or iodine (preferably chlorine or bromine), under the conditions already described above (see Scheme 5, conversion of compound IV to IIb).

[0074] Compounds of formula (XVII) (wherein R1 and A are as defined in formula I and Xa is a leaving group such as, for example, chlorine, bromine or iodine), in particular compounds where Xa is a halogen (even more preferably chlorine, bromine or iodine; particularly preferably chlorine or bromine), are commercially available or are known compounds that can be prepared by known methods as described in the literature, for example in WO 2016 / 071214.

[0075] Alternatively, a compound of formula II-Q5 (wherein R1, R3, R4, R6 and A are as defined in formula I) Scheme 9a: [ka] Compounds of formula II, where Q is Q5, may be prepared by cyclization under the conditions already described above (see Scheme 7, conversion of compound (XIV) to II-Q1) of compounds of formula (XXa), where R1, R3, R4, R5, R6 and A are as defined in formula I, or of positional isomers of formula (XXb), where the substituent definitions are equivalent, or of mixtures thereof in any ratio (Scheme 9a).

[0076] Compounds of formula (XXa) in which R1, R3, R4, R5, R6 and A are as defined in formula I or positional isomers of formula (XXb) in which the substituent definitions are equivalent, or mixtures thereof in any ratio, can be prepared by treatment of the above activated species (XII) with a compound of formula (XIX) in which R4, R5 and R6 are as defined in formula I, under the conditions already described above (see Scheme 7, conversion of compounds (XII) and (XIII) to compound (XIV)).

[0077] Compounds of formula (XIX), in which R4, R5 and R6 are as defined in formula I, are, for example, those described in WO 2016 / 023954, WO 2016 / 142326, WO 2017 / 133994 and WO 2018077565.

[0078] Alternatively, a compound of formula II-Q3, where R1, R4, R3 and A are as defined in formula I, Scheme 10 [ka] Compounds of formula II, where Q is Q3, can be prepared by condensing compounds of formula (XVI) above, where R1, R3 and A are as defined in formula I, and Xc is a leaving group such as, for example, chlorine, bromine or iodine (preferably chlorine or bromine), with compounds of formula (XXI), where R4 is as defined in formula I, in the presence of an inert solvent, for example ethanol, toluene or acetonitrile, optionally with a suitable base such as sodium carbonate, potassium carbonate or cesium carbonate (or sodium or potassium bicarbonate) or magnesium oxide, at a temperature of 80-150° C., optionally under microwave heating conditions (Scheme 10). Such processes have been previously described, for example, in WO 2011 / 074658. Compounds of formula (XXI), in which R4 is as defined in formula I, are commercially available or are known compounds that can be prepared by methods known to those skilled in the art (see, for example, WO 2011 / 074658 and WO 2010 / 083145).

[0079] Formula II-Q4 [ka] (wherein R1, R3, R4, G1, G2 and A are as defined in formula I). Compound Scheme 11 [ka] Compounds of formula II, where Q is Q4, may also be prepared via N-N bond formation reaction of azidoimines of compounds of formula (XXV), where R1, R4, R7, R8, A, G1, G2 and R2 are as defined in formula I, under pyrolysis conditions with favorable N2 emission (Scheme 11). Alternatively, this reaction may be carried out in the presence of a metal catalyst, such as a Cu(I) catalyst, for example CuI, CuBr, CuCl or CuCN, or more generally with a transition metal, in combination with a ligand such as tetramethylethylenediamine, 2,2'-bipyridine or 1,10-phenanthroline. Suitable solvents may include the use of toluene, chlorobenzene or xylene, at temperatures between room temperature and 200°C, preferably between 100 and 160°C, optionally under microwave heating conditions. Such reductive cyclization reaction conditions are described, for example, in Organic Letters, 2011, Vol. 13, No. 13, 3542-3545 and U.S. Patent Application Publication No. 2017 / 0260183.

[0080] Compounds of formula (XXV), in which R1, R3, R4, G1, G2 and A are as defined in formula I, can be prepared by reaction of compounds of formula (XXIII), in which R1, R3 and A are as defined in formula I, with compounds of formula (XXIV), in which G1, G2 and R4 are as defined in formula I, by heating in a suitable solvent, which may be used, for example, including toluene or xylene, at temperatures between room temperature and 200° C., preferably between 40 and 160° C., optionally under microwave heating conditions. The formation of compounds of formula (XXV) may require removal of water by azeotropic distillation or by drying agents such as TiCl4 or molecular sieves. The formation of such Schiff bases of formula (XXV) is known to those skilled in the art and is described, for example, in WO 2017 / 134066. The compound of formula XXIV has been reported in the literature (see CAS 2211908-96-0 reported in WO 2018 / 052136).

[0081] Compounds of formula XXIII can be prepared by reaction of compounds of formula XXII in the presence of an acid such as HCl, H2SO4, H3PO4, HNO3, TFA, etc. Such deprotection reactions of N-linked carbamates are well known to those skilled in the art and are described, for example, in RSC Advances, 5(5), 3200-3205;2015.

[0082] Compounds of formula XXII can be prepared by reaction of compounds of formula XIII with organic-azides or ammonia derivatives (e.g., NH4OH, NH3, NH2Boc) in the presence of a suitable base and in the presence or absence of Lewis acid and solvent at a temperature between 50°C and 200°C. Examples of organic-azides include TMSN3, sodium azide, diphenylphosphoryl azide or tosyl azide, and suitable solvents can be t-BuOH, toluene, xylene, THF or acetonitrile. Examples of suitable Lewis acids can include Zn(OTf)2. Such a reaction of converting a carboxylic acid to an amine is known to those skilled in the art under the name of Curtius reaction and has been reported in Org.Lett.,2005,7,4107-4110;Journal of Medicinal Chemistry,49(12),3614-3627;2006.

[0083] Alternatively, the compound of formula II-Q4, in which R1, R3, R4, G1, G2 and A are as defined in formula I, can be converted to a compound of formula (XXVI), in which R4, G1, G2 and L are as defined in formula I, by reaction in the presence of a base such as, for example, cesium carbonate, sodium carbonate, potassium carbonate or lithium carbonate or sodium hydride, optionally in the presence of copper(I) iodide or a palladium catalyst metal catalyst, with or without an additive such as L-proline, N,N'-dimethylethylenediamine or a phosphorus-based ligand, in an inert solvent such as acetonitrile, N,N-dimethylformamide, N-methyl-2-pyrrolidone or dimethylsulfoxide, at a temperature between room temperature and 200°C, optionally under microwave heating conditions. Gcan be prepared, for example, by reacting a compound of formula (XXVII) in which G1, G2 and R4 are as defined in formula I with a leaving group such as chlorine, bromine or iodine (preferably chlorine or bromine) or an aryl-, alkyl- or haloalkylsulfonate such as trifluoromethanesulfonic acid. Such aromatic nucleophilic substitution reaction conditions are described, for example, in WO 2017 / 134066. Compounds of formula XXVII can be obtained by the Sandmeyer reaction, i.e. diazotization of compound XXIII with NaNO2 or tBu-ONO in an inert solvent such as t-BuOH or water, followed by the addition of an inorganic halide such as CuBr2, CuCl or KI. Such Sandmeyer reactions are well known in the literature (see, for example, Synthesis, 2007, 2534-2538, Org. Lett., 2008, 10, 3961-3964 and the references cited therein).

[0084] 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, alkylamides, alkylenediamides, 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).

[0085] The reactants can be reacted with each other as is, i.e. without the addition of a solvent or diluent. In most cases, however, it is advantageous to add an inert solvent or diluent or a mixture thereof. When the reaction is carried out in the presence of a base, the base used in excess, such as triethylamine, pyridine, N-methylmorpholine or N,N-diethylaniline, can also serve as the solvent or diluent.

[0086] The reaction is advantageously carried out at a temperature in the range of about -80°C to about +140°C, preferably about -30°C to about +100°C, and in many cases in the range of ambient temperature to about +80°C.

[0087] Compounds of formula I may be converted into other compounds of formula I in a manner known per se by replacing one or more substituents of the starting compound of formula I with other substituents according to the invention in a conventional manner.

[0088] Depending on the respective suitable reaction conditions and the choice of starting materials, it is possible, for example, to simply replace one substituent with another substituent according to the invention in one reaction step, or several substituents may be replaced with other substituents according to the invention in the same reaction step.

[0089] 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 can be obtained by treatment with a suitable acid or with a suitable ion exchange reagent, and base salts can be obtained by treatment with a suitable base or with a suitable ion exchange reagent.

[0090] The salts of the compounds of formula I can be converted in a customary manner into acid addition salts of the free compounds I, for example by treatment with suitable basic compounds or with suitable ion exchange reagents, and into salts with bases, for example by treatment with a suitable acid or with a suitable ion exchange reagent.

[0091] Salts of compounds of formula I may be converted into other salts, e.g. acid addition salts, of compounds of formula I in a manner known per se, for example by treating the inorganic acid salt, e.g. the hydrochloride, with a suitable metal salt, such as the sodium, barium or silver salt of the acid, e.g. silver acetate, in a suitable solvent in which the inorganic salt that forms silver chloride is insoluble and therefore precipitates from the reaction mixture.

[0092] Depending on the procedure or reaction conditions, compounds of formula I having salt-forming properties may be obtained in free form or in salt form.

[0093] The compounds of formula I and, where appropriate, their tautomers, can exist in the form of one of the possible isomers or as mixtures thereof, in the form of pure isomers, such as, for example, enantiomers and / or diastereomers, or as isomeric mixtures, such as enantiomeric mixtures, for example racemates, diastereomeric mixtures or racemic mixtures, depending on the number, the absolute and relative configuration of asymmetric carbon atoms occurring in the molecule and / or depending on the configuration of non-aromatic double bonds occurring in the molecule, respectively in free or salt form; the invention relates to the pure isomers and also to all possible isomeric mixtures, and is to be understood in this sense above and below, respectively, even if the respective stereochemical details are not specifically stated.

[0094] Diastereomeric or racemic mixtures of compounds of formula I, in free or salt form, obtained depending on which starting materials and procedures are selected, may be separated in known manner into pure diastereomers or racemates on the basis of the physicochemical differences of the components, for example, by fractional crystallization, distillation and / or chromatography.

[0095] Enantiomeric mixtures, such as racemates, obtained in a similar manner can be resolved into their optical antipodes by known methods, for example by recrystallization from optically active solvents, by chromatography on chiral adsorbents, for example by high performance liquid chromatography (HPLC) on acetylcellulose using suitable microorganisms, by cleavage with specific immobilized enzymes via the formation of inclusion compounds, for example with chiral crown ethers, whereby only one enantiomer is complexed, or by conversion into diastereomeric salts, for example by reacting the basic end-product racemate with an optically active acid, such as a carboxylic acid, for example camphoric acid, tartaric acid or malic acid, or a sulfonic acid, for example camphorsulfonic acid, and separating the diastereomeric mixtures thus obtained, for example by fractional crystallization based on different solubilities, to obtain diastereomers from which the desired enantiomer can be released, by the action of a suitable substance, for example a basic substance.

[0096] Pure diastereomers or enantiomers can be obtained according to the invention not only by separating the appropriate isomeric mixtures, but also by generally known methods of diastereoselective or enantioselective synthesis, e.g. by carrying out the process according to the invention using starting materials that have stereochemical characteristics.

[0097] The N-oxides can be prepared by reacting the compounds of formula I with a suitable oxidizing agent, for example H2O2 / urea adduct, in the presence of an acid anhydride, for example trifluoroacetic anhydride. Such oxidations are known from the literature, for example from J. Med. Chem., 32(12), 2561-73, 1989 or WO 2000 / 15615.

[0098] Where the individual components have different biological activities, it may be advantageous to isolate or synthesize the more biologically effective isomer, e.g., enantiomer or diastereomer, or mixture of isomers, e.g., mixture of enantiomers or diastereomers, respectively.

[0099] The compounds of formula I and, where appropriate, their tautomers, may also be obtained in free or salt form, where appropriate, in the form of hydrates, and / or contain other solvents, for example solvents that may have been used for the crystallization of compounds present in solid form.

[0100] The compounds of formula I represented in the following tables Y-1 to Y-8, X-1 to X-8, U-1 to U-2 and V-1 to V-6 can be prepared according to the above-described methods. The following examples are intended to illustrate the invention and to show preferred compounds of formula I.

[0101] Tables Y-1 to Y-8 show the formula [ka] This refers to the compound.

[0102] [Table 1]

[0103] Table Y-1 provides eight compounds Y-1.001 to Y-1.008 of formula IaY, where A is CH, G1 is CH, G2 is CH, and R3, R4 are as defined in Table Z.

[0104] For example, compound Y-1.001 has the following structure: [ka] has.

[0105] Table Y-2 provides eight compounds Y-2.001 to Y-2.008 of formula IaY, where A is CH, G1 is CH, G2 is N, and R3, R4 are as defined in Table Z.

[0106] For example, compound Y-2.001 has the following structure: [ka] has.

[0107] Table Y-3 provides eight compounds Y-3.001 to Y-3.008 of formula IaY, where A is CH, G1 is N, G2 is CH, and R3, R4 are as defined in Table Z.

[0108] For example, compound Y-3.001 has the following structure: [ka] has.

[0109] Table Y-4 provides eight compounds Y-4.001 to Y-4.008 of formula IaY, where A is CH, G1 is N, G2 is N, and R3, R4 are as defined in Table Z.

[0110] For example, compound Y-4.001 has the following structure: [ka] has.

[0111] Table Y-5 provides eight compounds Y-5.001 to Y-5.008 of formula IaY, where A is N, G1 is CH, G2 is CH, and R3, R4 are as defined in Table Z.

[0112] For example, compound Y-5.001 has the following structure: [ka] has.

[0113] Table Y-6 provides eight compounds Y-6.001 to Y-6.008 of formula IaY, where A is N, G1 is CH, G2 is N, and R3, R4 are as defined in Table Z.

[0114] For example, compound Y-6.001 has the following structure: [ka] has.

[0115] Table Y-7 provides eight compounds Y-7.001 to Y-7.008 of formula IaY, where A is N, G1 is N, G2 is CH, and R3, R4 are as defined in Table Z.

[0116] For example, compound Y-7.001 has the following structure: [ka] has.

[0117] Table Y-8 provides eight compounds of formula IaY, Y-8.001 to Y-8.008, where A is N, G1 is N, G2 is N, and R3, R4 are as defined in Table Z.

[0118] For example, compound Y-8.001 has the following structure: [ka] has.

[0119] Tables X-1 to X-8 show the formula [ka] This refers to the compound.

[0120] Table X-1 provides eight compounds X-1.001 to X-1.008 of formula Iax, where A is CH, G1 is CH, G2 is CH, and R3, R4 are as defined in Table Z.

[0121] For example, compound X-1.001 has the following structure: [ka] has.

[0122] Table X-2 provides eight compounds X-2.001 to X-2.008 of formula Iax, where A is CH, G1 is CH, G2 is N, and R3, R4 are as defined in Table Z.

[0123] Table X-3 provides eight compounds X-3.001 to X-3.008 of formula Iax, where A is CH, G1 is N, G2 is CH, and R3, R4 are as defined in Table Z.

[0124] Table X-4 provides eight compounds X-4.001 to X-4.008 of formula Iax, where A is CH, G1 is N, G2 is N, and R3, R4 are as defined in Table Z.

[0125] Table X-5 provides eight compounds X-5.001 to X-5.008 of formula Iax, where A is N, G1 is CH, G2 is CH, and R3, R4 are as defined in Table Z.

[0126] Table X-6 provides eight compounds of formula Ib, X-6.001 to X-6.008, where A is N, G1 is CH, G2 is N, and R3, R4 are as defined in Table Z.

[0127] Table X-7 provides eight compounds of formula Ib, X-7.001 to X-7.008, where A is N, G1 is N, G2 is CH, and R3, R4 are as defined in Table Z.

[0128] Table X-8 provides eight compounds of formula Ib, X-8.001 to X-8.008, where A is N, G1 is N, G2 is N, and R3, R4 are as defined in Table Z.

[0129] The following Tables V-1 to V-6 illustrate certain compounds of formula I (wherein R2 is H and n is 1) of the present invention. [ka]

[0130] Table V-1 provides nine compounds V-1.001 to V-1.009 of formula I, where A is CH, R3 is CN, and Q is as defined in Table W.

[0131] [Table 2]

[0132] For example, compound V-1.002 has the following structure: [ka] has.

[0133] Table V-2 provides nine compounds V-2.001 to V-2.009 of formula I, where A is N, R3 is CN, and Q is as defined in Table W.

[0134] For example, compound V-2.005 has the following structure: [ka] has.

[0135] Table V-3 provides nine compounds V-3.001 to V-3.009 of formula I, where A is CH, R3 is H, and Q is as defined in Table W.

[0136] For example, compound V-3.008 has the following structure: [ka] has.

[0137] Table V-4 provides nine compounds V-4.001 to V-4.009 of formula I, where A is N, R3 is H, and Q is as defined in Table W.

[0138] For example, compound V-4.001 has the following structure: [ka] has.

[0139] Table V-5 provides nine compounds V-5.001 to V-5.009 of formula I, where A is CH, R3 is CONH2, and Q is as defined in Table W.

[0140] For example, compound V-5.007 has the following structure: [ka] has.

[0141] Table V-6 provides nine compounds V-6.001 to V-6.009 of formula I, where A is N, R3 is CONH2, and Q is as defined in Table W.

[0142] For example, compound V-6.006 has the following structure: [ka] has.

[0143] Tables U-1 to U-2 show the formula [ka] This refers to the compound.

[0144] Table U-1 provides eight compounds U-1.001 to U-1.008 of formula IaU, where A is CH and R3, R4 are as defined in Table Z.

[0145] For example, compound U-1.001 has the following structure: [ka] has.

[0146] Table U-2 provides eight compounds U-2.001 to U-2.008 of formula IaU, where A is N and R3, R4 are as defined in Table Z.

[0147] The compounds of formula I according to the invention are preventively and / or therapeutically beneficial active ingredients in the field of pest control, even at low application rates, which have a very favorable biocidal spectrum and are well tolerated by warm-blooded animal species, fish and plants. The active ingredients according to the invention act not only against normally susceptible animal pests, such as insects, molluscs, nematodes or representatives of the order Acarina, but also against all or individual development stages of resistant animal pests. The insecticidal, molluscicidal, nematocidal or acaricidal activity of the active ingredients according to the invention can be manifested directly, i.e. by the death of the pest, which occurs immediately or only after a certain time has elapsed (for example during molting), or indirectly (for example by a reduction in the egg-laying and / or hatching rate, a good activity corresponding to a death rate (mortality) of at least 50-60%).

[0148] The compounds of formula (I) according to the present invention may have 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 (e.g., higher biological activity, advantageous activity spectrum, high safety profile, improved physicochemical properties, or high biodegradability or environmental profile).In particular, it has been unexpectedly found that certain compounds of formula (I) exhibit advantageous safety profiles against non-target organisms, such as non-target arthropods, in particular pollinators, such as honeybees, solitary bees and bumblebees.More specifically, the Western honeybee (Apis mellifera).

[0149] In this regard, certain compounds of formula (I) of the present invention are distinguishable from known compounds by their high efficacy at low application rates, which can be verified by one skilled in the art using experimental procedures similar to or adapted from those outlined in the biological examples, using lower application rates as necessary, such as, for example, 50 ppm, 12.5 ppm, 6 ppm, 3 ppm, 1.5 ppm, 0.8 ppm or 0.2 ppm.

[0150] Moreover, it has been unexpectedly found that the compounds of formula (I) exhibit advantageous physicochemical properties for use in crop protection, in particular low melting point, low lipophilicity and high water solubility. Such properties have been found to be advantageous for plant uptake and systemic distribution to control certain pest species listed below, see for example A. Buchholz, S. Trapp, Pest Manag Sci 2016;72:929-939).

[0151] Examples of the above 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. 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. spp.), Rhizoglyphus spp., Sarcoptes spp., Steneotarsonemus spp., Tarsonemus spp. and Tetranychus spp.; From the order of the 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. 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., Scarabaeidae, 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. 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. 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., Clavigrella tomentosicollis, Creontiades spp., Distantiella theobroma, Dichelops furcatus, Dysdercus spp., Edessa spp. 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 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. 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., Corn scale (Lecanium corni), Lepidosaphes spp., False radish aphid (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, Bayberry whitefly, Parabemisia myricae, Paratrioza cockerelli, Parlatoria spp., Pemphigus spp., Corn planthopper, Peregrinus maidis, Perkinsiella spp., Hop wart aphid, Phorodon humuli, Phylloxera spp., Planococcus spp., Pseudaulacaspis spp., Pseudococcus spp., Pseudatomoscelis seriatus, Psylla spp., Pulvinaria aethiopica, Quadraspidiotus spp., Quesada gigas, Recilia dorsalis, Rhopalosiphum spp., Saissetia spp., Scaphoideus spp. spp.), Schizaphis spp., Sitobion spp.), Sogatella furcifera, Spisstilus festinus, Tarophagus Proserpina, Toxoptera spp, Trialeurodes spp, Tridiscus sporoboli, Trionymus spp, Trioza erytreae, Unaspis citri, Zygina flammigera, Zyginidia scutellaris;. From the order of Hymenoptera, for example, Acromyrmex, Arge spp., Atta spp., Cephus spp., Diprion spp., Diprionidae, Gilpinia polytoma, Hoplocampa spp., Lasius spp., Monomorium pharaonis, Neodiprion spp., Pogonomyrmex spp., Slenopsis invicta, Solenopsis spp. and Vespa spp.; 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, the genera 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 leucotoleta 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. 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.), pine sawfly moth (Panolis flammea), Papaipema nebris, red cotton bug (Pectinophora gossypiela), coffee leafminer (Perileucoptera coffeella), Pseudaletia unipuncta, potato tuber moth (Phthorimaea operculella), cabbage white butterfly (Pieris rapae), Pieris spp., diamondback moth (Plutella xylostella), Prays spp., Pseudoplusia spp., Rachiplusia nu, Richia albicosta, Scirpophaga spp., Sesamia spp.), Sparaganothis 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 of Orthoptera, for example, the genera 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, the silverfish (Lepisma saccharina).

[0152] The active ingredients according to the invention can be used to control, i.e. suppress or destroy, pests of the above-mentioned types which occur in particular on plants, in particular on useful plants and ornamental plants in agriculture, horticulture and forestry, or on organs such as the fruits, flowers, leaves, stems, tubers or roots of such plants, in some cases even plant organs which are formed at a later time remain protected from these pests.

[0153] Suitable target crops are in particular cereals such as wheat, barley, rye, oats, rice, maize or sorghum; beets such as sugar beet or fodder beet; fruits, such as pome fruits, stone fruits or soft fruits, such as apples, pears, plums, peaches, almonds, cherries or berries, such as strawberries, raspberries or blackberries; legumes, such as beans, lentils, peas or soybeans; rapeseed, mustard, poppy, olive, sunflower, palm, castor, cocoa or groundnut. nut; cucurbits, such as pumpkin, cucumber or melon; fibre plants, such as cotton, flax, hemp or jute; citrus fruits, such as orange, lemon, grapefruit or tangerine; vegetables, such as spinach, lettuce, asparagus, cabbage, carrot, onion, tomato, potato or pepper; plants of the Lauraceae family, such as avocado, cinnamon or camphor; and also tobacco, nuts, coffee, eggplant, sugar cane, tea, pepper, grapes, hops, plantain and latex plants.

[0154] The compositions and / or methods of the present invention may be used on any ornamental and / or vegetable crop, including flowers, shrubs, broadleaf trees and evergreens.

[0155] For example, the present invention may be used in any of the following ornamental plant 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., and the like. spp.) (ornamental plants), 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.), Lisianthus (Eustoma grandiflorum), Forsythia spp., Fuchsia spp., Geranium gnaphalium, Gerbera spp., Gomphrena globosa, Heliotropium spp., Helianthus spp., Hibiscus spp., Hortensia spp.), Hydrangea spp., Hypoestes phyllostachya, Impatiens spp. (I. Walleriana), Iresines spp., Kalanchoe spp., Lantana camara, Lavatera trimestris, Leonotis leonurus, Lilium spp., Mesembryanthemum spp., Mimulus spp., Monarda spp., Nemesia spp., Tagetes spp. spp.), Dianthus spp. (carnations), Canna spp., Oxalis spp., Bellis spp., Pelargonium spp. (P. peltatum, P. Zonale), Viola spp. (pansies), Petunia spp., Phlox spp., Plecthranthus spp., Poinsettia spp., Parthenocissus spp. (P. quinquefolia, P. tricuspidata), Primula spp. spp.), Ranunculus spp., Rhododendron spp., Rosa spp. (roses), 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.

[0156] For example, the present invention may be used with any of the following vegetable species: Allium spp. (garlic (A. sativum), onion (A. cepa), shallot (A. oschaninii), leek (A. Porrum), shallot (A. ascalonicum), green onion (A. fistulosum)), chervil (Anthriscus cerefolium), celery (Apium graveolus), asparagus (Asparagus officinalis), sugar beet (Beta vulgarus), Brassica spp. (B. Oleracea, Chinese cabbage (B. Pekinensis), turnip (B. rapa)), pepper (Capsicum annuum), chickpea (Cicer arietinum), endive (Cichorium endivia), chives (Cichorium spp.), thyme (Chrysanthemum vulgaris ... spp.) (chicory (C. intybus), endive (C. endivia)), watermelon (Citrillus lanatus), cucumber (Cucumis spp.) (saffron (C. sativus), melon (C. melo)), pumpkin (Cucurbita spp.) (Cucurbita pepo, C. maxima), Cyanara spp. (artichoke (C. scolymus), cardoon (C. cardunculus)), black carrot (Daucus carota), fennel (Foeniculum vulgare), Hypericum spp., lettuce (Lactuca sativa), tomato (Lycopersicon spp.) (tomato (L. esculentum), tomato (L. lycopersicum)), mint (Mentha spp.), basil (Ocimum basilicum), parsley (Petroselinum crispum), Phaseolus spp. (green bean (P. vulgaris), scarlet bean (P.coccineus), peas (Pisum sativum), radishes (Raphanus sativus), rhubarb (Rheum rhaponticum), rosemary (Rosemarinus spp.), butterbur (Salvia spp.), yellow rose (Scorzonera hispanica), eggplant (Solanum melongena), spinach (Spinacea oleracea), Valerianella spp. (Valerianella locusta, V. eriocarpa) and broad beans (Vicia faba).

[0157] Preferred ornamental plant species include African violet, Begonia, Dahlia, Gerbera, Hydrangea, Verbena, Rosa, Kalanchoe, Poinsettia, Aster, Centaurea, Coreopsis, Delphinium, Monarda, Phlox, and others. Examples of such herbs include Rudbeckia, Sedum, Petunia, Viola, Impatiens, Geranium, Chrysanthemum, Ranunculus, Fuchsia, Salvia, Hortensia, rosemary, sage, St. Johns wort, mint, pepper, tomato, and cucumber.

