Pest-killing heterocyclic derivatives having 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 pesticidal, particularly insecticidal, heterocyclic derivatives containing sulfoxyimine substituents, processes for their preparation, compositions comprising these compounds, and their use for controlling animal pests, particularly insects or representative examples of mites (Acarina). [Background technology]

[0002] Pesticide-active hetero-bicyclic substituted cyclopropyl derivatives having sulfur-containing substituents are known, for example, in International Publications 2018 / 077565, 2018 / 070502, 2017 / 146226, 2017 / 089190, 2017 / 084879, 2016 / 121997, and 201 This is described in publications such as 6 / 104746, International Publication 2016 / 096584, International Publication 2016 / 046071, International Publication 2016 / 071214, International Publication 2016 / 039441, International Publication 2016 / 026848, International Publication 2016 / 023954, International Publication 2014 / 142292, and International Publication 2016 / 020286. Pest-citerally active heterocyclic sulfoximine derivatives have been previously described in publications such as International Publication 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 [Overview of the Initiative] [Means for solving the problem]

[0004] Surprisingly, it was discovered that certain novel bicyclic sulfoxymine-containing substituted cyclopropyl derivatives possess desirable properties as pesticides. The present invention, therefore, is based on formula I [ka] (In the formula, A is either 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 And here, R7 is hydrogen, a C1-C6 alkyl group, or a C1-C6 haloalkyl group, and R8 is a C1-C6 alkyl group or a C1-C6 haloalkyl group; R9, R 10 These are, independently of each other, hydrogen or C1-C6 alkyl; R 11 These are C1-C6 alkyl groups; R3 is hydrogen, C1-C3 alkyl, C1-C3 haloalkyl, cyano, -CO2H, -CO2NH2, C1-C4 alkoxycarbonyl, C1-C4 alkylaminocarbonyl, or C1-C4 dialkylaminocarbonyl. n is either 0 or 1; Q is represented by equations Q1, Q2, Q3, Q4 and Q5 [ka] (In the formula, the arrows indicate the bonding points to the ring incorporating radical A; R4 is a halogen, C1-C6 haloalkyl, C1-C4 haloalkylsulfanyl, C1-C4 haloalkylsulfinyl, C1-C4 haloalkylsulfonyl, or C1-C6 haloalkoxy; X1 is either O or NR5; R5 is a C1-C4 alkyl group; R6 is a C1-C4 alkyl, C1-C4 haloalkyl, C1-C4 alkoxy, or C3-C6 cycloalkyl; G1 and G2 are either N or CH, independently of each other. (A radical selected from the group consisting of) The present invention provides agriculturally chemistry-acceptable salts, stereoisomers, enantiomers, tautomers, or N-oxides of the compound or compound of formula I. [Modes for carrying out the invention]

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

[0006] When used herein, "C1~C nThe term "alkyl" refers to saturated linear or branched hydrocarbon radicals having 1 to n carbon atoms bonded via any of the carbon atoms, such as methyl, ethyl, n-propyl, isopropyl, n-butyl, sec-butyl, isobutyl, t-butyl, pentyl, hexyl, and any one of these radicals, as well as their branched isomers. For example, one of the radicals such as 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 can also be cited. As described below, haloalkyl, haloalkylsulfanyl, haloalkylsulfinyl, haloalkylsulfonyl, alkoxy, and haloalkoxy radicals are derived from alkyl radicals.

[0007] Halogens generally refer to fluorine, chlorine, bromine, or iodine. This also applies to halogens in combination with other meanings such as haloalkyl.

[0008] When used herein, "C1~C n The term "haloalkyl" refers to a linear or branched saturated C1-C chain having 1-n carbon atoms (as described above). nRefers to an alkyl radical, and some or all of the hydrogen atoms in these radicals may be replaced by any one of fluorine, chlorine, bromine and / or iodine, that is, for example, as examples, 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, 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, the term "C1-C n alkoxy" refers to a straight-chain or branched saturated C1-C having 1 to n carbon atoms (as described above) bonded through an oxygen atom nThis refers to alkyl radicals, namely methoxy, ethoxy, propoxy, i-propoxy, n-butoxy, isobutoxy, sec-butoxy, t-butoxy, 1-methylpropoxy, 2-methylpropoxy, and 1,1-dimethylethoxy, as well as their isomers pentyloxy and hexyloxy radicals; preferably one of the radicals such as methoxy and ethoxy.

[0010] When used herein, "C1~C n The term "haloalkoxy" refers to C1-C n Similar to alkoxys, linear or branched saturated C1-C atoms have 1-n carbon atoms (as described above) bonded via oxygen atoms. n This refers to haloalkyl radicals.

[0011] When used herein, "C1~C n The term "alkylsulfanyl" refers to a linear or branched saturated alkyl radical having 1 to n carbon atoms (as described above) bonded via a sulfur atom, i.e., one of the following: methylthio, ethylthio, n-propylthio, 1-methylethylthio, butylthio, 1-methylpropylthio, 2-methylpropylthio, or 1,1-dimethylethylthio.

[0012] When used herein, "C1~C n The term "haloalkylsulfanyl" refers to the above C1-C atoms that are partially or completely substituted with fluorine, chlorine, bromine, and / or iodine. nThis refers to alkylsulfanyl radicals, namely, 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 - One of the following: 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 This refers to haloalkylsulfanyl (as described above), but the oxidation state of the sulfur differs; for example, sulfoxide-S(O)C1~C n Haloalkyl or sulfone-S(O)2C1~C n "C1~C" refers to haloalkyl n "Haloalkylsulfinyl" and "C1~C n This also applies to the term "haloalkylsulfonyl." Therefore, examples include trifluoromethylsulfinyl, trifluoromethylsulfonyl, or 2,2,2-trifluoroethylsulfonyl.

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

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

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

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

[0018] A terminal single bond (free radical) represents either a methyl group in relation to a given molecular structure, or a bond site in relation to the definition of a variable element group.

[0019] The compound of formula I according to the present invention also includes hydrates that may be formed during salt formation.

[0020] Embodiments of the present invention are described below.

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

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

[0023] Embodiment 3 provides the compound according to Embodiment 1 or its agrochemically acceptable salt, stereoisomer, enantiomer, tautomer, or N-oxide, wherein, A is either 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 the compound according to Embodiment 1 or its agrochemically acceptable salt, stereoisomer, enantiomer, tautomer, or N-oxide, wherein, A is either CH or N; R1 is ethyl; R2 is hydrogen; R3 is hydrogen, cyano or CO2NH2; and n is 1.

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

[0026] Embodiment 6 provides the compound according to Embodiment 1 or its agrochemically acceptable salt, stereoisomer, enantiomer, tautomer, or N-oxide, wherein, Q refers to Q1, Q2, Q4, and Q5 [ka] (In the formula, the arrows indicate the bonding points to the ring incorporating radical A; R4 is a C1-C2 haloalkyl, a C1-C2 haloalkylsulfanyl, a C1-C2 haloalkylsulfinyl, or a 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 either N or CH, independently of each other. It is a radical selected from among them.

[0027] Embodiment 7 provides the compound according to Embodiment 1 or its agrochemically acceptable salt, stereoisomer, enantiomer, tautomer, or N-oxide, wherein, Q1, Q2, and Q5 [ka] (In the formula, the arrows indicate the bonding points to the ring incorporating radical A; R4 is a 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 either N or CH, independently of each other. It is a radical selected from among them.

[0028] Embodiment 8 provides the compound according to Embodiment 1 or its agrochemically acceptable salt, stereoisomer, enantiomer, tautomer, or N-oxide, wherein, Q refers to Q1 and Q5 [ka] (In the formula, the arrows indicate the bonding points 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. It is a radical selected from among them.

[0029] Embodiment 9 provides the compound according to Embodiment 1 or its agrochemically acceptable salt, stereoisomer, enantiomer, tautomer, or N-oxide, wherein, Q stands for Radical Q1 [ka] (In the formula, the arrows indicate the bonding points to the ring incorporating radical A; R4 is trifluoromethyl; X1 is NCH3; and G1 is N and G2 is CH, or G1 is CH and G2 is N, or G1 and G2 are N. That is the case.

[0030] Embodiment 10 provides a compound according to Embodiment 1 or an agriculturally acceptable salt, stereoisomer, enantiomer, tautomer, or N-oxide thereof, wherein, A is either CH or N; R1 is ethyl, propyl, or isopropyl; R2 is hydrogen, cyano, C1-C3 alkyl, C1-C3 alkylcarbonyl, C1-C3 alkoxycarbonyl, or C1-C3 haloalkylcarbonyl; R3 is hydrogen, C1-C3 haloalkyl, cyano, CO2H, CO2NH2, or C1-C4 dialkylaminocarbonyl; n is 1; Q refers to Q1, Q2, Q4, and Q5 [ka] (In the formula, the arrows indicate the bonding points to the ring incorporating radical A; R4 is a C1-C2 haloalkyl, a C1-C2 haloalkylsulfanyl, a C1-C2 haloalkylsulfinyl, or a 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 either N or CH, independently of each other. It is a radical selected from among them.

[0031] Embodiment 11 provides the compound according to Embodiment 1 or its agrochemically acceptable salt, stereoisomer, enantiomer, tautomer, or N-oxide, wherein, A is either CH or N; R1 is ethyl; R2 is hydrogen; R3 is hydrogen, C1-C2 haloalkyl, cyano, CO2NH2, or C1-C2 dialkylaminocarbonyl; n is 1; Q refers to Q1, Q2, and Q5 [ka] (In the formula, the arrows indicate the bonding points to the ring incorporating radical A; R4 is a 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 either N or CH, independently of each other. It is a radical selected from among them.

[0032] Embodiment 12 provides the compound according to Embodiment 1 or its agrochemically acceptable salt, stereoisomer, enantiomer, tautomer, or N-oxide, wherein, A is either CH or N; R1 is ethyl; R2 is hydrogen; R3 is hydrogen, cyanopropyl alcohol, or CO2NH2; n is 1; Q refers to Q1 and Q5 [ka] (In the formula, the arrows indicate the bonding points 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. It is a radical selected from among them.

[0033] Embodiment 13 provides a compound according to Embodiment 1 or an agriculturally acceptable salt, stereoisomer, enantiomer, tautomer, or N-oxide thereof, wherein, A is either CH or N; R1 is ethyl; R2 is hydrogen; R3 is either hydrogen or cyanoacrylate; n is 1; Q stands for Radical Q1 [ka] (In the formula, the arrows indicate the bonding points to the ring incorporating radical A; R4 is trifluoromethyl; X1 is NCH3; and G1 is N and G2 is CH, or G1 is CH and G2 is N, or G1 and G2 are N. That is the case.

[0034] Embodiment 14 provides a compound according to Embodiments 1, 2, 3, 4, or 5, or an agriculturally 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] (In the formula, the arrows indicate the bonding points to the ring incorporating radical A; and R4 is trifluoromethyl, trifluoromethylsulfanyl, or trifluoromethylsulfonyl. It is a radical selected from among them.

[0035] Embodiment 15 provides the compound according to Embodiment 14 or its agrochemically acceptable salt, stereoisomer, enantiomer, tautomer, or N-oxide, wherein, Q is Q 1-2 Q 1-3 Q 1-4 and Q 1-5 It is a radical selected from among them.

[0036] Embodiment 16 provides a compound according to Embodiments 1, 2, 3, 4, or 5, or an agriculturally acceptable salt, stereoisomer, enantiomer, tautomer, or N-oxide thereof, wherein, Q is Q5 [ka] (In the formula, the arrows indicate the bonding points to the ring incorporating radical A; R4 is trifluoromethyl, trifluoromethylsulfanyl, or trifluoromethylsulfonyl; and R6 is OCH3, CH2CH3, or cyclopropyl. It is a radical selected from among them.

[0037] Embodiment 17 provides a compound according to Embodiments 1, 2, 3, 4, or 5, or an agriculturally acceptable salt, stereoisomer, enantiomer, tautomer, or N-oxide thereof, wherein, Q stands for Radical Q2 [ka] (In the formula, the arrows indicate the bonding points to the ring incorporating radical A; R4 is trifluoromethyl, trifluoromethylsulfanyl, or trifluoromethylsulfonyl; and G2 is N or CH. That is the case.

[0038] Embodiment 18 provides a compound according to Embodiments 1, 2, 3, 4, or 5, or an agriculturally 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 Embodiments 1, 2, 3, 4, or 5, or an agriculturally acceptable salt, stereoisomer, enantiomer, tautomer, or N-oxide thereof, wherein, Q is Q4 [ka] (In the formula, the arrows indicate the bonding points to the ring incorporating radical A; R4 is trifluoromethyl, trifluoromethylsulfanyl, or trifluoromethylsulfonyl; and G1 is N and G2 is CH, or G1 is CH and G2 is N, or G1 and G2 are CH, or G1 and G2 are N; preferably, G1 is CH and G2 is N. That is the case.

[0040] In other embodiments, the present invention provides a composition comprising an insecticidal, acaricidal, nematicidal, or molluscicidal amount of a compound of formula (I) as defined in any of the above embodiments 1 to 19, or an agriculturally acceptable salt, stereoisomer, enantiomer, tautomer, or N-oxide thereof, and optionally an auxiliary agent or diluent.

[0041] In a further embodiment, the present invention provides a method for controlling and eliminating insects, mites, nematodes, or mollusks, comprising the step of applying an insecticidal, acaricidal, nematodetic, or molluscicidal amount of a compound of formula (I) as defined in any of the above embodiments 1 to 19, or its grossically acceptable salt, stereoisomer, enantiomer, tautomer, or N-oxide, or the composition defined above, to a pest, a pest habitat, or a plant susceptible to attack by a pest.

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

[0043] The process according to the present invention for preparing compounds of formula (I) is carried out in principle by methods known to those skilled in the art. A subgroup of compounds of formula I where n is 0, i.e., sulfylimine 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 imination conditions (Step A, Scheme 1). A specific subgroup of compounds of formula I where n is 1, defined as sulfoximine I where R1, R2, R3, A and Q are as defined above, can be obtained by oxidation of sulfylimine 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, thereby allowing the sulfoximine compound of formula I, in which R1, R2, R3, A, and Q are as defined above, to be prepared from the sulfoxide of formula III, in which R1, R2, R3, A, and Q are as defined above, under appropriate imination reaction conditions (step A').

[0045] Typical preparation methods and reaction conditions for obtaining the compound of formula I (either leading to sulfylimine Ia (step A) or 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 imination reagents / conditions can be defined as NaN3 / H2SO4, O-mesitylenesulfonyl hydroxylamine (MSH), or metal-catalyzed methods such 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 oxaziridine (e.g., 3-(4-cyanophenyl)-oxaziridine-2-carboxylate t-butyl ester) [see OGMancheno, C.Bolm, Chem.Eur.J., 2007, 13, 6674-6681].

[0046] Of particular interest are metal-free imination methods for the sulfide of formula II and / or the sulfoxide of formula III to prepare the sulfylimine of formula Ia (step A) and / or the sulfoximine of formula I (step A'). Such imination reactions use R2-NH2 and an oxidizing agent, such as PhI(OAc)2 / R2-NH2, as described in GYCho, 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 also be used as an alternative, for example, as described in OGMancheno, C.Bolm, Org. Lett. 2007, 9, 3809-3811. Examples of hypochlorites used as oxidizing agents, such as sodium hypochlorite (NaOCl) or calcium hypochlorite (Ca(OCl)2), are described in International Publication No. 2008 / 106006.

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

[0048] Detailed preparation conditions useful for the synthesis of these sulfylimine and / or sulfoximine compounds of formulas Ia and I, respectively, are also described, for example, in International Publication 2006 / 061200 or International Publication 2007 / 080131.

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

[0050] The compound of formula Ib (where R1, R3, A, and Q are as defined above, n is 1, and R2 is CN) can be converted to the compound 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, for example, as described in OGMancheno, C.Bolm, Org.Lett.2007, 9, 3809-3811. The compound 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 the compound 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, for example, as described in H. Okamura, C. Bolm, Org. Lett. 2004, 6, 1305-1307. The compound 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 the compound 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, for example, as described in International Publication No. 09 / 111309. A chemical overview is shown in Scheme 2. Scheme 2 [ka]

[0051] The compound of formula Ie (where R1, R3, A, and Q are as defined above, n is 1, and R2 is a C1-C6 alkyl) is an alkylating agent of formula LG-R2 (where LG is a halogen (especially bromine or iodine), sulfonate OSO2R 12 (especially mesylate or tosylate) (where R 12It can be prepared from the compound of formula I (where R1, R3, A, and Q are as defined above, n is 1, and R2 is hydrogen) in an inert solvent at a temperature of -20 to 150°C, preferably 0 to 80°C, in the presence of a suitable base, preferably an alkali metal carbonate such as sodium carbonate or potassium carbonate, or an alkali metal hydride such as sodium hydride, or an alkali metal hydroxide such as sodium hydroxide and potassium hydroxide. 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 dimethyl sulfoxide.

[0052] Compounds of formula If (wherein R1, R3, A, and Q are as defined above, n is 1, and R2 is C(O)R7, and R7 is a C1-C6 alkyl or C1-C6 haloalkyl) can be optionally 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 the reagent of formula LG1-C(O)R7 or the anhydrous reagent of formula R7C(O)-OC(O)R7 (wherein R7 is as defined above, and LG1 is a leaving group such as a halogen (especially chlorine)) in an inert solvent at a temperature of 0-50°C, preferably in the presence of an acylation catalyst such as 4-dimethylaminopyridine (DMAP) and a base such as triethylamine, diisopropylethylamine, or pyridine. Examples of solvents that can be 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 dimethyl sulfoxide. This reaction can also be carried out in the presence of an excess amount of base, which can also act as a solvent or diluent.

[0053] Compounds of formula Ig (wherein R1, R3, A, and Q are as defined above, n is 1, and R2 is C(O)OR8, and R8 is a C1-C6 alkyl or C1-C6 haloalkyl) can be optionally 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 reagent of formula LG2-C(O)OR8 (wherein R8 is as defined above, and LG2 is a leaving group such as a halogen (especially chlorine)) in an inert solvent at a temperature of 0-50°C, preferably in the presence of an acylation catalyst such as 4-dimethylaminopyridine (DMAP) and a base such as triethylamine, diisopropylethylamine, or pyridine. 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 dimethyl sulfoxide. This reaction can also be carried out in the presence of an excess amount of base, which can also act as a solvent or diluent.

[0054] Compound 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 (These are 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 of 0-50°C, according to the formula LG3-C(O)NR9R 10 The reagent (where R9 and R 10The compound of formula I (where R1, R3, A, and Q are as defined above, n is 1, and R2 is hydrogen) can be prepared by treatment with a solvent (where R1, R3, A, and Q are as defined above, and LG3 is a leaving group such as a halogen (especially chlorine)). 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 dimethyl sulfoxide. The reaction can also be carried out in the presence of an excess amount of base, which can also act as a solvent or diluent.

[0055] Compound of formula II (where R1, R3, A and Q are as defined above, n is 1, and R2 is SO2R) 11 And R 11 (where is a C1-C6 alkyl group) is optionally converted in an inert solvent at a temperature of 0-50°C 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, using the formula LG4-SO2R 11 The reagent (where R 11The compound of formula I (where R1, R3, A, and Q are as defined above, n is 1, and R2 is hydrogen) can be prepared by treatment with a solvent (where R1, R3, A, and Q are as defined above, and LG4 is a leaving group such as a halogen (especially chlorine)). 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 dimethyl sulfoxide. The reaction can also be carried out in the presence of an excess amount of base, which can also act as a solvent or diluent. The compound of formula Ij (wherein 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 the compound of formula I (wherein R1, R3, A, and Q are as defined above, n is 1, and R2 is hydrogen) by treatment with a trialkyl orthoformate ester such as trimethyl orthoformate at a temperature of 0 to 180°C, optionally in the presence of an acid activator such as p-toluenesulfonic acid, or optionally in the presence of an inert organic solvent. This reaction can also be carried out in the presence of an excess amount of trialkyl orthoformate ester which can also act as a solvent or diluent. Such a process is illustrated, for example, in International Publication No. 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 several cases, for example: 2-(5-cyclopropyl-3-ethylsulfanyl-2-pyridyl)-5-(trifluoromethoxy)-1,3-benzoxazole, CAS [2128705-99-5], International Publication No. 2017146226; 2-(5-cyclopropyl-3-ethylsulfanyl-2-pyridyl)-5-(difluoromethylsulfanyl)-1,3-benzoxazole, CAS [2128706-06-7], International Publication No. 2017146226; 2-( 5-Cyclopropyl-3-ethylsulfanyl-2-pyridyl)-5-(difluoromethoxy)-1,3-benzoxazole, CAS [2128706-01-2], International Publication No. 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], International Publication No. 2017089190; 5-Cyclopropyl-2-(4-Cyclopropyl-2-ethylsulfanyl 2-(5-(5-(5-(5-(5-(5-(5-(5-(5-(3-(3--(3--(3--(3--(3--(3--(3--(3--(3---3--(3-(3--(3-3--(3-3--(3-3-3-3-33(33-33(33-33(333))-)-)-)-)-(3-(3-(3333)))-)-)-(3-(33333)))-)-)-(3333333333333333333333333333333333333333333333333333333333333333333333333333333333333333333333333333333333333333333333333333333333333333333333 1,3-Benzoxazole, CAS [1975147-94-4], International Publication No. 2017146226; 2-(5-Cyclopropyl-3-ethylsulfanyl-2-pyridyl)-1-methyl-5-(trifluoromethyl)benzimidazole, CAS [1975147-91-1], International Publication No. 2016121997; 2-(5-Cyclopropyl-3-ethylsulfanyl-2-pyridyl)-6-(trifluoromethyl)oxazolo[5,4-b]pyridine, CAS [1975147-87-5], International Publication No. 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], International Publication No. 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], International Publication No. 2016104746; 2-(5-cyclopropyl-3-ethylsulfanyl-2-pyridyl)-3-methyl-6-(trifluoromethyl)imidazo[4,5-b]pyridine, CAS [1951416-89-9], International Publication No. 2016096584; 2-(4-cyclopropyl-2-ethylsulfanyl-phenyl)-7-(trifluoromethyl )imidazo[1,2-c]pyrimidine, CAS[1923785-41-4], International Publication No. 2016071214; 2-(5-cyclopropyl-3-ethylsulfanyl-2-pyridyl)-7-(trifluoromethyl)imidazo[1,2-c]pyrimidine, CAS[1923784-36-4], International Publication No. 2016071214; 2-(4-cyclopropyl-2-ethylsulfanyl-phenyl)-5-eth Lu-3-methyl-6-(trifluoromethyl)imidazo[4,5-c]pyridine-4-one, CAS [1879051-89-4], International Publication No. 2016023954; 2-(4-cyclopropyl-2-ethylsulfanylphenyl)-3,5-dimethyl-6-(trifluoromethyl)imidazo[4,5-c]pyridine-4-one, CAS [1879051-88-3], International Publication No. 2016023954.

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

[0058] More specifically, the compound of formula IIa is (as described in Scheme 4) the compound of formula IIa and the compound of formula V (where X b1 This can be a halogen, preferably chlorine, bromine, or iodine, and Y b1 This includes, for example, boron-derived functional groups such as B(OH)2 or B(OR) such as pinacol boronic acid ester. b1 )2(Here, R b1 This can be a C1-C6 alkyl group, or two OR b1 The group can be prepared by reacting it with (which may form a 5-membered or 6-membered ring together with a boron atom) (see Suzuki cross coupling, 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 with palladium catalysts, e.g., 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 palladium cycle), (1,1'-bis(diphenylphosphino)-ferrocene)dichloropalladium-dichloromethane (1:1 complex) or Palladium acetate + phosphine ligand (e.g., triphenylphosphine or tricyclohexylphosphine) can be catalyzed in a solvent (e.g., toluene, 1,2-dimethoxyethane DME, tetrahydrofuran, or dioxane) or a solvent mixture such as a mixture of 1,2-dimethoxyethane (or dioxane, toluene, or tetrahydrofuran) and water, preferably in an inert atmosphere, in the presence of a base such as sodium carbonate, tripotassium phosphate, or cesium fluoride. The reaction temperature may preferably be in the range of ambient temperature to the boiling point of the reaction mixture, or alternatively, heating may be carried out under microwave irradiation.

[0059] Instead, the compound of formula IV (where X b1 (where Y is a halogen, preferably chlorine, bromine, or iodine) and a compound of formula V (where Y b1 This reaction can be carried out with a magnesium halide group such as -MgBr (Kumada cross-coupling) in the presence of an optional additive such as a zinc halide (Journal of Organic Chemistry, 75(19), 6677-6680; 2010). This reaction can be catalyzed with a palladium-based catalyst or may include a nickel-based catalyst such as 1,3-bis(diphenylphosphin)propanenickel dichloride (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 (where Y b1 The reaction with zinc halides such as -ZnBr (negi-cyclocoupling) is also known. This reaction can be catalyzed, for example, with a palladium-based catalyst containing (1,1'-bis(diphenylphosphin)-ferrocene)dichloropalladium Pd(dppf)Cl2 or bis(triphenylphosphine)palladium(II) dichloride, in the presence of an optional phosphine additive (e.g., 2-dicyclohexyl-phosphin-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 be in the range of 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], International Publication No. 2018 / 077565; 1-[3-ethylsulfanyl-4 Dazo[4,5-c]pyridine-2-yl]phenyl]cyclopropanecarbonitride, CAS[CAS[2225113-73-3], International Publication No. 2018 / 077565; 1-[4-[5-cyclopropyl-3-methyl-4-oxo-6-(trifluoromethyl)imidazo[4,5-c]pyridine-2-yl]-3-ethylsulfanyl-phenyl]cyclopropanecarbonitride, CAS[2098699-74-0], International Publication No. 2017 / 089190; 1-[6-[5-cyclopropyl- 3-Methyl-4-oxo-6-(trifluoromethyl)imidazo[4,5-c]pyridine-2-yl]-5-ethylsulfanyl-3-pyridyl]cyclopropanecarbonitri, CAS[2098699-59-1], International Publication No. 2017 / 089190; 1-[5-ethylsulfanyl-6-[5-(trifluoromethylsulfanyl)-1,3-benzoxazole-2-yl]-3-pyridyl]cyclopropanecarbonitri, CAS[1975148-53-8], International Publication No. 2016 / 12 Publication No. 1997; 1-[3-ethylsulfanyl-4-[7-(trifluoromethyl)imidazo[1,2-c]pyrimidine-2-yl]phenyl]cyclopropanecarbonitrile, CAS [1923785-47-0], International Publication No. 2016 / 071214; 1-[5-ethylsulfanyl-6-[7-(trifluoromethyl)imidazo[1,2-c]pyrimidine-2-yl]-3-pyridyl]cyclopropanecarbonitrile, CAS [1923784-42-2], International Publication No. 2016 / 071214.

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

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

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

[0065] The compound of formula IIb can be further used 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 or completely hydrolyzed to the compound of formula IId under acidic or basic conditions known to those skilled in the art. Optionally, treatment of the compound of formula IIc with a reagent such as SF4 or Fluolead (4-t-butyl-2,6-dimethylphenylsulfate trifluoride) in the presence of HF yields the compound of formula IIe (as described, e.g., in Organic Letters, 16, 6314-6317; 2014).

[0066] A method known to those skilled in the art, for example described in Tetrahedron, 2005, 61(46), 10827-10852, involves the activation of a compound of formula (IId) where R1, Q, and A are as defined in formula I, thereby forming an activated species (IIf) (where Q, R1, and A are as defined in formula I, and X0 is a halogen, preferably chlorine). For example, a 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 at a temperature of 20 to 100°C, preferably 25°C, in the presence of a catalytic amount of N,N-dimethylformamide DMF. Alternatively, for example, treatment of the compound of formula (IId) with 1-ethyl-3-(3-dimethylaminopropyl)carbodiimide EDC or dicyclohexylcarbodiimide DCC is performed at a temperature of 50-180°C in an inert solvent such as pyridine or tetrahydrofuran THF, optionally in the presence of a base such as triethylamine, to activate the species (XII) (where X0 is X, respectively). 01 or X 02 This results in the following: such an activated intermediate of formula Iif can be optionally activated in the presence of a base such as triethylamine, pyridine, or DMAP, in an inert solvent such as CH2Cl2, THF, or acetonitrile, and thus the HNR formula 101 R 012 The amine (where R 101 and R 102 (is hydrogen or C1-C6 alkyl) or HOR 103 It is possible to react these compounds with nucleophiles such as (where R103 is a C1-C6 alkyl group) to obtain compounds of formula Iig and Iih, respectively. Such reactions are well known to those skilled in the art. A post-conversion of cyanocyclopropyl is illustrated in Scheme 6. Scheme 6 [ka]

[0067] Formula II-Q1 [ka] (In the formula, R1, R3, R4, X1, G1, and G2 are as defined in formula I.) The compound of formula II that defines the compound (where Q is Q1) can be prepared as shown in scheme 7. Scheme 7 [ka]

[0068] As shown in Scheme 7, the compounds of formula II-Q1 can be prepared by cyclizing the compound of formula (XIV), where R1, R3, R4, A, X1, G1, and G2 are as defined in formula I, by heating in acetic acid or trifluoroacetic acid (preferably when X1 is NR5, where R5 is a C1-C4 alkyl group) at a temperature of 0-180°C, preferably 20-150°C, and optionally under microwave irradiation. The cyclization of the compound of formula (XIV) can also be achieved at a temperature of 25-180°C, preferably 100-170°C, in an inert solvent such as N-methylpyrrolidone, toluene, or xylene, in the presence of an acid catalyst such as methanesulfonic acid or p-toluenesulfonic acid p-TsOH. Such a process has been previously described, for example, in International Publication No. 2016096584. Alternatively, the compound of formula (XIV) can be converted to the compound of formula II-Q1 (preferably when X1 is O) at a temperature of 20-50°C in an inert solvent such as tetrahydrofuran THF using triphenylphosphine, di-isopropyl azodicarboxylate (or di-ethyl azodicarboxylate). Such Mitsunobu conditions have been previously described for these conversions (see International Publications 2009 / 131237 and 2016 / 121997).

[0069] Compounds of formula (XIV), where R1, R3, R4, A, X1, G1, and G2 are as defined in formula I, can be prepared by acylation as follows: i) Activation of a compound of formula (XIII) in which R1, R3, and A are as defined in formula I, by methods known to those skilled in the art and by the method described in Tetrahedron, 2005, 61(46), 10827-10852, in which an activated species (XII) (wherein R1, R3, and A are as defined in formula I, and X0 is a halogen, preferably chlorine) is formed. For example, compound (XII) in which X0 is a halogen, preferably chlorine, is 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 at a temperature of 20 to 100°C, preferably 25°C, in the presence of a catalytic amount of N,N-dimethylformamide DMF. Alternatively, the compound of formula (XIII) can be activated by treatment with, for example, 1-ethyl-3-(3-dimethylaminopropyl)carbodiimide EDC or dicyclohexylcarbodiimide DCC at a temperature of 50-180°C in an inert solvent such as pyridine or tetrahydrofuran THF, optionally in the presence of a base such as triethylamine (XII) (where X0 is X). 01 or X 02 (is) is generated; followed by, ii) Treatment of activated species (XII) with a compound of formula (XI) in which X1, G1, G2 and R4 are as defined in formula I, in the presence of a base such as triethylamine, N,N-diisopropyl-ethylamine 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 to 50°C, thereby forming a compound of formula (XIV). Compounds of formula XIII where R3 is H, i.e., compounds where R1 is ethyl, R3 is H, and A is N or CH, are known and described in International Publication No. 2017146226 or International Publication No. 2016121997 (5-cyclopropyl-3-ethylsulfanylpyridine-2-carboxylic acid, CAS [1975148-58-3]) and International Publication No. 2016023954 (4-cyclopropyl-2-ethylsulfanylbenzoic acid, CAS [1879052-58-0]). Compound XIII of formula (where R3 is cyano, R1 is ethyl, and A is CH) (4-(1-cyanocyclopropyl)-2-ethylsulfanylbenzoic acid, CAS [2225113-79-9]) and compound XIII of formula (where R3 is cyano, R1 is ethyl, and A is N) (5-(1-cyanocyclopropyl)-3-ethylsulfanylpyridine-2-carboxylic acid, CAS [2225113-77-7]) are known and described in International Publication No. 2018 / 077565.

[0070] Compounds of formula (XI), where X1, G1, G2, and R2 are as defined in formula I, have been described, for example, in International Publication No. 2012 / 086848, International Publication No. 2015 / 000715, and International Publication No. 2016 / 116338.

[0071] Compounds of formula II-Q2 (where R1, R3, R4, A, and G2 are as defined in formula I) Scheme 8 [ka] The compound of formula II that defines (where Q is Q2) can be prepared, for example, by condensing the compound of formula (XVI) (where R1, R3, and A are as defined in formula I, and Xc is a leaving group such as chlorine, bromine, or iodine (preferably chlorine or bromine)) with the compound of formula (XVI) (where G2 and R2 are as defined in formula I) at a temperature of 80 to 150°C, optionally under microwave heating conditions, in an inert solvent such as ethanol or acetonitrile (Scheme 8). Such a process has been previously described, for example, in International Publication No. 2012 / 49280 or International Publication No. 2003 / 031587. The compound of formula (XV), where G2 and R2 are as defined in formula I, is a known compound that is commercially available or can be prepared by methods known to those skilled in the art.

[0072] Compounds of formula (XVI) (where R1, R3, and A are as defined in formula I, and Xc is a leaving group such as chlorine, bromine, or iodine (preferably chlorine or bromine)). Scheme 9 [ka] 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 of 0°C to 150°C, preferably room temperature to 120°C, and optionally under microwave heating conditions, a halogenating agent such as N-bromosuccinimide, N-iodosuccinimide, N-chlorosuccinimide, I2, CuBr2, Br2 ("Xc") is heated. +It can be prepared by processing a compound of formula (XVIII) with R1, R3, and A as defined in formula I (Scheme 9). Such a process has been previously described, for example, in International Publication No. 2016 / 071214.

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

[0074] Compounds of formula (XVII) (where R1 and A are as defined in formula I, and Xa is a leaving group such as chlorine, bromine, or iodine), in particular where Xa is a halogen (more preferably chlorine, bromine, or iodine; especially preferably chlorine or bromine), are commercially available or known compounds that can be prepared by known methods described in literature such as International Publication No. 2016 / 071214.

[0075] Instead, the compound of formula II-Q5 (where R1, R3, R4, R6, and A are as defined in formula I) Scheme 9a: [ka] The compound of formula II that defines (where Q is Q5) can be prepared by cyclization of the compound of formula (XXa) or the positional isomer of formula (XXb) in which R1, R3, R4, R5, R6 and A are as defined in formula I, or of a mixture thereof in any ratio, under the conditions described above (see Scheme 7, Conversion of compound (XIV) to II-Q1) (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 treating the above-mentioned activating species (XII) with the compound of formula (XIX) in which R4, R5, and R6 are as defined in formula I, under the conditions 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 described, for example, in International Publication Nos. 2016 / 023954, 2016 / 142326, 2017 / 133994, and 2018077565.

[0078] Instead, the compound of formula II-Q3 (where R1, R4, R3, and A are as defined in formula I) Scheme 10 [ka] The compound of formula II that defines (where Q is Q3) can be prepared by condensing the compound of formula (XVI) (where R1, R3, and A are as defined in formula I, and Xc is a leaving group such as chlorine, bromine, or iodine (preferably chlorine or bromine)) with the compound of formula (XXI) (where R4 is as defined in formula I) at a temperature of 80 to 150°C, optionally under microwave heating conditions, in the presence of a suitable base such as an inert solvent, e.g., ethanol, toluene, or acetonitrile, optionally sodium carbonate, potassium carbonate, or cesium carbonate (or sodium bicarbonate or potassium bicarbonate), or magnesium oxide (Scheme 10). Such a process has been previously described, for example, in International Publication No. 2011 / 074658. Compounds of formula (XXI), where R4 is as defined in formula I, are commercially available or known compounds that can be prepared by methods known to those skilled in the art (see, for example, International Publication No. 2011 / 074658 and International Publication No. 2010 / 083145).

[0079] Formula II-Q4 [ka] (In the formula, R1, R3, R4, G1, G2, and A are as defined in formula I.) compounds Scheme 11 [ka] The compound of formula II that defines (where Q is Q4) can also be prepared via the NN bond formation reaction of the azidoimine of the compound of formula (XXV) where R1, R4, R7, R8, A, G1, G2 and R2 are as defined in formula I, under thermal decomposition conditions that promote the emission of N2 (Scheme 11). Alternatively, this reaction may be carried out in combination with ligands such as tetramethylethylenediamine, 2,2'-bipyridine or 1,10-phenanthroline, in the presence of a metal catalyst such as a Cu(I) catalyst such as CuI, CuBr, CuCl or CuCN, or more generally with a transition metal. Suitable solvents may include the use of toluene, chlorobenzene or xylene at a temperature of room temperature to 200°C, preferably 100 to 160°C, and 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), where R1, R3, R4, G1, G2, and A are as defined in formula I, can usually be prepared by the reaction of a compound of formula (XXIII), where R1, R3, and A are as defined in formula I, with a compound of formula (XXIV), where G1, G2, and R4 are as defined in formula I, by heating in a suitable solvent that can be used, such as toluene or xylene, at a temperature of room temperature to 200°C, preferably 40 to 160°C, and optionally under microwave heating conditions. The formation of compounds of formula (XXV) may require the removal of water by azeotropic distillation or by a desiccant such as TiCl4 or by molecular sieving. The formation of such Schiff bases of formula (XXV) is known to those skilled in the art and is described, for example, in International Publication No. 2017 / 134066. Compounds of formula XXIV have been reported in the literature (see CAS 2211908-96-0 reported in International Publication No. 2018 / 052136).

[0081] Compounds of formula XXIII can be prepared by the reaction of compounds of formula XXII in the presence of acids such as HCl, H2SO4, H3PO4, HNO3, and TFA. Such deprotection reactions of N-bonded 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 the reaction of compound XIII with an organic azide or ammonia derivative (e.g., NH4OH, NH3, NH2Boc) at a temperature of 50°C to 200°C in the presence or absence of a suitable base, a Lewis acid, and a solvent. Examples of organic azides include TMSN3, sodium azide, diphenyl phosphoryl azide, or tosyl azide, and suitable solvents may be t-BuOH, toluene, xylene, THF, or acetonitrile. An example of a suitable Lewis acid is Zn(OTf)2. Such reactions that convert carboxylic acids to amines are well known to those skilled in the art under the name of the Curtius reaction and have been reported in Org. Lett., 2005, 7, 4107-4110; Journal of Medicinal Chemistry, 49(12), 3614-3627; 2006.

[0083] Instead, the compounds of formula II-Q4, where R1, R3, R4, G1, G2 and A are as defined in formula I, are, for example, in the presence of a base such as cesium carbonate, sodium carbonate, potassium carbonate or lithium carbonate or sodium hydride, optionally in the presence of copper(I) iodide or a palladium-catalyzed metal catalyst, with or without additives such as L-proline, N,N'-dimethylethylenediamine or phosphorus-based ligands, in an inert solvent such as acetonitrile, N,N-dimethylformamide, N-methyl-2-pyrrolidone or dimethyl sulfoxide, at a temperature of room temperature to 200°C, optionally under microwave heating conditions, to produce the compounds of formula (XXVI) (where R4, G1, G2 are as defined in formula I, and L GThe compounds of formula XXVII can be prepared by reacting a leaving group (for example, chlorine, bromine, or iodine (preferably chlorine or bromine), or an aryl-, alkyl-, or haloalkyl sulfonate such as trifluoromethanesulfonic acid) with a compound of formula (XXVII) where G1, G2, and R4 are as defined in formula I. Conditions for such aromatic nucleophilic substitution reactions are described, for example, in International Publication No. 2017 / 134066. Compounds of formula XXVII can be obtained by the Sandmeyer reaction, i.e., diazotization of compound XXIII with NaNO2 or tBu-ONO by subsequent addition of an inorganic halide such as CuBr2, CuCl, or KI in an inert solvent such as t-BuOH or water. Such Sandmeyer reactions are well known in the literature (see, for example, Synthesis, 2007, 2534-2538, Org. Lett., 2008, 10, 3961-3964 and the literature cited therein).

[0084] The reactants can be reacted in the presence of a base. Suitable bases include 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 include 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]undeca-7-ene (DBU).

[0085] The reactants can react with each other as they are, i.e., without adding a solvent or diluent. However, in most cases, 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 act as a solvent or diluent.

[0086] The reaction is most advantageous when carried out at a temperature range of approximately -80°C to approximately +140°C, preferably approximately -30°C to approximately +100°C, and often within the range of approximately +80°C from the ambient temperature.

[0087] A compound of formula I can be converted to another compound of formula I in a manner known to itself by conventionally substituting one or more substituents of the starting compound of formula I with other substituents according to the present invention.

[0088] Depending on the selection of suitable reaction conditions and starting materials, for example, in one reaction step, one substituent may be simply substituted with another substituent according to the present invention, or multiple substituents may be substituted with other substituents according to the present invention in the same reaction step.