[0158] The active ingredients according to the invention are particularly suitable for controlling Aphis craccivora, Diabrotica balteata, Heliothis virescens, Myzus persicae, Plutella xylostella and Spodoptera littoralis in cotton, vegetable, corn, rice and soybean crops. The active ingredients according to the invention are further particularly suitable for controlling Mamestra (preferably in vegetables), Cydia pomonella (preferably in apple), Empoasca (preferably in vegetables, vineyards), Leptinotarsa ​​(preferably in potato) and Chilo supressalis (preferably in rice).

[0159] The active ingredients according to the invention are particularly suitable for controlling Aphis craccivora, Diabrotica balteata, Heliothis virescens, Myzus persicae, Plutella xylostella and Spodoptera littoralis in cotton, vegetable, corn, rice and soybean crops. The active ingredients according to the invention are particularly suitable for controlling Mamestra (preferably in vegetables), Cydia pomonella (preferably in apples), Empoasca (preferably in vegetables, vineyards), Leptinotarsa ​​(preferably in potatoes) and Chilo supressalis (preferably in rice).

[0160] In a further aspect, the present invention relates to plant parasitic nematodes (endoparasitic, semi-endoparasitic and ectoparasitic nematodes), in particular 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 clover cyst nematode, Heterodera trifolii and other Heterodera species; Root-knot nematodes, Anguina species; Spike and leaf nematodes, Aphelenchoides species; Sting nematodes, Belonolaimus longicaudatus and other Belonolaimus species; Pine nematodes, Bursaphelenchus xylophilus and other Bursaphelenchus species; Ring nematodes, nematode, Criconema spp., Criconemella spp., Criconemoides spp., Mesocriconema spp.; stem and rhizome nematodes, Ditylenchus destructor, Ditylenchus dipsaci and other Ditylenchus spp.; Awl nematode, Dolichodorus spp.;Spiral nematode, Heliocotylenchus multicinctus and other Helicotylenchus species;Sheath and sheathoid nematode, Hemicycliophora species and Hemicriconemoides species;Hirshmanniella species;Lance nematode, Hoploaimus species;False root-knot nematode, Nacobbus species;Needle nematode, Longidorus elongatus and other Longidorus species;Pin nematode, nematode, Pratylenchus spp.; Lesion nematode, Pratylenchus neglectus, Pratylenchus penetrans, Pratylenchus curvitatus, Pratylenchus goodeyi and other Pratylenchus spp.; Burrowing nematode, Radopholus similis and other Radopholus spp.; Reniform nematode, Rotylenchus robustus, Rotylenchus reniformis reniformis and other Rotylenchus species; Scutellonema species;plant parasitic nematodes such as the stubby root nematode, Trichodorus primitivus and other Trichodorus species, Paratrichodorus species; the stunt nematode, Tylenchorhynchus claytoni, Tylenchorhynchus dubius and other Tylenchorhynchus species; the Citrus nematode, Tylenchulus species; the Dagger nematode, Xiphinema species; and plant parasitic nematodes such as Subanguina spp., Hypsoperine spp. It also relates to a method for controlling damage to plants and plant parts caused by other plant parasitic nematode species such as Macroposthonia spp., Melinius spp., Punctodera spp. and Quinisulcius spp.;

[0161] The compounds of the present invention may also have activity against mollusks. Examples of mollusks include, for example, the family Ampullariidae; the genus Arion (A. ater, A. circumscriptus, A. hortensis, A. rufus); the family Bradybaenidae (Bradybaena furticum); fruticum); Cepaea (C. hortensis, C. nemoralis); ochlodina; Deroceras (D. agrestis, D. empiricorum, D. laeve, D. reticulatum) tum); Discus (D. rotundatus); Euomphalia; Galba (G. trunculata); Helicelia (H. itala, H. obvia); Helicidae Helicigona albustrum arbustorum); Helicodiscus; Helix (H. aperta); Limax (L. cinereoniger, L. flavus, L. marginatus, L. maximus, L. tenellus); Monoa These include the genera Lymnaea; Milax (M. gagates, M. marginatus, M. sowerbyi); Opeas; Pomacea (P. canaticulata); Vallonia and Zanitoides.

[0162] The term "crop plant" should also be understood to include crop plants that have been transformed by the use of recombinant DNA techniques so as to be capable of synthesizing one or more selectively acting toxins, such as those known to be derived from toxin-producing bacteria, particularly bacteria of the genus Bacillus.

[0163] Toxins which may be expressed by such transgenic plants include, for example, insecticidal proteins from Bacillus cereus or Bacillus popilliae; or δ-endotoxins, such as Cry1Ab, Cry1Ac, Cry1F, Cry1Fa2, Cry2Ab, Cry3A, Cry3Bb1 or Cry9C, insecticidal proteins from Bacillus thuringiensis or plant insecticidal proteins (Vip), such as Vip1, Vip2, Vip3 or Vip3A; or bacterial-colonizing nematodes, such as Photorhabdus spp., such as Photorhabdus luminescens, Xenorhabdus nematophilus or Xenorhabdus spp. spp.); toxins produced by animals, such as scorpion toxins, arachnid toxins, wasp toxins and neurotoxins specific to other insects; toxins produced by fungi, such as Streptomycetes toxins, plant lectins, such as pea lectin, barley lectin or snowdrop lectin; agglutinins; trypsin inhibitors, serine protease inhibitors, proteinase inhibitors, such as patatin, cystatin, papain inhibitors; ricin, maize-RIP, abrin, rufin, saporin, ribosome-inactivating proteins (RIPs) such as bryodin or bryodin; steroid metabolic enzymes such as 3-hydroxysteroid oxidase, ecdysteroid-UDP-glycosyl-transferase, cholesterol oxidase, ecdysone inhibitors, HMG-COA-reductase, ion channel blockers such as blockers of sodium or calcium channels, juvenile hormone esterase, diuretic hormone receptor, stilbene synthase, bibenzyl synthase, chitinase and glucanase.

[0164] In the context of the present invention, delta-endotoxins are understood to be, for example, Cry1Ab, Cry1Ac, Cry1F, Cry1Fa2, Cry2Ab, Cry3A, Cry3Bb1 or Cry9C or plant insecticidal proteins (Vip), such as Vip1, Vip2, Vip3 or Vip3A, and also, explicitly, hybrid toxins, truncated toxins and modified toxins. Hybrid toxins are produced recombinantly by new combinations of different domains of these proteins (see, for example, WO 2002 / 15701). Truncated toxins, such as truncated Cry1Ab, are known. In the case of modified toxins, one or more amino acids of the natural toxin are replaced. In such amino acid substitutions, preferably a non-naturally occurring protease recognition sequence is inserted into the toxin, for example in the case of Cry3A055, a cathepsin-G-recognition sequence is inserted into the Cry3A toxin (see WO 2003 / 018810).

[0165] Examples of such toxins or transgenic plants capable of synthesizing such toxins are disclosed, for example, in EP 0 374 753, WO 1993 / 07278, WO 1995 / 34656, EP 0 427 529, EP 451 878 and WO 2003 / 052073.

[0166] Methods for the preparation of such transgenic plants are generally known to those skilled in the art and are described, for example, in the above-mentioned publications. Deoxyribonucleic acids of the CryI type and their preparation are known, for example, from WO 95 / 34656, EP 0 367 474, EP 0 401 979 and WO 1990 / 13651.

[0167] The toxins contained in the transgenic plants confer resistance to the plants against pests found in a range of insect taxa, but are most commonly found in beetles (Coleoptera), two-winged insects (Diptera) and moths (Lepidoptera).

[0168] Transgenic plants containing one or more genes encoding insecticide resistance and expressing one or more toxins are known and some of them are commercially available. Examples of such plants are YieldGard® (a corn variety expressing the Cry1Ab toxin); YieldGard Rootworm® (a corn variety expressing the Cry3Bb1 toxin); YieldGard Plus® (a corn variety expressing the Cry1Ab and Cry3Bb1 toxins); Starlink® (a corn variety expressing the Cry9C toxin); Herculex I® (a corn variety expressing the Cry1Fa2 toxin and the enzyme phosphinothricin N-acetyltransferase (PAT) for resistance to the herbicide glufosinate ammonium); NuCOTN 33B® (a cotton variety expressing the Cry1Ac toxin); Bollgard I® (a cotton variety expressing the Cry1Ac toxin); Bollgard II® (a cotton variety expressing Cry1Ac and Cry2Ab toxins); VipCot® (a cotton variety expressing Vip3A and Cry1Ab toxins); NewLeaf® (a potato variety expressing Cry3A toxin); NatureGard®, Agrisure® GT Advantage (GA21 glyphosate tolerance trait), Agrisure® CB Advantage (Bt11 corn borer (CB) trait) and Protecta®.

[0169] Further examples of such transgenic crops are: 1. Bt11 maize, registration number C / FR / 96 / 05 / 10, from Syngenta Seeds SAS (Chemin de l'Hobit 27, F-31 790 St.Sauveur, France). Transgenic maize conferred resistance to attack by the European corn borer (Ostrinia nubilalis and Sesamia nonagrioides) by transgenic expression of a truncated Cry1Ab toxin. Bt11 maize also transgenicly expresses the enzyme PAT to confer tolerance to the herbicide glufosinate ammonium.

[0170] 2. Bt176 maize, registration number C / FR / 96 / 05 / 10, from Syngenta Seeds SAS (Chemin de l'Hobit 27, F-31 790 St.Sauveur, France). Transgenic maize conferred resistance to attack by the European corn borer (Ostrinia nubilalis and Sesamia nonagrioides) by transgenic expression of the Cry1Ab toxin. Bt176 maize also transgenicly expresses the enzyme PAT to confer tolerance to the herbicide glufosinate ammonium.

[0171] 3. MIR604 maize, registration number C / FR / 96 / 05 / 10, from Syngenta Seeds SAS (Chemin de l'Hobit 27, F-31 790 St. Sauveur, France). Maize made insect-resistant by transgenic expression of a modified Cry3A toxin. This toxin is Cry3A055 modified by the insertion of a cathepsin-G-protease recognition sequence. The preparation of such transgenic maize plants is described in WO 2003 / 018810.

[0172] 4. MON 863 maize, registration number C / DE / 02 / 9, from Monsanto Europe SA, 270-272 Avenue de Tervuren, B-1150 Brussels, Belgium. MON 863 expresses the Cry3Bb1 toxin and confers resistance to certain Coleoptera insects.

[0173] 5. IPC 531 cotton, registration number C / ES / 96 / 02, manufactured by Monsanto Europe SA, 270-272 Avenue de Tervuren, B-1150 Brussels, Belgium.

[0174] 6. 1507 maize, registration number C / NL / 00 / 10, from Pioneer Overseas Corporation, Avenue Tedesco, 7 B-1160 Brussels, Belgium. Genetically modified maize for expression of the protein Cry1F for resistance to certain Lepidoptera insects and the PAT protein for resistance to the herbicide glufosinate ammonium.

[0175] 7. NK603 x MON 810 maize, registration number C / GB / 02 / M3 / 03, from Monsanto Europe SA, 270-272 Avenue de Tervuren, B-1150 Brussels, Belgium. It consists of a conventionally bred hybrid maize variety by crossing the genetically modified varieties NK603 and MON 810. NK603 x MON 810 maize also genetically expresses the protein CP4 EPSPS from Agrobacterium sp. strain CP4, which confers resistance to the herbicide Roundup® (containing glyphosate), and the Cry1Ab toxin from Bacillus thuringiensis subsp. kurstaki, which confers resistance to certain Lepidoptera, including the European Corn Borer.

[0176] Transgenic crops of insect-resistant plants are also described in the BATS (Zentrum für Biosicherheit und Nachhaltigkeit, Zentrum BATS, Clarastrasse 13, 4058 Basel, Switzerland) Report 2003, (http: / / bats.ch).

[0177] The term "crop plant" should also be understood to include crop plants that have been transformed by the use of recombinant DNA techniques so as to be able to synthesize antipathogenic substances with selective action, such as, for example, so-called "pathogenicity-related proteins" (PRPs, see, for example, EP-A-0392225). Examples of such antipathogenic substances and transgenic plants capable of synthesizing such antipathogenic substances are known, for example, from EP-A-0392225, WO-A-1995 / 33818 and EP-A-0353191. Methods for producing such transgenic plants are generally known to the person skilled in the art and are described, for example, in the above-mentioned publications.

[0178] Anti-pathogenic substances which may be expressed by such transgenic plants include, for example, ion channel blockers, such as blockers of sodium or calcium channels, e.g. viral KP1, KP4 or KP6 toxins; stilbene synthases; bibenzyl synthases; chitinases; glucanases; so-called "pathogenesis related proteins" (PRPs; see, for example, EP 0 392 225); anti-pathogenic substances produced by microorganisms, such as peptide or heterocyclic antibiotics (see, for example, WO 1995 / 33818) or proteins or polypeptide factors involved in plant pathogen defense (so-called "plant disease resistance genes" as described in WO 2003 / 000906).

[0179] Further fields of use of the compositions according to the invention are the protection of storehouses and storage rooms and the protection of raw materials (such as wood and textiles), floor coverings and buildings and in the hygiene sector, in particular the protection of humans, domestic animals and productive livestock from pests of the abovementioned types.

[0180] 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 composition of the present invention to the target pest, its habitat, or a surface or substrate by brushing, rolling, spraying, painting, or immersion. By way of example, IRS (indoor residual spray) application of surfaces such as walls, ceilings, or floors is contemplated by the method of the present invention. In another embodiment, it is contemplated to apply such compositions to substrates such as nonwoven or woven materials in the form of (or that can be used to manufacture) netting, clothing, bedding, curtains, and tents.

[0181] In one embodiment, the method for controlling such pests comprises applying a pesticidally effective amount of the composition of the present invention to a target pest, its habitat, or a surface or substrate, so as to provide effective residual pest control activity to the surface or substrate. Such application can be performed by brushing, rolling, spraying, painting, or dipping the pesticidal composition of the present invention. By way of example, IRS application on surfaces such as walls, ceilings, or floors is contemplated by the method of the present invention, so as to provide effective residual pest control activity to the surface. In another embodiment, it is contemplated to apply such compositions for residual control of pests on substrates such as fabric materials in the form of (or that can be used to manufacture) netting, clothing, bedding, curtains, and tents.

[0182] The substrates to be treated, including nonwovens, fabrics or nets, can be made of natural fibers such as cotton, raffia, jute, flax, sisal, hemp or wool, or synthetic fibers such as polyamide, polyester, polypropylene, polyacrylonitrile. Polyesters are particularly suitable. Methods of textile treatment are known, for example, from WO 2008 / 151984, WO 2003 / 034823, US 5631072, WO 2005 / 64072, WO 2006 / 128870, EP 1724392, WO 2005 / 113886 or WO 2007 / 090739.

[0183] A further field of use for the compositions according to the invention is that of trunk injection / trunk treatment of all ornamental trees and also of all kinds of fruit and nut-bearing trees.

[0184] In the field of trunk injection / trunk treatment, the compounds according to the invention are particularly suitable against wood-boring insects of the abovementioned orders Lepidoptera and Coleoptera, in particular against those listed in Tables A and B below.

[0185] [Table 3]

[0186] [Table 4-1] [Table 4-2] [Table 4-3]

[0187] The present invention may also be used to control any insect pest that may be present in turfgrass, including, for example, beetles, caterpillars, fire ants, ground pearls, millipedes, pillbugs, mites, mole crickets, scale insects, mealybugs, mites, foxtails, southern chinch bugs, and grubs. The present invention may be used to control insect pests in various stages of their life cycle, including eggs, larvae, nymphs, and adults.

[0188] In particular, the present invention relates to the treatment of earthworms such as Cyclocephala spp. (e.g. masked chafer, C. lurida), Rhizotrogus spp. (e.g. European chafer, R. majalis), Cotinus spp. (e.g. blue swallowtail 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), and the like. turfgrass ataenius, A. spretulus), Maladera spp. (e.g., red-veined scarab beetle, M. castanea) and Tomarus spp.), cotton scales (Margarodes spp.), mole crickets (tawny, southern and brachypterous; Scapteriscus spp., Gryllotalpa africana) and leatherjackets (European crane fly, Tipula spp.).

[0189] The present invention may also be used to control straw-dwelling insect pests of turfgrass, including cutworms (such as Spodoptera frugiperda and the common armyworm (such as Pseudaletia unipuncta), cutworms, weevils (such as Sphenophorus spp., S. venatus verstitus and S. parvulus) and sod webworms (such as Crambus spp. and the tropical sod webworm, Herpetogramma phaeopteralis).

[0190] The present invention may also be used to control insect pests that live above ground and feed on turfgrass leaves, including the lesser stink bug (such as the southern kinkbug, Blissus insularis), Bermudagrass mite (Eriophyes cynodoniensis), rhodesgrass mealybug (Antonina graminis), two-lined spittlebug (Propsapia bicincta), leafhoppers, cutworms (Noctuidae), and greenbugs.

[0191] The present invention may also be used to control other pests of turfgrass, such as the red fire ant (Solenopsis invicta), which creates ant mounds in turfgrass.

[0192] In the hygiene field, the compositions according to the invention are effective against ectoparasites such as hard ticks, soft ticks, scabies mites, chiggers, flies (stable flies and licking flies), parasitic fly larvae, lice, pubic lice, biting lice and fleas. Examples of such parasites are: From the order Anoplurida: Haematopinus spp., Linognathus spp., Pediculus spp. and Phtirus spp., Solenopotes spp.

[0193] From the order Mallophagida: the genera Trimenopon spp., Menopon spp., Trinoton spp., Bovicola spp., Werneckiella spp., Lepikentron spp., Damalina spp., Trichodectes spp. and Felicola spp.

[0194] Among the order Diptera and its suborders Nematocerina and Brachycerina, for example, the genera 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., 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. spp.), Oestrus spp., Hypoderma spp., Gasterophilus spp., Hippobosca spp., Lipotena spp. and Melophagus spp.

[0195] Among the order Siphonapterida, for example, the genera Pulex spp., Ctenocephalides spp., Xenopsylla spp., and Ceratophyllus spp.

[0196] From the order Heteropterida, for example, Cimex spp., Triatoma spp., Rhodnius spp., Panstrongylus spp.

[0197] From the order Blattaridae, for example, Blatta orientalis, Periplaneta americana, Blattela germanica and Supella spp.

[0198] Among the subclass Acaria (Acarida) and the suborders Metastigmata and Mesostigmata, for example, the genera Argas spp., Ornithodorus spp., Otobius spp., Ixodes spp., Amblyomma spp., Boophilus spp., Dermacentor spp., Haemophysalis spp., Hyalomma spp., Rhipicephalus spp., Dermanyssus spp., Raillietia spp., spp.), Pneumonyssus spp., Sternostoma spp. and Varroa spp.

[0199] Among the orders Actinedida (Prostigmata) and Acaridida (Astigmata), for example, the genera Acarapis spp., Cheyletiella spp., Ornithocheyletia spp., Myobia spp., Psorergates spp., Demodex spp., Trombicula spp., Listrophorus spp., Acarus spp., Tyrophagus spp., Caloglyphus spp., Hypodectes spp., spp.), Pterolichus spp., Psoroptes spp., Chorioptes spp., Otodectes spp., Sarcoptes spp., Notoedres spp., Knemidocoptes spp., Cytodites spp. and Laminosioptes spp.

[0200] The compositions according to the invention are also suitable for protecting against insect infestation in materials such as wood, textiles, plastics, adhesives, glues, paints, paper and cardboard, leather, floor coverings and building materials.

[0201] The compositions according to the invention can be used, for example, against the following pests: 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, as well as hymenopteran insects such as Sirex juvencus, Urocerus gigas, Urocerus gigas taignus, and Urocerus augur, as well as Kalotermes flavicollis, Cryptotermes brevis, Heterotermes indicola, Reticulitermes flavipes, Reticulitermes santonensis, Reticulitermes lucifugus, and other insects of the genus Cyperus. Termites such as Mastotermes darwiniensis, Zootermopsis nevadensis and Coptotermes formosanus, and woodworms such as Lepisma saccharina.

[0202] The compounds according to the present invention can be used as pesticides in unmodified form, but they are generally formulated into compositions in various ways using formulation auxiliaries such as carriers, solvents and surfactants. The formulations can be in various physical forms, such as dusts, gels, wettable powders, water-dispersible granules, water-dispersible tablets, effervescent pellets, emulsifiable concentrates, microemulsifiable concentrates, oil-in-water emulsions, oil-based flowables, aqueous dispersions, oil-based dispersions, suspoemulsions, capsule suspensions, emulsifiable granules, soluble liquids, water-soluble concentrates (containing water or water-miscible organic solvents as carriers), impregnated polymer films or other forms known, for example, from the Manual on Development and Use of FAO and WHO Specifications for Pesticides, United Nations, First Edition, Second Revision (2010). Such formulations can be used directly or diluted before use. Dilution can be carried out, for example, with water, liquid fertilizers, micronutrients, biological organisms, oils or solvents.

[0203] The formulations can be prepared, for example, by mixing the active ingredient with formulation auxiliaries to obtain a composition in the form of a finely divided solid, granules, liquid, dispersion or emulsion. The active ingredient can also be formulated with other auxiliaries, 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.

[0204] The active ingredient may also be contained in fine microcapsules. The microcapsules contain the active ingredient in a porous carrier. This allows the active ingredient to be released in controlled amounts into the environment (e.g., sustained release). The microcapsules usually have a diameter of 0.1 to 500 μm. The microcapsules contain the active ingredient in an amount of about 25 to 95% by weight of the capsule weight. The active ingredient may be in the form of a monolithic solid, in the form of fine particles in a solid or liquid dispersion, or in the form of a suitable solution. The encapsulating membrane may, for example, comprise natural or synthetic rubber, cellulose, styrene / butadiene copolymer, polyacrylonitrile, polyacrylate, polyester, polyamide, polyurea, polyurethane or chemically modified polymers and starch xanthate or other polymers known to those skilled in the art. Alternatively, fine microcapsules may be formed in which the active ingredient is contained in the form of finely divided particles in a solid matrix of the base, but the microcapsules themselves are not encapsulated.

[0205] The formulation auxiliaries suitable for the preparation of the compositions according to the invention are known per se.As liquid carriers, the following 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, N,N-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, α-pinene, d-limonene, ethyl lactate, ethylene glycol, ethylene glycol butyl ether, ethylene glycol methyl ether, γ-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 carboxylic 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, xylene sulfonic acid, paraffin, mineral oil, trichloroethylene, perchloroethylene, ethyl acetate, amyl acetate, butyl acetate, propylene glycol methyl ether, diethylene glycol methyl ether, methanol, ethanol, isopropanol and higher molecular weight alcohols such as amyl alcohol, tetrahydrofurfuryl alcohol, hexanol, octanol, ethylene glycol, propylene glycol, glycerol, N-methyl-2-pyrrolidone, etc.,

[0206] Suitable solid carriers are, for example, talc, titanium dioxide, pyrophyllite clay, silica, attapulgite clay, diatomaceous earth, limestone, calcium carbonate, bentonite, calcium montmorillonite, cottonseed hulls, wheat flour, soybean flour, pumice, wood flour, ground walnut shells, lignin and similar materials.

[0207] Many surface-active substances can be used advantageously in both solid and liquid formulations, especially in formulations which may be diluted with a carrier before use. The surface-active substances can be anionic, cationic, nonionic or polymeric and they can be used as emulsifying agents, wetting agents or suspending agents or for other purposes. Typical surface-active materials include, for example, salts of alkyl sulfates, such as diethanolammonium lauryl sulfate; salts of alkylarylsulfonates, such as calcium dodecylbenzenesulfonate; alkylphenol / alkylene oxide adducts, such as nonylphenol ethoxylate; alcohol / alkylene oxide adducts, such as tridecyl alcohol ethoxylate; soaps, such as sodium stearate; salts of alkylnaphthalenesulfonates, such as sodium dibutylnaphthalenesulfonate; dialkyl esters of sulfosuccinates, 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 di-alkyl phosphate esters; and further materials, such as those described in McCutcheon's Detergents and Emulsifiers Annual, MC Publishing Corp., Ridgewood New Jersey (1981).

[0208] Further auxiliaries which may be used in the pesticide formulations include crystallization inhibitors, viscosity modifiers, suspending agents, dyes, antioxidants, foaming agents, light absorbers, mixing aids, defoamers, complexing agents, neutralizing or pH adjusting substances and buffers, corrosion inhibitors, fragrances, wetting agents, absorption enhancers, micronutrients, plasticizers, glidants, lubricants, dispersants, thickeners, antifreeze agents, fungicides and liquid and solid fertilizers.

[0209] The composition according to the invention may contain an additive comprising an oil of vegetable or animal origin, a mineral oil, an alkyl ester of such an oil or a mixture of such an oil and an oil derivative. The amount of the oil additive in the composition according to the invention is generally 0.01-10% based on the mixture to be applied. For example, the oil additive may be added to the spray tank at the desired concentration after the spray mixture is prepared. Preferred oil additives include mineral oil or oil of vegetable origin, such as rapeseed oil, olive oil or sunflower oil, emulsified vegetable oil, alkyl ester of oil of vegetable origin, such as methyl derivatives, or oil of animal origin, such as fish oil or beef tallow. Preferred oil additives are C8-C 22 Alkyl esters of fatty acids, especially C 12 ~C 18 Methyl derivatives of fatty acids, such as the methyl esters of lauric acid, palmitic acid, and oleic acid (methyl laurate, methyl palmitate, and methyl oleate, respectively). Many oil derivatives are described in the Compendium of Herbicide Adjuvants, 10 th Edition, Southern Illinois University, 2010.

[0210] The compositions of the invention generally contain 0.1-99% by weight, in particular 0.1-95% by weight, of the compound of the invention and 1-99.9% by weight of formulation auxiliaries, which preferably contain 0-25% by weight of surface-active substances. Commercial products may preferably be formulated as concentrates, but end users will usually use dilute formulations.

[0211] The application rates vary within wide limits and depend on the nature of the soil, the method of application, the crop plant, the pests to be controlled, the prevailing climatic conditions and other factors which depend on the method of application, the time of application and the target crop. As a general guideline, the compounds may be applied at a rate of 1 to 2000 l / ha, in particular 10 to 1000 l / ha.

[0212] A preferred formulation may have the following composition (by weight):

[0213] emulsion: Active ingredient: 1-95%, preferably 60-90% Surfactant: 1-30%, preferably 5-20% Liquid carrier: 1-80%, preferably 1-35%

[0214] Dust agent: Active ingredient: 0.1-10%, preferably 0.1-5% Solid carrier: 99.9 to 90%, preferably 99.9 to 99%

[0215] Suspension concentrates: Active ingredient: 5-75%, preferably 10-50% Water: 94-24%, preferably 88-30% Surfactant: 1-40%, preferably 2-30%

[0216] Wettable powder: Active ingredient: 0.5-90%, preferably 1-80% Surfactant: 0.5-20%, preferably 1-15% Solid carrier: 5 to 95%, preferably 15 to 90%

[0217] Granules: Active ingredient: 0.1-30%, preferably 0.1-15% Solid carrier: 99.5 to 70%, preferably 97 to 85%

[0218] The following examples further illustrate the present invention without, however, limiting it.

[0219] [Table 5]

[0220] This combination is thoroughly mixed with adjuvants and the mixture is thoroughly ground in a suitable mill to obtain a wettable powder, which is diluted with water to obtain a suspension of the desired concentration.

[0221] [Table 6]

[0222] This combination is thoroughly mixed with an adjuvant and the mixture is thoroughly ground in a suitable mill to obtain a dust which can be used directly for seed treatment.

[0223] [Table 7]

[0224] Emulsifiable concentrates of any desired dilution which can be used for plant protection are obtained from this concentrate by dilution with water.

[0225] [Table 8]

[0226] Ready-to-use dusts are obtained by combining and mixing with a carrier and grinding the mixture in a suitable mill. Such powders can also be used for dry dressing of seeds.

[0227] [Table 9]

[0228] This combination is mixed with an auxiliary agent, ground, the mixture is moistened with water, the mixture is extruded and then dried in a stream of air.

[0229] [Table 10]

[0230] This micronized combination is applied uniformly in a mixer to kaolin moistened with polyethylene glycol. In this way, dust-free coated granules are obtained.

[0231] [Table 11]

[0232] This micronized combination is intimately mixed with an adjuvant to obtain a suspension concentrate from which suspensions of any desired dilution rate can be obtained by dilution with water, with which living plants as well as plant propagation material can be treated and protected from microbial infestation by spraying, pouring or immersion.

[0233] [Table 12]

[0234] This micronized combination is intimately mixed with an adjuvant to obtain a suspension concentrate from which suspensions of any desired dilution are obtained by dilution with water, with which living plants as well as plant propagation material can be treated and protected from microbial infestation by spraying, pouring or immersion.

[0235] Sustained Release Capsule Suspension 28 parts of this combination are mixed with 2 parts of 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 polyvinyl alcohol, 0.05 parts of antifoaming agent and 51.6 parts of water until the desired particle size is obtained. A mixture of 2.8 parts of 1,6-diaminohexane in 5.3 parts of water is added to this emulsion. The mixture is stirred until the polymerization reaction is complete. The resulting capsule suspension is stabilized by adding 0.25 parts of thickener and 3 parts of dispersant. The capsule suspension formulation contains 28% active ingredient. The capsules have a median diameter of 8-15 μm. The resulting formulation is applied to the seeds as an aqueous suspension in a device suitable for the purpose in question.

[0236] Formulation types include emulsifiable concentrates (EC), suspension concentrates (SC), suspoemulsions (SE), capsule suspensions (CS), wettable granules (WG), emulsifiable granules (EG), water-in-oil emulsions (EO), oil-in-water emulsions (EW), microemulsions (ME), oil dispersions (OD), oil-miscible flowables (OF), oil-miscible liquids (OL), soluble concentrates (SL), suspension concentrates for microdispersion (SU), liquid concentrates for microdispersion (UL), technical concentrates (TK), dispersible concentrates (DC), wettable powders (WP), soluble granules (SG) or any technically feasible formulation in combination with agriculturally acceptable adjuvants. EXAMPLES

[0237] Preparation Example: "Mp" means melting point (° C.). The free radical represents a methyl group. 1 H NMR measurements were recorded on a Brucker 400 MHz spectrometer and chemical shifts are given in ppm relative to TMS standard. Spectra are measured in deuterated solvents as indicated. Compounds were characterized using one of the following LCMS methods. The characteristic LCMS values ​​obtained for each compound are the retention time ("R t ", recorded in minutes) and molecular ion (M+H) + or (MH) - The actual measured value was:

[0238] LCMS and GCMS Methods: Method 1: Spectra were recorded on a Waters mass spectrometer (SQD, SQDII single quadrupole mass spectrometer) equipped with an electrospray source (polarity: positive and negative ion, capillary: 3.00 kV, cone range: 30 V, extractor: 2.00 V, source temperature: 150° C., desolvation temperature: 350° C., cone gas flow: 50 l / h, desolvation gas flow: 650 l / h, mass range: 100-900 Da) and a Waters Acquity UPLC: binary pump, heated column compartment, diode-array detector and ELSD detector. Column: Waters UPLC HSS T3, 1.8 μm, 30 × 2.1 mm; Temperature: 60 °C; DAD wavelength range (nm): 210–500; Solvent gradient: A = water + 5% MeOH + 0.05% HCOOH, B = acetonitrile + 0.05% HCOOH; Gradient: 10 to 100% B in 1.2 min; Flow rate (ml / min) 0.85.

[0239] Method 2: Spectra were recorded on a Waters mass spectrometer (SQD, SQDII single quadrupole mass spectrometer) equipped with an electrospray source (polarity: positive and negative ions), capillary: 3.00 kV, cone range: 30 V, extractor: 2.00 V, source temperature: 150° C., desolvation temperature: 350° C., cone gas flow: 50 l / h, desolvation gas flow: 650 l / h, mass range: 100-900 Da) and a Waters Acquity UPLC: binary pump, heated column compartment, diode-array detector and ELSD detector. Column: Waters UPLC HSS T3, 1.8 μm, 30 × 2.1 mm; Temperature: 60 °C; DAD wavelength range (nm): 210–500; Solvent gradient: A = water + 5% MeOH + 0.05% HCOOH, B = acetonitrile + 0.05% HCOOH; Gradient: 10 to 100% B in 2.7 min; Flow rate (ml / min) 0.85.

[0240] Method 3: Spectra were recorded on a Waters mass spectrometer (SQD, SQDII or ZQ single quadrupole mass spectrometer) equipped with an electrospray source (polarity: positive and negative ion), capillary: 3.00 kV, cone range: 30 V, extractor: 2.00 V, source temperature: 150° C., desolvation temperature: 350° C., cone gas flow: 50 l / h, desolvation gas flow: 650 l / h, mass range: 100-900 Da) and a Waters Acquity UPLC: binary pump, heated column compartment, diode-array detector and ELSD detector. Column: Waters UPLC HSS T3, 1.8 μm, 30 × 2.1 mm; Temperature: 60 °C; DAD wavelength range (nm): 210–500; Solvent gradient: A = water + 5% MeOH + 0.05% HCOOH, B = acetonitrile + 0.05% HCOOH; Gradient: 0 to 10% B in 2.5 min; Flow rate (ml / min) 0.85.

[0241] Method 4: Spectra were recorded on a Waters mass spectrometer (SQD, SQDII single quadrupole mass spectrometer) equipped with an electrospray source (polarity: positive and negative ions), capillary: 3.00 kV, cone range: 30 V, extractor: 2.00 V, source temperature: 150° C., desolvation temperature: 350° C., cone gas flow: 50 l / h, desolvation gas flow: 650 l / h, mass range: 100-900 Da) and a Waters Acquity UPLC: binary pump, heated column compartment, diode-array detector and ELSD detector. Column: Waters UPLC HSS T3, 1.8 μm, 30 × 2.1 mm; Temperature: 60 °C; DAD wavelength range (nm): 210–500; Solvent gradient: A = water + 5% MeOH + 0.05% HCOOH, B = acetonitrile + 0.05% HCOOH; Gradient: 40 to 100% B in 1.2 min; Flow rate (ml / min) 0.85.

[0242] Method 5: Spectra were recorded on a Waters mass spectrometer (Acquity SDS mass spectrometer) equipped with an electrospray source (polarity: positive and negative polarity switch, capillary: 3.00 kV, cone voltage: 41.00 V, source temperature: 150 °C, desolvation gas flow: 1000 L / Hr., desolvation temperature: 500 °C, gas flow @ cone: 50 L / hr., mass range: 110-800 Da, PDA wavelength range: 210-400 nm. Column: Acquity UPLC HSS T3 C18, total length 30 mm, diameter 2.1 mm, particle size 1.8 μm. Column oven temperature 40 °C. Solvent gradient: A = water + 0.1% formic acid:acetonitrile (95:5 v / v). B = acetonitrile + 0.05% formic acid. Gradient = 90% A, 10% B for 0 min; 50% A, 50% B for 0.2 min; 0% A, 100% B for 0.7-1.3 min; 90% A, 10% B for 1.4-1.6 min. Flow rate 0.6 mL / min.

[0243] Example H1: Preparation of 1-[5-(ethylsulfonimidoyl)-6-[7-methyl-3-(trifluoromethyl)imidazo[4,5-c]pyridazin-6-yl]-3-pyridyl]cyclopropanecarbonitrile (Table P, Example P10) [ka] Step 1: Preparation of methyl 5-(1-cyano-2-ethoxy-2-oxo-ethyl)-3-ethylsulfanyl-pyridine-2-carboxylate [ka] Methyl 5-bromo-3-ethylsulfanyl-pyridine-2-carboxylate (32 g, 115.88 mmol), prepared as described in WO 2017 / 089190, was dissolved in dimethyl sulfoxide (350 mL). Ethyl 2-cyanoacetate (18.5 mL, 173.82 mmol), potassium carbonate (40.442 g, 289.70 mmol) and tetrabutylammonium bromide (3.81 g, 11.588 mmol) were then added sequentially at room temperature. The resulting suspension was stirred at 90 °C overnight and then cooled to room temperature. Water and ethyl acetate were added, the resulting mixture was cooled at 0 °C and the reaction was acidified to pH 4-5 by slow addition of hydrochloric acid (2 M). The aqueous layer was extracted three times with ethyl acetate. The combined organic layers were dried over sodium sulfate, filtered and concentrated in vacuo. The crude product obtained was heated in ethanol (250 ml) at 80° C. for 1 hour. The resulting solution was cooled to 0° C., stirred for 1 hour, and filtered. The precipitate was washed with cold ethanol to give methyl 5-(1-cyano-2-ethoxy-2-oxo-ethyl)-3-ethylsulfanyl-pyridine-2-carboxylate. LCMS (Method 1): 309 (M+H) + ;Retention time: 0.85 minutes. 1H NMR (400 MHz, chloroform-D) δ ppm 1.33 (t, J = 7.15 Hz, 3H) 1.45 (t, J = 7.34 Hz, 3H) 2.98-3.05 (m, 2H) 4.04 (s, 3H) 4.28-4.35 (m, 2H) 4.84 (s, 1H) 7.83 (d, J = 1.83 Hz, 1H) 8.49 (d, J = 1.83 Hz, 1H).

[0244] Step 2: Preparation of methyl 5-(cyanomethyl)-3-ethylsulfanyl-pyridine-2-carboxylate [ka] Methyl 5-(1-cyano-2-ethoxy-2-oxo-ethyl)-3-ethylsulfanyl-pyridine-2-(7.3 g, 24 mmol) was dissolved in dimethylsulfoxide (70 mL). To this was added NaCl (14 g, 240 mmol) and water (35 mL) successively at room temperature. The resulting suspension was stirred at 125° C. for 3 h. The reaction mixture was cooled to room temperature and diluted with 50 mL of water and 100 mL of ethyl acetate. The aqueous layer was extracted three times with ethyl acetate. The organic layers were combined, dried over sodium sulfate and concentrated in vacuum. The crude product was purified on silica gel to give methyl 5-(cyanomethyl)-3-ethylsulfanyl-pyridine-2-carboxylate. LCMS (Method 1): 237 (M+H) + ;Retention time: 0.72 minutes. 1H NMR (400 MHz, chloroform-D) δ ppm 1.45 (t, J = 7.52 Hz, 3H) 3.01 (q, J = 7.34 Hz, 2H) 3.87 (s, 2H) 4.04 (s, 3H) 7.72 (d, J = 1.83 Hz, 1H) 8.35-8.41 (m, 1H).

[0245] Step 3: Preparation of methyl 5-(1-cyanocyclopropyl)-3-ethylsulfanyl-pyridine-2-carboxylate [ka] Methyl 5-(cyanomethyl)-3-ethylsulfanyl-pyridine-2-carboxylate (5 g, 21.16 mmol) was dissolved in acetonitrile (170 mL) and treated with cesium carbonate (20.7 g, 63.48 mmol) and 1,2-dibromoethane (2.19 mL, 25.39 mmol) at room temperature. The resulting mixture was stirred at 80° C. for 3 h 30 min and then at room temperature overnight. The reaction mixture was diluted with water and ethyl acetate. The aqueous layer was extracted three times with ethyl acetate. The combined organic layers were washed with brine, dried over sodium sulfate, filtered and concentrated in vacuo to give the crude product, which was purified by chromatography to give methyl 5-(1-cyanocyclopropyl)-3-ethylsulfanyl-pyridine-2-carboxylate. LCMS (Method 1): 263 (M+H) + ;Retention time: 0.85 minutes. 1H NMR (400MHz, chloroform-D) δppm 1.45(t,J=7.34Hz,3H)1.54-1.62(m,2H)1.89-1.96(m,2H)3.01(q,J=7.34Hz,2H)4.02(s,3H)7.74(d,J=2.20Hz,1H)8.17(d,J=1.83Hz,1H).

[0246] Step 4: Preparation of 5-(1-cyanocyclopropyl)-3-ethylsulfanyl-pyridine-2-carboxylic acid [ka] Methyl 5-(1-cyanocyclopropyl)-3-ethylsulfanyl-pyridine-2-carboxylate (2.63 g, 10.0 mmol) was dissolved in tetrahydrofuran (50 mL) and water (15 mL). Lithium hydroxide (0.375 g, 15.0 mmol) was then added and the reaction was stirred at room temperature overnight. An additional portion of lithium hydroxide (0.160 g, 7.0 mmol) was then added and the reaction was stirred at room temperature for an additional 2 hours. The reaction mixture was concentrated in vacuum and the residue was dissolved in dichloromethane. Aqueous HCl 1M was added and the aqueous layer (pH 1) was extracted three times with dichloromethane. The combined organic layers were dried over sodium sulfate, filtered and concentrated in vacuum to give 5-(1-cyanocyclopropyl)-3-ethylsulfanyl-pyridine-2-carboxylic acid. LCMS (Method 1): 249 (M+H) + ;Retention time: 0.67 minutes. 1H NMR (400MHz, DMSO-d solvent) δppm 1.26(t,J=7.34Hz,3H)1.70-1.78(m,2H)1.83-1.92(m,2H)3.03(q,J=7.34 Hz,2H)7.63(d,J=2.20Hz,1H)8.37(d,J=1.83Hz,1H)13.16-13.40(m,1H).

[0247] Step 5. Preparation of 5-(1-cyanocyclopropyl)-3-ethylsulfanyl-N-[3-(methylamino)-6-(trifluoromethyl)pyridazin-4-yl]pyridine-2-carboxamide [ka] 5-(1-Cyanocyclopropyl)-3-ethylsulfanyl-pyridine-2-carboxylic acid (200 mg, 0.8055 mmol) was dissolved in dichloromethane (10 mL) and N,N-dimethylformamide (10.0 μL) was added. To this suspension was added oxalyl dichloride (0.118 mL, 1.369 mmol) dropwise via syringe. The resulting yellowish suspension was stirred at room temperature. After 1.5 h, the reaction mixture was concentrated in vacuo to give 5-(1-Cyanocyclopropyl)-3-ethylsulfanyl-pyridine-2-carbonyl chloride. Fresh 5-(1-cyanocyclopropyl)-3-ethylsulfanyl-pyridine-2-carbonyl chloride (250 mg, 0.9370 mmol) was dissolved in tetrahydrofuran (12 mL) and N,N-diethylethanamine (0.27 mL, 1.933 mmol) was added dropwise followed by N3-methyl-6-(trifluoromethyl)pyridazine-3,4-diamine (651 mg, 3.222 mmol) in tetrahydrofuran (12 mL) at 0° C. The resulting mixture was stirred at room temperature for 12 hours. The reaction mixture was then poured into water (20 ml) and extracted with dichloromethane (3×20 ml). The combined extracts were washed with brine (30 ml), dried over sodium sulfate, filtered and concentrated in vacuo. The crude product was purified by chromatography on silica gel to give N-[4-amino-6-(trifluoromethyl)pyridazin-3-yl]-5-(1-cyanocyclopropyl)-3-ethylsulfanyl-N-methyl-pyridine-2-carboxamide. LCMS (Method 2): Retention time: 1.04 min, 423(M+H) + .

[0248] Step 6: Preparation of 1-[5-ethylsulfanyl-6-[7-methyl-3-(trifluoromethyl)imidazo[4,5-c]pyridazin-6-yl]-3-pyridyl]cyclopropanecarbonitrile [ka] 5-(1-cyanocyclopropyl)-3-ethylsulfanyl-N-[3-(methylamino)-6-(trifluoromethyl)pyridazin-4-yl]pyridine-2-carboxamide (240 mg, 0.5682 mmol) and glacial acetic acid (3 mL) were mixed and stirred at reflux overnight, then cooled to room temperature. The acetic acid was removed under reduced pressure, and the resulting residue was dissolved in ethyl acetate and basified with aqueous bicarbonate. The aqueous layer was extracted with ethyl acetate (3×20 ml), and the combined organic layers were dried over sodium sulfate, filtered, and concentrated in vacuo. The crude product was purified by chromatography on silica gel to give 1-[5-ethylsulfanyl-6-[7-methyl-3-(trifluoromethyl)imidazo[4,5-c]pyridazin-6-yl]-3-pyridyl]cyclopropanecarbonitrile. LCMS (Method 2): Retention time: 1.05 min, (M+H) + 405. 1H NMR (400 MHz, chloroform-d) d ppm 1.34-1.46 (m, 1H) 1.38 (s, 2H) 1.62-1.66 (m, 2H) 1.89-2.02 (m, 2H) 2.97-3.10 (m, 2H) 4.26 (s, 3H) 7.76-7.84 (m, 1H) 8.22-8.27 (m, 1H) 8.34-8.41 (m, 1H).

[0249] Step 7: Preparation of 1-[5-(ethylsulfonimidoyl)-6-[7-methyl-3-(trifluoromethyl)imidazo[4,5-c]pyridazin-6-yl]-3-pyridyl]cyclopropanecarbonitrile (Table P, Example P10) [ka] 1-[5-Ethylsulfanyl-6-[7-methyl-3-(trifluoromethyl)imidazo[4,5-c]pyridazin-6-yl]-3-pyridyl]cyclopropanecarbonitrile (120 mg, 0.2967 mmol) was dissolved in methanol (6 mL). Ammonium carbamate (46 mg, 0.5935 mmol) and (diacetoxyiodo)benzene (243 mg, 0.7418 mmol) were then added at room temperature. After a few minutes the resulting suspension became a solution and was stirred at room temperature for 2 hours. The reaction mixture was quenched with water (20 ml) and extracted with dichloromethane (3×20 ml). The combined organic layers were washed with brine (30 ml), dried over anhydrous sodium sulfate, filtered and concentrated in vacuo. The residue was purified by chromatography on silica gel with methanol and dichloromethane to give 1-[5-(ethylsulfonimidoyl)-6-[7-methyl-3-(trifluoromethyl)imidazo[4,5-c]pyridazin-6-yl]-3-pyridyl]cyclopropanecarbonitrile. LCMS (Method 2): Retention time: 0.85 min, 436.36 (M+H) + . 1H NMR(400MHz,chloroform-d)d ppm 1.14-1.32(m,3H)1.25-1.32(m,2H)1.37-1.44(m,3H)1.67-1.77(m,2H)2.03-2.12(m,1H)2.06-2.10(m,1H)2.11(br dd,J=3.48,2.38Hz,1H)2.68-2.84(m,1H)3.71-3.81(m,1H)3.84-3.94(m,1H )4.00-4.14(m,3H)8.18(s,1H)8.36(d,J=2.20Hz,1H)9.04(d,J=2.20Hz,1H)

[0250] Example H2. Preparation of 1-[5-(ethylsulfonimidoyl)-6-[3-methyl-6-(trifluoromethyl)imidazo[4,5-b]pyridin-2-yl]-3-pyridyl]cyclopropanecarbonitrile (Example P6, Table P) [ka] Step 1: Preparation of 5-(1-cyanocyclopropyl)-3-ethylsulfanyl-N-[2-(methylamino)-5-(trifluoromethyl)-3-pyridyl]pyridine-2-carboxamide [ka] 5-(1-Cyanocyclopropyl)-3-ethylsulfanyl-pyridine-2-carboxylic acid (2.4 g, 9.7 mmol) was dissolved in dichloromethane (100 mL). N,N-Dimethylformamide (10.0 μL) was added, followed by dropwise addition of oxalyl dichloride (1 mL, 12 mmol) via syringe. The resulting yellowish suspension was stirred at room temperature for 1 h, then the solvent was concentrated in vacuum. The resulting solid was dissolved in tetrahydrofuran (30 ml) and added to a solution of N2-methyl-5-(trifluoromethyl)pyridine-2,3-diamine (1.8 g, 9.7 mmol) and N,N-diethylethanamine (3.3 mL, 23 mmol) in tetrahydrofuran (75 mL) at 0° C. The resulting mixture was stirred at 0° C. for 30 min and then at room temperature for 2 h. The reaction mixture was treated with saturated NH4Cl solution and diluted with ethyl acetate. The aqueous layer was extracted three times with ethyl acetate. The combined organic layers were washed with brine, dried over Na2SO4, filtered and concentrated in vacuo to give 5-(1-cyanocyclopropyl)-3-ethylsulfanyl-N-[2-(methylamino)-5-(trifluoromethyl)-3-pyridyl]pyridine-2-carboxamide, which was used crude in the next step without further purification. LCMS (Method 1): 422 (M+H) + ;Retention time: 1.03 minutes. 1H NMR(400MHz,chloroform-d)δppm 1.48(t,J=7.34Hz,3H)1.58-1.63(m,2H)1.93-1.99(m,2H)3.01(q,J=7.34Hz,2H)3.09(d,J=4.77Hz,3H)5.02(br d,J=4.03Hz,1H)7.71(d,J=2.20Hz,1H)7.94(d,J=2.20Hz,1H)8.16(d,J=2.20Hz,1H)8.36(d,J=0.73Hz,1H)9.53-9.60(m,1H).

[0251] Step 2: Preparation of 1-[5-ethylsulfanyl-6-[3-methyl-6-(trifluoromethyl)imidazo[4,5-b]pyridin-2-yl]-3-pyridyl]cyclopropanecarbonitrile [ka] 5-(1-Cyanocyclopropyl)-3-ethylsulfanyl-N-[2-(methylamino)-5-(trifluoromethyl)-3-pyridyl]pyridine-2-carboxamide (4.2 g, 10 mmol) was dissolved in acetic acid (100 mL) and the resulting solution was stirred for 18 hours at 110° C. The acetic acid was removed in vacuo and the crude product was purified by chromatography on silica gel to give 1-[5-ethylsulfanyl-6-[3-methyl-6-(trifluoromethyl)imidazo[4,5-b]pyridin-2-yl]-3-pyridyl]cyclopropanecarbonitrile (Mp 142-144° C.). LCMS (Method 1): 404 (M+H) + ;Retention time: 1.07 minutes. 1H NMR (400MHz, chloroform-d) δppm 1.40(t,J=7.34Hz,3H)1.59-1.64(m,2H)1.90-1.97(m,2H)3.03(q,J=7.46Hz,2H)4.07(s, 3H)7.77(d,J=2.20Hz,1H)8.35(d,J=2.20Hz,1H)8.42(d,J=1.47Hz,1H)8.73-8.78(m,1H).

[0252] Step 3: Preparation of 1-[5-(ethylsulfonimidoyl)-6-[3-methyl-6-(trifluoromethyl)imidazo[4,5-b]pyridin-2-yl]-3-pyridyl]cyclopropanecarbonitrile (Example P6, Table P) [ka] Sulfoximine formation as in Example H1, Step 7. LCMS (Method 1): 435 (M+H) +;Retention time: 0.87 min. 1 H NMR (400MHz, chloroform) δppm 1.44(t,J=7.34Hz,3H)1.75-1.80(m,2H)2.02-2.08(m,2H)3.94(s,3H)3.94-4.26(m,2H )8.33(d,J=1.47Hz,1H)8.39(d,J=2.20Hz,1H)8.79(d,J=1.47Hz,1H)9.06-9.09(m,1H).

[0253] Example H3: Preparation of 1-[5-(ethylsulfonimidoyl)-6-[5-methoxy-3-methyl-4-oxo-6-(trifluoromethyl)imidazo[4,5-c]pyridin-2-yl]-3-pyridyl]cyclopropanecarbonitrile (Example P8, Table P) [ka] Step 1: Preparation of N-[4-bromo-6-(difluoromethyl)-1-methoxy-2-oxo-3-pyridyl]-2,2,2-trifluoro-N-methyl-acetamide [ka] To a solution of 4-bromo-1-methoxy-3-(methylamino)-6-(trifluoromethyl)pyridin-2-one (5.0 g, 16.61 mmol) in dichloromethane (100 mL) was added trifluoroacetic anhydride (7.09 mL, 49.82 mmol) at room temperature. The reaction mixture was stirred at room temperature for 30 minutes and then concentrated in vacuum. Water (100 mL) was added followed by saturated aqueous potassium carbonate (50 mL) and the aqueous layer was extracted with ethyl acetate (100 mL). The organic layer was washed with brine (100 mL), dried over sodium sulfate, filtered and concentrated in vacuum. The crude product was purified on silica gel to give pure N-[4-bromo-6-(difluoromethyl)-1-methoxy-2-oxo-3-pyridyl]-2,2,2-trifluoro-N-methyl-acetamide. This material was used in the next step without further purification. LCMS (Method 5): 397 / 399 (M+H) +, retention time 0.96 min. 1 H NMR (400MHz, CDCl3) δppm 3.27 (s, 3H), 4.16 (s, 3H), 6.84 (s, 1H).

[0254] Step 2: Preparation of N-[4-azido-1-methoxy-2-oxo-6-(trifluoromethyl)-3-pyridyl]-2,2,2-trifluoro-N-methyl-acetamide [ka] To a solution of N-[4-bromo-1-methoxy-2-oxo-6-(trifluoromethyl)-3-pyridyl]-2,2,2-trifluoro-N-methyl-acetamide (11.8 g, 29.7 mmol) in N,N-dimethylformamide (110 mL) was added sodium azide (2.9 g, 44.6 mmol) at room temperature. The reaction mixture was stirred at room temperature overnight. The above reactions were carried out separately in duplicate, then the combined reaction mixture was diluted with cold water (500 mL) and extracted with ethyl acetate (3×150 mL). The combined organic layers were washed with water (100 mL) and brine, dried over sodium sulfate, filtered, and concentrated in vacuo below 40° C. to give N-[4-azido-1-methoxy-2-oxo-6-(trifluoromethyl)-3-pyridyl]-2,2,2-trifluoro-N-methyl-acetamide. This material was used in the next step without further purification. LCMS (Method 5): 360 (M+H) + , retention time 0.90 min. 1 H NMR (400MHz, CDCl3) δppm 3.23 (s, 3H), 4.15 (s, 3H), 6.40 (s, 1H).