[0089] Salts of the compounds of formula I can be prepared by known methods. For example, acid addition salts of the compounds of formula I can be obtained by treatment with a suitable acid or a suitable ion exchange reagent, and salts with a base can be obtained by treatment with a suitable base or a suitable ion exchange reagent.

[0090] Salts of the compound of formula I can be conventionally converted, for example, to acid addition salts of free compound I by treatment with a suitable basic compound or a suitable ion exchange reagent, and to base salts by treatment with a suitable acid or a suitable ion exchange reagent.

[0091] Salts of the compound of formula I can be converted to other salts of the compound of formula I, acid addition salts, such as other acid addition salts, by methods known to themselves, by treating an inorganic salt, such as a hydrochloride salt, with a suitable metal salt, such as a sodium salt, barium salt, or silver salt of an acid, such as silver acetate, in a suitable solvent in which the inorganic salt forming silver chloride is insoluble and therefore precipitates from the reaction mixture.

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

[0093] The compounds of formula I and, if applicable, their tautomers, may exist in free or salt form, in the form of one of the possible isomers or as mixtures thereof, depending on the number, absolute and relative configuration of chiral carbon atoms present in the molecule and / or the configuration of non-aromatic double bonds present in the molecule, for example, in the form of pure isomers such as anticarpone and / or diastereomers, or as isomer mixtures such as racemates, diastereomer mixtures or racemic mixtures; the present invention relates to pure isomers and also to all possible isomer mixtures, and should be understood in this sense above and below, respectively, even if stereochemical details are not specifically described for each.

[0094] A diastereomer or racemic mixture of compounds of formula I can be separated into pure diastereomers or racemates based on physicochemical differences of the components, for example by fractional crystallization, distillation and / or chromatography, in the free or salt forms obtained depending on the selected starting materials and procedure.

[0095] Enantiomer mixtures such as racemates obtained by similar methods can be broken down into optical enantiomers by known methods, for example, by recrystallization from an optically active solvent, by chromatography in a chiral adsorbent, for example by high-performance liquid chromatography (HPLC) in acetylcellulose using a suitable microorganism, by cleavage by a specific immobilized enzyme via the formation of an inclusion compound, for example using a chiral crown ether into which only one enantiomer is combined, or by conversion to a diastereomer salt, for example by reacting the basic final 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 camphor sulfonic acid, and separating the diastereomer mixture thus obtained, for example by fractional crystallization based on different solubility, to obtain a diastereomer from which the desired enantiomer can be released by the action of a suitable substance, for example a basic substance.

[0096] Pure diastereomers or enantioisomers can be obtained not only by separating a suitable mixture of isomers according to the present invention, but also by generally known methods of diastereoselective or enantioselective synthesis, for example, by performing the method according to the present invention using starting materials having stereochemical properties.

[0097] N-oxides can be prepared by reacting the compound of formula I with a suitable oxidizing agent, such as an H2O2 / urea adduct, in the presence of an acid anhydride, such as trifluoroacetic anhydride. Such oxidation is known from literature such as J.Med.Chem.,32(12),2561-73,1989 or International Publication No. 2000 / 15615.

[0098] When individual components have different biological activities, it is advantageous to isolate or synthesize each component into a more biologically effective isomer, such as an enantiomer or diastereomer, or a mixture of isomers, such as a mixture of enantiomers or diastereomers.

[0099] The compounds of formula I and, optionally, their tautomers may be obtained in free form or salt form, and optionally in hydrate form, and / or in other solvents, such as solvents that have been used to crystallize compounds existing 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 methods described above. The following examples are intended to illustrate the present invention and show preferred compounds of formula I.

[0101] Tables Y-1 to Y-8 are formulas [ka] It 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 and R4 are as defined in Table Z.

[0104] For example, compound Y-1.001 has the following structure; [ka] It 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 and R4 are as defined in Table Z.

[0106] For example, compound Y-2.001 has the following structure; [ka] It 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 and R4 are as defined in Table Z.

[0108] For example, compound Y-3.001 has the following structure; [ka] It 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 and R4 are as defined in Table Z.

[0110] For example, compound Y-4.001 has the following structure; [ka] It 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 and R4 are as defined in Table Z.

[0112] For example, compound Y-5.001 has the following structure; [ka] It 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 and R4 are as defined in Table Z.

[0114] For example, compound Y-6.001 has the following structure; [ka] It 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 and R4 are as defined in Table Z.

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

[0117] Table Y-8 provides eight compounds Y-8.001 to Y-8.008 of formula IaY, 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;

Chem.

[0119] Tables X-1 to X-8 refer to compounds of the formula

Chem.

[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;

Chem.

[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 X-6.001 to X-6.008 of formula Ib, 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 X-7.001 to X-7.008 of formula Ib, 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 X-8.001 to X-8.008 of formula Ib, 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 compounds of formula I of the present invention, where R2 is H and n is 1.

Chemical formula

[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:

Chem.

[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:

Chem.

[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:

Chem.

[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:

Chem.

[0139] Table V-5 provides nine compounds of formula I, V-5.001 to V-5.009, 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] It 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] It has.

[0143] Tables U-1 to U-2 are formulas [ka] It 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 and R4 are as defined in Table Z.

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

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

[0147] The compound of Formula I according to the present invention is an active ingredient that is beneficial preventively and / or therapeutically in the field of pest control even at low application rates, and it has a very favorable biocidal spectrum and exhibits good tolerance by warm-blooded animal species, fish, and plants. The active ingredient according to the present invention acts not only on commonly susceptible animal pests, such as typical examples of insects, mollusks, nematodes, or mites (Acarina), but also on all or individual developmental stages of resistant animal pests. The insecticidal, molluscicidal, nematodicidal, or acaricidal activity of the active ingredient according to the present invention can be manifested directly (i.e., death of pests that occur immediately or only after a certain period of time (e.g., during molting)) or indirectly (e.g., reduction of oviposition and / or hatching rates, good activity corresponding to a mortality rate of at least 50-60%).

[0148] The compounds of formula (I) according to the present invention may have any number of advantages, including, in particular, advantageous levels of biological activity for protecting plants from insects or excellent properties for use as agricultural chemical active ingredients (e.g., higher biological activity, advantageous activity range, high safety profile, improved physicochemical properties, or high biodegradability or environmental profile). In particular, certain compounds of formula (I) have been unexpectedly found to exhibit advantageous safety profiles for non-target organisms such as non-target arthropods, especially pollinators such as honeybees, solitary honeybees and bumblebees. More specifically, the European honeybee (Apis mellifera).

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

[0150] Furthermore, surprisingly, the compound of formula (I) was found to exhibit advantageous physicochemical properties, particularly for crop protection applications, such as a low melting point, low lipophilicity, and high water solubility. These properties have been found to be advantageous for plant uptake and systemic distribution in controlling the specific 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 as follows: From the order Acari (Acarina), for example, genera such as Acalitus spp., Aculus spp., Acaricalus spp., Aceria spp., Acarus siro, Amblyomma spp., Argas spp., Boophilus spp., Brevipalpus spp., Bryobia spp., Calipitrimerus spp., Chorioptes spp., Dermanyssus gallinae, Dermatophagoides spp., Eotetranychus spp.) Eriophyes spp., Hemitarsonemus spp., Hyalomma spp., Ixodes spp., Olygonychus spp., Ornithodoros spp., Polyphagotarsone latus, Panonychus spp., Phyllocoptruta oleivora, Phytonemus spp., Polyphagotarsonemus spp., Psoroptes spp., Rhipicephalus (spp.), genera Rhizoglyphus, Sarcoptes, Steneotarsonemus, Tarsonemus, and Tetranychus; From the order Anoplura, for example, the genera Haematopinus, Linognathus, Pediculus, Pemphigus, and Phylloxera; From the order Coleoptera, for example, the genera Agriotes spp., Amphimallon majale, Anomala orientalis, Anthonomus spp., Aphodius spp., Astylus atromaculatus, Atenius spp., Atomaria linearis, Chaetocnema tibialis, Cerotoma spp., Connoderus spp., Cosmopolites spp., Cotinis nitida, Curculio spp.), Cyclocephala spp., Dermestes spp., Diabrotica spp., Diloboderus abderus, Epilachna spp., Eremnus spp., Heteronychus arator, Hypothenemus hampei, Lagria vilosa, Leptinotarsa ​​decemLineata, Lissorhoptrus spp., Liogenys spp., Maecolaspis spp., Maledra *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 family, Sitophilus spp., Sitotroga spp., Somaticus spp., Sphenophorus spp., Sternechus subsignatus, Tenebrio spp., Tribolium spp., and Trogoderma spp.; From the order Diptera, for example, genera such as Aedes, Anopheles, Antherigona soccata, Bactrocea oleae, Bibio hortulanus, Bradysia, Calliphora erythrocephala, Ceratitis, Chrysomyia, Culex, Cuterebra, Dacus, Delia, Drosophila melanogaster, and Fannia. spp.), Gastrophilus spp., Geomyza tripunctata, Glossina spp., Hypoderma spp., Hyppobosca spp., Liriomyza spp., Lucilia spp., Melanagromyza spp., Musca spp., Oestrus spp., Orseolia spp., Oscinella frit, Pegomyia hyoscyami, Phorbia (spp.), Rhagoletis spp., Riveria quadrifasciata, Scatella spp., Sciara spp., Stomoxys spp., Tabanus spp., Tannia spp., and Tipula spp.; From the order Hemiptera, for example, Acanthocoris scabrator, Acrosternum spp., Adelphocoris lineolatus, Amblypelta nitida, Bathycoelia thalassina, Blissus spp., Cimex spp., Clavigralla tomentosicollis, Creontiades spp., Distantiella theobroma, Dichelops furcatus, Dysdercus spp., Edessa spp.) Euschistus spp., Eurydema pulchrum, Eurygaster spp., Halyomorpha halys, Horcias nobilellus, Leptocorisa spp., Lygus spp., Margarodes spp., Murgantia histrionic, Neomegalotomus spp., Nesidiocoris tenuis, Nezara spp., Nysius simulans, Oebalus insularis Piesma spp., Piezodorus spp., Rhodnius spp., Sahlbergella singularis, Scaptocoris castanea, Scotinophara spp.), *Thyanta* spp., *Triatoma* spp., *Vatiga illudens*; Acyrthosium pisum, Adalges spp., Agalliana ensigera, Aganoscena targionii, Aleurodicus spp., Aleurocanthus spp., Aleurolobus barodensis, Aleurothrixus floccosus, Aleyrodes brassicae, Amarasca biguttula, Amritodus atkinsoni, Aonidiella (spp.), Aphididae family, Aphis spp., Aspidiotus spp., Aulacorthum solani, Bactericera cockerelli, Bemisia spp, Brachycaudus spp, Brevicoryne brassicae, Cacopsylla spp, Cavariella aegopodii Scop., Ceroplaster spp.), Chrysomphalus aonidium, Greenhouse scale insect (Chrysomphalus dictyospermi), Cicadella spp., White leafhopper (Cofana spectra), Cryptomyzus spp., Cicadulina spp., Flat scale insect (Coccus hesperidum), Dalbulus maidis, Dialeurodes spp., Citrus psyllid (Diaphorina citri), Diuraphis noxia, Dysaphis spp., Empoasca spp., Apple woolly aphid (Eriosoma larigerum), Erythroneura spp., Gascardia spp., Glycaspis brimblecombei, Hyadaphis pseudobrassicae, Hyalopterus spp., Hyperomyzus pallidus, Idioscopus clypealis, Jacobiasca lybica, Laodelphax spp., Lecanium corni, Lepidosaphes spp., Lopaphis erysimi), Lyogenys maidis, Macrosiphum spp., Mahanarva spp., Metcalfa pruinosa, Metopolophium dirhodum, Myndus crudus, Myzus spp.), Neotoxoptera sp., Nephotettix spp., Nilaparvata spp., Nippolachnus piri Mats, Odonaspis ruthae, Oregma lanigera Zehnter, Parabemisia myricae, Paratrioza cockerelli, Parlatoria spp., Pemphigus spp., Peregrinus maidis, Perkinsiella spp., Phorodon humuli), Phylloxera spp., Planococcus spp., Pseudaulacaspis spp., Pseudococcus spp., Cotton flea beetle (Pseudatomoscelis seriatus), Psylla spp., Pulvinaria aethiopica, Quadraspidiotus spp., Quesada gigas, Lightning leafhopper (Recilia dorsalis), Rhopalosiphum spp., Saissetia spp., Scaphoideus (spp.), Schizaphis spp., Sitobion spp.), Sogatella furcifera, Spissistilus festinus, Tarophagus Proserpina, Toxoptera spp., Trialeurodes spp., Tridiscus sporoboli, Trionymus spp., Trioza erytreae, Unaspis citri, Zygina flammigera, Zyginidia scutellaris; From the order Hymenoptera, for example, the genera Acromyrmex, Arge, Atta, Cephus, Diprion, Diprionidae, Gilpinia polytoma, Hoplocampa, Lasius, Monomorium pharaonis, Neodiprion, Pogonomyrmex, Slenopsis invicta, Solenopsis, and Vespa; From the order Isoptera, for example, the genera Coptotermes, Corniternes cumulans, Incisitermes, Macrotermes, Mastotermes, Microtermes, Reticulitermes, and Solenopsis gemminate. 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), peach fruit moth (Carposina nipponensis), Chilo spp., Choristoneura spp., Chrysoteuchia topiaria, grape leafroller (Clysia ambiguella), Cnaphalocrocis spp., Cnephasia spp., Cochylis spp., Coleophora spp., Colias lesbia, cotton leafroller (Cosmophila flava), Crambus spp., hairy leafroller (Crocidolomia binotalis), Cryptophlebia leucotoreta 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.), fall webworm (Hyphantria cunea), Keiferia lycopersicella, sorghum moth (Lasmopalpus lignosellus), Leucoptera scitella, Lithocollethis spp., Lobesia botrana, Loxostege bifidalis, Lymantria spp., Lyonetia spp., Malacosoma spp., armyworm (Mamestra brassicae), tobacco hawk moth (Manduca sexta), Mythimna spp., Noctua spp., Operophtera spp., Orniodes indica, Ostrinia nubilalis, Pammene spp., Pandemis spp.), pine moth (Panolis flammea), Papaipema nebris, cotton beetle (Pectinophora gossypiela), coffee leafminer (Perileucoptera coffeella), Pseudaletia unipuncta, potato 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.), genera Sparganothis, Spodoptera, Sylepta derogate, Synanthedon, Thaumetopoea, Tortrix, Trichoplusia ni, Tuta absoluta, and Yponomeuta spp.); From the order Mallophaga, for example, the genera Damalinea and Trichodectes; From the order Orthoptera, for example, the genera Blatta, Blattella, Grilloalpa, Leucophaea maderae, Locusta, Neocurtilla hexadactyla, Periplaneta, Scapteriscus, and Schistocerca; From the order Psocoptera, for example, the genus Liposcelis spp.; From the order Siphonaptera, for example, the genera Ceratophyllus, Ctenocephalides, and Xenopsylla cheopis; From the order Thysanoptera, for example, Calliothrips phaseoli, Frankliniella spp., Heliothrips spp., Hercinotothrips spp., Parthenothrips spp., Scirtothrips aurantii, Sericothrips variabilis, Taeniothrips spp., and Thrips spp.; From the silvery-eyed species (Thysanura), for example, the European silverfish (Lepisma saccharina).

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

[0153] Suitable target crops include grains such as wheat, barley, rye, oats, rice, maize, or sorghum; beets such as sugar beets or fodder beets; fruits such as apples, pears, plums, peaches, almonds, cherries, or berries; pome fruits such as strawberries, raspberries, or blackberries; drupes or soft fruits; legumes such as kidney beans, lentils, peas, or soybeans; rapeseed, mustard, poppies, olives, sunflowers, palms, castor beans, cocoa, or ground potatoes. Oil crops such as nuts; cucurbitaceous plants such as pumpkins, cucumbers, or melons; fiber plants such as cotton, flax, hemp, or jute; citrus fruits such as oranges, lemons, grapefruit, or tangerines; vegetables such as spinach, lettuce, asparagus, cabbage, carrots, onions, tomatoes, potatoes, or bell peppers; plants of the Lauraceae family such as avocados, cinnamon, or camphor; and further, tobacco, nuts, coffee, eggplant, sugarcane, tea, pepper, grapes, hops, plants of the Plantaginaceae family, and latex plants.

[0154] The compositions and / or methods of the present invention may also be used for any ornamental plants and / or vegetable crops, including flowers, shrubs, broad-leaved trees and evergreen trees.

[0155] For example, the present invention can be used for 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., Elatior begonia, B. semperflorens, B. tubereux), Bougainvillea spp., Brachycome spp., Brassica (Ornamental plants), Calceolaria spp., Capsicum annuum, Catharanthus roseus, Canna spp., Centaurea spp., Chrysanthemum spp., Cineraria spp. (Dusty Miller (C. maritime)), Coreopsis spp., Crassula coccinea, Cuphea ignea, Dahlia spp., Delphinium spp., Dicentra spectabilis, Dorotheanthus spp.), Eustoma grandiflorum, Forsythia spp., Fuchsia spp., Geranium gnaphalium, Gerbera spp., Gomphrena globosa, Heliotropium spp., Helianthus spp., Hibiscus spp., Hortensia spp.), Hydrangea spp., Hypoestes phyllostachya, Impatiens spp. (African balsam (I. Walleriana)), Iresine spp., Kalanchoe spp., Lantana camara, Lavatera trimestris, Leonotis leonurus, Lilium spp., Mesembryanthemum spp., Mimulus spp., Monarda spp., Nemesia spp., Tagetes spp.), Dianthus spp. (carnation), Canna spp., Oxalis spp., Bellis spp., Pelargonium spp. (ivy geranium (P. peltatum), P. Zonale), Viola spp. (pansy), Petunia spp., Phlox spp., Plectranthus spp., Poinsettia spp., Parthenocissus spp. (American ivy (P. quinquefolia), Ivy (P. tricuspidata)), Primula spp. Ranunculus spp., Rhododendron spp., Rosa spp., Rudbeckia spp., Saintpaulia spp., Salvia spp., Blue fan flower (Scaevola aemola), Schizanthus wisetonensis, Sedum spp., Solanum spp., Surfinia spp., Tagetes spp.), tobacco (Nicotinia spp.), verbena species (Verbena spp.), zinnia spp., and other bedding plants.

[0156] For example, the present invention can be used for 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. (wild cabbage (B. Oleracea), Chinese cabbage (B. Pekinensis), turnip (B. rapa)), chili pepper (Capsicum annuum), chickpea (Cicer arietinum), endive (Cichorium endivia), Cichorium (spp.) (Chicory (C. intybus), Endive (C. endivia)), Watermelon (Citrillus lanatus), Cucumis spp. (Saffron (C. sativus), Melon (C. melo)), Pumpkin (Cucurbita spp.) (Pepo pumpkin (C. pepo), European pumpkin (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)), Mentha spp., Basil (Ocimum basilicum), Parsley (Petroselinum crispum), Phaseolus spp. (Green bean (P. vulgaris), Red bean (P.Coccineus, peas (Pisum sativum), radishes (Raphanus sativus), round-leaved rhubarb (Rheum rhaponticum), rosemarinus spp., Salvia spp., yellow rose lily (Scorzonera hispanica), eggplant (Solanum melongena), spinach (Spinacea oleracea), Valerianella spp. (Valerianella locusta, Italian corn salad (Valerianella eriocarpa)), and broad beans (Vicia faba).

[0157] Preferred ornamental plant species include African violet, begonia, dahlia, gerbera, hydrangea, verbena, rose, kalanchoe, poinsettia, aster, cornflower, coreopsis, delphinium, monarda, phlox, and sedge. Examples include the genera Rudbeckia, Sedum, Petunia, Viola, Impatiens, Geranium, Chrysanthemum, Ranunculus, Fuchsia, Salvia, Hortensia, rosemary, sage, St. Johnsworth, mint, bell pepper, tomato, and cucumber.

[0158] The active ingredient according to the present invention is particularly suitable for controlling bean aphids (Aphis craccivora), Diabrotica balteata, Heliothis virescens, Myzus persicae, diamondback moth (Plutella xylostella), and Egyptian armyworm (Spodoptera littoralis) in cotton, vegetables, corn, rice, and soybean crops. The active ingredient according to the present invention is further particularly suitable for controlling the genera Mamestra (preferably in vegetables), codling moth (Cydia pomonella) (preferably in apples), the genera Empoasca (preferably in vegetables and vineyards), the genera Leptinotarsa ​​(preferably in potatoes), and rice stem borer (Chilo supressalis) (preferably in rice).