[0255] Step 3: Preparation of 4-azido-1-methoxy-3-(methylamino)-6-(trifluoromethyl)pyridin-2-one [ka] To a solution of N-[4-azido-1-methoxy-2-oxo-6-(trifluoromethyl)-3-pyridyl]-2,2,2-trifluoro-N-methyl-acetamide (4.6 g, 13.0 mmol) in methanol (100 mL) was added potassium carbonate (4.7 g, 33.0 mmol). The reaction mixture was stirred at room temperature overnight and then diluted with water (150 mL). The aqueous layer was extracted with ethyl acetate (2×75 mL) and the combined organic layers were washed with brine (150 mL), dried over sodium sulfate, filtered, and concentrated in vacuo. The crude product was purified on silica gel (40% ethyl acetate in cyclohexane) to give 4-azido-1-methoxy-3-(methylamino)-6-(trifluoromethyl)pyridin-2-one (2.2 g, 8.4 mmol). LCMS (Method E): 264 (M+H) + , retention time 0.94 min. 1 H NMR (400MHz, CDCl3) δppm 3.18 (s, 3H), 4.11 (s, 3H), 6.46 (s, 1H).

[0256] Step 4: Preparation of 4-amino-1-methoxy-3-(methylamino)-6-(trifluoromethyl)pyridin-2-one [ka] To a solution of 4-azido-1-methoxy-3-(methylamino)-6-(trifluoromethyl)pyridin-2-one (1.7 g, 6.5 mmol) in tetrahydrofuran (50 mL) and water (5 mL) at room temperature was added triphenylphosphine (5.1 g, 19 mmol) and the resulting mixture was stirred at room temperature for 2 h. 2M aqueous hydrochloric acid (9 mL, 18 mmol, 2 mol / L) was added and stirring was continued at room temperature overnight. The reaction mixture was concentrated and quenched with saturated aqueous potassium carbonate (20 mL). The aqueous layer was extracted with ethyl acetate (2×75 mL) and the combined organic layers were washed with brine (100 mL), dried over sodium sulfate, filtered and concentrated in vacuo. The residue was purified on silica gel (50-60% ethyl acetate in cyclohexane) to give 4-amino-1-methoxy-3-(methylamino)-6-(trifluoromethyl)pyridin-2-one. LCMS (Method 5): 238 (M+H) + , retention time 0.18 min. 1 H NMR (400MHz, d6-DMSO) δppm 2.60 (s, 3H), 3.98 (s, 3H), 5.75 (s, 2H), 6.42 (s, 1H).

[0257] Step 5: Preparation of 5-(1-cyanocyclopropyl)-3-ethylsulfanyl-N-[1-methoxy-3-(methylamino)-2-oxo-6-(trifluoromethyl)-4-pyridyl]pyridine-2-carboxamide and N-[4-amino-1-methoxy-2-oxo-6-(trifluoromethyl)-3-pyridyl]-5-(1-cyanocyclopropyl)-3-ethylsulfanyl-N-methyl-pyridine-2-carboxamide (mixture of isomers) [ka] To a suspension of 5-(1-cyanocyclopropyl)-3-ethylsulfanyl-pyridine-2-carboxylic acid (400 mg, 1.61 mmol) in dichloromethane (16 mL) was added catalytic amounts of N,N-dimethylformamide (2 drops) and oxalyl chloride (3.22 mmol, 0.287 mL). The reaction was stirred at room temperature for 6 hours and the solvent was removed in vacuo to give 5-(1-cyanocyclopropyl)-3-ethylsulfanyl-pyridine-2-carbonyl chloride.

[0258] A solution of the above 5-(1-cyanocyclopropyl)-3-ethylsulfanyl-pyridine-2-carbonyl chloride (428 mg, 1.60 mmol) in dry tetrahydrofuran (20 mL) was slowly added to a mixture of 4-amino-1-methoxy-3-(methylamino)-6-(trifluoromethyl)pyridin-2-one (456.6 mg, 1.92 mmol) and triethylamine (0.678 mL, 4.81 mmol) in tetrahydrofuran (9.6 mL). The reaction mixture was stirred at room temperature for 2 hours, then quenched with water and extracted with dichloromethane (100 ml). The combined organic layers were washed with water and brine, dried over anhydrous sodium sulfate, and concentrated in vacuo to give the desired isomeric mixture of 5-(1-cyanocyclopropyl)-3-ethylsulfanyl-N-[1-methoxy-3-(methylamino)-2-oxo-6-(trifluoromethyl)-4-pyridyl]pyridine-2-carboxamide and N-[4-amino-1-methoxy-2-oxo-6-(trifluoromethyl)-3-pyridyl]-5-(1-cyanocyclopropyl)-3-ethylsulfanyl-N-methyl-pyridine-2-carboxamide (750 mg, 1.60 mmol). This material was used in the next step without further purification. LCMS (Method 5): 468 (M+H) + , retention time 0.86 min.

[0259] Step 6: Preparation of 1-[5-ethylsulfanyl-6-[5-methoxy-3-methyl-4-oxo-6-(trifluoromethyl)imidazo[4,5-c]pyridin-2-yl]-3-pyridyl]cyclopropanecarbonitrile [ka] A solution of the above isomeric mixture of 5-(1-cyanocyclopropyl)-3-ethylsulfanyl-N-[1-methoxy-3-(methylamino)-2-oxo-6-(trifluoromethyl)-4-pyridyl]pyridine-2-carboxamide and N-[4-amino-1-methoxy-2-oxo-6-(trifluoromethyl)-3-pyridyl]-5-(1-cyanocyclopropyl)-3-ethylsulfanyl-N-methyl-pyridine-2-carboxamide (750 mg, 1.60 mmol) in acetic acid (4.8 mL) was heated to 100° C. for 48 hours. After cooling to room temperature, the reaction mixture was concentrated in vacuum. The residue was poured into water and extracted with ethyl acetate (3×100 mL), and the combined organic layers were washed with brine, dried over sodium sulfate, and concentrated in vacuum. The crude product was purified by chromatography on silica gel (40% ethyl acetate in cyclohexane) to give the desired product 1-[5-ethylsulfanyl-6-[5-methoxy-3-methyl-4-oxo-6-(trifluoromethyl)imidazo[4,5-c]pyridin-2-yl]-3-pyridyl]cyclopropanecarbonitrile (350 mg) as a solid. LCMS (Method E): 450 (M+H). + , retention time 1.03 min. 1 H NMR(400MHz,CDCl3)δppm 1.37(t,3H),1.59(m,2H),1.93(m,2H),3.01(q,2H),4.20(s,3H),4.21(s,3H),7.25(s,1H),7.76(d,J=2.0Hz,1H),8.32(d,J=2.0Hz,1H).

[0260] Step 7: Preparation of 1-[5-(ethylsulfonimidoyl)-6-[5-methoxy-3-methyl-4-oxo-6-(trifluoromethyl)imidazo[4,5-c]pyridin-2-yl]-3-pyridyl]cyclopropanecarbonitrile (Example P8, Table P) [ka] Sulfoximine formation as in Example H1, Step 7. LCMS (Method 5): 481 (M+H) + ;Retention time: 0.85 minutes. 1H NMR(400MHz,DMSO-d6)δppm 1.14(t,J=7.40Hz,3H)1.83-1.94(m,2H)1.97-2.06(m,2H)3.44-3.66(m,2H)3.86(s, 3H)4.12(s,3H)4.56(s,1H)7.41(s,1H)8.38(d,J=2.20Hz,1H)8.90(d,J=2.20Hz,1H).

[0261] Example H4: Preparation of 1-[3-(ethylsulfonimidoyl)-4-[3-methyl-6-(trifluoromethylsulfanyl)imidazo[4,5-c]pyridin-2-yl]phenyl]cyclopropanecarbonitrile (Example P9, Table P) [ka] Step 1: Preparation of N-[4-amino-6-(trifluoromethylsulfanyl)-3-pyridyl]-4-bromo-2-ethylsulfanyl-N-methyl-benzamide [ka] Under an argon atmosphere, 4-bromo-2-ethylsulfanyl-benzoic acid (prepared as described in WO 2016 / 120182 (1.96 g, 7.51 mmol)) was suspended in dichloromethane (30 mL) and 2 drops of DMF were added. Oxalyl dichloride (1.24 g, 0.851 mL, 9.76 mmol) was added dropwise and gas evolution was observed. The mixture was stirred at room temperature for 4 hours and then concentrated in vacuo to give 4-bromo-2-ethylsulfanyl-benzoyl chloride as the product of the first step. Under an argon atmosphere, freshly prepared crude 4-bromo-2-ethylsulfanyl-benzoyl chloride (2.07 g, 7.39 mmol) was dissolved in tetrahydrofuran (20 mL) and N3-methyl-6-(trifluoromethylsulfanyl)pyridine-3,4-diamine (1.50 g, 6.72 mmol) prepared as described in WO 2016 / 169886 was added. The resulting mixture was stirred at room temperature overnight and then at 70° C. for 8 hours. After cooling at room temperature, sodium bicarbonate and water were added. The aqueous layer was extracted twice with ethyl acetate. The combined organic layers were dried over sodium sulfate, filtered, and concentrated in vacuo to give a mixture containing N-[4-amino-6-(trifluoromethylsulfanyl)-3-pyridyl]-4-bromo-2-ethylsulfanyl-N-methyl-benzamide. LCMS (Method 1): 450 (M+H) + ;Retention time: 1.14 minutes.

[0262] Step 2: Preparation of 2-(4-bromo-2-ethylsulfanyl-phenyl)-3-methyl-6-(trifluoromethylsulfanyl)imidazo[4,5-c]pyridine [ka] N-[4-amino-6-(trifluoromethylsulfanyl)-3-pyridyl]-4-bromo-2-ethylsulfanyl-N-methyl-benzamide (3.4 g, 5.1 mmol) was dissolved in acetic acid (51 mL). The resulting solution was stirred at 120° C. overnight and then cooled at room temperature. The acetic acid was removed under reduced pressure and the crude product was purified by chromatography on silica gel. The resulting mixture was dissolved in ethyl acetate, washed with bicarbonate, dried over sodium sulfate, filtered and concentrated in vacuum to give 2-(4-bromo-2-ethylsulfanyl-phenyl)-3-methyl-6-(trifluoromethylsulfanyl)imidazo[4,5-c]pyridine. LCMS (Method 1): 450 (M+H) + ;Retention time: 1.14 minutes. 1H NMR (400 MHz, chloroform) δ ppm 1.29 (t, J = 7.34 Hz, 3H) 2.92 (q, J = 7.34 Hz, 2H) 3.79 (s, 3H) 7.32 (d, J = 8.07 Hz, 1H) 7.50 (dd, J = 8.07, 1.83 Hz, 1H) 7.61 (d, J = 1.83 Hz, 1H) 8.15-8.17 (m, 1H) 8.90 (d, J = 1.10 Hz, 1H).

[0263] Step 3: Preparation of 4-[3-ethylsulfanyl-4-[3-methyl-6-(trifluoromethylsulfanyl)imidazo[4,5-c]pyridin-2-yl]phenyl]isoxazole [ka] DMSO (1.11 mL) and water (0.53 mL) were added to a microwave vial under argon atmosphere, and the solution was purged with argon for 5 minutes. Then, 2-(4-bromo-2-ethylsulfanyl-phenyl)-3-methyl-6-(trifluoromethylsulfanyl)imidazo[4,5-c]pyridine (0.2 g, 0.446 mmol), 4-isoxazoleboronic acid pinacol ester (0.104 g, 0.535 mmol) and potassium fluoride (0.077 g, 1.33 mmol) were added. Dichloropalladium; triphenylphosphane (0.0031 g, 0.0044 mmol) were added, and the resulting mixture was purged with argon for 5 minutes, stirred in a microwave system at 90° C. for 40 minutes, cooled at room temperature, and then poured into ice water. The aqueous layer was extracted three times with dichloromethane. The cloudy aqueous layer was then filtered and the resulting solid was dissolved in dichloromethane and added to the organic layer. The combined organic layers were dried over sodium sulfate, filtered and concentrated in vacuum. The resulting oil was washed with water. A precipitate formed in the water was filtered and then redissolved in dichloromethane and the solvent was concentrated in vacuum to give 4-[3-ethylsulfanyl-4-[3-methyl-6-(trifluoromethylsulfanyl)imidazo[4,5-c]pyridin-2-yl]phenyl]isoxazole, which was used directly in the next step. LCMS (Method 1): 437 (M+H) + ;Retention time: 0.95 minutes.

[0264] Step 4: Preparation of 2-[3-ethylsulfanyl-4-[3-methyl-6-(trifluoromethylsulfanyl)imidazo[4,5-c]pyridin-2-yl]phenyl]acetonitrile [ka] 4-[3-Ethylsulfanyl-4-[3-methyl-6-(trifluoromethylsulfanyl)imidazo[4,5-c]pyridin-2-yl]phenyl]isoxazole (236 mg, 0.3785 mmol, 70% by weight) was dissolved in methanol (2 mL) and water (1.14 mL) and potassium fluoride (1.14 mL, 1.135 mmol) was added. The reaction mixture was stirred at 90° C. for 3 hours. The deep red reaction mixture (suspension) was filtered, washed with dichloromethane and concentrated in vacuum. The crude product was purified by chromatography on a silica gel column to give 2-[3-ethylsulfanyl-4-[3-methyl-6-(trifluoromethylsulfanyl)imidazo[4,5-c]pyridin-2-yl]phenyl]acetonitrile. LCMS (Method 1): 409 (M+H) + ;Retention time: 0.98 minutes. 1H NMR (400 MHz, chloroform) δ ppm 1.29 (t, J = 7.34 Hz, 4H) 2.93 (q, J = 7.34 Hz, 2H) 3.80 (s, 3H) 3.89 (s, 2H) 7.34 (dd, J = 7.89, 1.65 Hz, 1H) 7.47-7.48 (m, 1H) 7.48-7.51 (m, 1H) 8.16-8.18 (m, 1H) 8.92 (d, J = 0.73 Hz, 1H).

[0265] Step 5: Preparation of 1-[3-ethylsulfanyl-4-[3-methyl-6-(trifluoromethylsulfanyl)imidazo[4,5-c]pyridin-2-yl]phenyl]cyclopropanecarbonitrile [ka] 1-[3-Ethylsulfanyl-4-[3-methyl-6-(trifluoromethylsulfanyl)imidazo[4,5-c]pyridin-2-yl]phenyl]cyclopropanecarbonitrile (0.108 g, 0.2644 mmol) was dissolved in acetonitrile (1.322 mL). Then, dicesium carbonate (0.2584 g, 0.7931 mmol) and 1,2-dibromoethane (0.1490 g, 0.0683 mL, 0.7931 mmol) were added. The reaction mixture was stirred at 100° C. for 2 hours under a microwave system. The reaction mixture was concentrated in vacuum. The residue was dissolved in ethyl acetate and washed several times with water and brine. The organic layer was dried over sodium sulfate, filtered and concentrated in vacuum. The crude product was purified by chromatography on silica gel to give 1-[3-ethylsulfanyl-4-[3-methyl-6-(trifluoromethylsulfanyl)imidazo[4,5-c]pyridin-2-yl]phenyl]cyclopropanecarbonitrile. LCMS (Method 1): 435 (M+H) + ;Retention time: 1.04 minutes. 1 H NMR(400MHz,chloroform)δppm 1.28(t,J=7.34Hz,4H)1.55(br d,J=2.20Hz,2H)1.86-1.91(m,2H)2.93(q,J=7.58Hz,2H)3.79(s,3H)7.17(dd,J=7.89,2.02H z,1H)7.44-7.47(m,1H)7.52(d,J=1.83Hz,1H)8.16(d,J=0.73Hz,1H)8.91(d,J=0.73Hz,1H).

[0266] Step 6: Synthesis of 1-[3-(ethylsulfonimidoyl)-4-[3-methyl-6-(trifluoromethylsulfanyl)imidazo[4,5-c]pyridin-2-yl]phenyl]cyclopropanecarbonitrile (Example P9, Table P) [ka] Sulfoximine formation was carried out as described in Example H1, step 7. LCMS (Method 1): 466 (M+H)+ ;Retention time: 0.86 minutes.

[0267] Example H5: Synthesis of 1-[3-(ethylsulfonimidoyl)-4-[3-methyl-6-(trifluoromethyl)imidazo[4,5-c]pyridin-2-yl]phenyl]cyclopropanecarbonitrile (Example P13, Table P) [ka] Step 1: Preparation of 1-[3-ethylsulfanyl-4-[3-methyl-6-(trifluoromethyl)imidazo[4,5-c]pyridin-2-yl]phenyl]cyclopropanecarbonitrile [ka] To a mixture of 2-(4-bromo-2-ethylsulfanyl-phenyl)-3-methyl-6-(trifluoromethyl)imidazo[4,5-c]pyridine (0.5 g, 1.201 mmol), Pd2dba3 (0.056 g, 0.060 mmol) and BINAP (0.077 g, 0.120 mmol) in tetrahydrofuran (1.2 mL) was added cyclopropanecarbonitrile (0.090 g, 1.32 mmol) and cyclopropyl methyl ether (1.20 mL) at room temperature under an argon atmosphere. The mixture was cooled to -25 °C and lithium bis(trimethylsilyl)amide (1.3 mL, 1.321 mmol) was added dropwise at -25 °C under an argon atmosphere. The mixture was stirred at 80 °C for 2 h. After cooling at room temperature, the mixture was filtered through a pad of Celite, which was washed with ethyl acetate. The filtrate was washed with water. The aqueous layer was separated and extracted twice with ethyl acetate. The organic layers were combined, dried over anhydrous sodium sulfate, filtered, and concentrated in vacuo. The crude product was purified by chromatography on silica gel to give 1-[3-ethylsulfanyl-4-[3-methyl-6-(trifluoromethyl)imidazo[4,5-c]pyridin-2-yl]phenyl]cyclopropanecarbonitrile. LCMS (Method 1): 403 (M+H) +;Retention time: 1.00 min. 1H NMR (400MHz, chloroform) δppm 1.27(t,J=7.34Hz,3H)1.52-1.57(m,2H)1.86-1.91(m,2H)2.91(q,J=7.46Hz,2H)3.82(s,3H)7.18(dd ,J=8.07,1.83Hz,1H)7.46(d,J=8.07Hz,1H)7.52(d,J=1.83Hz,1H)8.14(d,J=0.73Hz,1H)8.95(s,1H).

[0268] Step 2: Synthesis of 1-[3-(ethylsulfonimidoyl)-4-[3-methyl-6-(trifluoromethyl)imidazo[4,5-c]pyridin-2-yl]phenyl]cyclopropanecarbonitrile (Example P13, Table P) [ka] The desired product was prepared using the standard procedure described in Step 7, Example H1. LCMS (Method 1): 434 (M+H) + ;Retention time: 0.83 minutes. 1H NMR (400MHz, chloroform) δppm 1.28(t,J=7.34Hz,3H)1.63-1.68(m,2H)1.96-2.01(m,2H)3.42-3.62(m,2H)3.75(s,3H)7.56(d,J=8.0 7Hz,1H)7.89(dd,J=7.89,2.02Hz,1H)8.05(d,J=1.83Hz,1H)8.10(d,J=0.73Hz,1H)8.93-8.96(m,1H).

[0269] Example H5: Synthesis of 1-[3-(ethylsulfonimidoyl)-4-[3-methyl-6-(trifluoromethyl)imidazo[4,5-b]pyridin-2-yl]phenyl]cyclopropanecarbonitrile (Example P15, Table P) [ka] Step 1: Synthesis of methyl 2-ethylsulfanyl-4-isoxazol-4-yl-benzoate [ka] To a solution of methyl 4-bromo-2-ethylsulfanyl-benzoate (WO 2016 / 023954) (250 mg, 0.91 mmol) in dimethylsulfoxide (8 mL) under argon atmosphere was added water (4 mL), 4-isoxazoleboronic acid pinacol ester (213 mg, 1.09 mmol) and potassium fluoride (158 mg, 2.73 mmol). The thick reaction mixture was purged with argon for 5 min, then bis(triphenylphosphine)palladium(II) dichloride (6.4 mg, 0.009 mmol) was added. The vial was sealed and the mixture was stirred in a microwave at 90° C. for 40 min. The reaction mixture was poured into ice water and the resulting yellowish suspension was filtered and washed with cold water. The solid was dissolved in dichloromethane and the solution was dried over sodium sulfate and reduced to dryness under reduced pressure to give methyl 2-ethylsulfanyl-4-isoxazol-4-yl-benzoate as a yellowish solid which was used in the next step without further purification. LCMS (Method 1): 262 (MH) - , retention time 0.88 min.

[0270] Step 2: Synthesis of methyl 4-(cyanomethyl)-2-ethylsulfanyl-benzoate [ka] To a solution of methyl 2-ethylsulfanyl-4-isoxazol-4-yl-benzoate (760 mg, 2.89 mmol) in methanol (15 mL) was added 1 M potassium fluoride solution in water (8.66 mL, 8.66 mmol). The reaction mixture was stirred at reflux for 3 h. After cooling, the suspension was filtered and the filtrate was concentrated in vacuo. The residue was purified by Combiflash on silica gel to give methyl 4-(cyano-methyl)-2-ethylsulfanyl-benzoate as a gum. LCMS (Method 5): 236 (M+H) + , retention time 0.90 min. 1 H NMR (400MHz, CDCl3) δppm 1.42(t,3H),2.99(q,2H),3.80(s,2H),3.93(s,3H),7.10(dd,1H),7.28(d,1H),7.99(d,1H).

[0271] Step 3: Synthesis of methyl 4-(1-cyanocyclopropyl)-2-ethylsulfanyl-benzoate [ka] To a solution of methyl 4-(cyano-methyl)-2-ethylsulfanyl-benzoate (300 mg, 1.275 mmol) in acetonitrile (15 mL) was added cesium carbonate (1.24 g, 3.825 mmol) and 1,2-dibromoethane (719 mg, 3.825 mmol). The reaction mixture was stirred at reflux for 90 min. After cooling, the suspension was filtered and the filtrate was concentrated in vacuo. The residue was purified by Combiflash on silica gel to give methyl 4-(cyano-methyl)-2-ethylsulfanyl-benzoate as an oil. LCMS (Method 1): 262 (M+H) + , retention time 0.98 min. 1 H NMR (400MHz, CDCl3) δppm 1.43(t,3H),1.48(m,2H),1.82(m,2H),3.01(q,2H),3.92(s,3H),6.88(dd,1H),7.35(d,1H),7.94(d,1H).

[0272] Step 4: Synthesis of 4-(1-cyanocyclopropyl)-2-ethylsulfanyl-benzoic acid [ka] To a solution of methyl 4-(1-cyanocyclopropyl)-2-ethylsulfanyl-benzoate (198 mg, 0.758 mmol) in a mixture of tetrahydrofuran (9 mL) and water (3 mL) at 0-5° C. was added lithium hydroxide (1.5 equiv., 1.137 mmol) and the reaction mixture was stirred at room temperature overnight. The solution was concentrated in vacuo and the residue was diluted with t-butyl methyl ether (10 mL) and acidified with 1 M aqueous hydrochloric acid (10 mL). The organic layer was separated, the aqueous layer was extracted with t-butyl methyl ether, and the combined organic layers were washed with water and brine, dried over sodium sulfate, filtered, and concentrated in vacuo to give 4-(1-cyanocyclopropyl)-2-ethylsulfanyl-benzoate as a solid. This material was used in the next step without further purification. LCMS (Method 5): 246 (MH) - , retention time 0.83 min. 1 H NMR (400MHz, CDCl3) δppm 1.44(t,3H),1.51(m,2H),1.85(m,2H),3.03(q,2H),6.90(dd,1H),7.41(d,1H),8.10(d,1H).

[0273] Step 5. Preparation of 1-[3-ethylsulfanyl-4-[3-methyl-6-(trifluoromethyl)imidazo[4,5-b]pyridin-2-yl]phenyl]cyclopropanecarbonitrile [ka] 4-(1-Cyanocyclopropyl)-2-ethylsulfanyl-benzoic acid (1.7 g, 6.9 mmol) was dissolved in nitrobenzene (14 mL) and N2-methyl-5-(trifluoromethyl)pyridine-2,3-diamine (WO2017 / 043342) (1.6 g, 1.2 eq.) was added followed by slow addition of phosphoryl chloride (1.6 mL, 17 mmol) at room temperature. The resulting solution was heated at 120° C. for 7 h and monitored by TLC and LC-MS. The reaction mass was quenched with 30% sodium hydroxide solution and water (100 mL) was added. The aqueous layer was extracted with ethyl acetate (3×100 ml). The combined organic layers were dried over sodium sulfate, filtered and concentrated in vacuum. The crude product was purified by chromatography to give 1-[3-ethylsulfanyl-4-[3-methyl-6-(trifluoromethyl)imidazo[4,5-b]pyridin-2-yl]phenyl]cyclopropanecarbonitrile. LCMS (Method 2): 403 (M+H) + ;Retention time: 1.18 minutes. 1H NMR(400MHz,chloroform-d)d ppm 1.26(t,J=7.34Hz,3H)1.44-1.61(m,2H)1.80-1.92(m,2H)2.91(q,J=7.42Hz,2H)3.78(s,3 H)7.16(dd,J=8.01,1.77Hz,1H)7.44(d,J=7.60Hz,1H)7.50(s,1H)8.33(s,1H)8.72(s,1H).

[0274] Step 6: Preparation of 1-[3-(ethylsulfonimidoyl)-4-[3-methyl-6-(trifluoromethyl)imidazo[4,5-b]pyridin-2-yl]phenyl]cyclopropanecarbonitrile (Example P15, Table P) [ka] The desired product was prepared using the standard procedure described in Example H1, step 7. LCMS (Method 1): 434 (M+H) + ;Retention time: 0.88 minutes. 1H NMR (400MHz, chloroform) δppm 1.28(t,J=7.34Hz,4H)1.63-1.68(m,2H)1.96-2.01(m,2H)3.41-3.62(m,2H)3.75(s,3H)7.56(d,J=8.0 7Hz,1H)7.89(dd,J=7.89,2.02Hz,1H)8.05(d,J=1.83Hz,1H)8.10(d,J=0.73Hz,1H)8.94-8.97(m,1H).