[0159] The active ingredient according to the present invention is particularly suitable for controlling bean aphids (Aphis craccivora), Diabrotica balteata, Heliothis virescens, Myzus persicae, diamondback moth (Plutella xylostella), and Egyptian armyworm (Spodoptera littoralis) in cotton, vegetables, corn, rice, and soybean crops. The active ingredient according to the present invention is even more particularly suitable for controlling armyworms (Mamestra) (preferably in vegetables), codling moths (Cydia pomonella) (preferably in apples), the genus Empoasca (preferably in vegetables and vineyards), the genus Leptinotarsa ​​(preferably in potatoes), and rice stem borer (Chilo supressalis) (preferably in rice).

[0160] In a further embodiment, the present invention relates to plant parasitic nematodes (endoparasitic, semi-endoparasitic and ectoparasitic nematodes), particularly root-knot nematodes, northern root-knot nematodes (Meloidogyne hapla), sweet potato root-knot nematodes (Meloidogyne incognita), Javan root-knot nematodes (Meloidogyne javanica), arenaria root-knot nematodes (Meloidogyne arenaria) and other species of the genus Meloidogyne; cyst-forming nematodes, potato cyst nematodes (Globodera rostochiensis) and other species of the genus Globodera; wheat cyst nematodes (Heterodera avenae), soybean cyst nematodes (Heterodera glycines), sugar beet cyst nematodes (Heterodera schachtii), clover cyst nematodes (Heterodera (trifolii) and other species of the genus Heterodera; seed nematodes, species of the genus Anguina; stem nematodes and rose nematodes, species of the genus Aphelenchoides; sting nematodes, Belonolaimus longicaudatus and other species of the genus Belonolaimus; pine nematodes, pine wood nematodes (Bursaphelenchus xylophilus) and other species of the genus Bursaphelenchus; ring nematodes nematodes), species of the genera Criconema, Criconemella, Criconemoides, and Mesocriconema; stem and linkage nematodes, Ditylenchus destructor, Ditylenchus dipsaci, and other Ditylenchus species; Awl nematode, and Dolichodorus species;Spiral nematodes, Heliocotylenchus multicinctus and other Helicotylenchus species; Sheath and sheathoid nematodes, Hemicycliophora and Hemicriconemoides species; Hirshmanniella species; Lance nematodes, Hoploaimus species; False root-knot nematodes, Nacobbus species; Needle nematodes, Longidorus elongatus and other Longidorus species; Pin nematodes Platylenchus species; Lesion nematode, Pratylenchus neglectus, Pratylenchus penetrans, Pratylenchus curvitatus, Pratylenchus goodeyi and other Platylenchus species; Burrowing nematode, Radopholus similis and other Radopholus species; Reniform nematode, Rotylenchus robustus, Rotylenchus reniformis *Rotylenchus reniformis* and other species of the genus *Rotylenchus*; species of the genus *Scutellonema*;Plant parasitic nematodes such as Stubby root nematode, Trichodorus primitivus and other Trichodorus species, Paratrichodorus species; Stunt nematode, Tylenchorhynchus claytoni, Tylenchorhynchus dubius and other Tylenchorhynchus species; Citrus nematode, Tylenchulus species; Dagger nematode, Xiphinema species, and other plant parasitic nematodes; as well as Subanguina spp. and Hypsoperine This also relates to methods 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 be active against mollusks. Examples of mollusks include, for example, the family Ampullariidae; the genus Arion (A. ater, A. circumscriptus, A. hortensis, A. rufus); and the family Bradybaenidae (Bradybaena furticum). fruticum); Cepaea (Cepaea hortensis, Cepaea nemoralis); ochlodina; Deloceras (Deroceras agrestis, Deroceras empiricorum, Deroceras laeve, Deroceras reticulatum) tum); Discus genus (D. rotundatus); Euomphalia genus; Galba genus (G. trunculata); Heliceria genus (H. itala, H. obvia); Helicidae family Helicigona albustrum arbustorum); Helicodiscus; Helix (H. aperta); Limax (L. cinereoniger, L. flavus, L. marginatus, L. maximus, L. tenellus); Monoa Examples include the genera Lymnaea, Milax (M. gagates, M. marginatus, M. sowerbyi), Opeas, Pomacea (Pomacea canaticulata), Vallonia, and Zanitoides.

[0162] The term “crop” should be understood to also include crops transformed by the use of recombinant DNA technology, for example, to synthesize 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 that may be expressed by such transgenic plants include, for example, insecticidal proteins derived from Bacillus cereus or Bacillus popilliae; or δ-endotoxins, such as Cry1Ab, Cry1Ac, Cry1F, Cry1Fa2, Cry2Ab, Cry3A, Cry3Bb1 or Cry9C, insecticidal proteins derived from Bacillus thuringiensis or plant insecticidal proteins (Vip), such as Vip1, Vip2, Vip3 or Vip3A; or bacterial colony-forming nematodes, such as Photorhabdus luminescens, Xenorhabdus nematophilus, and other species of the genus Photorhabdus (Photorhabdus spp. or Xenorhabdus). Insecticidal proteins (spp.); toxins produced by animals, such as scorpion venom, arachnid venom, wasp venom, and neurotoxins specific to other insects; toxins produced by fungi, such as Streptomycetes toxins; plant lectins, such as pea lectin, barley lectin, or saxifrage lectin; agglutinins; proteinase inhibitors, such as trypsin inhibitors, serine protease inhibitors, patain, cystatin, and papain inhibitors; lysine, maize-RIP, abrin, rufin, saporine Examples include ribosome-inactivating proteins (RIPs) such as ribosomal protein (RIP) or briodin; steroid metabolic enzymes such as 3-hydroxysteroid oxidase, ecdysteroid-UDP-glycosyl-transferase, cholesterol oxidase, ecdysone inhibitors, and HMG-COA-reductase; ion channel blockers such as sodium channel or calcium channel blockers; juvenile hormone esterase, diuretic hormone receptor, stilbenzyl synthase, bibenzyl synthase, chitinase, and glucanase.

[0164] In relation to the present invention, δ-endotoxins are understood, 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, more specifically, as hybrid toxins, cleavage toxins and modified toxins. Hybrid toxins are produced by recombination through novel combinations of different domains of those proteins (see, for example, International Publication No. 2002 / 15701). Cleavage toxins, such as cleavage Cry1Ab, are known. In the case of modified toxins, one or more amino acids of the natural toxin are substituted. In such amino acid substitutions, preferably, a protease recognition sequence that does not exist in nature is inserted into the toxin; for example, in the case of Cry3A055, a cathepsin-G recognition sequence is inserted into the Cry3A toxin (see International Publication No. 2003 / 018810).

[0165] Examples of such toxins or transgenic plants capable of synthesizing such toxins are disclosed, for example, in European Patent Publication No. 0374753, International Publication No. 1993 / 07278, International Publication No. 1995 / 34656, European Patent Publication No. 0427529, European Patent Publication No. 451878, and International Publication No. 2003 / 052073.

[0166] Methods for preparing such transgenic plants are generally known to those skilled in the art and are described, for example, in the publications mentioned above. CryI-type deoxyribonucleic acids and their preparations are known, for example, from International Publication No. 95 / 34656, European Patent Application Publication No. 0367474, European Patent Application Publication No. 0401979, and International Publication No. 1990 / 13651.

[0167] The toxins contained in transgenic plants confer resistance to pests. Such insects are found in various insect taxonomic groups, but are particularly common in beetles (Coleoptera), diptera (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 include: YieldGard® (maize variety expressing Cry1Ab toxin); YieldGard Rootworm® (maize variety expressing Cry3Bb1 toxin); YieldGard Plus® (maize variety expressing Cry1Ab and Cry3Bb1 toxins); Starlink® (maize variety expressing Cry9C toxin); Herculex I® (maize variety expressing Cry1Fa2 toxin and the enzyme phosphinothrysin N-acetyltransferase (PAT) for resistance to the herbicide glufosinate ammonium); NuCOTN 33B® (cotton variety expressing Cry1Ac toxin); Bollgard I® (cotton variety expressing Cry1Ac toxin); Bollgard These include II (registered trademark) (a cotton variety expressing Cry1Ac and Cry2Ab toxins); VipCot (registered trademark) (a cotton variety expressing Vip3A and Cry1Ab toxins); NewLeaf (registered trademark) (a potato variety expressing Cry3A toxin); NatureGard (registered trademark), Agrisure (registered trademark) GT Advantage (GA21 glyphosate resistance trait), Agrisure (registered trademark) CB Advantage (Bt11 corn borer (CB) trait), and Protecta (registered trademark).

[0169] Further examples of such transgenic crops are as follows: 1. Bt11 maize, manufactured by Syngenta Seeds SAS (Chemin de l'Hobit 27, F-31 790 St. Sauveur, France), registration number C / FR / 96 / 05 / 10. Genetically modified maize that has been given resistance to attacks by the European corn borer (Ostrinia nubilalis and Sesamia nonagrioides) through transgenic expression of the cleavage Cry1Ab toxin. Bt11 maize also expresses the enzyme PAT through genetic modification to obtain resistance to the herbicide glufosinate ammonium.

[0170] 2. Bt176 maize, manufactured by Syngenta Seeds SAS (Chemin de l'Hobit 27, F-31 790 St. Sauveur, France), registration number C / FR / 96 / 05 / 10. Genetically modified maize that has been given resistance to attacks by the European corn borer (Ostrinia nubilalis and Sesamia nonagrioides) through transgenic expression of the Cry1Ab toxin. Bt176 maize also expresses the enzyme PAT through genetic modification to obtain resistance to the herbicide glufosinate ammonium.

[0171] 3. MIR604 maize, manufactured by Syngenta Seeds SAS (Chemin de l'Hobit 27, F-31 790 St. Sauveur, France), registration number C / FR / 96 / 05 / 10. This maize was made insect-resistant through transgenic expression of a modified Cry3A toxin. The toxin is Cry3A055, modified by the insertion of a cathepsin-G protease recognition sequence. The preparation of such transgenic maize plants is described in International Publication No. 2003 / 018810.

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

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

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

[0175] 7. NK603×MON 810 maize, registration number C / GB / 02 / M3 / 03, manufactured by Monsanto Europe SA (270-272 Avenue de Tervuren, B-1150 Brussels, Belgium). This hybrid maize variety is bred using conventional methods by crossing the genetically modified varieties NK603 and MON 810. NK603×MON 810 maize also expresses, through genetic modification, the protein CP4 EPSPS obtained from the Agrobacterium sp. strain CP4, which provides resistance to the herbicide Roundup® (containing glyphosate), and the Cry1Ab toxin obtained from Bacillus thuringiensis subsp. kurstaki, which provides resistance to certain Lepidoptera, including the European corn borer.

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

[0177] The term “crop” should be understood to include crops transformed by the use of recombinant DNA technology so that selectively active antipathogenic substances can be synthesized, such as so-called “pathogenicity-associated proteins” (PRP, see, for example, European Patent Application Publication No. 0392225). Examples of such antipathogenic substances and transgenic plants capable of synthesizing such antipathogenic substances are known, for example, from European Patent Application Publication No. 0392225, International Publication No. 1995 / 33818 and European Patent Application Publication No. 0353191. Methods for producing such transgenic plants are generally known to those skilled in the art and are described, for example, in the publications mentioned above.

[0178] Examples of antipathogenic substances that may be expressed by such transgenic plants include ion channel blockers such as sodium channel or calcium channel blockers, such as viral KP1, KP4, or KP6 toxins; stilbene synthase; vibenzyl synthase; chitinase; glucanase; so-called "pathogenicity-associated proteins" (PRPs; see, for example, European Patent Application Publication No. 0392225); antipathogenic substances produced by microorganisms, such as peptide antibiotics or heterocyclic antibiotics (see, for example, International Publication No. 1995 / 33818); or proteins or polypeptide factors involved in plant pathogen defense (so-called "plant disease resistance genes" as described in International Publication No. 2003 / 000906).

[0179] Further applications of the compositions according to the present invention include the protection of stored goods and storage rooms, and the protection of raw materials (such as wood and textiles), flooring materials and buildings, and hygiene, particularly the protection of humans, livestock and productive livestock from the above-mentioned types of pests.

[0180] The present invention also provides methods for controlling pests (such as mosquitoes and other pathogenic animals; see also http: / / www.who.int / malaria / vector_control / irs / en / ). In one embodiment, a method for controlling pests includes the step of applying the composition of the present invention to a target pest, its habitat, or surface or substrate by brush application, roller application, spraying, coating, or immersion. For example, IRS (Indoor Residual Spray) application to surfaces such as walls, ceilings, or floors is envisioned by the method of the present invention. In another embodiment, such a composition is envisioned to be applied to a substrate such as a nonwoven or fabric material in the form of a net, clothing, bedding, curtains, and tents (or in a form that can be used to manufacture these).

[0181] In one embodiment, a method for controlling such pests includes the step of applying an organismally effective amount of the composition of the present invention to a target pest, its habitat, or a surface or substrate so as to impart effective, persistent pest control activity to the surface or substrate. Such application may be carried out by brush application, roller application, spraying, coating, or immersion of the organismally effective composition of the present invention. For example, IRS application on surfaces such as walls, ceilings, or floors is envisioned by the method of the present invention to impart effective, persistent pest control activity to the surface. In another embodiment, such a composition is envisioned for the persistent control of pests on substrates such as fabric materials in the form of nets, clothing, bedding, curtains, and tents (or forms that may be used in the manufacture thereof).

[0182] The substrate to be treated, including nonwoven fabrics, cloths, or nets, can be made from natural fibers such as cotton, raffia, jute, flax, sisal, hemp cloth, or wool, or from synthetic fibers such as polyamide, polyester, polypropylene, or polyacrylonitrile. Polyester is particularly preferred. Methods for treating textiles are known, for example, from International Publication No. 2008 / 151984, International Publication No. 2003 / 034823, U.S. Patent No. 5631072, International Publication No. 2005 / 64072, International Publication No. 2006 / 128870, European Patent No. 1724392, International Publication No. 2005 / 113886, or International Publication No. 2007 / 090739.

[0183] A further field of application of the composition according to the present invention is the field of trunk injection / trunk treatment of all ornamental trees and all kinds of fruit trees and nut-bearing trees.

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

[0185] [Table 3]

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

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

[0188] In particular, this invention relates to ground beetles (genus Cyclocephala (e.g., masked chafer, C. lurida), Rhizotrogus (e.g., European chafer, R. majalis), Cotinus (e.g., blue-spotted chafer, C. nitida), Popillia (e.g., Japanese beetle, P. japonica), Phyllophaga (e.g., May / June beetle), and Athenius (e.g., Black Turfgrass Athenius) It can be used to control insect pests that feed on turfgrass roots, including turfgrass ataenius, A. spretulus, Maladera spp. (e.g., red velvet beetle, M. castanea, and Tomarus spp.), cottony cotton scales (Margarodes spp.), mole crickets (tawny, southern, and brachyptera; Scapteriscus spp., mole cricket (Gryllotalpa africana)), and leatherjacket (European crane fly, Tipula spp.).

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

[0190] The present invention can also be used to control insect pests that live on the ground and feed on grass leaves, including the Southern kink bug (Blissus insularis, etc.), Bermudagrass mites (Eriophyes cynodoniensis), African rhodesgrass mealybugs (Antonina graminis), two-lined spittlebugs (Propsapia bicincta), leafhoppers, cutworms (Noctuidae), and wheat aphids.

[0191] This invention can also be used to control other pests of turfgrass, such as the red imported fire ant (Solenopsis invicta), which builds ant mounds in lawns.

[0192] In the field of hygiene, the compositions according to the present invention are effective against external parasites 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 as follows: Among the orders Anoplurida: the genera Haematopinus, Linognathus, Pediculus, Phtirus, and Solenopotes.

[0193] Among the orders Mallophagida: the genera Trimenopon, Menopon, Trinoton, Bovicola, Werneckiella, Lepikentron, Damalina, Trichodectes, and Felicola.

[0194] Among the order Diptera and its suborders Nematocerina and Brachycerina, for example, the genera Aedes, Anopheles, Culex, Simulium, Eusimulium, Phlebotomus, Lutzomyia, Culicoides, Chrysops, Hybomitra, Atylotus, Tabanus, and Haematopota spp.) , Philippomyia 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., Lipoptena spp., and Melophagus spp..

[0195] Within the order Siphonapterida, for example, there are genera such as Pulex spp., Ctenocephalides spp., Xenopsylla spp., and Ceratophyllus spp..

[0196] Among the order Heteropterida, for example, there are genera such as bed bugs (Cimex spp.), assassin bugs (Triatoma spp.), Rhodnius spp., and Panstrongylus spp.

[0197] Among the order Blattardia, for example, the oriental cockroach (Blatta orientalis), the American cockroach (Periplaneta americana), the German cockroach (Blattelagermanica), and the genus Supella.

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

[0199] Among the orders Acari (Actinedida) (Prostigmata) and Acaridida (Astigmata), for example, the genera Acarapis, Cheyletiella, Ornithocheyletia, Myobia, Psorergates, Demodex, Trombicula, Listrophorus, Acarus, Tyrophagus, Caloglyphus, and Hypodectes. 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 present invention are also suitable for protecting materials such as wood, textiles, plastics, adhesives, glues, paints, paper and cardboard, leather, flooring materials and buildings from insect infestation.

[0201] The composition according to the present invention can be used, for example, against the following pests: European house beetle (Hylotrupes bajulus), Chlorophorus pilosis, Anobium punctatum, Xestobium rufovillosum, Ptilinuspecticornis, Dendrobium pertinex, pine wood beetle (Ernobius mollis), large wood beetle (Priobium carpini), flat bark beetle (Lyctus brunneus), African flat bark beetle (Lyctus africanus), American flat bark beetle (Lyctus planicollis), oak flat bark beetle (Lyctus *) and beetles such as Dinoderus minutus, as well as hymenopteran insects such as Sirex juvencus, Urocerus gigas, Urocerus gigas taignus and Urocerus augur, and Kalotermes flavicollis, Cryptotermes brevis, Heterotermes indicola, Reticulitermes flavipes, Reticulitermes santonensis, Reticulitermes lucifugus Termites such as *Lucifugus*, *Mastotermes darwiniensis*, *Zootermopsis nevadensis*, and *Coptotermes formosanus*, as well as silverfish such as *Lepisma saccharina*.

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

[0203] Formulations can be prepared, for example, by mixing an active ingredient with formulation aids to obtain compositions in the form of micronized solids, granules, liquids, dispersions, or emulsions. The active ingredient can also be formulated with other aids such as micronized solids, mineral oils, plant or animal oils, modified plant or animal oils, organic solvents, water, surfactants, or combinations thereof.

[0204] The active ingredient may also be contained in fine microcapsules. Microcapsules contain the active ingredient in a porous carrier. This allows for the release of the active ingredient into the environment in a controlled amount (e.g., sustained release). Microcapsules typically have a diameter of 0.1 to 500 μm. Microcapsules contain the active ingredient in an amount of approximately 25 to 95% by weight of the capsule. The active ingredient may be in the form of a monolithic solid, fine particles in a solid or liquid dispersion, or a suitable solution. The encapsulation membrane may include, for example, natural or synthetic rubber, cellulose, styrene / butadiene copolymer, polyacrylonitrile, polyacrylate, polyester, polyamide, polyurea, polyurethane or chemically modified polymers and starch xanthetes 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 ground particles in a solid matrix of a base, but the microcapsule itself is not encapsulated.

[0205] Formulation aids suitable for preparing the compositions according to the present invention are known in themselves. The following can be used as liquid carriers: water, toluene, xylene, petroleum ether, vegetable oil, acetone, methyl ethyl ketone, cyclohexanone, acid anhydride, acetonitrile, acetophenone, amyl acetate, 2-butanone, butylene carbonate, chlorobenzene, cyclohexane, cyclohexanol, alkyl ester of acetate, 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, Ole phenol, 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 amyl alcohol, tetrahydrofurfuryl alcohol, hexanol, octanol and other higher molecular weight alcohols, ethylene glycol, propylene glycol, glycerol, N-methyl-2-pyrrolidone, etc.

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

[0207] Many surfactants can be advantageously used in both solid and liquid formulations, particularly in formulations that may be diluted with a carrier before use. Surfactants can be anionic, cationic, nonionic, or polymeric, and they can be used as emulsifiers, wetting agents, or suspending agents or for other purposes. Typical surfactants include, for example, alkyl sulfate salts such as diethanolammonium lauryl sulfate; alkylaryl sulfonate salts such as calcium dodecylbenzenesulfonate; alkylphenol / alkylene oxide addition products such as nonylphenol ethoxylate; alcohol / alkylene oxide addition products such as tridecyl alcohol ethoxylate; soaps such as sodium stearate; alkylnaphthalene sulfonate salts such as sodium dibutylnaphthalene sulfonate; 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 substances described, for example, in McCutcheon's Detergents and Emulsifiers Annual, MC Publishing Corp., Ridgewood, New Jersey (1981).

[0208] Further auxiliary agents that may be used in biological agents include crystallization inhibitors, viscosity modifiers, suspending agents, dyes, antioxidants, foaming agents, light absorbers, mixing aids, defoaming agents, complexing agents, neutralizing agents or pH adjusters and buffers, corrosion inhibitors, fragrances, wetting agents, absorption enhancers, micronutrients, plasticizers, lubricants, dispersants, thickeners, antifreezes, fungicides, and liquid and solid fertilizers.

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

[0210] The compositions of the present invention generally contain 0.1 to 99% by weight, particularly 0.1 to 95% by weight, of the compound of the present invention and 1 to 99.9% by weight of a formulation aid (which preferably includes 0 to 25% by weight of a surfactant). Commercial products may preferably be formulated as concentrates, but end users will typically use diluted formulations.

[0211] The application rate varies widely and depends on soil properties, application method, crop plants, pests being controlled, prevailing climatic conditions, and other factors related to the application method, timing, and target crop. As a general guideline, the compound may be applied at rates of 1 to 2000 l / ha, particularly 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% Surfactants: 1-30%, preferably 5-20% Liquid carrier: 1-80%, preferably 1-35%

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

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

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

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

[0218] The following examples illustrate the present invention further, but do not limit it.

[0219] [Table 5]

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

[0221] [Table 6]

[0222] This combination, when thoroughly mixed with an auxiliary agent, yields a powder that can be thoroughly ground in a suitable mill and used directly for seed processing.

[0223] [Table 7]

[0224] An emulsion of any required dilution ratio, which can be used for plant protection, can be obtained from this concentrate by dilution with water.

[0225] [Table 8]

[0226] A ready-to-use dusting agent is obtained by mixing it with a carrier and grinding the mixture in a suitable mill. Such powders can also be used for dry dusting of seeds.

[0227] [Table 9]

[0228] This combination is mixed with an auxiliary agent, ground, and the mixture is wetted with water. The mixture is then extruded and dried in an airflow.

[0229] [Table 10]

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

[0231] [Table 11]

[0232] This pulverized combination is homogeneously mixed with an auxiliary agent to obtain a suspension concentrate, from which suspensions of any desired dilution ratio can be obtained by dilution with water. Using such dilutions, living plants and plant propagation materials can be treated and protected from microbial infestation by spraying, pouring, or immersion.

[0233] [Table 12]

[0234] This pulverized combination is homogeneously mixed with an auxiliary agent to obtain a suspension concentrate, from which suspensions of any desired dilution ratio can be obtained by dilution with water. Using such dilutions, living plants and plant propagation materials can be treated and protected from microbial infestation by spraying, pouring, or immersion.

[0235] Sustained-release capsule suspension Mix 28 parts of this combination with 2 parts of aromatic solvent and 7 parts of toluene diisocyanate / polymethylene-polyphenyl isocyanate mixture (8:1). Emulsify this mixture in a mixture of 1.2 parts polyvinyl alcohol, 0.05 parts defoamer, and 51.6 parts water until the desired particle size is obtained. Add a mixture of 2.8 parts 1,6-diaminohexane in 5.3 parts water to this emulsion. Stir the mixture until the polymerization reaction is complete. Stabilize the resulting capsule suspension by adding 0.25 parts thickener and 3 parts dispersant. The capsule suspension formulation contains 28% active ingredient. The intermediate diameter of the capsules is 8-15 μm. Apply the resulting formulation to seeds as an aqueous suspension in an apparatus suitable for the relevant purpose.

[0236] Formulation types include emulsion concentrates (EC), suspension concentrates (SC), suspend emulsions (SE), capsule suspensions (CS), wettable granules (WG), emulsifying granules (EG), water-in-oil emulsions (EO), oil-in-water emulsions (EW), microemulsions (ME), oily dispersions (OD), oil-miscible flowables (OF), oil-miscible liquids (OL), soluble concentrates (SL), suspensions for micro-spraying (SU), liquids for micro-spraying (UL), industrial concentrates (TK), dispersible concentrates (DC), wettable powders (WP), soluble granules (SG), or any technically feasible formulations combined with agriculturally acceptable adjuvants. [Examples]

[0237] Preparation Examples: "Mp" stands for melting point (°C). The free radical represents a methyl group. 1 ¹H NMR measurements were recorded using a Brucker 400 MHz spectrometer, and the chemical shift is shown in ppm relative to the TMS standard. As shown, the spectrum was measured in a deuterated solvent. The compounds were characterized using one of the following LCMS methods. The characteristic LCMS values ​​obtained for each compound were given by the retention time ("R"). t ", recorded in minutes, and molecular ions (M+H) + or (MH) - This was the measured value.

[0238] LCMS and GCMS methods: Method 1: Spectra were recorded using a Waters mass spectrometer (SQD, SQDII single quadrupole mass spectrometer) equipped with an electrospray source (polarity: cations and anions, capillary: 3.00kV, cone range: 30V, extractor: 2.00V, source temperature: 150℃, desolvation temperature: 350℃, cone gas flow: 50l / h, desolvation gas flow: 650l / h, mass range: 100~900Da) 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 over 1.2 minutes; Flow rate (ml / min): 0.85.

[0239] Method 2: Spectra were recorded using a Waters mass spectrometer (SQD, SQDII single quadrupole mass spectrometer) equipped with an electrospray source (polarity: cations and anions), capillary: 3.00kV, cone range: 30V, extractor: 2.00V, source temperature: 150℃, desolvation temperature: 350℃, cone gas flow: 50l / h, desolvation gas flow: 650l / h, mass range: 100~900Da), as well as 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 over 2.7 minutes; Flow rate (ml / min): 0.85.

[0240] Method 3: Spectra were recorded using a Waters mass spectrometer (SQD, SQDII, or ZQ single quadrupole mass spectrometer) equipped with an electrospray source (polarity: cations and anions), capillary: 3.00kV, cone range: 30V, extractor: 2.00V, source temperature: 150℃, desolvation temperature: 350℃, cone gas flow: 50l / h, desolvation gas flow: 650l / h, mass range: 100~900Da), as well as 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 over 2.5 minutes; Flow rate (ml / min): 0.85.

[0241] Method 4: Spectra were recorded using a Waters mass spectrometer (SQD, SQDII single quadrupole mass spectrometer) equipped with an electrospray source (polarity: cations and anions), capillary: 3.00kV, cone range: 30V, extractor: 2.00V, source temperature: 150℃, desolvation temperature: 350℃, cone gas flow: 50l / h, desolvation gas flow: 650l / h, mass range: 100~900Da), 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 over 1.2 minutes; Flow rate (ml / min): 0.85.

[0242] Method 5: The spectrum was recorded using a Waters mass spectrometer (Acquity SDS mass spectrometer) with an electrospray source (polarity: positive and negative polarity switch, capillary: 3.00kV, cone voltage: 41.00V, source temperature: 150℃, desolvation gas flow: 1000L / Hr., desolvation temperature: 500℃, gas flow @ cone: 50L / hr., mass range: 110~800Da, PDA wavelength range: 210~400nm). 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 minutes; 50% A, 50% B for 0.2 minutes; 0% A, 100% B for 0.7-1.3 minutes; 90% A, 10% B for 1.4-1.6 minutes. 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]cyclopropanecarbonitride (Table P, Example P10) [ka] Step 1: Preparation of methyl 5-(1-cyano-2-ethoxy-2-oxo-ethyl)-3-ethylsulfanylpyridine-2-carboxylate [ka] Methyl 5-bromo-3-ethylsulfanylpyridine-2-carboxylate (32 g, 115.88 mmol), prepared as described in International Publication No. 2017 / 089190, was dissolved in dimethyl sulfoxide (350 mL). Then, 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 added sequentially at room temperature. The resulting suspension was stirred overnight at 90°C and then cooled to room temperature. Water and ethyl acetate were added, and the resulting mixture was cooled to 0°C. Hydrochloric acid (2 M) was slowly added to acidify the reaction to pH 4-5. The aqueous layer was extracted three times with ethyl acetate. The combined organic layers were dried over sodium sulfate, filtered, and concentrated under reduced pressure. 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 obtain methyl 5-(1-cyano-2-ethoxy-2-oxo-ethyl)-3-ethylsulfanylpyridine-2-carboxylate. LCMS (Method 1): 309 (M+H) + Holding time: 0.85 minutes. ¹H NMR (400MHz, chloroform-D) δppm 1.33 (t, J=7.15Hz, 3H) 1.45 (t, J=7.34Hz, 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=1.83Hz, 1H) 8.49 (d, J=1.83Hz, 1H).

[0244] Step 2: Preparation of methyl 5-(cyanomethyl)-3-ethylsulfanylpyridine-2-carboxylate [ka] Methyl 5-(1-cyano-2-ethoxy-2-oxo-ethyl)-3-ethylsulfanylpyridine-2-(7.3 g, 24 mmol) was dissolved in dimethyl sulfoxide (70 mL). NaCl (14 g, 240 mmol) and water (35 mL) were added sequentially at room temperature. The resulting suspension was stirred at 125 °C for 3 hours. 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 under reduced pressure. The crude product was purified over silica gel to obtain methyl 5-(cyanomethyl)-3-ethylsulfanylpyridine-2-carboxylate. LCMS (Method 1): 237 (M+H) + Holding time: 0.72 minutes. ¹H NMR (400MHz, chloroform-D) δppm 1.45 (t, J=7.52Hz, 3H) 3.01 (q, J=7.34Hz, 2H) 3.87 (s, 2H) 4.04 (s, 3H) 7.72 (d, J=1.83Hz, 1H) 8.35-8.41 (m, 1H).

[0245] Step 3: Preparation of methyl 5-(1-cyanocyclopropyl)-3-ethylsulfanylpyridine-2-carboxylate [ka] Methyl 5-(cyanomethyl)-3-ethylsulfanylpyridine-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 hours and 30 minutes, 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 under reduced pressure to obtain the crude product, which was purified by chromatography to obtain methyl 5-(1-cyanocyclopropyl)-3-ethylsulfanylpyridine-2-carboxylate. LCMS (Method 1): 263 (M+H) + Holding 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-ethylsulfanylpyridine-2-carboxylic acid [ka] Methyl 5-(1-cyanocyclopropyl)-3-ethylsulfanylpyridine-2-carboxylate (2.63 g, 10.0 mmol) was dissolved in tetrahydrofuran (50 mL) and water (15 mL). Then, lithium hydroxide (0.375 g, 15.0 mmol) was added, and the reaction was stirred overnight at room temperature. Subsequently, an additional amount of lithium hydroxide (0.160 g, 7.0 mmol) was added, and the reaction was stirred for a further 2 hours at room temperature. The reaction mixture was concentrated under reduced pressure, and the residue was dissolved in dichloromethane. 1 M aqueous HCl 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 under reduced pressure to obtain 5-(1-cyanocyclopropyl)-3-ethylsulfanylpyridine-2-carboxylic acid. LCMS (Method 1): 249 (M+H) + Holding 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)pyridazine-4-yl]pyridine-2-carboxamide [ka] 5-(1-cyanocyclopropyl)-3-ethylsulfanylpyridine-2-carboxylic acid (200 mg, 0.8055 mmol) was dissolved in dichloromethane (10 mL), and N,N-dimethylformamide (10.0 μL) was added. Oxalyl dichloride (0.118 mL, 1.369 mmol) was added dropwise to this suspension via syringe. The resulting yellowish suspension was stirred at room temperature. After 1.5 hours, the reaction mixture was concentrated under reduced pressure to obtain 5-(1-cyanocyclopropyl)-3-ethylsulfanylpyridine-2-carbonyl chloride. Fresh 5-(1-cyanocyclopropyl)-3-ethylsulfanylpyridine-2-carbonyl chloride (250 mg, 0.9370 mmol) was dissolved in tetrahydrofuran (12 mL), N,N-diethylethaneamine (0.27 mL, 1.933 mmol) was added dropwise, and then N3-methyl-6-(trifluoromethyl)pyridazine-3,4-diamine (651 mg, 3.222 mmol) in tetrahydrofuran (12 mL) was added 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 extract was washed with brine (30 mL), dried over sodium sulfate, filtered, and concentrated under reduced pressure. The crude product was purified by silica gel chromatography to obtain N-[4-amino-6-(trifluoromethyl)pyridazin-3-yl]-5-(1-cyanocyclopropyl)-3-ethylsulfanyl-N-methylpyridine-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]cyclopropanecarbonitride [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 overnight under reflux, then cooled to room temperature. The acetic acid was removed under reduced pressure, and the resulting residue was dissolved in ethyl acetate and basicized with an aqueous bicarbonate solution. The aqueous layer was extracted with ethyl acetate (3 × 20 ml), and the combined organic layers were dried over sodium sulfate, filtered, and concentrated under reduced pressure. The crude product was purified by silica gel chromatography to obtain 1-[5-ethylsulfanyl-6-[7-methyl-3-(trifluoromethyl)imidazo[4,5-c]pyridazin-6-yl]-3-pyridyl]cyclopropanecarbonitride. LCMS (Method 2): Retention time: 1.05 min, (M+H) + 405. ¹H NMR (400MHz, 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]cyclopropanecarbonitride (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). Then, ammonium carbamate (46 mg, 0.5935 mmol) and (diacetoxyiodo)benzene (243 mg, 0.7418 mmol) were 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 inactivated 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 under reduced pressure. The residue was purified by chromatography using methanol and dichloromethane with silica gel to obtain 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] Preparation of Example H2.1-[5-(ethylsulfonimidoyl)-6-[3-methyl-6-(trifluoromethyl)imidazo[4,5-b]pyridin-2-yl]-3-pyridyl]cyclopropanecarbonitride (Example P6, Table P) [ka] Step 1: Preparation of 5-(1-cyanocyclopropyl)-3-ethylsulfanyl-N-[2-(methylamino)-5-(trifluoromethyl)-3-pyridyl]pyridin-2-carboxamide [ka] 5-(1-cyanocyclopropyl)-3-ethylsulfanylpyridine-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 the dropwise addition of oxalyl dichloride (1 mL, 12 mmol) via syringe. The resulting yellowish suspension was stirred at room temperature for 1 hour, and then the solvent was concentrated under reduced pressure. The resulting solid was dissolved in tetrahydrofuran (30 mL) and added at 0°C to a solution of N2-methyl-5-(trifluoromethyl)pyridine-2,3-diamine (1.8 g, 9.7 mmol) and N,N-diethylethaneamine (3.3 mL, 23 mmol) in tetrahydrofuran (75 mL). The resulting mixture was stirred at 0°C for 30 minutes, and then at room temperature for 2 hours. The reaction mixture was treated with a 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 under reduced pressure to obtain 5-(1-cyanocyclopropyl)-3-ethylsulfanyl-N-[2-(methylamino)-5-(trifluoromethyl)-3-pyridyl]pyridin-2-carboxamide, which was used in the next step without further purification. LCMS (Method 1): 422 (M+H) + Holding 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]cyclopropanecarbonitrine [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 at 110°C for 18 hours. The acetic acid was removed under reduced pressure, and the crude product was purified by silica gel chromatography to obtain 1-[5-ethylsulfanyl-6-[3-methyl-6-(trifluoromethyl)imidazo[4,5-b]pyridin-2-yl]-3-pyridyl]cyclopropanecarbonitride (Mp 142-144°C). LCMS (Method 1): 404 (M+H) + Holding 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]cyclopropanecarbonitride (Example P6, Table P) [ka] Example H1, sulfoximine formation similar to step 7. LCMS (Method 1): 435 (M+H) +Holding time: 0.87 minutes. 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]cyclopropanecarbonitride (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-methylacetamide [ka] A solution of 4-bromo-1-methoxy-3-(methylamino)-6-(trifluoromethyl)pyridine-2-one (5.0 g, 16.61 mmol) in dichloromethane (100 mL) was mixed with anhydrous trifluoroacetic acid (7.09 mL, 49.82 mmol) at room temperature. The reaction mixture was stirred at room temperature for 30 minutes and then concentrated under reduced pressure. Water (100 mL) and then saturated potassium carbonate aqueous solution (50 mL) were added, 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 under reduced pressure. The crude product was purified over silica gel to obtain pure N-[4-bromo-6-(difluoromethyl)-1-methoxy-2-oxo-3-pyridyl]-2,2,2-trifluoro-N-methylacetamide. This material was used in the next step without further purification. LCMS (Method 5): 397 / 399 (M+H) +Holding time: 0.96 minutes. 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-methylacetamide [ka] Sodium azide (2.9 g, 44.6 mmol) was added at room temperature to a solution of N-[4-bromo-1-methoxy-2-oxo-6-(trifluoromethyl)-3-pyridyl]-2,2,2-trifluoro-N-methylacetamide (11.8 g, 29.7 mmol) in N,N-dimethylformamide (110 mL). The reaction mixture was stirred overnight at room temperature. The above reactions were carried out separately and repeatedly, and then the combined reaction mixtures were diluted with cold water (500 mL) and extracted with ethyl acetate (3 × 150 mL). The combined organic layer was washed with water (100 mL) and brine, dried over sodium sulfate, filtered, and concentrated under reduced pressure below 40°C to obtain N-[4-azido-1-methoxy-2-oxo-6-(trifluoromethyl)-3-pyridyl]-2,2,2-trifluoro-N-methylacetamide. This material was used in the next step without further purification. LCMS (Method 5): 360 (M+H) + Holding time: 0.90 minutes. 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)pyridine-2-one [ka] 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 with potassium carbonate (4.7 g, 33.0 mmol). The reaction mixture was stirred overnight at room temperature and then diluted with water (150 mL). The aqueous layer was extracted with ethyl acetate (2 × 75 mL), the combined organic layers were washed with brine (150 mL), dried over sodium sulfate, filtered, and concentrated under reduced pressure. The crude product was purified by silica gel (40% ethyl acetate in cyclohexane) to afford 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 minutes. 1 1H NMR (400 MHz, CDCl3) δ ppm 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

Chemical formula

[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-methylpyridine-2-carboxamide (isomer mixture) [ka] A suspension of 5-(1-cyanocyclopropyl)-3-ethylsulfanylpyridine-2-carboxylic acid (400 mg, 1.61 mmol) in dichloromethane (16 mL) was joined dropwise with 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 under reduced pressure to obtain 5-(1-cyanocyclopropyl)-3-ethylsulfanylpyridine-2-carbonyl chloride.

[0258] The above solution of 5-(1-cyanocyclopropyl)-3-ethylsulfanylpyridine-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)pyridine-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 deactivated 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 under reduced pressure to obtain a mixture of the desired isomers 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-methylpyridine-2-carboxamide (750 mg, 1.60 mmol). This material was used in the next step without further purification. LCMS (Method 5): 468 (M+H) + Holding time: 0.86 minutes.

[0259] Step 6: Preparation of 1-[5-ethylsulfanyl-6-[5-methoxy-3-methyl-4-oxo-6-(trifluoromethyl)imidazo[4,5-c]pyridine-2-yl]-3-pyridyl]cyclopropanecarbonitrine [ka] A solution of the above-mentioned mixture of isomers 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 at 100 °C for 48 hours. After cooling to room temperature, the reaction mixture was concentrated under reduced pressure. The residue was poured into water and extracted with ethyl acetate (3 × 100 mL). The combined organic layers were washed with brine, dried over sodium sulfate, and concentrated under reduced pressure. 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 minutes. 1 H NMR (400 MHz, CDCl3) δ ppm 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 = 2.0 Hz, 1H), 8.32 (d, J = 2.0 Hz, 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)

Chemical Structure

[0261] Example H4: Preparation of 1-[3-(ethylsulfonimidoyl)-4-[3-methyl-6-(trifluoromethylsulfanyl)imidazo[4,5-c]pyridine-2-yl]phenyl]cyclopropanecarbonitride (Example P9, Table P) [ka] Step 1: Preparation of N-[4-amino-6-(trifluoromethylsulfanyl)-3-pyridyl]-4-bromo-2-ethylsulfanyl-N-methylbenzamide [ka] Under an argon atmosphere, 4-bromo-2-ethylsulfanylbenzoic acid (prepared as described in International Publication No. 2016 / 120182 (1.96 g, 7.51 mmol)) was suspended in dichloromethane (30 mL), and two drops of DMF were added. When oxalyl dichloride (1.24 g, 0.851 mL, 9.76 mmol) was added dropwise, gas generation was observed. The mixture was stirred at room temperature for 4 hours, and then concentrated under reduced pressure to obtain 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 International Publication No. 2016 / 169886, was added. The resulting mixture was stirred overnight at room temperature, then at 70°C for 8 hours. After cooling to 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 under reduced pressure to obtain a mixture containing N-[4-amino-6-(trifluoromethylsulfanyl)-3-pyridyl]-4-bromo-2-ethylsulfanyl-N-methyl-benzamide. LCMS (Method 1): 450 (M+H) + Holding time: 1.14 minutes.