[0275] Example H6: [5-Cyclopropyl-2-[7-(trifluoromethyl)imidazo[1,2-b]pyridazin-2-yl]-3-pyridyl]-ethyl-imino-oxo-λ 6 -Synthesis of sulfane (Example P16, Table P). [ka] Step 1. Preparation of 2-bromo-1-(5-bromo-3-ethylsulfanyl-2-pyridyl)ethanone [ka] A sample of 1-(5-bromo-3-ethylsulfanyl-2-pyridyl)ethanone (prepared as described in WO 2016 / 071214) (1 g, 3.8439 mmol) was suspended in acetonitrile (3 mL) and chloroform (3 mL). Dibromocopper (1.7171 g, 7.6879 mmol) was added and the reaction mixture was heated to 70° C. and stirred for 22 hours, after which LC-MS showed the reaction to be complete. The reaction mixture was filtered through Celite with dichloromethane. The filtrate was concentrated in vacuo and the resulting residue was purified by chromatography on silica gel to give 2-bromo-1-(5-bromo-3-ethylsulfanyl-2-pyridyl)ethanone. LCMS (Method 1): Retention time 1.10 minutes; 339 / 341 (M+H) + . 1H NMR(400MHz,DMSO)δppm 1.28(t,J=7.34Hz,3H)3.06(q,J=7.34Hz,2H)4.93(s,2H)8.11(d,J=1.83Hz,1H)8.58-8.60(m,1H).

[0276] Step 2: Preparation of 2-(5-bromo-3-ethylsulfanyl-2-pyridyl)-7-(trifluoromethyl)imidazo[1,2-b]pyridazine [ka] In a three-neck flask equipped with a reflux condenser, 2-bromo-1-(5-bromo-3-ethylsulfanyl-2-pyridyl)ethanone (0.50 g, 1.5 mmol) and 5-(trifluoromethyl)pyridazin-3-amine (CAS [1211591-88-6]) (0.27 g, 1.5 mmol) were suspended in acetonitrile (11 mL) and magnesium oxide (0.12 g, 2.9 mmol) was added. The resulting mixture was heated to 90° C. and stirred overnight. The reaction mixture was filtered and the filtrate was concentrated in vacuum. The resulting solid was dissolved in ethyl acetate and washed once with saturated NaHCO3 solution. The organic layer was pre-dried with brine, dried over sodium sulfate, filtered and concentrated in vacuum. The crude product was purified by chromatography on silica gel to give 2-(5-bromo-3-ethylsulfanyl-2-pyridyl)-7-(trifluoromethyl)imidazo[1,2-b]pyridazine. LCMS (Method 1): Retention time 1.15 minutes; 403 / 405 (M+H) + . 1H NMR (400 MHz, chloroform) δ ppm 1.44 (t, J = 7.34 Hz, 3H) 3.04 (q, J = 7.34 Hz, 2H) 7.82 (d, J = 1.83 Hz, 1H) 8.33-8.39 (m, 1H) 8.57 (dd, J = 3.85, 2.02 Hz, 2H) 8.81-8.86 (m, 1H).

[0277] Step 3: Preparation of 2-(5-cyclopropyl-3-ethylsulfanyl-2-pyridyl)-7-(trifluoromethyl)imidazo[1,2-b]pyridazine [ka] A 100 ml three-neck flask was charged with toluene (14 mL) and water (0.69 mL) and flushed with argon for 5 minutes. Under argon atmosphere, 2-(5-bromo-3-ethylsulfanyl-2-pyridyl)-7-(trifluoromethyl)imidazo[1,2-b]pyridazine (0.30 g, 0.74 mmol), cyclopropylboronic acid (0.087 g, 0.97 mmol), tripotassium phosphate (0.58 g, 2.6 mmol), tricyclohexylphosphane (0.022 g, 0.074 mmol) and palladium(II) acetate (0.0084 g, 0.050 equiv, 0.037 mmol) were added. The brown reaction mixture was heated below 110° C. and stirred overnight. The mixture was then cooled to room temperature and water and ethyl acetate were added. The resulting mixture was filtered through Celite and the Celite cake was washed with ethyl acetate. The organic layer was separated, dried over sodium sulfate, filtered, and concentrated under reduced pressure. The crude product was purified by chromatography on silica gel to give 2-(5-cyclopropyl-3-ethylsulfanyl-2-pyridyl)-7-(trifluoromethyl)imidazo[1,2-b]pyridazine. LCMS (Method 1): Retention time 1.08 minutes; 365 (M+H) + . 1H NMR (400 MHz, chloroform) δ ppm 0.81-0.86 (m, 2H) 1.09-1.16 (m, 2H) 1.39 (t, J = 7.34 Hz, 3H) 1.94-2.03 (m, 1H) 3.00 (q, J = 7.34 Hz, 2H) 7.36-7.39 (m, 1H) 8.33 (d, J = 1.83 Hz, 1H) 8.33 (s, 1H) 8.54 (d, J = 2.20 Hz, 1H) 8.83-8.86 (m, 1H).

[0278] Step 4: [5-Cyclopropyl-2-[7-(trifluoromethyl)imidazo[1,2-b]pyridazin-2-yl]-3-pyridyl]-ethyl-imino-oxo-λ 6 - Preparation of sulfane ((Example P16, Table P)). [ka] 2-(5-Cyclopropyl-3-ethylsulfanyl-2-pyridyl)-7-(trifluoromethyl)imidazo[1,2-b]pyridazine (0.07 g, 0.1921 mmol) was suspended in methanol (0.5763 mL) and PhI(OAc)2 (0.1894 g, 0.5763 mmol) and ammonium carbamate (0.03826 g, 0.4802 mmol) were added at room temperature. The reaction was stirred at room temperature and after 45 minutes it was quenched with ice water and sodium thiosulfate. The aqueous layer was extracted twice with ethyl acetate. The organic layers were combined, washed with brine, dried over anhydrous sodium sulfate, filtered and concentrated. The crude product was purified by chromatography on silica gel to give [5-cyclopropyl-2-[7-(trifluoromethyl)imidazo[1,2-b]pyridazin-2-yl]-3-pyridyl]-ethyl-imino-oxo-λ 6 -Sulfane was obtained. LCMS (Method 1): Retention time 0.87 min; 396(M+H) + . 1H NMR (400MHz, chloroform) δppm 0.89-0.95(m,2H)1.18-1.25(m,2H)1.36(t,J=7.52Hz,3H)2.08(tt,J=8.44,5.14Hz,1H)3.21-3.37(br s,1H)3.71-3.98(m,2H)8.19(d,J=2.20Hz,1H)8.26-8.29(m,1H)8.58(d,J=2.20Hz,1H)8.64(d,J=2.20Hz,1H)8.71-8.74(m,1H).

[0279] Example H7: [5-Cyclopropyl-2-[6-(trifluoromethyl)pyrazolo[4,3-c]pyridin-2-yl]-3-pyridyl]-ethyl-imino-oxo-λ 6 Synthesis of sulfane (Example P7, Table P) [ka] Step 1: Preparation of 2,5-dibromo-3-ethylsulfanyl-pyridine [ka] A solution of diethyl disulfide (7.76 g, 63.5 mmol, 2.00 equiv) and t-butyl nitrite (4.91 g, 47.6 mmol, 1.50 equiv) in DCE (60 mL) and DCM (40 mL) was heated to 40° C. To this mixture, a solution of 2,5-dibromopyridin-3-amine (8.00 g, 31.7 mmol, 1.00 equiv) in dichloroethane (200 mL) was added slowly over 90 minutes and the reaction mixture was stirred at 40° C. for an additional hour. After completion of the reaction, the reaction mass was cooled, diluted with water (100 mL) and extracted with dichloromethane (2×100 mL). The organic layer was separated and the combined organic layer was dried over sodium sulfate, filtered and concentrated in reduced pressure. The crude product was purified by column chromatography (silica gel, 5-15% ethyl acetate / cyclohexane) to give 2,5-dibromo-3-ethylsulfanyl-pyridine. LCMS (Method 4): 296 (M+H) + , retention time 1.16 min. 1 H NMR (400MHz, CDCl3) δ / ppm: 1.32 (t, 3H), 2.98 (m, 2H), 7.52 (s, 1H) 8.19 (s, 1H).

[0280] Step 2: Preparation of (5-bromo-3-ethylsulfanyl-2-pyridyl)hydrazine [ka] To a solution of 2,5-dibromo-3-ethylsulfanyl-pyridine (1 g, 3.3669 mmol) in 1,4-dioxane (10.34 g) was added hydrazine monohydrate (1.0113 g, 20.201 mmol) and the resulting mixture was stirred at 120° C. for 10 hours. After the reaction was completed, the mixture was diluted with water (30 ml) and extracted with ethyl acetate. The combined organic layers were washed with water (20 ml), dried over sodium sulfate, filtered and concentrated in vacuo to give (5-bromo-3-ethylsulfanyl-2-pyridyl)hydrazine. LCMS: 250 (M+H) + , retention time 0.6 min. 1H NMR (400 MHz, chloroform-d) d ppm 1.26 (t, 3H) 2.81 (q, 2H) 3.10 (br 2H) 6.67 (br s, 1H) 7.65 (d, 1H) 8.15 (d, 1H).

[0281] Step 3: Preparation of 4-[2-(5-bromo-3-ethylsulfanyl-2-pyridyl)hydrazino]-6-(trifluoromethyl)pyridine-3-carboxylic acid [ka] 4-Chloro-6-(trifluoromethyl)pyridine-3-carboxylic acid (CAS [1060810-66-3]) (20 g, 88.672 mmol), (5-bromo-3-ethylsulfanyl-2-pyridyl)hydrazine (33.005 g, 133.01 mmol) and pentan-1-ol (120 mL) were mixed and the mixture was stirred at 110° C. for 15 hours. After the reaction was complete, the mixture was concentrated in vacuum to remove all the pentanol. The resulting residue was co-evaporated with toluene. The crude product was diluted with water (100 ml), brine (100 ml) and extracted with ethyl acetate (3×200 ml). The combined organic layers were dried over sodium sulfate, filtered and concentrated in vacuum. The resulting solid was triturated with cyclohexane to give 4-[2-(5-bromo-3-ethylsulfanyl-2-pyridyl)hydrazino]-6-(trifluoromethyl)pyridine-3-carboxylic acid. LCMS (Method 5): Retention time 1.50 min, 439 (M+2) + . 1H NMR(400MHz,DMSO-d6)ppm 1.26(t,3H)3.05(q,2H)7.16(s,1H)7.89(d,1H)8.11(d,1H)8.77(s,1H)8.88(s,1H)9.83(s,1H)13.38-14.36(m,1H).

[0282] Step 4: Preparation of 2-(5-bromo-3-ethylsulfanyl-2-pyridyl)-3-chloro-6-(trifluoromethyl)pyrazolo[4,3-c]pyridine [ka] 4-[2-(5-Bromo-3-ethylsulfanyl-2-pyridyl)hydrazino]-6-(trifluoromethyl)pyridine-3-carboxylic acid (22.87 mmol, 10 g) was dissolved in phosphorus oxychloride (100 mL) and the resulting mixture was heated at 110° C. The resulting clear solution was refluxed at 110° C. for 50 minutes. After the reaction was complete, the mixture was concentrated (phosphorus oxychloride was distilled off under reduced pressure) and the reaction was diluted with dichloromethane (110 ml) and poured into ice water (200 mL). The aqueous layer was extracted with dichloromethane (2×100 ml). The combined organic layers were washed with water (200 ml), dried over sodium sulfate, filtered and concentrated in vacuum. The crude product was purified by chromatography on silica gel to give 2-(5-bromo-3-ethylsulfanyl-2-pyridyl)-3-chloro-6-(trifluoromethyl)pyrazolo[4,3-c]pyridine. LCMS: 437 (M+H) + , retention time 1.21 min. 1H NMR (400 MHz, chloroform-d) d ppm 1.34 (m, 3H) 2.85 (m, 2H) 7.92 (S, 2H) 8.02 (m, 1H) 8.60 (m, 1H) 9.32 (m, 1H).

[0283] Step 5: Preparation of 2-(5-bromo-3-ethylsulfanyl-2-pyridyl)-6-(trifluoromethyl)pyrazolo[4,3-c]pyridine [ka] 2-(5-Bromo-3-ethylsulfanyl-2-pyridyl)-3-chloro-6-(trifluoromethyl)pyrazolo[4,3-c]pyridine (0.2mmol, 0.1g) was dissolved in acetic acid (2mL) and zinc (0.5mmol, 0.03g) was added slowly to the mixture. The reaction mass was stirred at 55°C for 40 minutes. The reaction was monitored by LCMS&TLC. After completion, the reaction mixture was poured into water (30ml) and the resulting solution was extracted with ethyl acetate (20ml x 3). The combined organic layer was washed with saturated aqueous sodium chloride solution (30ml), dried over anhydrous sodium sulfate, filtered and concentrated in reduced pressure. The residue was subjected to silica gel column chromatography to obtain 2-(5-Bromo-3-ethylsulfanyl-2-pyridyl)-6-(trifluoromethyl)pyrazolo[4,3-c]pyridine. H NMR (400 MHz, chloroform-d) d ppm 1.29 (m, 4H) 2.95 (m, 2H) 7.85 (m, 1H) 8.35 (m, 1H) 8.38 (d, 1H) 8.95 (m, 1H) 9.44 (m, 1H). LCMS: Retention time 1.6 min, 403 (M+H) + .

[0284] Step 6: Preparation of 2-(5-cyclopropyl-3-ethylsulfanyl-2-pyridyl)-6-(trifluoromethyl)pyrazolo[4,3-c]pyridine [ka] In a microwave vial was added 2-(5-bromo-3-ethylsulfanyl-2-pyridyl)-6-(trifluoromethyl)pyrazolo[4,3-c]pyridine (0.1 g, 0.2 mmol), cyclopropylboronic acid (0.03 g, 0.3 mmol), tripotassium phosphate (0.2 g, 0.9 mmol), tricyclohexylphosphane (0.007 g, 0.02 mmol) in toluene (2 mL) and water (1 mL). The reaction mass was purged with nitrogen for 30 minutes. To this was then added palladium(II) acetate (0.003 g, 0.01 mmol) and the reaction mixture was stirred at 150° C. under microwave for 4 hours. At room temperature the reaction mixture was then diluted with ethyl acetate (20 mL) and washed with water (20 mL). The organic layer was washed with water (20 ml) and the organic layer was dried over sodium sulfate, filtered and concentrated in reduced pressure. The compound was isolated by chromatography on silica gel to give 2-(5-cyclopropyl-3-ethylsulfanyl-2-pyridyl)-6-(trifluoromethyl)pyrazolo[4,3-c]pyridine. LCMS: 365 (M+H) + , retention time 1.12 min. 1H NMR (400 MHz, chloroform-d) d ppm 0.86 (m, 2H) 1.13 (br, 2H) 1.23 (m, 4H) 2.90 (q, 2H) 7.47 (d, 1H) 8.13 (m, 2H) 8.94 (s, 1H) 9.40 (m, 1H).

[0285] Step 7: [5-Cyclopropyl-2-[6-(trifluoromethyl)pyrazolo[4,3-c]pyridin-2-yl]-3-pyridyl]-ethyl-imino-oxo-λ 6 -Synthesis of sulfane Example P7, Table P) [ka] The desired product was prepared using standard methods as described in Example H1, step 7. LCMS (Method 5): Retention time 0.94 min, 396 (M+H) + . 1H NMR (400 MHz, chloroform-d) d ppm 1.25 (m, 4H) 1.44 (m, 3H) 2.16 (m, 1H) 3.87 (m, 2H) 8.06 (s, 1H) 8.29 (d, 1H) 8.56 (d, 1H) 8.87 (d, 1H) 9.40 (s, 1H).

[0286] Example H8: [5-Cyclopropyl-2-[5-(trifluoromethylsulfanyl)-1,3-benzoxazol-2-yl]-3-pyridyl]-ethyl-imino-oxo-λ 6 Synthesis of sulfane (Example P18, Table P) [ka] The desired product was prepared using the standard method described in Example H1, step 7 starting from 2-(5-cyclopropyl-3-ethylsulfanyl-2-pyridyl)-5-(trifluoromethylsulfanyl)-1,3-benzoxazole (known from WO 19 / 009307). LCMS (Method 5): 428 (M+H) + , Retention time: 1.03 min.

[0287] Further compounds of the invention can be prepared similarly to the methods described above. Table P lists compounds that have been prepared to further illustrate the invention.

[0288] [Table 13-1] [Table 13-2] [Table 13-3]

[0289] The activity of the composition according to the present invention can be considerably broadened and adapted to the general situation by adding other insecticidal, acaricidal and / or fungicidal active ingredients.The mixture of the compound of formula I with other insecticidal, acaricidal and / or fungicidal active ingredients can also have further unexpected advantages, which may be described as synergistic activity in a broader sense.For example, it is better tolerated by plants, reduces phytotoxicity, insects can be controlled at different developmental stages, or it behaves better during their preparation, for example during grinding or mixing, during their storage or during their use.

[0290] Suitable additives to the active ingredients herein are, for example, exemplified by the following classes of active ingredients: organophosphorus compounds, nitrophenol derivatives, thioureas, juvenile hormones, formamidines, benzophenone derivatives, urea, pyrrole derivatives, carbamates, pyrethroids, chlorinated hydrocarbons, acylurea, pyridylmethyleneamino derivatives, macrolides, neonicotinoids and Bacillus thuringiensis preparations.