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

[0263] Step 3: Preparation of 4-[3-ethylsulfanyl-4-[3-methyl-6-(trifluoromethylsulfanyl)imidazo[4,5-c]pyridine-2-yl]phenyl]isoxazole [ka] DMSO (1.11 mL) and water (0.53 mL) were added to a microwave vial under an argon atmosphere, and the solution was purged with argon for 5 minutes. Then, 2-(4-bromo-2-ethylsulfanylphenyl)-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;triphenylphosphan (0.0031 g, 0.0044 mmol) was added, the resulting mixture was purged with argon for 5 minutes, stirred in a microwave system at 90°C for 40 minutes, cooled to room temperature, and then poured into ice water. The aqueous layer was extracted three times with dichloromethane. Next, the turbid aqueous layer was 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 under reduced pressure. The resulting oil was washed with water. The precipitate formed in water was filtered, then dissolved again in dichloromethane, and the solvent was concentrated under reduced pressure to obtain 4-[3-ethylsulfanyl-4-[3-methyl-6-(trifluoromethylsulfanyl)imidazo[4,5-c]pyridine-2-yl]phenyl]isoxazole, which was used as is in the next step. LCMS (Method 1): 437 (M+H) + Holding time: 0.95 minutes.

[0264] Step 4: Preparation of 2-[3-ethylsulfanyl-4-[3-methyl-6-(trifluoromethylsulfanyl)imidazo[4,5-c]pyridine-2-yl]phenyl]acetonitrile [ka] 4-[3-ethylsulfanyl-4-[3-methyl-6-(trifluoromethylsulfanyl)imidazo[4,5-c]pyridine-2-yl]phenyl]isoxazole (236 mg, 0.3785 mmol, 70% by mass) 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 under reduced pressure. The crude product was purified by silica gel column chromatography to obtain 2-[3-ethylsulfanyl-4-[3-methyl-6-(trifluoromethylsulfanyl)imidazo[4,5-c]pyridine-2-yl]phenyl]acetonitrile. LCMS (Method 1): 409 (M+H) + Holding time: 0.98 minutes. ¹H NMR (400MHz, chloroform) δppm: 1.29 (t, J=7.34Hz, 4H), 2.93 (q, J=7.34Hz, 2H), 3.80 (s, 3H), 3.89 (s, 2H), 7.34 (dd, J=7.89, 1.65Hz, 1H), 7.47-7.48 (m, 1H), 7.48-7.51 (m, 1H), 8.16-8.18 (m, 1H), 8.92 (d, J=0.73Hz, 1H).

[0265] Step 5: Preparation of 1-[3-ethylsulfanyl-4-[3-methyl-6-(trifluoromethylsulfanyl)imidazo[4,5-c]pyridine-2-yl]phenyl]cyclopropanecarbonitride [ka] 1-[3-ethylsulfanyl-4-[3-methyl-6-(trifluoromethylsulfanyl)imidazo[4,5-c]pyridine-2-yl]phenyl]cyclopropanecarbonitrile (0.108 g, 0.2644 mmol) was dissolved in acetonitrile (1.322 mL). Then, discesium 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 under reduced pressure. 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 under reduced pressure. The crude product was purified by silica gel chromatography to obtain 1-[3-ethylsulfanyl-4-[3-methyl-6-(trifluoromethylsulfanyl)imidazo[4,5-c]pyridine-2-yl]phenyl]cyclopropanecarbonitrile. LCMS (Method 1): 435 (M+H) + Holding 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]pyridine-2-yl]phenyl]cyclopropanecarbonitride (Example P9, Table P) [ka] Sulfoximine formation was carried out as described in Step 7 of Example H1. LCMS (Method 1): 466 (M+H)+ Holding time: 0.86 minutes.

[0267] Example H5: Synthesis of 1-[3-(ethylsulfonimidoyl)-4-[3-methyl-6-(trifluoromethyl)imidazo[4,5-c]pyridine-2-yl]phenyl]cyclopropanecarbonitride (Example P13, Table P) [ka] Step 1: Preparation of 1-[3-ethylsulfanyl-4-[3-methyl-6-(trifluoromethyl)imidazo[4,5-c]pyridine-2-yl]phenyl]cyclopropanecarbonitride [ka] To a mixture of 2-(4-bromo-2-ethylsulfanylphenyl)-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), prepared as described in International Publication No. 2016 / 030229, in tetrahydrofuran (1.2 mL), cyclopropane carbonitrile (0.090 g, 1.32 mmol) and cyclopropyl methyl ether (1.20 mL) were added 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 hours. After cooling to room temperature, the mixture was filtered through a Celite pad and 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 under reduced pressure. The crude product was purified by silica gel chromatography to obtain 1-[3-ethylsulfanyl-4-[3-methyl-6-(trifluoromethyl)imidazo[4,5-c]pyridine-2-yl]phenyl]cyclopropanecarbonitrile. LCMS (Method 1): 403 (M+H) +Holding time: 1.00 minute. 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]pyridine-2-yl]phenyl]cyclopropanecarbonitrile (Example P13, Table P) [ka] The desired product was prepared using the standard method described in Step 7, Example H1. LCMS (Method 1): 434 (M+H) + Holding 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]pyridine-2-yl]phenyl]cyclopropanecarbonitrile (Example P15, Table P) [ka] Step 1: Synthesis of methyl 2-ethylsulfanyl-4-isoxazole-4-yl-benzoate [ka] A solution of methyl 4-bromo-2-ethylsulfanyl benzoate (International Publication No. 2016 / 023954) (250 mg, 0.91 mmol) in dimethyl sulfoxide (8 mL) was mixed with water (4 mL), 4-isoxazoleboronic acid pinacol ester (213 mg, 1.09 mmol), and potassium fluoride (158 mg, 2.73 mmol) under an argon atmosphere. The concentrated reaction mixture was purged with argon for 5 minutes, and 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 minutes. The reaction mixture was poured into ice water, and the resulting yellowish suspension was filtered and washed with cold water. This solid was dissolved in dichloromethane, the solution was dried over sodium sulfate, and reduced under reduced pressure until dry to obtain methyl 2-ethylsulfanyl-4-isoxazole-4-yl-benzoate as a yellowish solid. This material was used in the next step without further purification. LCMS (Method 1): 262 (MH) - Holding time: 0.88 minutes.

[0270] Step 2: Synthesis of methyl 4-(cyanomethyl)-2-ethylsulfanyl benzoate [ka] A solution of methyl 2-ethylsulfanyl-4-isoxazole-4-yl benzoate (760 mg, 2.89 mmol) in methanol (15 mL) was mixed with 1 M potassium fluoride solution in water (8.66 mL, 8.66 mmol). The reaction mixture was stirred under reflux for 3 hours. After cooling, the suspension was filtered, and the filtrate was concentrated under reduced pressure. The residue was purified by combiflash with silica gel to obtain methyl 4-(cyanomethyl)-2-ethylsulfanyl benzoate as a gum. LCMS (Method 5): 236 (M+H) + Holding time: 0.90 minutes. 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] A solution of methyl 4-(cyanomethyl)-2-ethylsulfanylbenzoate (300 mg, 1.275 mmol) in acetonitrile (15 mL) was mixed with cesium carbonate (1.24 g, 3.825 mmol) and 1,2-dibromoethane (719 mg, 3.825 mmol). The reaction mixture was stirred under reflux for 90 minutes. After cooling, the suspension was filtered, and the filtrate was concentrated under reduced pressure. The residue was purified by silica gel combiflash to obtain methyl 4-(cyanomethyl)-2-ethylsulfanylbenzoate as an oil. LCMS (Method 1): 262 (M+H) + Holding time: 0.98 minutes. 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-ethylsulfanylbenzoic acid [ka] To a solution of methyl 4-(1-cyanocyclopropyl)-2-ethylsulfanylbenzoate (198 mg, 0.758 mmol) in a mixture of tetrahydrofuran (9 mL) and water (3 mL), lithium hydroxide (1.5 equivalents, 1.137 mmol) was added at 0-5°C, and the reaction mixture was stirred overnight at room temperature. The solution was concentrated under reduced pressure, 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, the combined organic layers were washed with water and brine, dried over sodium sulfate, filtered, and concentrated under reduced pressure to obtain 4-(1-cyanocyclopropyl)-2-ethylsulfanylbenzoic acid as a solid. This material was used in the next step without further purification. LCMS (Method 5): 246 (MH) - Holding time: 0.83 minutes. 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 5.1 Preparation of [3-ethylsulfanyl-4-[3-methyl-6-(trifluoromethyl)imidazo[4,5-b]pyridine-2-yl]phenyl]cyclopropanecarbonitride [ka] 4-(1-cyanocyclopropyl)-2-ethylsulfanylbenzoic acid (1.7 g, 6.9 mmol) was dissolved in nitrobenzene (14 mL), and N2-methyl-5-(trifluoromethyl)pyridine-2,3-diamine (International Publication No. 2017 / 043342) (1.6 g, 1.2 equivalents) was added, followed by the slow addition of phosphoryl chloride (1.6 mL, 17 mmol) at room temperature. The resulting solution was heated at 120 °C for 7 hours and monitored by TLC and LC-MS. The reaction mixture was inactivated 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 under reduced pressure. The crude product was purified by chromatography to obtain 1-[3-ethylsulfanyl-4-[3-methyl-6-(trifluoromethyl)imidazo[4,5-b]pyridine-2-yl]phenyl]cyclopropanecarbonitrile. LCMS (Method 2): 403 (M+H) + Holding 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]pyridine-2-yl]phenyl]cyclopropanecarbonitride (Example P15, Table P) [ka] The desired product was prepared using the standard method described in Example H1, Step 7. LCMS (Method 1): 434 (M+H) + Holding 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 1.2 Preparation of 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 International Publication No. 2016 / 071214) (1 g, 3.8439 mmol) was suspended in acetonitrile (3 mL) and chloroform (3 mL). Dibromo copper (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 indicated completion of the reaction. The reaction mixture was filtered through Celite with dichloromethane. The filtrate was concentrated under reduced pressure, and the resulting residue was purified by silica gel chromatography to obtain 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-necked flask fitted with a reflux condenser, 2-bromo-1-(5-bromo-3-ethylsulfanyl-2-pyridyl)ethanone (0.50 g, 1.5 mmol) and 5-(trifluoromethyl)pyridazine-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 under reduced pressure. The resulting solid was dissolved in ethyl acetate and washed once with a saturated NaHCO3 solution. The organic layer was pre-dried with brine, dried over sodium sulfate, filtered, and concentrated under reduced pressure. The crude product was purified by silica gel chromatography to obtain 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 (400MHz, chloroform) δppm 1.44 (t, J=7.34Hz, 3H) 3.04 (q, J=7.34Hz, 2H) 7.82 (d, J=1.83Hz, 1H) 8.33-8.39 (m, 1H) 8.57 (dd, J=3.85, 2.02Hz, 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] Toluene (14 mL) and water (0.69 mL) were charged into a 100 mL three-necked flask and flushed with argon for 5 minutes. Under an 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 equivalents, 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 silica gel chromatography to obtain 2-(5-cyclopropyl-3-ethylsulfanyl-2-pyridyl)-7-(trifluoromethyl)imidazo[1,2-b]pyridazine. LCMS (Method 1): Retention time 1.08 min; 365(M+H) + . ¹H NMR (400MHz, chloroform) δppm 0.81-0.86 (m, 2H) 1.09-1.16 (m, 2H) 1.39 (t, J=7.34Hz, 3H) 1.94-2.03 (m, 1H) 3.00 (q, J=7.34Hz, 2H) 7.36-7.39 (m, 1H) 8.33 (d, J=1.83Hz, 1H) 8.33 (s, 1H) 8.54 (d, J=2.20Hz, 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 inactivated 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 silica gel chromatography to obtain [5-cyclopropyl-2-[7-(trifluoromethyl)imidazo[1,2-b]pyridazin-2-yl]-3-pyridyl]-ethyl-imino-oxo-λ 6 - Obtained sulfane. 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-ethylsulfanylpyridine [ka] Solutions of diethyl disulfide (7.76 g, 63.5 mmol, 2.00 equivalents) and t-butyl nitrite (4.91 g, 47.6 mmol, 1.50 equivalents) in DCE (60 mL) and DCM (40 mL) were heated to 40°C. To this mixture, a solution of 2,5-dibromopyridine-3-amine (8.00 g, 31.7 mmol, 1.00 equivalent) in dichloroethane (200 mL) was slowly added over 90 minutes, and the reaction mixture was stirred at 40°C for a further 1 hour. After the reaction was complete, the reaction mixture was cooled, diluted with water (100 mL), and extracted with dichloromethane (2 × 100 mL). The organic layers were separated, and the combined organic layers were dried over sodium sulfate, filtered, and concentrated under reduced pressure. The crude product was purified by column chromatography (silica gel, 5-15% ethyl acetate / cyclohexane) to obtain 2,5-dibromo-3-ethylsulfanylpyridine. LCMS (Method 4): 296 (M+H) + Holding time: 1.16 minutes. 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-ethylsulfanylpyridine (1 g, 3.3669 mmol) in 1,4-dioxane (10.34 g), hydrazine monohydrate (1.0113 g, 20.201 mmol) was added, and the resulting mixture was stirred at 120°C for 10 hours. After the reaction was complete, the mixture was diluted with water (30 ml) and extracted with ethyl acetate. The combined organic layer was washed with water (20 ml), dried over sodium sulfate, filtered, and concentrated under reduced pressure to obtain (5-bromo-3-ethylsulfanyl-2-pyridyl)hydrazine. LCMS:250(M+H) + Holding time: 0.6 minutes. ¹H NMR (400MHz, 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 under reduced pressure to remove all pentanol. The resulting residue was evaporated simultaneously with toluene. The crude product was diluted with water (100 ml) and brine (100 ml) and extracted with ethyl acetate (3 × 200 ml). The combined organic layer was dried over sodium sulfate, filtered, and concentrated under reduced pressure. The obtained solid was doubled with cyclohexane to obtain 4-[2-(5-bromo-3-ethylsulfanyl-2-pyridyl)hydrazino]-6-(trifluoromethyl)pyridine-3-carboxylic acid. LCMS (Method 5): Retention time 1.50 minutes, 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 clear solution obtained at 110°C was refluxed for 50 minutes. After the reaction was complete, the mixture was concentrated (phosphorus oxychloride was removed by distillation under reduced pressure), 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 layer was washed with water (200 ml), dried over sodium sulfate, filtered, and concentrated under reduced pressure. The crude product was purified by silica gel chromatography to obtain 2-(5-bromo-3-ethylsulfanyl-2-pyridyl)-3-chloro-6-(trifluoromethyl)pyrazolo[4,3-c]pyridine. LCMS:437(M+H) + Holding time: 1.21 minutes. ¹H NMR (400MHz, 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 (0.2 mmol, 0.1 g) was dissolved in acetic acid (2 mL), and zinc (0.5 mmol, 0.03 g) was slowly added to the mixture. The reaction mixture was stirred at 55°C for 40 minutes. The reaction was monitored by LC-MS and TLC. After completion, the reaction mixture was poured into water (30 ml), and the resulting solution was extracted with ethyl acetate (20 ml x 3). The combined organic layer was washed with saturated sodium chloride aqueous solution (30 ml), dried over anhydrous sodium sulfate, filtered, and concentrated under 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. ¹H NMR (400MHz, 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 minutes, 403 (M+H) + .

[0284] Step 6: Preparation of 2-(5-cyclopropyl-3-ethylsulfanyl-2-pyridyl)-6-(trifluoromethyl)pyrazolo[4,3-c]pyridine [ka] 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), and tricyclohexylphosphane (0.007 g, 0.02 mmol) were added to a microwave vial in toluene (2 mL) and water (1 mL). The reaction mixture was purged with nitrogen for 30 minutes. Palladium(II) acetate (0.003 g, 0.01 mmol) was then added, and the reaction mixture was stirred under microwave conditions at 150 °C for 4 hours. The reaction mixture was then diluted with ethyl acetate (20 mL) at room temperature and washed with water (20 mL). The organic layer was washed with water (20 mL), dried over sodium sulfate, filtered, and concentrated under reduced pressure. The compound was isolated by silica gel chromatography to obtain 2-(5-cyclopropyl-3-ethylsulfanyl-2-pyridyl)-6-(trifluoromethyl)pyrazolo[4,3-c]pyridine. LCMS:365(M+H) + Holding time: 1.12 minutes. ¹H NMR (400MHz, 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 the standard method described in Example H1, Step 7. LCMS (Method 5): Retention time 0.94 min, 396 (M+H) + . ¹H NMR (400MHz, 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-benzoxazole-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 Step 7 of Example H1, starting with 2-(5-cyclopropyl-3-ethylsulfanyl-2-pyridyl)-5-(trifluoromethylsulfanyl)-1,3-benzoxazole (known from International Publication No. 19 / 009307). LCMS (Method 5): 428 (M+H) + Holding time: 1.03 minutes.

[0287] Further compounds of the present invention can be prepared in the same manner as described above. Compounds prepared to further illustrate the present invention are listed in Table P.

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

[0289] The activity of the compositions according to the present invention can be considerably broadened and adapted to general situations by adding other insecticidal, acaricidal, and / or fungicidal active components. Mixtures of the compound of Formula I with other insecticidal, acaricidal, and / or fungicidal active components may also have further unexpected advantages, which may be described in a broader sense as synergistic activity. For example, there may be better tolerance by plants, reduced plant toxicity, the ability to control insects at different developmental stages, or better behavior during their manufacture, e.g., during grinding or mixing, during their storage, or during their use.

[0290] Suitable additives to the active ingredients in this specification include, for example, the following types of active ingredients: organophosphorus compounds, nitrophenol derivatives, thiourea, juvenile hormones, formamidine, benzophenone derivatives, urea, pyrrole derivatives, carbamates, pyrethroids, chlorinated hydrocarbons, acylureas, pyridylmethyleneamino derivatives, macrolides, neonicotinoids, and Bacillus thuringiensis preparations.