[0291] The following mixtures of 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 Y-1 to Y-8, X-1 to X-8, U-1 to U-2 and V-1 to V-6 and Table P of the present invention"): an adjuvant selected from the group of substances consisting of petroleum (alternative name) (628) + TX, 1,1-Bis(4-chlorophenyl)-2-ethoxyethanol (IUPAC name) (910) + TX, 2,4-dichlorophenylbenzenesulfonate (IUPAC / Chemical Abstracts name) (1059) + TX, 2-fluoro-N-methyl-N-1-naphthylacetamide (IUPAC name) (1295) + TX, 4-chlorophenyl phenyl sulfone (IUPAC name) (981) + TX, abamectin (1) + TX, acequinocyl (3) + TX, Cetoprol [CCN] + TX, Acrinathrin (9) + TX, Aldicarb (16) + TX, Aldoxicarb (863) + TX, α-Cypermethrin (202) + TX, Amidithione (870) + TX, Amidoflumet [CCN] + TX, Amidothioate (872) + TX, Amiton (875) + TX, Amiton hydrogen oxalate (875) + TX, Amitraz (24) + TX, Aramite (881) + TX, Diarsenic trioxide (882) + TX, AVI 382 (compound code) + TX, AZ 60541 (compound code) + TX, azinphos-ethyl (44) + TX, azinphos-methyl (45) + TX, azobenzene (IUPAC name) (888) + TX, azocyclotine (46) + TX, azotoate (889) + TX, benomyl (62) + TX, benoxafos (alternative name) [CCN] + TX, benzoximate (71) + TX, benzyl benzoate (IUPAC name) [CCN] + TX, bifenazate (74) + TX, bifenthrin (76) + TX, binapacryl (907) + TX, brofenvalerate (alternative name) + TX , Bromocyclen (918) + TX, Bromophos (920) + TX, Bromophos-ethyl (921) + TX, Bromopropylate (94) + TX, Buprofezin (99) + TX, Butocarboxim (103) + TX, Butoxycarboxim (104) + TX, Butylpyridaben (alternative name) + TX, Calcium polysulfide (IUPAC name) (111) + TX, Camphechlor (941) + TX, Carbanolate (943) + TX, Carbaryl (115) + TX, Carbofuran (118) + TX, Carbophenothione (947) + TX, CGA 50'439 (development code) (125) + TX, quinomethionate (126) + TX, chlorbeneside (959) + TX, chlordimeform (964) + TX, chlordimeform hydrochloride (964) + TX,Chlorfenapyr (130) + TX, Chlorphenetole (968) + TX, Chlorphenesulfide (971) + TX, Chlorfenvinphos (131) + TX, Chlorobenzilate (975) + TX, Chloromebform (977) + TX, Chloromethiuron (978) + TX, Chloropropylate (983) + TX, Chlorpyrifos (145) + TX, Chlorpyrifos-methyl (146) + TX, Chlorthiophos (994) + TX, Cineline I (696) + TX, Cineline II (696) + TX, Cineline (69 6) + TX, Clofentezine (158) + TX, Closantel (alternative name) [CCN] + TX, Coumaphos (174) + TX, Crotamiton (alternative name) [CCN] + TX, Crotoxyphos (1010) + TX, Kufuraneb (1013) + TX, Cyanthoate (1020) + TX, Cyflumetofen (CAS registration number: 400882-07-7) + TX, Cyhalothrin (196) + TX, Cyhexatin (199) + TX, Cypermethrin (201) + TX, DCPM (1032) + TX, DDT (219) + TX, Demefion (1037) + TX, Demef Ion-O (1037) + TX, Demefion-S (1037) + TX, Demeton (1038) + TX, Demeton-Methyl (224) + TX, Demeton-O (1038) + TX, Demeton-O-Methyl (224) + TX, Demeton-S (1038) + TX, Demeton-S-Methyl (224) + TX, Demeton-S-Methyl Sulfone (1039) + TX, Diafenthiuron (226) + TX, Dimpropyridaz + TX, Diarifos (1042) + TX, Diazinon (227) + TX, Dichlofluanid (230) + TX, Dichlorvos (236) + TX, Dicrifos (alternative name) + TX, Dicofol (242) + TX, Dicrotophos (243) + TX, Dienochlor (1071) + TX, Dimefox (1081) + TX, Dimethoate (262) + TX, Dinactin (alternative name) (653) + TX, Zinex (1089) + TX, Zinex-Diclexin (1089) + TX, Zinobuton (269) + TX, Dinocap (270) + TX, Dinocap-4 [CCN] + TX, Dinocap-6 [CCN] + TX, Dinokton (1090) + TX, Dinopenton (1092) + TX, Dinosulfone (1097) + TX,Dinotervone (1098) + TX, Dioxathione (1102) + TX, Diphenylsulfone (IUPAC name) (1103) + TX, Disulfiram (alternative name) [CCN] + TX, Disulfotone (278) + TX, DNOC (282) + TX, Dofenapine (1113) + TX, Doramectin (alternative name) [CCN] + TX, Endosulfan (294) + TX, Endothion (1121) + TX, EPN (297) + TX, Eprinomectin (alternative name) [CCN] + TX, Ethion (309) + TX, Ethoate-methyl (1134) + TX, Etoxazole (320) + TX, Etrimphos (1142) + TX, Fenazaflor (1147) + TX, Fenazaquin (328) + TX, Fenbutas oxide (330) + TX, fenothiocarb (337) + TX, fenpropathrin (342) + TX, fenpyrad (alternative name) + TX, fenpyroximate (345) + TX, fenson (1157) + TX, fentrifanil (1161) + TX, fenvalerate (349) + TX, fipronil (354) + TX, fluacrypyrim (360) + TX, fluazuron (1166) + TX, flubenzimine (1167) + TX, flucycloxuron (366) + TX, flucythrinate (367) + TX, fluenethyl (1169) + TX, flufenoxuron (370) + TX, flumethrin (372) + TX, fluorbenside (1174) + TX, fluvalinate (1184) + TX, FMC 1137 (development code) (1185) + TX, formetanate (405) + TX, formetanate hydrochloride (405) + TX, formothion (1192) + TX, formoparanate (1193) + TX, γ-HCH (430) + TX, gliodin (1205) + TX, halfenprox (424) + TX, heptenophos (432) + TX, hexadecylcyclopropanecarboxylate (IUPAC / Chemical Calabstract name) (1216) + TX, Hexythiazox (441) + TX, Iodomethane (IUPAC name) (542) + TX, Isocarbophos (alternative name) (473) + TX, Isopropyl O-(methoxyaminothiophosphoryl) salicylate (IUPAC name) (473) + TX, Ivermectin (alternative name) [CCN] + TX, Jasmolin I (696) + TX, Jasmolin II (696) + TX,Iodofenphos (1248) + TX, Lindane (430) + TX, Lufenuron (490) + TX, Malathion (492) + TX, Malonoben (1254) + TX, Mecarbam (502) + TX, Mephosphoran (1261) + TX, Mesulfen (alternative name) [CCN] + TX, Methacrifos (1266) + TX, Methamidophos (527) + TX, Methidathion (529) + TX, Methiocarb (530) + TX, Methomyl (531) + TX, Methyl bromide (537) + TX, Metolcarb (550) + TX, Mevinphos (556) + TX, Mexaka Rubate (1290) + TX, Milbemectin (557) + TX, Milbemycin oxime (alternative name) [CCN] + TX, Mipafox (1293) + TX, Monocrotophos (561) + TX, Morphothion (1300) + TX, Moxidectin (alternative name) [CCN] + TX, Naled (567) + TX, NC-184 (compound code) + TX, NC-512 (compound code) + TX, Nifluridide (1309) + TX, Nikkomycin (alternative name) [CCN] + TX, Nitrilacarb (1313) + TX, Nitrilacarb 1:1 zinc chloride complex (1313) +TX, NNI-0101 (compound code) +TX, NNI-0250 (compound code) +TX, omethoate (594) +TX, oxamyl (602) +TX, oxydeprophos (1324) +TX, oxydisulfoton (1325) +TX, pp'-DDT (219) +TX, parathion (615) +TX, permethrin (626) +TX, petroleum (alternative name) (628) +TX, phenkapton (1330) +TX, phenthoate (631) +TX, phorate (636) +TX, phosalone (637) +TX, phospholane (1338) +TX, phosalone (638) +TX, phosalone (639) +TX, phosalone (639) +TX, phosalone (639) +TX, phosalone (639) +TX, phosalone (639) +TX, phosalone (639) +TX, phosalone (639) +TX, phosalone (639) +TX, phosalone (639) +TX, phosalone (640 ... Sumeet (638) + TX, Phosphamidon (639) + TX, Phoxim (642) + TX, Pirimiphos-methyl (652) + TX, Polychloroterpene (common name) (1347) + TX, Polynactin (alternative name) (653) + TX, Proclonol (1350) + TX, Profenofos (662) + TX, Promasyl (1354) + TX, Propargite (671) + TX, Propetamphos (673) + TX, Propoxer (678) + TX, Protidathion (1360) + TX, Protoate (1362) + TX, Pyrethrin I (696) + TX,Pyrethrin II (696) + TX, Pyrethrin (696) + TX, Pyridaben (699) + TX, Pyridaphenthion (701) + TX, Pyrimidifen (706) + TX, Pyrimitate (1370) + TX, Quinalphos (711) + TX, Quinthiox (1381) + TX, R-1492 (development code) (1382) + TX, RA-17 (development code) (1383) + TX, Rotenone (722) + TX, Schraderdan (1389) + TX, Cebufos (alternative name) + TX, Selamectin (alternative name) [CCN] + T X, SI-0009 (compound code) + TX, sofamid (1402) + TX, spirodiclofen (738) + TX, spiromesifen (739) + TX, SSI-121 (development code) (1404) + TX, sulfuram (alternative name) [CCN] + TX, sulfuramide (750) + TX, sulfotep (753) + TX, sulfur (754) + TX, SZI-121 (development code) (757) + TX, tau-fluvalinate (398) + TX, tebufenpyrad (763) + TX, TEPP (1417) + TX, Tetrabam (alternative name) + TX, Tetrachlorvinphos (777) + TX, Tetradifon (786) + TX, Tetranactin (alternative name) (653) + TX, Tetrasulf (1425) + TX, Thiafenox (alternative name) + TX, Thiocarboxim (1431) + TX, Thiofanox (800) + TX, Thiometon (801) + TX, Thioquinox (1436) + TX, Thuringiensin (alternative name) [CCN] + acaricides selected from the group of substances consisting of TX, triamiphos (1441) + TX, triaraten (1443) + TX, triazophos (820) + TX, triazuron (alternative name) + TX, trichlorfon (824) + TX, triphenofos (1455) + TX, trinactin (alternative name) (653) + TX, vamidothion (847) + TX, vaniliprole [CCN] and YI-5302 (compound code) + TX, an algicide selected from the group of substances consisting of bethoxadin [CCN] + TX, copper dioctanoate (IUPAC name) (170) + TX, copper sulfate (172) + TX, sibutrin [CCN] + TX, dichloron (1052) + TX, dichlorophen (232) + TX, endothal (295) + TX, fentin (347) + TX, hydrated lime [CCN] + TX, nabam (566) + TX, quinoclamine (714) + TX, quinonamide (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, 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 avian repellent 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, 1-Hydroxy-1H-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, dichlorophene (232) + TX, dipyrithione (1105) + TX, dodysine (1112) + TX, phenaminosulf (1144) + TX, formaldehyde (404) + TX, hydrargafen (alternative name) [CCN] + a fungicide selected from the group of substances consisting of 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; 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 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 (51)+TX, Bacillus thuringiensis subsp. japonensis (51)+TX, Bacillus thuringiensis subsp. kurstaki (51)+TX, Bacillus thuringiensis subsp. tenebrionis (51)+TXtenebrionis (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. lecontilecontei 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, feltiae (alternate name) (742)+TX, Steinernema glaseri (alternate name) (742)+TX, Steinernema riobrave (alternate name) (742)+TX, Steinernema riobravis (alternate name) (742)+TX, Steinernema scapterisci (alternate name) (742)+TX, Steinernema spp. (alternate name) (742)+TX, Trichogramma spp. (alternate name) (826)+TX, Typhlodromus a biological agent selected from the group of substances consisting of 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; sterilizing agents selected from the group of substances consisting of Afolate [CCN] + TX, Visadyl (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 Afolate [CCN] + TX, Morzide [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, (E)-Deca-5-en-1-yl acetate and (E)-deca-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)-tetradec-4,1 0-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-11-en-1-yl acetate (IUPAC name) (438) + TX Sadec-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)-Tetradeca-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 and 4-methylnonan-5-one (IUPAC name) (544) + TX, α-multistriatin (alternative name) [CCN] + TX, Brevicomin (alternative name) [CCN] + TX, Codrelure (alternative name) [CCN] + TX, Codlemone (alternative name) (167) + TX, Curua ( 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, Dodec-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, Gossip Lua (alternative name)(420)+TX, Grand Lua (421)+TX, Grand Lua I (alternative name)(421)+TX, Grand Lua II (alternative name)(421)+TX, Grand Lua III (alternative name)(421)+TX, Grand Lua IV (alternative name)(421)+TX, Hexalua[CCN]+TX, Ipsdienol (alternative name)[CCN]+TX, Ipsenol (alternative name[ CCN] + TX, Japonirua (alternative name) (481) + TX, Lineatin (alternative name) [CCN] + TX, Litrur (alternative name) [CCN] + TX, Lupulur (alternative name) [CCN] + TX, Medulur [CCN] + TX, Megatomoic acid (alternative name) [CCN] + TX, Methyleugenol (alternative name) (540) + TX, Muscarua (563) + TX, Octadeca-2,13-dien-1-yl acetate (IUPAC name) (588) + TX, Octadeca-3,13-Dien-1-yl acetate (IUPAC name) (589) + TX, Olfrular (alternative name) [CCN] + TX, Orictalure (alternative name) (317) + TX, Ostramon (alternative name) [CCN] + TX, Siglua [CCN] + TX, Soldidin (alternative name) (736) + TX, Sulcatol (alternative name) [CCN] + TX, Tetradec-11-en-1-yl acetate (IUPAC name) (589) + TX an insect pheromone selected from the group of substances consisting of trimedlure (PAC name) (785) + TX, trimedlure (839) + TX, trimedlure A (alternative name) (839) + TX, trimedlure B1 (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, dimethylcarbate [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; 1-Dichloro-1-nitroethane (IUPAC / Chemical Abstracts name) (1058) + TX, 1,1-dichloro-2,2-bis(4-ethylphenyl)ethane (IUPAC name) (1056) + TX, 1,2-dichloropropane (IUPAC / Chemical Abstracts name) (1062) + TX, 1,2-dichloropropane and 1,3-dichloropropene (IUPAC names) (1063) + TX, 1-bromo-2-chloroethane (IUPAC / Chemical Abstracts name) (916) + TX , 2,2,2-trichloro-1-(3,4-dichlorophenyl)ethyl acetate (IUPAC name) (1451) + TX, 2,2-dichlorovinyl 2-ethylsulfinylethyl methylphosphate (IUPAC name) (1066) + TX, 2-(1,3-dithiolan-2-yl)phenyl dimethylcarbamate (IUPAC / Chemical Abstracts name) (1109) + TX, 2-(2-butoxyethoxy)ethyl thiocyanate (IUPAC / Chemical Abstracts name) (935) + T X, 2-(4,5-dimethyl-1,3-dioxolan-2-yl)phenylmethylcarbamate (IUPAC / Chemical Abstracts name) (1084) + TX, 2-(4-chloro-3,5-xylyloxy)ethanol (IUPAC name) (986) + TX, 2-chlorovinyl diethyl phosphate (IUPAC name) (984) + TX, 2-imidazolidone (IUPAC name) (1225) + TX, 2-isovalerylindan-1,3-dione (IUPAC name) (1246) + TX, 2-methyl (Prop-2-ynyl)aminophenylmethylcarbamate (IUPAC name) (1284) + TX, 2-thiocyanatoethyl laurate (IUPAC name) (1433) + TX, 3-bromo-1-chloroprop-1-ene (IUPAC name) (917) + TX, 3-methyl-1-phenylpyrazol-5-yldimethylcarbamate (IUPAC name) (1283) + TX, 4-methyl(prop-2-ynyl)amino-3,5-xylylmethylcarbamate (IUPAC name) (1285) + TX, 5,5-Dimethyl-3-oxocyclohex-1-enyl dimethylcarbamate (IUPAC name) (1085) + TX, abamectin (1) + TX, acephate (2) + TX, acetamiprid (4) + TX, acetione (alternative name) [CCN] + TX, acetoprole [CCN] + TX, acrinathrin (9) + TX, acrylonitrile (IUPAC name) (861) + TX, alanycarb (15) + TX, aldicarb (16) + TX, aldoxycarb (863) + TX, aldrin (864) + TX, aretho Phosphorus (17) + TX, Allosamidin (alternative name) [CCN] + TX, Alixycarb (866) + TX, α-Cypermethrin (202) + TX, α-Ecdysone (alternative name) [CCN] + TX, Aluminum phosphide (640) + TX, Amidithione (870) + TX, Amidothioate (872) + TX, Aminocarb (873) + TX, Amiton (875) + TX, Amiton hydrogen oxalate (875) + TX, Amitraz (24) + TX, Anabasine (877) + TX, Atidathion (883) + TX, AVI 382 (compound code) + TX, AZ 60541 (compound code) + TX, Azadirachtin (alternative name) (41) + TX, Azamethiphos (42) + TX, Azinphos-ethyl (44) + TX, Azinphos-methyl (45) + TX, Azotoate (889) + TX, Bacillus thuringiensis delta endotoxin (alternative name) (52) + TX,, Barium hexafluorosilicate (alternative name) [CCN] + TX, Barium polysulfide (IUPAC / Chemical Abstracts name) (892) + TX, Bartholin [CCN] + TX, Bayer 22 / 190 (development code) (893) + TX, Bayer 22408 (development code) (894) + TX, bendiocarb (58) + TX, benfuracarb (60) + TX, bensultap (66) + TX, β-cyfluthrin (194) + TX, β-cypermethrin (203) + TX, bifenthrin (76) + TX, bioallethrin (78) + TX, bioallethrin S-cyclopentenyl isomer (alternative name) (79) + TX, bioethanomethrin [CCN] + TX, biopermethrin (908) + TX, bioresmethrin (80) + TX, bis(2-cyclopentenyl) bromoethyl)ether (IUPAC name) (909) + TX, bistrifluron (83) + TX, borax (86) + TX, bromovalerate (alternative name) + TX, bromfenvinphos (914) + TX, bromocyclen (918) + TX, bromo-DDT (alternative name) [CCN] + TX, bromophos (920) + TX, bromophos-ethyl (921) + TX, bufencarb (924) + TX, buprofezin (99) + TX, butacarb (926) + TX, butathiophos (927) + TX, Butocarboxim (103) + TX, butonate (932) + TX, butoxycarboxim (104) + TX, butylpyridaben (alternative name) + TX, cadusafos (109) + TX, calcium arsenate [CCN] + TX, calcium cyanide (444) + TX, calcium polysulfide (IUPAC name) (111) + TX, camphechlor (941) + TX, carbanolate (943) + TX, carbaryl (115) + TX, carbofuran (118) + TX, carbon disulfide (IUPAC / Chemical Abstracts Lactose name (945) + TX, Carbon tetrachloride (IUPAC name) (946) + TX, Carbophenothione (947) + TX, Carbosulfan (119) + TX, Cartap (123) + TX, Cartap hydrochloride (123) + TX, Cevadine (alternative name) (725) + TX, Chlorbicyclen (960) + TX, Chlordane (128) + TX, Chlordecone (963) + TX, Chlordimeform (964) + TX, Chlordimeform hydrochloride (964) + TX, Chlorethoxyphos (129) + TX,Chlorfenapyr (130) + TX, Chlorfenvinphos (131) + TX, Chlorfluazuron (132) + TX, Chlormephos (136) + TX, Chloroform [CCN] + TX, Chloropicrin (141) + TX, Chlorphoxim (989) + TX, Chlorprazophos (990) + TX, Chlorpyrifos (145) + TX, Chlorpyrifos-methyl (146) + TX, Chlorthiophos (994) + TX, Chromafenozide (150) + TX, Cinerin I (696) + TX, Cinerin II (696) + TX, Cinerin (696) + TX , cis-resmethrin (alternative name) + TX, cismethrin (80) + TX, clocithrin (alternative name) + TX, cloethocarb (999) + TX, closantel (alternative name) [CCN] + TX, clothianidin (165) + TX, copper acetoarsenite [CCN] + TX, copper arsenate [CCN] + TX, copper oleate [CCN] + TX, coumaphos (174) + TX, coumithoate (1006) + TX, crotamiton (alternative name) [CCN] + TX, crotoxyphos (1010) + TX, crufomate (1011) + TX, cryolite (alternative name) (177) + TX, CS 708 (development code) (1012) + TX, cyanofenphos (1019) + TX, cyanophos (184) + TX, cyanthoate (1020) + TX, ciclethrin [CCN] + TX, cycloprothrin (188) + TX, cyfluthrin (193) + TX, cyhalothrin (196) + TX, cypermethrin (201) + TX, cyphenothrin (206) + TX, cyromazine (209) + TX, cythioate (alternative name) [CCN] + TX, d-limonene (alternative name) [CCN] + TX, d-tetramethrin (alternative name) (788) + TX, DAEP (1031) + TX , Dazomet (216) + TX, DDT (219) + TX, Decarbofuran (1034) + TX, Deltamethrin (223) + TX, Demefion (1037) + TX, Demefion-O (1037) + TX, Demefion-S (1037) + TX, Demeton (1038) + TX, Demeton-Methyl (224) + TX, Demeton-O (1038) + TX, Demeton-O-Methyl (224) + TX, Demeton-S (1038) + TX, Demeton-S-Methyl (224) + TX, Demeton-S-Methyl Sulfone (1039) + TX, Diafenthiuron (226) + TX,Diarifos (1042) + TX, Diamidaphos (1044) + TX, Diazinon (227) + TX, Dicapthion (1050) + TX, Diclofenthion (1051) + TX, Dichlorvos (236) + TX, Dicrifos (alternative name) + TX, Dicresyl (alternative name) [CCN] + TX, Dicrotophos (243) + TX, Dicyclanil (244) + TX, Dieldrin (1070) + TX, Diethyl 5-methylpyrazol-3-yl phosphate (IUPAC name) (1076) + TX, Diflubenzuron (250) + TX, Dirol (alternative name) [CCN] + TX, Dimefluthrin [CCN] + TX, Dimefox (1081) + TX , Dimethane (1085) + TX, Dimethoate (262) + TX, Dimethryne (1083) + TX, Dimethylvinphos (265) + TX, Dimethylan (1086) + TX, Zinex (1089) + TX, Zinex-diclexin (1089) + TX, Dinoprop (1093) + TX, Dinosam (1094) + TX, Dinoseb (1095) + TX, Dinotefuran (271) + TX, Diofenolan (1099) + TX, Dioxabenzophos (1100) + TX, Dioxacarb (1101) + TX, Dioxathione (1102) + TX, Disulfoton (278) + TX, Dicyclophos (1108) + TX, DNOC (282) + TX, Doramectin (alternative name) [CCN] + TX, DSP (1115) + TX, Ecdysterone (alternative name) [CCN] + TX, EI 1642 (development code) (1118) + TX, Emamectin (291) + TX, Emamectin benzoate (291) + TX, EMPC (1120) + TX, Empenthrin (292) + TX, Endosulfan (294) + TX, Endothion (1121) + TX, Endrin (1122) + TX, EPBP (1123) + TX, EPN (297) + TX, Epofenonane (1124) + TX, Eprinomectin (alternative name) [CCN] + TX, Esfenvalerate (302) + TX, Etaphos (alternative name) [CCN] + T X, Ethiophenecarb (308) + TX, Ethion (309) + TX, Ethiprole (310) + TX, Ethoate-methyl (1134) + TX, Ethoprophos (312) + TX, Ethyl formate (IUPAC name) [CCN] + TX, Ethyl-DDD (alternative name) (1056) + TX, Ethylene dibromide (316) + TX, Ethylene dichloride (chemical name) (1136) + TX, Ethylene oxide [CCN] + TX, Etofenprox (319) + TX, Etrimphos (1142) + TX, EXD (1143) + TX, Fanfa -(323)+TX, fenamiphos (326)+TX, fenazaflor (1147)+TX, fenchlorphos (1148)+TX, fenetacarb (1149)+TX, fenfluthrin (1150)+TX, fenitrothion (335)+TX, fenobucarb (336)+TX, fenoxacrim (1153)+TX, fenoxycarb (340)+TX, fenpyritrin (1155)+TX, fenpropathrin (342)+TX, fenpyrad (alternative name)+TX, fensulfothion (1158)+TX, fen Fenthion (346) + TX, Fenthion-ethyl [CCN] + TX, Fenvalerate (349) + TX, Fipronil (354) + TX, Flonicamid (358) + TX, Flubendiamide (CAS registration number: 272451-65-7) + TX, Flucofuron (1168) + TX, Flucycloxuron (366) + TX, Flucythrinate (367) + TX, Fluenethyl (1169) + TX, Flufenerim [CCN] + TX, Flufenoxuron (370) + TX, Flufenprox (1171) + TX,Flumethrin (372) + TX, Fluvalinate (1184) + TX, FMC 1137 (development code) (1185) + TX, Fonofos (1191) + TX, Formetanate (405) + TX, Formetanate hydrochloride (405) + TX, Formothion (1192) + TX, Formoparanate (1193) + TX, Fosmetiran (1194) + TX, Fospirate (1195) + TX, Hostiazate (408) + TX, Hostiethane (1196) + TX, Furathiocarb (412) + TX, Frethrin (1200) + TX, γ-Cyhalothrin (197) + TX, γ-HCH (430) + TX, Guazatine (422) + TX, guazatine acetate (422) + TX, GY-81 (development code) (423) + TX, halfenprox (424) + TX, halofenozide (425) + TX, HCH (430) + TX, HEOD (1070) + TX, heptachlor (1211) + TX, heptenophos (432) + TX, heterophos [CCN] + TX, hexaflumuron (439) + TX, HHDN (864) + TX, hydramethylnon (443) + TX, hydrogen cyanide (444) + TX, hydroprene (445) + TX, hikincarb (1223) + TX, Imidacloprid (458) + TX, Imiprothrin (460) + TX, Indoxacarb (465) + TX, Iodomethane (IUPAC name) (542) + TX, IPSP (1229) + TX, Isazophos (1231) + TX, Isobenzane (1232) + TX, Isocarbophos (alternative name) (473) + TX, Isodrin (1235) + TX, Isofenphos (1236) + TX, Isorane (1237) + TX, Isoprocarb (472) + TX, Isopropyl O-(methoxyaminothiophosphoryl) salicylate (IUPAC name) ( 473) + TX, isoprothiolane (474) + TX, isothioate (1244) + TX, isoxathion (480) + TX, ivermectin (alternative name) [CCN] + TX, jasmolin I (696) + TX, jasmolin II (696) + TX, iodofenphos (1248) + TX, juvenile hormone I (alternative name) [CCN] + TX, juvenile hormone II (alternative name) [CCN] + TX, juvenile hormone III (alternative name) [CCN] + TX, kereban (1249) + TX, kinoprene (484) + TX, lambda-cyhalothrin (198) + TX,Lead arsenate [CCN] + TX, Lepimectin (CCN) + TX, Leptophos (1250) + TX, Lindane (430) + TX, Lilimfos (1251) + TX, Lufenuron (490) + TX, Ritidathion (1253) + TX, m-Cumenylmethylcarbamate (IUPAC name) (1014) + TX, Magnesium phosphide (IUPAC name) (640) + TX, Malathion (492) + TX, Malonoben (1254) + TX, Magidox (1255) + TX, Mecarbam (502) + TX, Mecarbone (1258) + TX, Menazon (1260) + TX, Mephosphorane (1261) + TX, mercurous chloride (513) + TX, mesulfenphos (1263) + TX, metaflumizone (CCN) + TX, metam (519) + TX, metam-potassium (alternative name) (519) + TX, metam-sodium (519) + TX, methacrifos (1266) + TX, methamidophos (527) + TX, methanesulfonyl fluoride (IUPAC / Chemical Abstracts name) (1268) + TX, methidathion (529) + TX, methiocarb (530) + TX, metoclotophos (1273) + TX, methomyl (531) + TX, metham Toprene (532) + TX, Methoxin-butyl (1276) + TX, Methotrin (alternative name) (533) + TX, Methoxychlor (534) + TX, Methoxyfenozide (535) + TX, Methyl bromide (537) + TX, Methyl isothiocyanate (543) + TX, Methyl chloroform (alternative name) [CCN] + TX, Methylene chloride [CCN] + TX, Metofluthrin [CCN] + TX, Metolcarb (550) + TX, Methoxadiazone (1288) + TX, Mevinphos (556) + TX, Mexacarbate (1290) + TX, Milbemectin (557 )+TX, Milbemycin oxime (alternative name) [CCN]+TX, Mipahox (1293)+TX, Mirex (1294)+TX, Monocrotophos (561)+TX, Morphothion (1300)+TX, Moxidectin (alternative name) [CCN]+TX, Naphthalophos (alternative name) [CCN]+TX, Naled (567)+TX, Naphthalene (IUPAC / Chemical Abstracts name) (1303)+TX, NC-170 (development code) (1306)+TX, NC-184 (compound code)+TX, Nicotine (578)+TX, Nicotine sulfate (578)+TX,Nifluridide (1309) + TX, Nitenpyram (579) + TX, Nithiazine (1311) + TX, Nitrilacarb (1313) + TX, Nitrilacarb 1:1 zinc chloride complex (1313) + TX, NNI-0101 (compound code) + TX, NNI-0250 (compound code) + TX, Nornicotine (common name) (1319) + TX, Novaluron (585) + TX, Noviflumuro (586) + TX, O-5-dichloro-4-iodophenyl O-ethyl ethyl phosphonothioate (IUPAC name) (1057) + TX, O,O-diethyl O-4-methyl-2-oxo-2H-chromen-7-yl phosphorothioate (IUPAC name) (1074) + TX, O,O-diethyl O-6-methyl-2-propylpyrimidin-4-yl phosphorothioate (IUPAC name) C name) (1075) + TX, O,O,O',O'-tetrapropyldithiopyrophosphate (IUPAC name) (1424) + TX, oleic acid (IUPAC name) (593) + TX, omethoate (594) + TX, oxamyl (602) + TX, oxydemeton-methyl (609) + TX, oxydeprophos (1324) + TX, oxydisulfoton (1325) + TX, pp' -DDT (219) + TX, para-dichlorobenzene [CCN] + TX, parathion (615) + TX, parathion-methyl (616) + TX, penfluron (alternative name) [CCN] + TX, pentachlorophenol (623) + TX, pentachlorophenyl laurate (IUPAC name) (623) + TX, permethrin (626) + TX, petroleum (alternative name) (628) + TX, PH 60-38 (development code) (1328) + TX, phenkaptone (1330) + TX, fenothrin (630) + TX, phenthoate (631) + TX, phorate (636) + TX, phosalone (637) + TX, phosphorane (1338) + TX, phosmet (638) + TX, phosniclor (1339) + TX, phosphamidon (639) + TX, phosphine (IUPAC name) (640) + TX, phoxim (642) + TX, phoxim-methyl (1340) + TX, Pirimetaphos (1344) + TX, Pirimicarb (651) + TX, Pirimiphos-ethyl (1345) + TX, Pirimiphos-methyl (652) + TX, Polychlorodicyclopentadiene isomers (IUPAC name) (1346) + TX, Polychloroterpenes (common name) (1347) + TX, Potassium arsenite [CCN] + TX, Potassium thiocyanate [CCN] + TX, Prallethrin (655) + TX, Precocene I (alternative name) [CCN] + TX , Precocene II (alternative name) [CCN] + TX, Precocene III (alternative name) [CCN] + TX, Primidophos (1349) + TX, Profenofos (662) + TX, Profluthrin [CCN] + TX, Promacyl (1354) + TX, Promecarb (1355) + TX, Propafos (1356) + TX, Propetamphos (673) + TX, Propoxar (678) + TX, Protidathion (1360) + TX, Prothiofos (686) + T X, protoate (1362) + TX, protrifen bute [CCN] + TX, pymetrozine (688) + TX, pyraclofos (689) + TX, pyrazophos (693) + TX, pyresmethrin (1367) + TX, pyrethrin I (696) + TX, pyrethrin II (696) + TX, pyrethrin (696) + TX, pyridaben (699) + TX, pyridalyl (700) + TX, pyridaphenthion (701) + TX, pyrimidifen ( 706)+TX, Pirimitate (1370)+TX, Pyriproxyfen (708)+TX, Quassia (alternative name) [CCN]+TX, Quinalphos (711)+TX, Quinalphos-methyl (1376)+TX, Quinothione (1380)+TX, Quinthiox (1381)+TX, R-1492 (development code) (1382)+TX, Lafoxanide (alternative name) [CCN]+TX, Resmethrin (719)+TX, Rotenone (722)+TX, RU 15525 (development code) (723) + TX, RU 25475 (development code) (1386) + TX, Riania (alternative name) (1387) + TX, Ryanodine (common name) (1387) + TX, Sabadilla (alternative name) (725) + TX, Schraderdan (1389) + TX, Cebufos (alternative name) + TX, Selamectin (alternative name) [CCN] + TX, SI-0009 (compound code) + TX, SI-0205 (compound code) + TX,SI-0404 (compound code) + TX, SI-0405 (compound code) + TX, silafluofen (728) + TX, SN 72129 (development code) (1397) + TX, sodium arsenite [CCN] + TX, sodium cyanide (444) + TX, sodium fluoride (IUPAC / Chemical Abstracts name) (1399) + TX, sodium hexafluorosilicate (1400) + TX, sodium pentachlorophenoxide (623) + TX, sodium selenate (IUPAC name) (1401) + TX, sodium thiocyanate [CCN] + TX, sofamide (1402) + TX, spinosad (737) + TX, spiromesifen (7 39)+TX, spirotetramat (CCN)+TX, sulcofuron (746)+TX, sulcofuron-sodium (746)+TX, sulfuramide (750)+TX, sulfotep (753)+TX, sulfuryl fluoride (756)+TX, sulproos (1408)+TX, tard oil (alternative name) (758)+TX, tau-fluvalinate (398)+TX, tazimcarb (1412)+TX, TDE (1414)+TX, tebufenozide (762)+TX, tebufenpyrad (763)+TX, tebupirimfos (764) +TX, Teflubenzuron (768) +TX, Tefluthrin (769) +TX, Temephos (770) +TX, TEPP (1417) +TX, Teralethrin (1418) +TX, Terbam (alternative name) +TX, Terbufos (773) +TX, Tetrachloroethane [CCN] +TX, Tetrachlorvinphos (777) +TX, Tetramethrin (787) +TX, θ-Cypermethrin (204) +TX, Thiacloprid (791) +TX, Thiafenox (alternative name) +TX, Thiamethoxam (792) +TX, Tyclophos (14 28)+TX, thiocarboxim (1431)+TX, thiocyclam (798)+TX, thiocyclam hydrogen oxalate (798)+TX, thiodicarb (799)+TX, thiofanox (800)+TX, thiometon (801)+TX, thionazine (1434)+TX, thiosultap (803)+TX, thiosultap-sodium (803)+TX, thuringiensin (alternative name) [CCN]+TX, tolfenpyrad (809)+TX, tralomethrin (812)+TX, transfluthrin (813)+TX,Transpermethrin (1440) + TX, Triamiphos (1441) + TX, Triazamate (818) + TX, Triazophos (820) + TX, Triazuron (alternative name) + TX, Trichlorfon (824) + TX, Trichlormethaphos-3 (alternative name) [CCN] + TX, Trichloronate (1452) + TX, Trifenophos (1455) + TX, Triflumuron (835) + TX, Trimethacarb (840) + TX, Triplen (145 9) + TX, vamidothion (847) + TX, vaniliprole [CCN] + TX, veratridine (alternative name) (725) + TX, veratrine (alternative name) (725) + TX, XMC (853) + TX, xylylcarb (854) + TX, YI-5302 (compound code) + TX, zeta-cypermethrin (205) + TX, zetamethrin (alternative name) + TX, zinc phosphide (640) + TX, zolaprophos (1469) and ZXI 8901 (development code) (858) + TX, cyantraniliprole [736994-63-19 + TX, chlorantraniliprole [500008-45-7] + TX, cyenopyrafen [560121-52-0] + TX, cyflumetofen [400882-07-7] + TX, pyrifluquinazon [337458-27-2] + TX, spinetoram [187166-40-1 + 187166-15-0] + TX, spirotetramat [203313-25-1] + TX, sulfoxaflor [946578-00-3] + TX, flufiprole [704886-18-0] + TX, meperfluthrin [915288-13-0] + TX, tetramethy Insecticides selected from the group of substances consisting of rufluthrin [84937-88-2] + TX, triflumezopyrim (disclosed in WO 2012 / 092115) + TX, fluxamethamide (WO 2007 / 026965) + TX, ε-metofluthrin [240494-71-7] + TX, ε-momfluorothrin [1065124-65-3] + TX, fluazaindolizine [1254304-22-7] + TX, chloroprallethrin [399572-87-3] + TX, fluxamethamide [928783-29-3] + TX, cyhalodiamide [1262605-53-7] + TX, thioxazaphen [330459-31-9] + TX,Broflanilide [1207727-04-5] + TX, flufiprole [704886-18-0] + TX, cyclaniliprole [1031756-98-5] + TX, tetraniliprole [1229654-66-3] + TX, guadipyr (described in WO 2010 / 060231) + TX, cycloxapride (described in WO 2005 / 077934) + TX, spiropydione + TX, afidopiropen + TX, flupirimine + TX, monfluorothrin + TX, kappa-bifenthrin + TX, kappa-tefluthrin + TX, dichloromezothiaz + TX, tetrachloraniliprole + TX, benzpyrimoxane + TX; Bis(tributyltin)oxide (IUPAC name) (913) + TX, Bromoacetamide [CCN] + TX, Calcium arsenate [CCN] + TX, Cloethocarb (999) + TX, Copper acetarsenite [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, Pentachloroethane (518) + TX, a molluscicide selected from the group of substances consisting of: thazimcarb (623) + TX, sodium pentachlorophenoxide (623) + TX, thazimcarb (1412) + TX, thiodicarb (799) + TX, tributyltin oxide (913) + TX, triphenmorph (1454) + TX, trimethacarb (840) + TX, triphenyltin acetate (IUPAC name) (347) and triphenyltin hydroxide (IUPAC name) (347) + TX, pyriprole [394730-71-3] + TX, AKD-3088 (compound code) + TX, 1,2-dibromo-3-chloropropane (IUPAC / Chemical Abstracts Name) (1045) + TX, 1,2-dichloropropane (IUPAC / Chemical Abstracts Name) (1062) + TX, 1,2-dichloropropane and 1,3-dichloropropene (IUPAC name) (1063) + TX, 1,3-dichloropropene (233) + TX, 3,4-dichlorotetrahydrothiophene 1,1-dioxide (IUPAC / Chemical Abstracts Name) (1062) + TX, (substruct 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, aldoxicarb (863) + TX, AZ60541 (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, cytokinin (alternative name) (210) + TX, dazomet (216 )+TX, DBCP(1045)+TX, DCIP(218)+TX, Diamidaphos(1044)+TX, Diclofenthion(1051)+TX, Dicrifos(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, Fenpyrad (alternative name) +TX, Fensulfothion (1158) +TX, Hostiazate (408) +TX, Hostiethane (1196) +TX, Furfural (alternative name) [CCN] +TX, GY-81 (development code) (423) +TX, Heterofos [CCN] +TX, Iodomethane (IUPAC name) (542) +TX, Isamidophos (1230) +TX, Isazophos (1231) +TX, Ivermectin CCN+TX, Kinetin(alternative name)(210)+TX, Mecarfone(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, Myrotheciumverrucaria composition (alternative name) (565) + TX, NC-184 (compound code) + TX, oxamyl (602) + TX, phorate (636) + TX, phosphamidon (639) + TX, phosphocarb [CCN] + TX, cebufos (alternative name) + TX, selamectin (alternative name) [CCN] + TX, spinosad (737) + TX, terbam (alternative name) + TX, terbufos (773) + TX, tetrachlorothiophene (IU a nematicide selected from the group of substances consisting of PAC / Chemical Abstracts Name (1422) + TX, Thiafenox (alternative name) + TX, Thionazine (1434) + TX, Triazophos (820) + TX, Triazuron (alternative name) + TX, Xylenol [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, 2-Isovalerylindan-1,3-dione (IUPAC name) (1246) + TX, 4-(quinoxalin-2-ylamino)benzenesulfonamide (IUPAC name) (748) + TX, α-chlorohydrin [CCN] + TX, aluminum phosphide (640) + TX, antu (880) + TX, arsenic trioxide (882) + TX, barium carbonate (891) + TX, bisthiosemi (912) + TX, brodifacoium (89) + TX, bromadiolone (91) + TX, brome Talin (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, Flocoumafe Fluoroacetamide (379) + TX, flupropidine (1183) + TX, flupropidine hydrochloride (1183) + TX, γ-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, norboramide (1318) + TX, fosacetim (1336) + TX, phosphinium rodenticides selected from the group of substances consisting of arsenic (IUPAC name) (640) + TX, phosphorus [CCN] + TX, pindone (1341) + TX, potassium arsenite [CCN] + TX, pyrinuron (1371) + TX, sciliroside (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 and nerolidol (alternative names) (324) + TX, MB-599 (development code) (498) + TX, MGK 264 (development code) (296) + TX, piperonyl butoxide (649) + TX, piperotal (1343) + TX, propyl isomer (1358) + TX, S421 (development code) (724) + TX, sesamex (1393) + TX, sesamolin (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 acetate (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 virucidal agent 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, and Azaconazole (60207-31-0) + TX, Bitertanol [70585-36-3] + TX, Bromuconazole [116255-48-2] + TX, Cyproconazole [94361-06-5] + TX, Difenoconazole [119446-68-3] + TX, Diniconazole [83657-24-3] + TX, Epoxiconazole [106325-08-0] + TX, Fenbuconazole [114369-43-6] + TX, Fluquinconazole [136426-54-5] + TX, Flusilazole [85509-19-9] + TX, Flu Triafol [76674-21-0] + TX, Hexaconazole [79983-71-4] + TX, Imazalil [35554-44-0] + TX, Imibenconazole [86598-92-7] + TX, Ipconazole [125225-28-7] + TX, Metconazole [125116-23-6] + TX, Myclobutanil [88671-89-0] + TX, Pefurazoate [101903-30-4] + TX, Penconazole [66246-88-6] + TX, Prothioconazole [178928-70-6] + TX, Pyrifenox [882 83-41-4]+TX, Prochloraz [67747-09-5]+TX, Propiconazole [60207-90-1]+TX, Simeconazole [149508-90-7]+TX, Tebuconazole [107534-96-3]+TX, Tetraconazole [112281-77-3]+TX, Triadimefon [43121-43-3]+TX, Triadimenol [55219-65-3]+TX, Triflumizole [99387-89-0]+TX, Triticonazole [131983-72-7]+TX, Ancymidol [12771-68-5]+T X, fenarimol [60168-88-9] + TX, nuarimol [63284-71-9] + TX, bupirimate [41483-43-6] + TX, dimethirimol [5221-53-4] + TX, ethirimol [23947-60-6] + TX, dodemorph [1593-77-7] + TX, fenpropidin [67306-00-7] + TX, fenpropimorph [67564-91-4] + TX, spiroxamine [118134-30-8] + TX, tridemorph [81412-43-3] + TX, cyprodinil [121552-61-2] + TX,Mepanipyrim [110235-47-7] + TX, pyrimethanil [53112-28-0] + TX, fenpiclonil [74738-17-3] + TX, fludioxonil [131341-86-1] + TX, benalaxyl [71626-11-4] + TX, furalaxyl [57646-30-7] + TX, metalaxyl [57837-19-1] + TX, R-metalaxyl [70630-17-0] + TX, ofrace [58810-48-3] + TX, oxadixyl [77732-09-3] + TX, benomyl [17804-35-2] + TX, Carbendazim [10605-21-7] + TX, Debacarb [62732-91-6] + TX, Fuberidazole [3878-19-1] + TX, Thiabendazole [148-79-8] + TX, Chlozolinate [84332-86-5] + TX, Diclozolin [24201-58-9] + TX, Iprodione [36734-19-7] + TX, Mycorzolin [54864-61-8] + TX, Procymidone [32809-16-8] + TX, Vinclozolin [50471-44-8] + TX, Boscalid [188425-85-6] + TX, Carbo oxacin [5234-68-4] + TX, fenfuram [24691-80-3] + TX, flutolanil [66332-96-5] + TX, mepronil [55814-41-0] + TX, oxycarboxin [5259-88-1] + TX, penthiopyrad [183675-82-3] + TX, thifluzamide [130000-40-7] + TX, guazatine [108173-90-6] + TX, dodine [2439-10-3] [112-65-2] (free base) + TX, iminoctadine [13516-27-3] + TX, azoxystrobin [13186 0-33-8]+TX, dimoxystrobin [149961-52-4]+TX, enesterobulin {Proc.BCPC,Int.Congr.,Glasgow,2003,1,93}+TX, fluoxastrobin [361377-29-9]+TX, kresoxim-methyl [143390-89-0]+TX, metominostrobin [133408-50-1]+TX, trifloxystrobin [141517-21-7]+TX, oryzastrobin [248593-16-0]+TX, picoxystrobin [117428-22-5]+TX,Pyraclostrobin [175013-18-0] + TX, ferbam [14484-64-1] + TX, mancozeb [8018-01-7] + TX, maneb [12427-38-2] + TX, metiram [9006-42-2] + TX, propineb [12071-83-9] + TX, thiram [137-26-8] + TX, zineb [12122-67-7] + TX, ziram [137-30-4] + TX, captafol [2425-06-1] + TX, captan [133-06-2] + TX, dichlofluanid [1085-98-9] + TX, fluoroin mide [41205-21-4] + TX, folpet [133-07-3] + TX, tolylfluanid [731-27-1] + TX, Bordeaux mixture [8011-63-0] + TX, copper hydroxide [20427-59-2] + TX, copper oxychloride [1332-40-7] + TX, copper sulfate [7758-98-7] + TX, copper oxide [1317-39-1] + TX, mancopper [53988-93-5] + TX, copper oxine [10380-28-6] + TX, dinocap [131-72-6] + TX, isopropyl nitrotar [105 52-74-6]+TX, edifenphos [17109-49-8]+TX, iprobenfos [26087-47-8]+TX, isoprothiolane [50512-35-1]+TX, phosdifen [36519-00-3]+TX, pyrazophos [13457-18-6]+TX, tolclofos-methyl [57018-04-9]+TX, acibenzolar-S-methyl [135158-54-2]+TX, anilazine [101-05-3]+TX, benthiavalicarb [413615-35-7]+TX, blasticidin-S [2079-00-7 ]+TX, quinomethionate [2439-01-2]+TX, chloroneb [2675-77-6]+TX, chlorothalonil [1897-45-6]+TX, cyflufenamid [180409-60-3]+TX, cymoxanil [57966-95-7]+TX, dicloron [117-80-6]+TX, diclocymet [139920-32-4]+TX, diclomedine [62865-36-5]+TX, dicloran [99-30-9]+TX, diethofencarb [87130-20-9]+TX, dimethomorph [110488-70-5]+TX,SYP-LI90 (Flumorph) [211867-47-9] + TX, Dithianone [3347-22-6] + TX, Ethaboxam [162650-77-3] + TX, Etridiazole [2593-15-9] + TX, Famoxadone [131807-57-3] + TX, Fenamidone [161326-34-7] + TX, Fenoxanil [115852-48-7] + TX, Fentin [668-34-8] + TX, Ferimzone [89269-64-7] + TX, Fluazinam [79622-59-6 ]+TX, fluopicolide [239110-15-7]+TX, flusulfamide [106917-52-6]+TX, fenhexamid [126833-17-8]+TX, fosetyl-aluminum [39148-24-8]+TX, hymexazol [10004-44-1]+TX, iprovalicarb [140923-17-7]+TX, IKF-916 (cyazofamid) [120116-88-3]+TX, kasugamycin [6980-18-3]+TX, methasulfocarb [66952-49-6 ]+TX, Metrafenone [220899-03-6]+TX, Pencycuron [66063-05-6]+TX, Phthalide [27355-22-2]+TX, Polyoxin [11113-80-7]+TX, Probenazole [27605-76-1]+TX, Propamocarb [25606-41-1]+TX, Proquinazide [189278-12-4]+TX, Pyroquilon [57369-32-1]+TX, Quinoxyfen [124495-18-7]+TX, Quintozene [82-68-8]+TX, Sulfur [7704-34-9]+TX, tiadinil [223580-51-6]+TX, triazoxide [72459-58-6]+TX, tricyclazole [41814-78-2]+TX, triforine [26644-46-2]+TX, validamycin [37248-47-8]+TX, zoxamide (RH7281) [156052-68-5]+TX, mandipropamide [374726-62-2]+TX, isopyrazam [881685-58-1]+TX, sedaxane [874967-67-6]+TX,3-Difluoromethyl-1-methyl-1H-pyrazole-4-carboxylic acid (9-dichloromethylene-1,2,3,4-tetrahydro-1,4-methano-naphthalen-5-yl)-amide (disclosed in WO 2007 / 048556) + TX, 3-Difluoromethyl-1-methyl-1H-pyrazole-4-carboxylic acid (3',4',5'-trifluoro-biphenyl-2-yl)-amide (disclosed in WO 2006 / 087343) + TX, [(3S,4R,4aR,6S,6aS,12R,12aS,12bS)-3-[(cycloproline Pyricarbonyl)oxy]-1,3,4,4a,5,6,6a,12,12a,12b-decahydro-6,12-dihydroxy-4,6a,12b-trimethyl-11-oxo-9-(3-pyridinyl)-2H,11H naphtho[2,1-b]pyrano[3,4-e]pyran-4-yl]methyl-cyclopropanecarboxylate [915972-17-7] + TX and 1,3,5-trimethyl-N-(2-methyl-1-oxopropyl)-N-[3-(2-methylpropyl)-4-[2,2,2-trifluoro-1-methoxy-1-(trifluoromethyl) a biologically active compound selected from the group of substances consisting of lancotrione [1486617-21-3] + TX, florpyrauxifen [943832-81-3] + TX, ipfentrifluconazole [1417782-08-1] + TX, mefentrifluconazole [1417782-03-6] + TX, quinofumelin [861647-84-9] + TX, chloroprallethrin [399572-87-3] + TX, cyhalodiamide [1262 605-53-7]+TX, fluazaindolizine [1254304-22-7]+TX, fluxamethamide [928783-29-3]+TX, ε-metofluthrin [240494-71-7]+TX, ε-monfluorothrin [1065124-65-3]+TX, pydiflumetofen [1228284-64-7]+TX, κ-bifenthrin [439680-76-9]+TX, broflanilide [1207727-04-5]+TX, dichloromezothiazide [1263629-39-5]+TX, dipimethitrone [16114-35-5]+TX,Pyraziflumid [942515-63-1] + TX and kappa-tefluthrin [391634-71-2] + TX, fenpicoxamide [517875-34-2] + TX; flufenpyrrolidone + TX, benzpyrimoxane [1449021-97-9] + TX; isocycloceram + TX, lescalle [64309-03-1] + TX; aminopyrifen [1531626-08-0] + TX; and Microorganisms including: Acinetobacter lwoffii + 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 alternata + TX, Alternaria cassiae + TX, cassia)+TX, Alternaria 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 cyst (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 I-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 Bacillus subtilis strain QST 713 (CEASE(R)+TX, Serenade(R)+TX, Rhapsody(R))+TX, Bacillus subtilis strain QST 714(JAZZ(R))+TX, Bacillus subtilis strain AQ153+TX, Bacillus subtilis Bacillus subtilis strain AQ743+TX, Bacillus subtilis strain QST3002+TX, Bacillus subtilis strain QST3004+TX, Bacillus subtilis var. amyloliquefaciens.amyloliquefaciens strain FZB24 (Taegro®+TX, Rhizopro®)+TX, Bacillus thuringiensis Cry 2Ae+TX, Bacillus thuringiensis Cry1Ab+TX, Bacillus thuringiensis aizawai GC 91 (Agree®)+TX, Bacillus thuringiensis israelensis (BMP123®+TX, Aquabac®+TX, VectoBac®)+TX, Bacillus thuringiensis kurstakii 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 / 3P®)+TX, Bacillus thuringiensis strain BD#32+TX, Bacillus thuringiensis strain AQ52+TX, Bacillus thuringiensis var. aizawai (XenTari®+TX, DiPel®)+TX, bacterial spp.) (GROWMEND® + TX, GROWSWEET® + TX, Shootup®) + TX, Clavipacter michiganensis bacteriophage (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. 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 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 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 perparascens + TX, purpurascens)+TX, Epicoccum spp.)+TX, Filobasidium floriforme+TX, Fusarium acuminatum+TX, Fusarium chlamydosporum+TX, Fusarium oxysporum (Fusaclean® / Biofox C®)+TX, Fusarium proliferatum+TX, Fusarium spp.+TX, Galactomyces geotrichum+TX, Gliocladium catenulatum (Primastop®+TX, Prestop®)+TX, Gliocladium roseum 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®)+TX, 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 + TX, 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-dissolving 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 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, Pseudomonas 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 glutinis+TX, Rhodotorula graminis+TX, Rhodotorula mucilagnosa+TX, Rhodotorula rubra+TX, Saccharomyces cerevisiae. 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 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 supplemental micronutrients (Natural II®)+TX, various fungi (Millennium Microbes®)+TX, Verticillium chlamydosporium+TX, Verticillium lecanii (Mycotal®+TX, Vertalec®)+TX, Vip3Aa20 (VIPtera®)+TX, Virgibaclillus marismortui+TX, Xanthomonas campestris pv.Poae (Camperico®)+TX, Xenorhabdus bovienii+TX, Xenorhabdus nematophilus; and. Plant extracts including: Pine oil (Retenol®) +TX, Azadirachtin (Plasma Neem Oil® +TX, AzaGuard® +TX, MeemAzal® +TX, Molt-X® +TX, Botanical IGRs (Neemazad® +TX, Neemix®) +TX, Rapeseed oil (Lilly Miller Vegol®) +TX, Chenopodium ambrosioides near ambrosioides (Requiem®) +TX, Chrysanthemum extract (Crisant®) +TX, Neem oil extract (Trilogy®) +TX, Labiatae essential oil (Botania®) +TX, Clove rosemary peppermint and thyme oil extract (Garden insect killer®)+TX, glycine betaine (Greenstim®)+TX, garlic+TX, lemongrass oil (GreenMatch®)+TX, neem oil+TX, catnip (Nepeta cataria) (catnip oil)+TX, catnip (Nepeta catarina)+TX, nicotine+TX, oregano oil (MossBuster®)+TX, Pedaliaceae oil (Nematon®)+TX, pyrethrum+TX, soapberry (Quillaja saponaria) (NemaQ®)+TX, Reynoutria sachalinensis (Regalia®+TX, Sakalia®)+TX, rotenone (Eco Roten®)+TX, Rutaceae extract (Soleo®)+TX, soybean oil (Ortho ecosense®)+TX, Tea Tree Oil (Timorex Gold®)+TX, Thyme Oil+TX, AGNIQUE® MMF+TX, BugOil®+TX, Mixture of Rosemary Sesame Peppermint Thyme and Cinnamon Extracts (EF300®) + TX, a mixture of clove rosemary and peppermint extracts (EF 400®) + TX, a mixture of clove peppermint garlic oil and mint (Soil Shot®) + TX, kaolin (Screen®) + TX, storage glucan from brown algae (Laminarin®); and Pheromones including: blackheaded fireworm pheromone (3M Sprayable Blackheaded Fireworm Pheromone®)+TX, codling moth pheromone (Paramount dispenser-(CM) / Isomate C-Plus®)+TX, grapeberry moth pheromone (3M MEC-GBM Sprayable Pheromone®)+TX, leafroller moth pheromone (3M MEC-LR Sprayable Pheromone®)+TX, muskamone (Snip7 Fly Bait®+TX, Starbar Premium Fly Bait®)+TX, oriental fruit moth pheromone (3M oriental fruit moth sprayable pheromone®)+TX, peachtree moth pheromone (3M oriental fruit moth sprayable pheromone®)+TX, 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; and 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 andersonii 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 hesperidum+TX, Anagrus atomus+TX, Anagyrus fusciventris+TX, Anagyrus kamali+TX, Anagyrus roeckii+TXloecki+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 gifensis 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 terrestris) (Natupol Beehive®) + TX, Bombus terrestris) (Beeline® + TX, Tripol®) + TX, Cephalonomia stephanoderisstephanoderis+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 (Planopar®)+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 clausiikrausii+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 siphoninisiphonini + 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, (registered trademark)) + TX, Galendromus occidentalis + TX, Goniozus legneri + TX, Habrobracon hebetor + TX, Harmonia axyridis (HarmoBeetle®) + TX, Heterorhabditis spp. (Lawn Patrol®) + TX, Heterorhabditis bacteriophora (NemaShield®) + TX, 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 eponaepona+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 tenuis) (NesidioBug® + TX, Nesibug®) + TX, Ophyra aenescens (Biofly®) + TX, Orius insidiosus (Thripor-I® + TX, Oriline i®) + TX, Orius laevigatus (Thripor-L® + TX, Orilinel(R))+TX, Orius majusculus (Oriline m(R))+TX, Orius strigicollis (Thripor-S(R))+TX, Pauesia juniperorum (Pauesia juniperorum)+TX, Pediobius foveolatus (Phasmarhabditis hermaphrodita (Nemaslug(R))+TX, Phymastichus coffea (Phytoseiulus macropilus)+TX, Phytoseiulus persimilis (Spidex(R))+TX, Phytoline p(R))+TX, Podisus maculiventris (Podisus(R))+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 avenaeavenae) (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 sf®+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, Steinernema spp. (Guardian Nematodes®)+TX, Stethorus punctillum (Stethorus®)+TX, Tamarixia radiate+TX, Tetrastychus setifer)+TX, Thripobius semiluteus+TX, Torymus sinensis+TX, Trichogramma brassicae(Tricholineb(registered trademark))+TX, Trichogramma brassicae (Tricho-Strip(registered trademark))+TX, Trichogramma evanescens+TX, Trichogramma minutum+TX, Trichogramma ostriniae+TX, Trichogramma platneri+TX, Trichogramma pretiosum+TX, Xanthopimpla stemmator; and Other biological products include: Abscisic acid +TX, bioSea® +TX, Chondrostereum purpureum (Chontrol Paste®) +TX, Colletotrichum gloeosporioides (Collego®) +TX, Copper octanoate (Cueva®) +TX, Delta Trap (Trapline d®) +TX, Erwinia amylovora (Harpin) (ProAct® +TX, Ni-HIBIT Gold CST®) +TX, Ferri-phosphate (Ferramol®) +TX, Funnel Trap (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, Aminomit®+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 + potassium thiocyanate (Enzicur®) + TX, SuffOil-X® + TX, spider venom + TX, Nosema locustae (Semaspore Organic Grasshopper Control®) + TX, sticky traps (TraplineYF®+TX, Rebell Amarillo®)+TX and trap (Takitrapline y+b®)+TX; or Broflutrinate + TX, diflovidazin + TX, flometoquin + TX, fluhexafon + TX, diamondback moth (Plutella xylostella) granulosis virus + TX, codling moth (Cydia pomonella) granulosis virus + TX, imicyaphos + TX, false tobacco budworm (Heliothis virescens) nucleopolyhedron virus + TX, Heliothis punctigera nucleopolyhedron virus + TX, tobacco budworm (Helicoverpa zea) nucleopolyhedron virus + TX, Spodoptera frugiperda nucleopolyhedron virus + TX, diamondback moth (Plutella a biologically active ingredient or agent selected from (A. xylostella) nucleopolyhedrovirus + TX, p-cymene + TX, piflubumid + TX, pyrafluprole + TX, QRD420 + TX, QRD452 + TX, QRD460 + TX, terpenoid blend + TX, terpenoid + TX, tetraniliprole + TX, and alpha-terpinene + TX; or Code AE1887196 (BSC-BX60309) + TX, Code NNI-0745GR + TX, Code IKI-3106 + TX, Code JT-L001 + TX, Code ZNQ-08056 + TX, Code IPPA152201 + TX, Code HNPC-A9908 (CAS: [660411-21-2]) + TX, Code HNPC-A2005 (CAS: [860028-12-2]) + TX, Code JS118 + TX, Code ZJ0967 + TX, Code ZJ2242 + TX, Code JS7119 (CAS: [929545-74-4]) + TX, Code SN-1172 + TX, Code HNPC-A9835 + TX, Code HNPC-A active substances referenced by code+TX, such as 9955+TX, code HNPC-A3061+TX, code Chuanhua89-1+TX, code IPP-10+TX, code ZJ3265+TX, code JS9117+TX, code ZJ3757+TX, code ZJ4042+TX, code ZJ4014+TX, code ITM-121+TX, code DPX-RAB55(DKI-2301)+TX, code NA-89+TX, code MIE-1209+TX, code MCI-8007+TX, code BCS-CL73507+TX, code S-1871+TX, code DPX-RDS63+TX, code AKD-1193+TX; or Quinofumelin + TX, Mefentrifluconazole + TX, Fenpicoxamide + TX, Fluindapyr + TX, Inpirfluxam + TX or Indiflumetpyr + TX, Isoflucipram + TX, Pyrapropoin + TX, Florylpicoxamide + TX, Methyltetraprole + TX, Ipurfenoquin + TX, Pyridaclomethyl + TX or Clopyridifur + TX, Tetrachlorantraniliprole + TX, Tetrachloraniliprole + TX, Tetflupyrrolimet + TX, Triflufenpyrrolidone + TX, Cyclopyrazoflor + TX, Flupirimine + TX or Pyrifluramide + TX, Benzpyrimoxa and other biologically active ingredients or agents selected from: benzosfil+TX, beflubutamide-M+TX, benzosfil+TX or oxazosulfil+TX, ethopirafen+TX, acinonapyr+TX or pyrinonaphen+TX, oxotrione+TX, bixlozone+TX or clofendizone+TX or dichloroxyzone+TX, cyclopyranyl+TX or pyrazoclonyl+TX or cyclopyrazonyl+TX, alpha-bromadiolone+TX, oxathiapiproline+TX, fluopyram+TX, penflufen+TX, fluoxopyrrosad+TX, fluoxapiproline+TX and flupyradifurone+TX.

[0292] The reference numbers in square brackets after the active ingredient, e.g. [3878-19-1], refer to Chemical Abstracts Registration Numbers. The above mixture partners are known. When the active ingredients are included in "The Pesticide Manual" [The Pesticide Manual-A World Compendium; Thirteenth Edition; Editor: CDS Tomlin; The British Crop Protection Council], they are listed therein under the section number shown in parentheses above for the specific compound; for example, the compound "Abamectin" is listed under section number (1). When "[CCN]" is added above to a specific compound, the corresponding compound 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 listed at the Internet address: http: / / www.alanwood.net / pesticides / acetoprole.html.

[0293] In the present specification above, most of the active ingredients mentioned above are referred to by the so-called "common name", the relevant "ISO common name" or other "common name" used in individual cases. In the absence of a "common name" designation, the nature of the designation used instead is stated in parentheses for the particular compound; in this case, the IUPAC name, IUPAC / Chemical Abstracts name, "chemical name", "common name", "chemical compound name" or "development code" is used, or if none of these designations or "common name" is used, the "alternative name" is adopted. "CAS Registry Number" means Chemical Abstracts Registry Number.

[0294] The active ingredient mixture of the compound of formula I selected from Tables Y-1 to Y-8, X-1 to X-8, U-1 to U-2 and V-1 to V-6 as well as Table P with the above-mentioned active ingredient is preferably a mixture ratio of 100:1 to 1:6000, in particular 50:1 to 1:50, more in particular 20:1 to 1:20, even more in particular 10:1 to 1:10, very in particular 5:1 and 1:5 (a ratio of 2:1 to 1:2 is particularly preferred, a ratio of 4:1 to 2:1 is likewise preferred), in particular 1:1 or 5: 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. These mixing ratios are by weight.

[0295] The mixture may be used in a method for controlling pests, the method comprising the step of applying a composition comprising the mixture to the pest or its environment, except for methods for the treatment of the human or animal body by surgery or therapy and diagnostic methods performed on the human or animal body.

[0296] Mixtures comprising a compound of formula I selected from Tables Y-1 to Y-8, X-1 to X-8, U-1 to U-2 and V-1 to V-6 and Table P and one or more active ingredients as described above can be applied, for example, in a single ready-mix form, as a combined spray mixture composed of separate formulations of a single active ingredient, such as a "tank mix", and in combination with a single active ingredient when applied sequentially, i.e., one after the other over a fairly short period of time, such as a few hours or days. The order of application of the compound of formula I selected from Tables Y-1 to Y-8, X-1 to X-8, U-1 to U-2 and V-1 to V-6 and Table P and the active ingredients as described above is not critical to carrying out the present invention.

[0297] The compositions according to the invention may also comprise further solid or liquid auxiliaries, such as stabilizers, for example non-epoxidized or epoxidized vegetable oils (for example epoxidized palm oil, rapeseed oil or soybean oil), antifoaming agents, for example silicone oils, preservatives, viscosity regulators, binders and / or tackifiers, fertilizers or other active ingredients for obtaining specific effects, for example bactericides, fungicides, nematicides, plant activators, molluscicides or herbicides.

[0298] The compositions according to the invention are prepared in a manner known per se, for example in the absence of auxiliaries, by grinding, sieving and / or compressing the solid active ingredient, and in the presence of at least one auxiliary, for example by intimately mixing the active ingredient with one or more auxiliaries and / or grinding.These methods for preparing the compositions and the use of compound I for preparing these compositions are also the subject of the present invention.

[0299] The application methods for the compositions, i.e. spraying, misting, dusting, brushing, dusting, spreading or pouring (which should be selected according to the intended purpose in the prevailing situation), are other subjects of the present invention, as well as the use of the compositions for controlling the above-mentioned types of pests. Typical concentration rates are 0.1-1000 ppm, preferably 0.1-500 ppm, of active ingredient. The application rate per hectare is generally 1-2000 g of active ingredient per hectare, in particular 10-1000 g / ha, preferably 10-600 g / ha.

[0300] The preferred method of application in the field of crop protection is application to the foliage of the plant (foliar application), whereby the frequency and rate of application can be selected according to the risk of infestation by the relevant pest. Alternatively, the active ingredient can reach the plant via the root system (systemic action) by irrigating the plant habitat with a liquid composition or by introducing the active ingredient in solid form, for example in the form of granules, into the plant habitat, for example the soil (soil application). In the case of rice plants, such granules can be metered into the paddy field.

[0301] The compounds of the invention and their compositions are also suitable for the protection of plant propagation material, for example seeds or seedlings such as fruits, tubers or grains, from the above-mentioned types of pests. The propagation material can be treated with the compounds before planting, for example seeds can be treated before sowing. Alternatively, the compounds can be applied to the seed kernels by immersing the latter in a liquid composition or by applying a layer of a solid composition (coating). If the propagation material is planted at the site of application, it is also possible to apply the compositions in the furrows, for example at the time of drilling. These treatment methods for plant propagation material and the plant propagation material thus treated are further subjects of the present invention. Typical treatment rates depend on the plant and the pests / fungi to be controlled and are generally between 1 and 200 grams per 100 kg of seeds, preferably between 5 and 150 grams per 100 kg of seeds, such as between 10 and 100 grams per 100 kg of seeds.

[0302] The term seed encompasses all types of seeds and plant propagules, including but not limited to true seeds, seed pieces, suckers, corn kernels, bulbs, fruits, tubers, grains, rootstocks, cuttings, cuttings, and the like, and in a preferred embodiment refers to true seeds.

[0303] The present invention also includes seeds coated or treated with or containing a compound of formula I. The term "coated or treated with and / or containing" generally indicates that the active ingredient is most often on the surface of the seed when applied, but depending on the application method, some of the ingredient may penetrate more or less into the seed material. When the seed product is (re)planted, the active ingredient may be absorbed. In one embodiment, the present invention makes available a plant propagation material to which a compound of formula (I) is attached. Furthermore, this makes available a composition comprising a plant propagation material treated with a compound of formula (I).

[0304] Seed treatment includes all suitable seed treatment techniques known in the art, such as seed dressing, seed coating, seed dusting, seed soaking and seed pelleting. Seed treatment application of the compound of formula (I) can be carried out by any known method, such as by spraying or dusting the seeds before sowing or at the time of sowing / planting the seeds.

[0305] Biological Examples Example B1: Activity against Bemisia tabaci (cotton whitefly) Cotton leaf discs were placed on agar in 24-well microtiter plates and sprayed with aqueous test solutions prepared from a 10,000 ppm DMSO stock solution. After drying, the leaf discs were infested with adult whiteflies. After 6 days of incubation, samples were checked for mortality.

[0306] The following compounds caused at least 80% mortality at an application rate of 00 ppm: P3, P4, P6, P8, P10, P13, P14 and P15.

[0307] Example B2: Activity against Diabrotica balteata (corn beetle) Corn sprouts placed on an agar layer in 24-well microtiter plates were treated by spraying with test solutions prepared from a 10'000 ppm DMSO stock solution. After drying, the plates were infested with L2 larvae (6-10 per well). Four days after infestation, samples were assessed in comparison with untreated samples for mortality and growth inhibition.

[0308] The following compounds provided at least 80% efficacy in at least one of two categories (mortality or growth inhibition) at a rate of 200 ppm: P3, P4, P5, P7, P8, P10, P11, P12, P13, P14 and P16.

[0309] Example B3: Activity against Euschistus heros (Neotropical Brown Stink Bug) Soybean leaves on agar in 24-well microtiter plates were sprayed with test solutions prepared from a 10,000 ppm DMSO stock solution. After drying, the leaves were infested with N2 nymphs. Five days after infestation, samples were assessed for mortality and growth inhibition compared to untreated samples.

[0310] The following compounds provided at least 80% efficacy in at least one of two categories (mortality or growth inhibition) at a rate of 200 ppm: P3, P4, P8, P9, P10, P13, P14 and P15.

[0311] Example B4: Activity against Myzus persicae (green peach aphid): Sunflower leaf discs were placed on agar in 24-well microtiter plates and sprayed with aqueous test solutions prepared from a 10'000 ppm DMSO stock solution. After drying, the leaf discs were infested with aphid populations of various ages. Six days after infestation, samples were assessed for mortality.

[0312] The following compounds caused at least 80% mortality at a rate of 200 ppm: P3, P4, P5, P6, P7, P8, P9, P10, P11, P12, P13, P14, P15, P16 and P17.

[0313] Example B5: Activity against Myzus persicae (green peach aphid). Roots of pea seedlings infested with aphid populations of various ages were placed directly into test solutions prepared from a 10'000 ppm DMSO stock solution. Six days after the seedlings were placed in the test solutions, samples were assessed for mortality.

[0314] The following compounds produced at least 80% mortality at a test dose of 24 ppm: P3, P4, P5, P6, P7, P8, P9, P10, P11, P12, P13, P14, P15, P16 and P17.

[0315] Example B6: Activity against Plutella xylostella (diamondback moth) 24-well microtiter plates containing artificial diet were treated by pipette with test solutions prepared from a 10,000 ppm DMSO stock solution. After drying, the plates were infested with L2 larvae (10-15 per well). Five days after infestation, samples were assessed for mortality and growth inhibition compared to untreated samples.

[0316] The following compounds provided at least 80% efficacy in at least one of two categories (mortality or growth inhibition) at a rate of 200 ppm: P3, P4, P5, P6, P7, P8, P11, P12, P14 and P15.

[0317] Example B7: Activity against Spodoptera littoralis (Egyptian armyworm) Cotton leaf discs were placed on agar in 24-well microtiter plates and sprayed with aqueous test solutions prepared from a 10,000 ppm DMSO stock solution. After drying, the leaf discs were infested with five L1 larvae. Three days after infestation, samples were evaluated in comparison to untreated samples for mortality, antifeedant effect and growth inhibition. Control of Spodoptera littoralis by the test sample was achieved if at least one category of mortality, antifeedant effect and growth inhibition was higher than that of the untreated sample.

[0318] The following compounds provided at least 80% control at a rate of 200 ppm: P3, P4, P5, P7, P8, P11, P12, P14, P15 and P16.

[0319] Example B8: Activity against Nilaparvata lugens (brown planthopper) Rice plants were treated with the diluted test solutions in a spray chamber. After drying, the plants were infested with approximately 20 N3 nymphs. Seven days after treatment, samples were evaluated for mortality and growth regulation. P6, P10, P11, P12, P13 and P15

[0320] Example B9: Activity against Nilaparvata lugens (brown planthopper) In a vegetative culture system, rice plants grown in a nutrient solution were treated with the diluted test solutions. One day after application, the plants were infested with approximately 20 N3 nymphs. Seven days after infestation, samples were evaluated for mortality and growth regulation. P6, P10, P11, P12, P13 and P15

[0321] Example B10: Activity against Tetranychus urticae (two-spotted spider mite): French bean leaf discs on agar in 24-well microtiter plates were sprayed with test solutions prepared from a 10'000 ppm DMSO stock solution. After drying, the discs were infested with mite populations of various ages. Eight days after infestation, samples were assessed for mortality in the mixed population (mobile).

[0322] The following compounds caused at least 80% mortality at a rate of 200 ppm: P3.

[0323] Example B11: Activity against Plutella xylostella (diamondback moth) 24-well microtiter plates containing artificial diet were treated by pipette with test solutions prepared from a 10,000 ppm DMSO stock solution. After drying, diamondback moth eggs were pipetted through a plastic stencil onto gel blotting paper and the plate was closed with this. Eight days after infestation, samples were assessed for mortality and growth inhibition compared to untreated samples.

[0324] The following compounds provided at least 80% efficacy in at least one of two categories (mortality or growth inhibition) at a rate of 200 ppm: P16, P17, P18 and P19.

[0325] Example B12: Activity against sugar beet cyst nematode (Heterodera schachtii), in vitro profiling of larval mobility in 96-well plates Test solutions are prepared with a TECAN robot from a 10,000 ppm DMSO stock solution to obtain 20 μL of 500, 100, 50, 25, 12.5 and 6.25 ppm. Three replicates are performed for each concentration. To each well, 80 μL of nematode solution containing 100-150 freshly collected second stage larvae of the sugar beet cyst nematode (Heterodera schachtii) are added. Plates are covered and kept in the dark at room temperature and incubated for 48 hours. Motility of exposed larvae in treated wells is measured using an imaging tool and compared to the average of 12 untreated replicates.

[0326] The following compounds achieved at least 60% control at 100 ppm after 48 hours: P10, P15.

Claims

1. Formula (I) 【Chemistry 1】 (In the formula, A is CH or N; R 1 is C 1 ~C 4 is alkyl, R 2 is hydrogen, cyano, -C(O)R7, -C(O)OR8, C 1 ~C 6 Alkyl or -CONR 9 R 10 , S.O. 2 R 11 where: R 7 is hydrogen, C 1 ~C 6 Alkyl or C 1 ~C 6 haloalkyl, R 8 is C 1 ~C 6 Alkyl or C 1 ~C 6 haloalkyl; R 9 , R 10 are each independently hydrogen or C 1 ~C 6 is alkyl; R 11 is C 1 ~C 6 is alkyl; R 3 is hydrogen, C 1 ~C 3 Alkyl, C 1 ~C 3 Haloalkyl, cyano, -CO 2 H, -CO 2 N.H. 2 , C 1 ~C 4 Alkoxycarbonyl, C 1 ~C 4 Alkylaminocarbonyl, C 1 ~C 4 dialkylaminocarbonyl, n is 0 or 1; Q is the formula Q 1 , Q 2 , Q 3 , Q 4 and Q. 5 【Chemistry 2】 wherein the arrow indicates the point of attachment to the ring incorporating said group A; R 4 is halogen, C 1 ~C 6 Haloalkyl, C 1 ~C 4 Haloalkylsulfanyl, C 1 ~C 4 Haloalkylsulfinyl, C 1 ~C 4 Haloalkylsulfonyl or C 1 ~C 6 haloalkoxy; X 1 is O or NR 5 and R 5 is C 1 ~C 4 is alkyl; R 6 is C 1 ~C 4 Alkyl, C 1 ~C 4 Haloalkyl, C 1 ~C 4 Alkoxy or C 3 ~C 6 is cycloalkyl; G 1 and G 2 are each independently N or CH. is a group selected from the group consisting of or an agrochemically acceptable salt, stereoisomer, enantiomer, tautomer or N-oxide of a compound of formula I.

2. A is CH or N; R 1 is ethyl, propyl or isopropyl; R 2 is hydrogen, cyano, C 1 ~C 3 Alkyl, C 1 ~C 3 Alkylcarbonyl, C 1 ~C 3 Alkoxycarbonyl, C 1 ~C 3 haloalkylcarbonyl; R 3 is hydrogen, C 1 ~C 3 Haloalkyl, cyano, -CO 2 H, -CO 2 N.H. 2 , C 1 ~C 4 dialkylaminocarbonyl; and n is 1; The compound of claim 1.

3. A is CH or N; R 1 is ethyl; R 2 is hydrogen; R 3 is hydrogen, C 1 ~C 2 Haloalkyl, cyano, -CO 2 N.H. 2 , C 1 ~C 2 dialkylaminocarbonyl; and n is 1; The compound of claim 1.

4. A is CH or N; R 1 is ethyl; R 2 is hydrogen; R 3 is hydrogen, cyano or CO 2 N.H. 2 and n is 1; The compound of claim 1.

5. A is CH or N; R 1 is ethyl; R 2 is hydrogen; R 3 is hydrogen or cyano; and n is 1; The compound of claim 1.

6. Q is Q 1 , Q 2 , Q 4 and Q. 5 【Chemistry 3】 wherein the arrow indicates the point of attachment to the ring incorporating said group A; R 4 is C 1 ~C 2 Haloalkyl, C 1 ~C 2 Haloalkylsulfanyl, C 1 ~C 2 Haloalkylsulfinyl or C 1 ~C 2 haloalkylsulfonyl; X 1 is oxygen or NCH 3 and R 6 is C 1 ~C 2 Alkyl, C 1 ~C 2 Haloalkyl, C 1 ~C 2 alkoxy or cyclopropyl; and G 1 and G 2 are each independently N or CH. The compound according to any one of claims 1 to 5, which is a group selected from the group consisting of

7. Q 1 , Q 2 and Q. 5 【Chemistry 4】 wherein the arrow indicates the point of attachment to the ring incorporating said group A; R 4 is C 1 ~C 2 fluoroalkyl, trifluoromethylsulfanyl, trifluoromethylsulfinyl, trifluoromethylsulfonyl, difluoromethylsulfanyl, difluoromethylsulfinyl or difluoromethylsulfonyl; X 1 is NCH 3 and R 6 is methyl, ethyl, 2,2,2-trifluoroethyl, methoxy or cyclopropyl; and G 1 and G 2 are each independently N or CH. The compound according to any one of claims 1 to 5, which is a group selected from the group consisting of

8. Q is Q 1 and Q. 5 【Chemistry 5】 wherein the arrow indicates the point of attachment to the ring incorporating said group A; R 4 is trifluoromethyl, pentafluoroethyl, trifluoromethylsulfanyl, trifluoromethylsulfinyl or trifluoromethylsulfonyl; X 1 is NCH 3 and R 6 is ethyl, methoxy or cyclopropyl; and G 1 is N and G 2 is CH or G 1 is CH, and G 2 is N or G 1 and G 2 is N or G 1 and G 2 is CH) The compound according to any one of claims 1 to 5, which is a group selected from the group consisting of

9. Q is the radical Q 1 【Chemistry 6】 wherein the arrow indicates the point of attachment to the ring incorporating said group A; R 2 is trifluoromethyl; X 1 is NCH 3 and G 1 is N and G 2 is CH or G 1 is CH, and G 2 is N or G 1 and G 2 is N) The compound according to any one of claims 1 to 5,

10. A is CH or N; R 1 is ethyl, propyl or isopropyl; R 2 is hydrogen, cyano, C 1 ~C 3 Alkyl, C 1 ~C 3 Alkylcarbonyl, C 1 ~C 3 Alkoxycarbonyl, C 1 ~C 3 haloalkylcarbonyl; R 3 is hydrogen, C 1 ~C 3 Haloalkyl, cyano, CO 2 H, CO 2 N.H. 2 , C 1 ~C 4 dialkylaminocarbonyl; n is 1; Q is Q 1 , Q 2 , Q 4 and Q. 5 【Chemistry 7】 wherein the arrow indicates the point of attachment to the ring incorporating said group A; R 4 is C 1 ~C 2 Haloalkyl, C 1 ~C 2 Haloalkylsulfanyl, C 1 ~C 2 Haloalkylsulfinyl or C 1 ~C 2 haloalkylsulfonyl; X 1 is oxygen or NCH 3 and R 6 is C 1 ~C 2 Alkyl, C 1 ~C 2 Haloalkyl, C 1 ~C 2 alkoxy or cyclopropyl; and G 1 and G 2 are each independently N or CH. The compound according to claim 1, wherein the compound is a group selected from the group consisting of:

11. A is CH or N; R 1 is ethyl; R 2 is hydrogen; R 3 is hydrogen, C 1 ~C 2 Haloalkyl, cyano, CO 2 N.H. 2 , C 1 ~C 2 dialkylaminocarbonyl; n is 1; Q is Q 1 , Q 2 and Q. 5 【Chemistry 8】 wherein the arrow indicates the point of attachment to the ring incorporating said group A; R 4 is C 1 ~C 2 fluoroalkyl, trifluoromethylsulfanyl, trifluoromethylsulfinyl, trifluoromethylsulfonyl, difluoromethylsulfanyl, difluoromethylsulfinyl or difluoromethylsulfonyl; X 1 is NCH 3 and R 6 is methyl, ethyl, 2,2,2-trifluoroethyl, methoxy or cyclopropyl; and G 1 and G 2 are each independently N or CH. The compound according to claim 1, wherein the compound is a group selected from the group consisting of:

12. A is CH or N; R 1 is ethyl; R 2 is hydrogen; R 3 is hydrogen, cyano or CO 2 N.H. 2 and n is 1; Q is Q 1 and Q. 5 【Chemistry 9】 wherein the arrow indicates the point of attachment to the ring incorporating said group A; R 4 is trifluoromethyl, pentafluoroethyl, trifluoromethylsulfanyl, trifluoromethylsulfinyl or trifluoromethylsulfonyl; X 1 is NCH 3 and R 6 is ethyl, methoxy or cyclopropyl; and G 1 is N and G 2 is CH or G 1 is CH, and G 2 is N or G 1 and G 2 is N or G 1 and G 2 is CH) The compound according to claim 1, wherein the compound is a group selected from the group consisting of:

13. A is CH or N; R 1 is ethyl; R 2 is hydrogen; R 3 is hydrogen or cyano; n is 1; Q is a group Q 1 【Chemistry 10】 wherein the arrow indicates the point of attachment to the ring incorporating said group A; R 2 is trifluoromethyl; X 1 is NCH 3 and G 1 is N and G 2 is CH or G 1 is CH, and G 2 is N or G 1 and G 2 is N) 2. The compound of claim 1 ,

14. Q is Q 1-1 , Q 1-2 , Q 1-3 , Q 1-4 and Q. 1-5 【Chemistry 11】 wherein the arrow indicates the point of attachment to the ring incorporating said group A; and R 4 is trifluoromethyl, trifluoromethylsulfanyl or trifluoromethylsulfonyl) Preferably, Q is a group selected from Q 1-2 , Q 1-3 , Q 1-4 and Q. 1-5 The compound according to any one of claims 1 to 5, which is a group selected from the group consisting of

15. Q is Q 5 【Chemistry 12】 wherein the arrow indicates the point of attachment to the ring incorporating said group A; R 4 is trifluoromethyl, trifluoromethylsulfanyl or trifluoromethylsulfonyl; and R 6 is OCH 3 , C.H. 2 CH 3 or cyclopropyl) The compound according to any one of claims 1 to 5, which is a group selected from the group consisting of

16. Q is Q 4 【Chemistry 13】 wherein the arrow indicates the point of attachment to the ring incorporating said group A; R 4 is trifluoromethyl, trifluoromethylsulfanyl or trifluoromethylsulfonyl; and G 1 is N and G 2 is CH or G 1 is CH, and G 2 is N or G 1 and G 2 is CH or G 1 and G 2 is N; preferably, G 1 is CH, and G 2 is N) The compound according to any one of claims 1 to 5, which is a group selected from the group consisting of

17. 1-[5-(ethylsulfonimidoyl)-6-[7-methyl-3-(trifluoromethyl)imidazo[4,5-c]pyridazin-6-yl]-3-pyridyl]cyclopropanecarboxamide (compound P1); 1-[3-(ethylsulfonimidoyl)-4-[3-methyl-6-(trifluoromethyl)imidazo[4,5-b]pyridin-2-yl]phenyl]cyclopropanecarboxamide (compound P2); [5-cyclopropyl-2-[3-methyl-6-(trifluoromethylsulfonyl)imidazo[4,5-c]pyridin-2-yl]-3-pyridyl]-ethyl-imino-oxo-lambda 6 -sulfane (compound P3); [5-cyclopropyl-2-[3-methyl-6-(trifluoromethylsulfanyl)imidazo[4,5-c]pyridin-2-yl]-3-pyridyl]-ethyl-imino-oxo-lambda 6 -sulfane (compound P4); [5-cyclopropyl-2-[3-methyl-6-(trifluoromethyl)imidazo[4,5-c]pyridin-2-yl]-3-pyridyl]-ethyl-imino-oxo-lambda 6 -sulfane (compound P5); 1-[5-(ethylsulfonimidoyl)-6-[3-methyl-6-(trifluoromethyl)imidazo[4,5-b]pyridin-2-yl]-3-pyridyl]cyclopropanecarbonitrile (compound P6); [5-cyclopropyl-2-[6-(trifluoromethyl)pyrazolo[4,3-c]pyridin-2-yl]-3-pyridyl]-ethyl-imino-oxo-lambda 6 -sulfane (compound P7); 1-[5-(ethylsulfonimidoyl)-6-[5-methoxy-3-methyl-4-oxo-6-(trifluoromethyl)imidazo[4,5-c]pyridin-2-yl]-3-pyridyl]cyclopropanecarbonitrile (compound P8); 1-[3-(ethylsulfonimidoyl)-4-[3-methyl-6-(trifluoromethylsulfanyl)imidazo[4,5-c]pyridin-2-yl]phenyl]cyclopropanecarbonitrile (compound P9); 1-[5-(ethylsulfonimidoyl)-6-[7-methyl-3-(trifluoromethyl)imidazo[4,5-c]pyridazin-6-yl]-3-pyridyl]cyclopropanecarbonitrile (compound P10); [5-cyclopropyl-2-[7-methyl-3-(trifluoromethyl)imidazo[4,5-c]pyridazin-6-yl]-3-pyridyl]-ethyl-imino-oxo-lambda 6 -sulfane (compound P11); [5-cyclopropyl-2-[3-methyl-6-(trifluoromethyl)imidazo[4,5-b]pyridin-2-yl]-3-pyridyl]-ethyl-imino-oxo-lambda 6 -sulfane (compound P12); 1-[3-(ethylsulfonimidoyl)-4-[3-methyl-6-(trifluoromethyl)imidazo[4,5-c]pyridin-2-yl]phenyl]cyclopropanecarbonitrile (compound P13); 1-[6-[5-ethyl-3-methyl-4-oxo-6-(trifluoromethyl)imidazo[4,5-c]pyridin-2-yl]-5-(ethylsulfonimidoyl)-3-pyridyl]cyclopropanecarbonitrile (compound P14); 1-[3-(ethylsulfonimidoyl)-4-[3-methyl-6-(trifluoromethyl)imidazo[4,5-b]pyridin-2-yl]phenyl]cyclopropanecarbonitrile (compound P15); [5-cyclopropyl-2-[7-(trifluoromethyl)imidazo[1,2-b]pyridazin-2-yl]-3-pyridyl]-ethyl-imino-oxo-lambda 6 -sulfane (compound P16); 1-[5-(ethylsulfonimidoyl)-6-[6-(trifluoromethyl)pyrazolo[4,3-c]pyridin-2-yl]-3-pyridyl]cyclopropanecarbonitrile (compound P17); [5-cyclopropyl-2-[5-(trifluoromethylsulfanyl)-1,3-benzoxazol-2-yl]-3-pyridyl]-ethyl-imino-oxo-lambda 6 -sulfane (compound P18); and [5-cyclopropyl-2-[5-(trifluoromethylsulfonyl)-1,3-benzoxazol-2-yl]-3-pyridyl]-ethyl-imino-oxo-lambda 6 -Sulfane (compound P19) 2. The compound of formula (I) according to claim 1, selected from the group consisting of:

18. 20. A composition comprising an insecticidally, acaricidally, nematicidally or molluscicidally effective amount of a compound of formula (I) as defined in any one of claims 1 to 17 or an agrochemically acceptable salt, stereoisomer, enantiomer, tautomer or N-oxide thereof, and optionally an auxiliary or diluent.

19. A method for combating and controlling insects, acaridae, nematodes or molluscs, comprising the step of applying to the pest, the pest's habitat or plants susceptible to attack by the pest an insecticidally, acaricidally, nematicidally or molluscicidally effective amount of a compound of formula (I) as defined in any one of claims 1 to 17 or an agrochemically acceptable salt, stereoisomer, enantiomer, tautomer or N-oxide thereof, or applying a composition as defined in claim 18.

20. 20. A method for protecting plant propagation material from attack by insects, acarids, nematodes or mollusks, comprising treating the propagation material or the locus in which the propagation material is planted with a composition according to claim 17.

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