[0291] The following mixtures of the compound of formula I and the active ingredient are preferred (the abbreviation "TX" means "one compound selected from the group consisting of the compounds listed 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"): Auxiliary agent 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 Abstract name)(1059)+TX, 2-Fluoro-N-methyl-N-1-naphthylacetamide (IUPAC name)(1295)+TX, 4-Chlorophenylphenylsulfone (IUPAC name)(981)+TX, Abamectin(1)+TX, Acequinosyl(3)+TX, A Cetoprole [CCN] + TX, Acrinatrin (9) + TX, Aldicarb (16) + TX, Aldoxycarb (863) + TX, α-Cypermethrin (202) + TX, Amidithione (870) + TX, Amidoflumet [CCN] + TX, Amidothioate (872) + TX, Amiton (875) + TX, Amiton Hydroxalate (875) + TX, Amitraz (24) + TX, Aramite (881) + TX, Arsenic Trioxide (882) + TX, AVI 382 (compound code) + TX, AZ 60541 (compound code) + TX, Adinphos-ethyl (44) + TX, Adinphos-methyl (45) + TX, Azobenzene (IUPAC name) (888) + TX, Azocyclotin (46) + TX, Azothoate (889) + TX, Benomyl (62) + TX, Benoxaphos (alternative name) [CCN] + TX, Benzoximate (71) + TX, Benzyl benzoate (IUPAC name) [CCN] + TX, Bifenazate (74) + TX, Bifenthrin (76) + TX, Binapacril (907) + TX, Blofenvalerate (alternative name) + TX Bromocyclene (918) + TX, Bromophos (920) + TX, Bromophos-ethyl (921) + TX, Bromopropylate (94) + TX, Buprofezin (99) + TX, Butocarboxime (103) + TX, Butoxycarboxime (104) + TX, Butylpyridaben (alternative name) + TX, Calcium polysulfide (IUPAC name) (111) + TX, Campechlor (941) + TX, Carbanolate (943) + TX, Carbaryl (115) + TX, Carbofuran (118) + TX, Carbophenothion (947) + TX, CGA 50'439 (development code) (125) + TX, Quinomethionat (126) + TX, Chlorbenside (959) + TX, Chlordimeform (964) + TX, Chlordimeform hydrochloride (964) + TX,Chlorfenapyr (130) + TX, Chlorphenetol (968) + TX, Chlorphensone (970) + TX, Chlorphensulfide (971) + TX, Chlorphenvinphos (131) + TX, Chlorbenzylate (975) + TX, Chloromebform (977) + TX, Chloromethirone (978) + TX, Chloropropylate (983) + TX, Chlorpyrifos (145) + TX, Chlorpyrifos-methyl (146) + TX, Chlorthiofos (994) + TX, Synerin I (696) + TX, Synerin II (696) + TX, Synerin (69 6) +TX, clofentezine (158) +TX, closantel (alternative name) [CCN] +TX, coumaphos (174) +TX, crotamiton (alternative name) [CCN] +TX, clotoxyphos (1010) +TX, cufraneb (1013) +TX, cyanthoate (1020) +TX, cyflumetofen (CAS registry number: 400882-07-7) +TX, cyhalotrin (196) +TX, cyhexatine (199) +TX, cypermethrin (201) +TX, DCPM (1032) +TX, DDT (219) +TX, demefion (1037) +TX, demef Demephion-O(1037)+TX, Demephion-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-methylsulfone(1039)+TX, Diafenthiurone(226)+TX, Diympropyridaz+TX, Dialiphos(1042)+TX, Diazinon(227)+TX, Diclofluanide(230)+TX, Dichlorvos(236)+TX, Diclifos (alternative name) + TX, Dicofor (242) + TX, Diclotophos (243) + TX, Dienochlor (1071) + TX, Dimehox (1081) + TX, Dimethoate (262) + TX, Dinactin (alternative name) (653) + TX, Dynex (1089) + TX, Dynex-Dicrexin (1089) + TX, Dinobutone (269) + TX, Dinocap (270) + TX, Dinocap-4 [CCN] + TX, Dinocap-6 [CCN] + TX, Dinoctone (1090) + TX, Dinopenton (1092) + TX, Dinosulfone (1097) + TX,Dinoterbone (1098) + TX, Dioxathion (1102) + TX, Diphenylsulfone (IUPAC name) (1103) + TX, Disulfiram (alternative name) [CCN] + TX, Disulfoton (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, Ethoxazole (320) + TX, Etrimphos (1142) + TX, Fenazaflor (1147) + TX, Fenazaquin (328) + TX, Fenbutas oxide Zu (330) + TX, Phenothiocarb (337) + TX, Fenpropathrin (342) + TX, Fenpyrad (alternative name) + TX, Fenpyroximate (345) + TX, Fenson (1157) + TX, Fentriphanil (1161) + TX, Fenvalerate (349) + TX, Fipronil (354) + TX, Fluacrypilim (360) + TX, Fluazuron (1166) + TX, Flubendimine (1167) + TX, Flucycloxuron (366) + TX, Flucitrinate (367) + TX, Fluenetil (1169) + TX, Flufenoxuron (370) + TX, Flumetrin (372) + TX, Fluolbenside (1174) + TX, Fluvalinate (1184) + TX, FMC 1137 (development code) (1185) + TX, Formetanate (405) + TX, Formetanate hydrochloride (405) + TX, Formotho (1192) + TX, Formparanate (1193) + TX, γ-HCH (430) + TX, Gliodin (1205) + TX, Halfenprox (424) + TX, Heptenofos (432) + TX, Hexadecylcyclopropane carboxylate (IUPAC / Chemical Cal abstract 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,Iodophenphos (1248) + TX, Lindan (430) + TX, Lufenuron (490) + TX, Malathion (492) + TX, Malonoben (1254) + TX, Mecarbum (502) + TX, Mephosphoran (1261) + TX, Mesulfen (alternative name) [CCN] + TX, Methacryphos (1266) + TX, Methamidophos (527) + TX, Methidathion (529) + TX, Methiocarb (530) + TX, Methomyl (531) + TX, Methyl bromide (537) + TX, Metolcarb (550) + TX, Mevinphos (556) + TX, Mexac Rubate (1290) + TX, Milbemectin (557) + TX, Milbemycin oxime (alternative name) [CCN] + TX, Mipahox (1293) + TX, Monoclotophos (561) + TX, Morphothion (1300) + TX, Moxidectin (alternative name) [CCN] + TX, Nared (567) + TX, NC-184 (compound code) + TX, NC-512 (compound code) + TX, Niflulidide (1309) + TX, Nicomycin (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, Oxydisulfon (1325) +TX, pp'-DDT (219) +TX, Parathion (615) +TX, Permethrin (626) +TX, Petroleum (alternative name) (628) +TX, Fenkapton (1330) +TX, Fenthoate (631) +TX, Phorate (636) +TX, Phosalon (637) +TX, Phosphorane (1338) +TX, Ho Smet (638) + TX, Phosphamidone (639) + TX, Foxim (642) + TX, Pirimiphos-methyl (652) + TX, Polychloroterpene (common name) (1347) + TX, Polynactin (alternative name) (653) + TX, Proclonol (1350) + TX, Profenofos (662) + TX, Promacil (1354) + TX, Propargit (671) + TX, Propetamphos (673) + TX, Propoxar (678) + TX, Protidathion (1360) + TX, Protoate (1362) + TX, Pyrethrin I (696) + TX,Pyrethrin II (696) + TX, Pyrethrin (696) + TX, Pyridaben (699) + TX, Pyridafenthion (701) + TX, Pyrimidifen (706) + TX, Pyrimitate (1370) + TX, Quinalfos (711) + TX, Quinthiokis (1381) + TX, R-1492 (development code) (1382) + TX, RA-17 (development code) (1383) + TX, Rotenone (722) + TX, Schladan (1389) + TX, Cebufos (alternative name) + TX, Selamectin (alternative name) [CCN] + T X, SI-0009 (compound code) + TX, Sofamide (1402) + TX, Spirodiclofen (738) + TX, Spiromesifen (739) + TX, SSI-121 (development code) (1404) + TX, Sulfiram (alternative name) [CCN] + TX, Sulfuramide (750) + TX, Sulfotep (753) + TX, Sulfur (754) + TX, SZI-121 (development code) (757) + TX, τ-Fulvalinate (398) + TX, Tebufenpyrad (763) + TX, TEPP (1417) + TX, Terbam (alternative name) + TX, Tetrachlorvinphos (777) + TX, Tetradiphon (786) + TX, Tetranactin (alternative name) (653) + TX, Tetrasul (1425) + TX, Thiafenox (alternative name) + TX, Thiocarboxim (1431) + TX, Thiofanox (800) + TX, Thiometon (801) + TX, Thioquinox (1436) + TX, Turingiencin (alternative name) [CCN] + Acaricide selected from the group consisting of TX, triamiphos (1441) + TX, triatene (1443) + TX, triazophos (820) + TX, triazuron (alternative name) + TX, trichlorfon (824) + TX, triphenofos (1455) + TX, trinactin (alternative name) (653) + TX, bamidthione (847) + TX, vaniliprole [CCN] and YI-5302 (compound code) + TX. Algicidal agents selected from the group consisting of vethoxazine [CCN] + TX, copper dioctanoate (IUPAC name) (170) + TX, copper sulfate (172) + TX, sibutrin [CCN] + TX, diclon (1052) + TX, dichlorophen (232) + TX, endotar (295) + TX, fenthin (347) + TX, slaked lime [CCN] + TX, narbaum (566) + TX, quinoclamin (714) + TX, quinonamide (1379) + TX, simazine (730) + TX, triphenyltin acetate (IUPAC name) (347), and triphenyltin hydroxide (IUPAC name) (347) + TX. Anthelmintics 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. A birdicide selected from the group consisting of chloralose (127) + TX, endrin (1122) + TX, fenthion (346) + TX, pyridine-4-amine (IUPAC name) (23), and strychnine (745) + TX. 1-H-pyridine-2-thion (IUPAC name) (1222) + TX, 4-(quinoxaline-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, dodicine (1112) + TX, phenaminosulf (1144) + TX, formaldehyde (404) + TX, hydrargafen (alternative name) [CCN] + A bactericide selected from the group of substances consisting of TX, kasugamycin (483) + TX, kasugamycin hydrochloride hydrate (483) + TX, nickel bis(dimethyldithiocarbamate) (IUPAC name) (1308) + TX, nitrapyrine (580) + TX, octylinone (590) + TX, oxolinic acid (606) + TX, oxytetracycline (611) + TX, potassium hydroxyquinoline sulfate (446) + TX, probenazole (658) + TX, streptomycin (744) + TX, streptomycin sesquisulfate (744) + TX, tecrophthalam (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 aphidiminiza 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. islaensis subsp.israelensis)(scientific name)(51)+TX, Bacillus thuringiensis subsp.japonensis(scientific name)(51)+TX, Bacillus thuringiensis subsp.kurstaki(scientific name)(51)+TX, Bacillus thuringiensis subsp.tenebryonis(scientific name)tenebrionis) (scientific name) (51) + TX, Beauveria bassiana (alternative name) (53) + TX, Beauveria brongniartii (alternative name) (54) + TX, Chrysoperla carnea (alternative name) (151) + TX, Cryptolaemus montrouzieri (alternative name) (178) + TX, Cydia pomonella GV (alternative name) (191) + TX, Dacnusa sibirica (alternative name) (212) + TX, Diglyphus isaea (alternative name) (254) + TX, Encarsia formosa) (scientific name) (293) + TX, desert parasitic wasp (Eretmocerus eremicus) (alternative name) (300) + TX, American tobacco budworm (Helicoverpa zea) NPV (alternative name) (431) + TX, Heterorhabditis bacteriophora and H. megidis (alternative name) (433) + TX, ladybug (Hippodamia convergens) (alternative name) (442) + TX, Leptomastix dactylopii (alternative name) (488) + TX, Macrolophus caliginosus (alternative name) (491) + TX, cutworm (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. reconti (N.lecontei)NPV (alternative name)(575)+TX, Orius spp. (alternative name)(596)+TX, Paecilomyces fumosoroseus (alternative name)(613)+TX, Phytoseiulus persimilis (alternative name)(644)+TX, Spodoptera exigua polycapsid nucleus polyhedrosis virus (scientific name)(741)+TX, Steinernema bibionis (alternative name)(742)+TX, Steinernema carpocapsae (alternative name)(742)+TX, Steinernema feltiae (Steinernema feltiae) (alternative name) (742) + TX, Steinernema glaseri (alternative name) (742) + TX, Steinernema riobrave (alternative name) (742) + TX, Steinernema riobravis (alternative name) (742) + TX, Steinernema scapterisci (alternative name) (742) + TX, Steinernema spp. (alternative name) (742) + TX, Trichogramma spp. (alternative name) (826) + TX, Typhlodromus osidentalis A biological agent selected from the group of substances consisting of *Occidentalis* (alternative name) (844) and *Verticillium lecanii* (alternative name) (848) + TX. A soil sterilizer selected from the group consisting of iodomethane (IUPAC name) (542) and methyl bromide (537) + TX, A sterilizing agent selected from the group of substances consisting of aphorate [CCN]+TX, bisadil (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 aphorate [CCN]+TX, molzide [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)-trideca-4-en-1-yl acetate (IUPAC name)(829)+TX, (E)-6-methylhepta-2-en-4-ol (IUPAC name)(541)+TX, (E,Z)-tetradeca-4,1 0-diene-1-ylacetate (IUPAC name)(779)+TX, (Z)-dodeca-7-ene-1-ylacetate (IUPAC name)(285)+TX, (Z)-hexadeca-11-enal (IUPAC name)(436)+TX, (Z)-hexadeca-11-ene-1-ylacetate (IUPAC name)(437)+TX, (Z)-hex Sadeca-13-en-11-in-1-ylacetate (IUPAC name) (438) + TX, (Z)-icos-13-en-10-on (IUPAC name) (448) + TX, (Z)-tetradeca-7-en-1-ar (IUPAC name) (782) + TX, (Z)-tetradeca-9-en-1-ol (IUPAC name) (783) + TX, ( Z)-Tetradeca-9-ene-1-ylacetate (IUPAC name)(784)+TX, (7E,9Z)-Dodeca-7,9-diene-1-ylacetate (IUPAC name)(283)+TX, (9Z,11E)-Tetradeca-9,11-diene-1-ylacetate (IUPAC name)(780)+TX, (9Z,12E)-Tetradeca-9,12-Diene-1-yl acetate (IUPAC name) (781) + TX, 14-Methyloctadeca-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, Chodrelua (alternative name) [CCN] + TX, Codremon (alternative name) (167) + TX, Curea ( Alternative name)(179)+TX, Dispara(277)+TX, Dodeca-8-en-1-ylacetate(IUPAC name)(286)+TX, Dodeca-9-en-1-ylacetate(IUPAC name)(287)+TX, Dodeca-8+TX, 10-dien-1-ylacetate(IUPAC name)(284)+TX, Dominicala(alternative name)[CCN]+TX, 4-methyloctanoate ethyl(IUPAC name)(317)+TX, Eugenol(alternative name )[CCN]+TX, Frontalin (alternative name)[CCN]+TX, Gossiplua (alternative name)(420)+TX, Grandlua (421)+TX, Grandlua I (alternative name)(421)+TX, Grandlua II (alternative name)(421)+TX, Grandlua III (alternative name)(421)+TX, Grandlua IV (alternative name)(421)+TX, Hexalua[CCN]+TX, Ipsdienol (alternative name)[CCN]+TX, Ipsenol (alternative name)[ CCN]+TX, Japonila (alternative name) (481)+TX, Lineatin (alternative name) [CCN]+TX, Littlea (alternative name) [CCN]+TX, Lupula (alternative name) [CCN]+TX, Medolua [CCN]+TX, Megatomoic acid (alternative name) [CCN]+TX, Methyl eugenol (alternative name) (540)+TX, Muscarua (563)+TX, Octadeca-2,13-diene-1-ylacetate (IUPAC name) (588)+TX, Octadeca-3,13-Diene-1-Ilacetate (IUPAC name)(589)+TX, Orphlurua (alternative name)[CCN]+TX, Orictalua (alternative name)(317)+TX, Ostramon (alternative name)[CCN]+TX, Sigrua[CCN]+TX, Solzidine (alternative name)(736)+TX, Sulcatol (alternative name)[CCN]+TX, Tetradeca-11-en-1-Ilacetate (IU Insect pheromones selected from the group of substances consisting of PAC name)(785)+TX, trimedlua(839)+TX, trimedlua A(alternative name)(839)+TX, trimedlua B1(alternative name)(839)+TX, trimedlua B2(alternative name)(839)+TX, trimedlua C(alternative name)(839), and trunk-call(alternative name)[CCN]+TX, Insect repellents selected from the group consisting of 2-(octylthio)ethanol (IUPAC name) (591) + TX, butopyrronoxyl (933) + TX, butoxy(polypropylene glycol) (936) + TX, dibutyl adipate (IUPAC name) (1046) + TX, dibutyl phthalate (1047) + TX, dibutyl succinate (IUPAC name) (1048) + TX, diethyltoluamide [CCN] + TX, dimethyl carbate [CCN] + TX, dimethyl phthalate [CCN] + TX, ethylhexanediol (1137) + TX, hexaamide [CCN] + TX, methquin-butyl (1276) + TX, methylneodecanamide [CCN] + TX, oxamate [CCN] and picaridin [CCN] + TX. 1-Dichloro-1-nitroethane (IUPAC / Chemical Abstract name)(1058) + TX, 1,1-Dichloro-2,2-bis(4-ethylphenyl)ethane (IUPAC name)(1056), + TX, 1,2-Dichloropropane (IUPAC / Chemical Abstract name)(1062) + TX, 1,2-Dichloropropane and 1,3-Dichloropropene (IUPAC name)(1063) + TX, 1-Bromo-2-chloroethane (IUPAC / Chemical Abstract name)(916) + TX , 2,2,2-trichloro-1-(3,4-dichlorophenyl)ethyl acetate (IUPAC name) (1451) + TX, 2,2-dichlorovinyl 2-ethylsulfinylethylmethyl phosphate (IUPAC name) (1066) + TX, 2-(1,3-dithiolan-2-yl)phenyldimethylcarbamate (IUPAC / chemical abstract name) (1109) + TX, 2-(2-butoxyethoxy)ethylthiocyanate (IUPAC / chemical abstract 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-chlorovinyldiethylphosphate (IUPAC name) (984) + TX, 2-imidazolidone (IUPAC name) (1225) + TX, 2-isovalerylindan-1,3-dione (IUPAC name) (1246) + TX, 2-methyl (propa-2-inyl)aminophenylmethylcarbamate (IUPAC name) (1284) + TX, 2-thiocyanatoethyl laurate (IUPAC name) (1433) + TX, 3-bromo-1-chloropropa-1-ene (IUPAC name) (917) + TX, 3-methyl-1-phenylpyrazole-5-yldimethylcarbamate (IUPAC name) (1283) + TX, 4-methyl(propa-2-inyl)amino-3,5-xylylmethylcarbamate (IUPAC name) (1285) + TX, 5,5-dimethyl-3-oxocyclohexa-1-enyldimethylcarbamate (IUPAC name) (1085) + TX, abamectin (1) + TX, acephate (2) + TX, acetamiprid (4) + TX, acetylone (alternative name) [CCN] + TX, acetoprole [CCN] + TX, acrinatrin (9) + TX, acrylonitrile (IUPAC name) (861) + TX, alanicarb (15) + TX, aldicarb (16) + TX, aldoxycarb (863) + TX, aldrin (864) + TX, areto Phosphorus (17) + TX, Allosamidin (alternative name) [CCN] + TX, Alixicarb (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, azothoate (889) + TX, Bacillus thuringiensis delta-endotoxin (alternative name) (52) + TX, Barium hexafluorosilicate (alternative name) [CCN] + TX, barium polysulfide (IUPAC / chemical abstract name) (892) + TX, bartholin [CCN] + TX, Bayer 22 / 190 (development code) (893) + TX, Bayer 22408 (development code) (894) + TX, bengiocarb (58) + TX, benfuracarb (60) + TX, bensultap (66) + TX, β-cyfluthrin (194) + TX, β-cypermethrin (203) + TX, bifenthrin (76) + TX, biorethrin (78) + TX, biorethrin S-cyclopentenyl isomer (alternative name) (79) + TX, bioetanomethrin [CCN] + TX, biopermethrin (908) + TX, violethmethrin (80) + TX, bis(2-c Loroethyl ether (IUPAC name) (909) + TX, Bistriflurone (83) + TX, Borax (86) + TX, Brofenvalerate (alternative name) + TX, Bromufenbinphos (914) + TX, Bromocyclene (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, Butocarboxime (103) + TX, Butonate (932) + TX, Butoxycarboxime (104) + TX, Butylpyridaben (alternative name) + TX, Cazusaphos (109) + TX, Calcium arsenate [CCN] + TX, Calcium cyanide (444) + TX, Calcium polysulfide (IUPAC name) (111) + TX, Campechlor (941) + TX, Carbanolate (943) + TX, Carbaryl (115) + TX, Carbofuran (118) + TX, Carbon disulfide (IUPAC / Chemical Abstract) Lactose (945) + TX, Carbon tetrachloride (946) + TX, Carbophenothione (947) + TX, Carbosulfan (119) + TX, Cartap (123) + TX, Cartap hydrochloride (123) + TX, Sebazin (725) + TX, Chlorbicyclene (960) + TX, Chlordan (128) + TX, Chlordecone (963) + TX, Chlordimeform (964) + TX, Chlordimeform hydrochloride (964) + TX, Chlorethoxyphos (129) + TX,Chlorfenapir (130) + TX, Chlorfenbinfos (131) + TX, Chlorfluazuron (132) + TX, Chlormefos (136) + TX, Chloroform [CCN] + TX, Chloropicrin (141) + TX, Chlorhoxime (989) + TX, Chlorprazofos (990) + TX, Chlorpyrifos (145) + TX, Chlorpyrifos-methyl (146) + TX, Chlorthiofos (994) + TX, Chromafenozide (150) + TX, Synerin I (696) + TX, Synerin II (696) + TX, Synerin (696) + TX , cis-resmethrin (alternative name) + TX, cismethrin (80) + TX, crocitrin (alternative name) + TX, chloetocarb (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, clotoxyphos (1010) + TX, culfomate (1011) + TX, cryolite (alternative name) (177) + TX, CS 708 (development code) (1012) + TX, cyanophenphos (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-methylsulfone (1039) + TX, diafenthiuron (226) + TX,Dialifos (1042) + TX, Diamidafos (1044) + TX, Diazinon (227) + TX, Dicapthion (1050) + TX, Diclofenthion (1051) + TX, Dichlorvos (236) + TX, Diclifos (alternative name) + TX, Dicrecyl (alternative name) [CCN] + TX, Diclotophos (243) + TX, Dicyclanil (244) + TX, Dierdrin (1070) + TX, Diethyl 5-methylpyrazole-3-ylphosphate (IUPAC name) (1076) + TX, Diflubenzuron (250) + TX, Dirol (alternative name) [CCN] + TX, Dimefluthrin [CCN] + TX, Dimehox (1081) + TX , dimethane (1085) + TX, dimethoate (262) + TX, dimethrin (1083) + TX, dimethylvinphos (265) + TX, dimethilane (1086) + TX, dynex (1089) + TX, dynex-dicrexin (1089) + TX, dinoprop (1093) + TX, dynosam (1094) + TX, dynoseb (1095) + TX, dinotefuran (271) + TX, diophenolane (1099) + TX, dioxabenzophos (1100) + TX, dioxacarb (1101) + TX, dioxathion (1102) + TX, disulfon (278) + TX, diticlophos (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, Epophenonane (1124) + TX, Eprinomectin (alternative name) [CCN] + TX, Esfenvalerate (302) + TX, Etaphos (alternative name) [CCN] + T X, Ethiofencarb (308) + TX, Ethion (309) + TX, Ethiprole (310) + TX, Ethoate-methyl (1134) + TX, Etoprophos (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, phenamifos(326)+TX, phenazaflor(1147)+TX, fenchlorfos(1148)+TX, phenetacarb(1149)+TX, fenfluthrin(1150)+TX, fenitrothion(335)+TX, phenobucarb(336)+TX, phenoxacrim(1153)+TX, phenoxycarb(340)+TX, fenpyritrin(1155)+TX, fenpropathrin(342)+TX, fenpyrad(alternative name)+TX, fensulfothione(1158)+TX, F Fenthion (346) + TX, Fenthion-ethyl [CCN] + TX, Fenvalerate (349) + TX, Fipronil (354) + TX, Flunicamide (358) + TX, Flubendiamide (CAS Registry No.: 272451-65-7) + TX, Flucoflon (1168) + TX, Flucycloxlon (366) + TX, Flucitrinate (367) + TX, Fluenetil (1169) + TX, Fluphenelim [CCN] + TX, Flufenoxlon (370) + TX, Flufenprox (1171) + TX,Flumethrin (372) + TX, Fluvalinate (1184) + TX, FMC 1137 (development code) (1185) + TX, Honofos (1191) + TX, Formetanate (405) + TX, Formetanate hydrochloride (405) + TX, Formothione (1192) + TX, Formparanate (1193) + TX, Fosmethilane (1194) + TX, Fosspire (1195) + TX, Fosthiazate (408) + TX, Fosthiethane (1196) + TX, Frathiocarb (412) + TX, Fretorin (1200) + TX, γ-Cyhalothrin (197) + TX, γ-HCH (430) + TX, Guazatin (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, Heptenofos (432) + TX, Heterophos [CCN] + TX, Hexaflumurone (439) + TX, HHDN (864) + TX, Hydramethylnon (443) + TX, Hydrogen cyanide (444) + TX, Hydroprene (445) + TX, Hikincarb (1223) + TX, Imidaclopride (458) + TX, Imiprothrin (460) + TX, Indoxacarb (465) + TX, Iodomethane (IUPAC name) (542) + TX, IPSP (1229) + TX, Isazofos (1231) + TX, Isobenzane (1232) + TX, Isocarbos (alternative name) (473) + TX, Isodrine (1235) + TX, Isofenphos (1236) + TX, Isolane (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, Iodophenphos (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, Quinoprene (484)+TX, λ-Cyhalothrin (198)+TX,Lead arsenate [CCN] + TX, lepimectin (CCN) + TX, leptophos (1250) + TX, lindan (430) + TX, lilimphos (1251) + TX, lufenuron (490) + TX, ritidathione (1253) + TX, m-cumenylmethylcarbamate (IUPAC name) (1014) + TX, magnesium phosphide (IUPAC name) (640) + TX, malathion (492) + TX, malonoben (1254) + TX, majidox (1255) + TX, mecarbam (502) + TX, mecarphone (1258) + TX, menazone (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, Methacryphos (1266) + TX, Methamidophos (527) + TX, Methanesulfonyl fluoride (IUPAC / chemical abstract name) (1268) + TX, Methidathion (529) + TX, Methiocarb (530) + TX, Metoclotophos (1273) + TX, Methomyl (531) + TX, Me Toprene (532) + TX, Methquine-butyl (1276) + TX, Methotrin (alternative name) (533) + TX, Methoxychlor (534) + TX, Methoxyphenozide (535) + TX, Methyl bromide (537) + TX, Methyl isothiocyanate (543) + TX, Methylchloroform (alternative name) [CCN] + TX, Methylene chloride [CCN] + TX, Metofluthrin [CCN] + TX, Metolcarb (550) + TX, Methoxadiazone (1288) + TX, Mevinphos (556) + TX, Mexacalbate (1290) + TX, Milbemectin (557 )+TX, Milbemycin oxime (alternative name) [CCN]+TX, Mipahox (1293)+TX, Mirex (1294)+TX, Monoclotophos (561)+TX, Morphothion (1300)+TX, Moxidectin (alternative name) [CCN]+TX, Naphthalophos (alternative name) [CCN]+TX, Nared (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,Niflulidide (1309) + TX, Nitenpyram (579) + TX, Nichiazine (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, Novalon (585) + TX, Noviflurum (586) + TX, O-5-dichloro-4-iodophenyl O-ethylethyl 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-propylpyrimidine-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, oxydisulfone (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, Fencapton (1330) + TX, Phenothrin (630) + TX, Fenthoate (631) + TX, Phorate (636) + TX, Phosalon (637) + TX, Phosphane (1338) + TX, Phosmet (638) + TX, Fosnicrol (1339) + TX, Phosphamidone (639) + TX, Phosphine (IUPAC name) (640) + TX, Phoxime (642) + TX, Phoxime-methyl (1340) + TX, Pirimethaphos (1344) + TX, Pirimicarbe (651) + TX, Pirimichos-ethyl (1345) + TX, Pirimichos-methyl (652) + TX, Polychlorodicyclopentadiene isomer (IUPAC name) (1346) + TX, Polychloroterpene (common name) (1347) + TX, Potassium arsenite [CCN] + TX, Potassium thiocyanate [CCN] + TX, Prallethrin (655) + TX, Precosen I (alternative name) [CCN] + TX , Precosen II (alternative name) [CCN] + TX, Precosen III (alternative name) [CCN] + TX, Primidophos (1349) + TX, Profenofos (662) + TX, Profluthrin [CCN] + TX, Promacil (1354) + TX, Promecarb (1355) + TX, Propaphos (1356) + TX, Propetamphos (673) + TX, Propoxar (678) + TX, Protidathione (1360) + TX, Prothiofos (686) + TX X, Protoate (1362) + TX, Protrefene Butte [CCN] + TX, Pymetrozine (688) + TX, Piraclofos (689) + TX, Pirazofos (693) + TX, Pyrethmetrin (1367) + TX, Pyrethrin I (696) + TX, Pyrethrin II (696) + TX, Pyrethrin (696) + TX, Pyridaben (699) + TX, Pyridaryl (700) + TX, Pyridafenthion (701) + TX, Pyrimidifen ( 706)+TX, Pyrimitate (1370)+TX, Pyriproxyfen (708)+TX, Quassia (alternative name) [CCN]+TX, Quinalphos (711)+TX, Quinalphos-methyl (1376)+TX, Quinotion (1380)+TX, Quinthiokis (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, Lianya (alternative name) (1387) + TX, Lianodine (common name) (1387) + TX, Sabajira (alternative name) (725) + TX, Schladan (1389) + TX, Cebuphos (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 abstract name) (1399) + TX, Sodium hexafluorosilicate (1400) + TX, Sodium pentachlorophenoxide (623) + TX, Sodium selenite (IUPAC name) (1401) + TX, Sodium thiocyanate [CCN] + TX, Sofamide (1402) + TX, Spinosad (737) + TX, Spiromesifen (7 39) +TX, Spirotetramate (CCN) +TX, Sulcoflon (746) +TX, Sulcoflon-sodium (746) +TX, Sulfuramide (750) +TX, Sulfotep (753) +TX, Sulfuryl fluoride (756) +TX, Sulpros (1408) +TX, Tar oil (alternative name) (758) +TX, τ-Fulvalinate (398) +TX, Tadimucarb (1412) +TX, TDE (1414) +TX, Tebufenozide (762) +TX, Tebufenpyrad (763) +TX, Tebupirimphos (764) +TX, teflubenzuron (768) +TX, tefluthrin (769) +TX, temephos (770) +TX, TEPP (1417) +TX, teralethrin (1418) +TX, terbam (alternative name) +TX, terbuphos (773) +TX, tetrachloroethane [CCN] +TX, tetrachlorvinphos (777) +TX, tetramethrin (787) +TX, θ-cypermethrin (204) +TX, thiacloprid (791) +TX, thiaphenox (alternative name) +TX, thiamethoxam (792) +TX, ticlophos (14 28)+TX, Thiocarboxim (1431)+TX, Thiocyclam (798)+TX, Thiocyclam Hydroxalate (798)+TX, Thiodicarb (799)+TX, Thiofanox (800)+TX, Thiometon (801)+TX, Thionadin (1434)+TX, Thiosultap (803)+TX, Thiosultap-Sodium (803)+TX, Turingiencin (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, triazurone (alternative name) + TX, trichlorfon (824) + TX, trichlormetaphos-3 (alternative name) [CCN] + TX, trichloronate (1452) + TX, triphenofos (1455) + TX, triflumulone (835) + TX, trimetacarb (840) + TX, triprene (145 9)+TX, Bamidthione (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, ζ-Cypermethrin (205)+TX, Zetamethrin (alternative name)+TX, Zinc phosphide (640)+TX, Zolaprofos (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, Tetrameth Insecticides selected from the group consisting of substances comprising flufluthrin [84937-88-2] + TX, triflumezopyrim (disclosed in International Publication No. 2012 / 092115) + TX, fluxamethamide (International Publication No. 2007 / 026965) + TX, ε-metofluthrin [240494-71-7] + TX, ε-monfluorothrin [1065124-65-3] + TX, fluazandinidine [1254304-22-7] + TX, chloroprallethrin [399572-87-3] + TX, fluxamethamide [928783-29-3] + TX, cyhalodiamide [1262605-53-7] + TX, thioxazafen [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 International Publication No. 2010 / 060231) + TX, Cycloxapride (described in International Publication No. 2005 / 077934) + TX, Spiropidione + TX, Afidopiropen + TX, Flupyrimine + TX, Monfluorothrin + TX, κ-Bifenthrin + TX, κ-Tefluthrin + TX, Dichloromezothiaz + TX, Tetrachloraniliprole + TX, Benzpyrimoxane + TX; Bis(tributyltin) oxide (IUPAC name) (913) + TX, bromoacetamide [CCN] + TX, calcium arsenate [CCN] + TX, chloetocarb (999) + TX, copper acetoarsenite [CCN] + TX, copper sulfate (172) + TX, fentin (347) + TX, ferric phosphate (IUPAC name) (352) + TX, metaldehyde (518) + TX, methiocarb (530) + TX, niclosamide (576) + TX, niclosamide-olamine (576) + TX, pentachloro A molluscicide selected from the group consisting of lophenol (623) + TX, sodium pentachlorophenoxide (623) + TX, tadimucarb (1412) + TX, thiodicarb (799) + TX, tributyltin oxide (913) + TX, triphenmorph (1454) + TX, trimetacarb (840) + TX, triphenyltin acetate (IUPAC name) (347) and triphenyltin hydroxide (IUPAC name) (347) + TX, and pyriprole [394730-71-3] + TX. AKD-3088 (compound code) + TX, 1,2-dibromo-3-chloropropane (IUPAC / chemical abstract name) (1045) + TX, 1,2-dichloropropane (IUPAC / chemical abstract 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 abstract name) (IUPAC name)(1065)+TX, 3-(4-chlorophenyl)-5-methylrhodanine(IUPAC name)(980)+TX, 5-methyl-6-thioxo-1,3,5-thiadiadinane-3-ylacetic acid(IUPAC name)(1286)+TX, 6-isopentenylaminopurine(alternative name)(210)+TX, abamectin(1)+TX, acetoprole[CCN]+TX, aranicarb(15)+TX, aldicarb(16)+TX, aldoxycarb(863)+TX, AZ60541 (compound code) + TX, bencrotiaz [CCN] + TX, benomyl (62) + TX, butylpyridaben (alternative name) + TX, kazusafos (109) + TX, carbofuran (118) + TX, carbon disulfide (945) + TX, carbosulfan (119) + TX, chloropicrin (141) + TX, chlorpyrifos (145) + TX, chloetocarb (999) + TX, cytokinin (alternative name) (210) + TX, dazomet (216 )+TX, DBCP(1045)+TX, DCIP(218)+TX, Diamidaphos(1044)+TX, Diclofenthion(1051)+TX, Diclifos(alternative name)+TX, Dimethoate(262)+TX, Doramectin(alternative name)[CCN]+TX, Emamectin(291)+TX, Emamectin benzoate(291)+TX, Eprinomectin(alternative name)[CCN]+TX, Etoprofos(312)+TX, Dibromide(316) +TX, Fenamifos (326) +TX, Fenpyrad (alternative name) +TX, Fensulfothione (1158) +TX, Fosthiazate (408) +TX, Fosthiethane (1196) +TX, Furfural (alternative name) [CCN] +TX, GY-81 (development code) (423) +TX, Heterophos [CCN] +TX, Iodomethane (IUPAC name) (542) +TX, Isamidophos (1230) +TX, Isazofos (1231) +TX, Ivermectin N (alternative name) [CCN] + TX, Kinetin (alternative name) (210) + TX, Mecarphone (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, Mulberry dark spot disease fungus (MyrotheciumVerrucaria composition (alternative name) (565) + TX, NC-184 (compound code) + TX, oxamyl (602) + TX, phorate (636) + TX, phosphamidone (639) + TX, phosphocarb [CCN] + TX, sebuphos (alternative name) + TX, selamectin (alternative name) [CCN] + TX, spinosad (737) + TX, terbam (alternative name) + TX, terbuphos (773) + TX, tetrachlorothiophene (IU Nematicidals selected from the group consisting of substances comprising PAC / chemical abstract name)(1422)+TX, thiafenox(alternative name)+TX, thionazine(1434)+TX, triazophos(820)+TX, triazurone(alternative name)+TX, xylenol[CCN]+TX, YI-5302(compound code), and zeatin(alternative name)(210)+TX, fluensulfone[318290-98-1]+TX, and fluopyram+TX. A nitrification inhibitor selected from the group consisting of potassium ethylxanthogenicate [CCN] and nitrapyrine (580) + TX, A plant activator selected from the group consisting of acibenzolar(6)+TX, acibenzolar-S-methyl(6)+TX, probenazole(658), and Japanese knotweed (Reynoutria sachalinensis) extract (alternative name)(720)+TX, 2-Isovalerylindan-1,3-dione (IUPAC name) (1246) + TX, 4-(Quinoxaline-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, brodiphacomum (89) + TX, bromadiolon (91) + TX, brome Tallinn (92) + TX, Calcium cyanide (444) + TX, Chloralose (127) + TX, Chlorophacinone (140) + TX, Cholecalciferol (alternative name) (850) + TX, Coumacrol (1004) + TX, Coumafuryl (1005) + TX, Coumatetralyl (175) + TX, Crimidine (1009) + TX, Diphenacome (246) + TX, Difethiaron (249) + TX, Diphacinone (273) + TX, Ergocalciferol (301) + TX, Furocumafe N(357)+TX, Fluoroacetamide(379)+TX, Flupropadine(1183)+TX, Flupropadine hydrochloride(1183)+TX, γ-HCH(430)+TX, HCH(430)+TX, Hydrogen cyanide(444)+TX, Iodomethane(IUPAC name)(542)+TX, Lyndan(430)+TX, Magnesium phosphide(IUPAC name)(640)+TX, Methyl bromide(537)+TX, Norbormid(1318)+TX, Fosacetim(1336)+TX, Phosphy A rodenticide selected from the group of substances consisting of n (IUPAC name) (640) + TX, phosphorus [CCN] + TX, pidocroline (1341) + TX, potassium arsenite [CCN] + TX, pyrinulone (1371) + TX, siriloside (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. Synergistic agents selected from the group consisting of 2-(2-butoxyethoxy)ethylpiperonylate (IUPAC name) (934) + TX, 5-(1,3-benzodioxol-5-yl)-3-hexylcyclohexa-2-enone (IUPAC name) (903) + TX, farnesol and nerolidol (alternative name) (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 consisting of anthraquinone (32) + TX, chloralose (127) + TX, copper naphthenate [CCN] + TX, copper oxychloride (171) + TX, diazinon (227) + TX, dicyclopentadiene (chemical name) (1069) + TX, guazatin (422) + TX, guazatin acetate (422) + TX, methiocarb (530) + TX, pyridine-4-amine (IUPAC name) (23) + TX, thyram (804) + TX, trimetacarb (840) + TX, zinc naphthenate [CCN], and thyram (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 consisting of mercuric oxide (512) + TX, octylinone (590), and thiophanate-methyl (802) + TX, and Azaconazole (60207-31-0) + TX, Vitertanol [70585-36-3] + TX, Bromconazole [116255-48-2] + TX, Cyproconazole [94361-06-5] + TX, Difenoconazole [119446-68-3] + TX, Diniconasol [83657-24-3] + TX, Epoxyconazole [106325-08-0] + TX, Fenbuconazole [114369-43-6] + TX, Fluquinconazole [136426-54-5] + TX, Flusilazole [85509-19-9] + TX, Flu Triafoll [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, Mycrobutanil [88671-89-0] + TX, Pefurazoate [101903-30-4] + TX, Penconazole [66246-88-6] + TX, Prothioconazole [178928-70-6] + TX, Pyriphenox [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, Triadimephon[43121-43-3]+TX, Triadimenol[55219-65-3]+TX, Triflumizole[99387-89-0]+TX, Triticonazole[131983-72-7]+TX, Ancimidor[12771-68-5]+T X, phenalimol [60168-88-9] + TX, nualimol [63284-71-9] + TX, bupirimate [41483-43-6] + TX, dimethilimol [5221-53-4] + TX, ethilimol [23947-60-6] + TX, dodemorph [1593-77-7] + TX, fenpropidine [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, Benalaxil [71626-11-4] + TX, Flalaxil [57646-30-7] + TX, Metalaxil [57837-19-1] + TX, R-Metalaxil [70630-17-0] + TX, Offrace [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, Clozolinate [84332-86-5] + TX, Diclozoline [24201-58-9] + TX, Iprodione [36734-19-7] + TX, Microzoline [54864-61-8] + TX, Procymidone [32809-16-8] + TX, Vinclozoline [50471-44-8] + TX, Boscalid [188425-85-6] + TX, Carbo Xyn[5234-68-4]+TX, Fenflam[24691-80-3]+TX, Flutolanil[66332-96-5]+TX, Mepronil[55814-41-0]+TX, Oxycarboxyne[5259-88-1]+TX, Penthiopyrad[183675-82-3]+TX, Tifluzamide[130000-40-7]+TX, Guazatine[108173-90-6]+TX, Dozin[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, kresoxime-methyl [143390-89-0]+TX, metminostrobin [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, Methylam [9006-42-2] + TX, Propineb [12071-83-9] + TX, Thiram [137-26-8] + TX, Zineb [12122-67-7] + TX, Ziram [137-30-4] + TX, Captahol [2425-06-1] + TX, Captan [133-06-2] + TX, Diclofluanide [1085-98-9] + TX, Fluoroi Mido[41205-21-4]+TX, Holpet[133-07-3]+TX, Tollfluanide[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, Oxine copper[10380-28-6]+TX, Dinocap[131-72-6]+TX, Nitrotar-isopropyl[105 52-74-6]+TX, Edifenphos[17109-49-8]+TX, Iprobenphos[26087-47-8]+TX, Isoprothiolane[50512-35-1]+TX, Phosdiphen[36519-00-3]+TX, Pyrazophos[13457-18-6]+TX, Torukurophos-methyl[57018-04-9]+TX, Acibenzolar-S-methyl[135158-54-2]+TX, Anirazine[101-05-3]+TX, Bentiavaricarb[413615-35-7]+TX, Blastocydin-S[2079-00-7 ]+TX, Quinomethionat [2439-01-2]+TX, Chloroneb [2675-77-6]+TX, Chlorthalonil [1897-45-6]+TX, Cyflufenamid [180409-60-3]+TX, Cymoxanil [57966-95-7]+TX, Diclone [117-80-6]+TX, Diclosimet [139920-32-4]+TX, Diclomazine [62865-36-5]+TX, Dichloran [99-30-9]+TX, Dietofencarb [87130-20-9]+TX, Dimethomorph [110488-70-5]+TX,SYP-LI90 (full morph) [211867-47-9] + TX, dithianone [3347-22-6] + TX, etavoxam [162650-77-3] + TX, etridiazole [2593-15-9] + TX, famoxadone [131807-57-3] + TX, phenamidone [161326-34-7] + TX, phenoxanil [115852-48-7] + TX, fentin [668-34-8] + TX, ferimzon [89269-64-7] + TX, fluazinam [79622-59-6] ]+TX, fluopicolide [239110-15-7]+TX, flusulfamide [106917-52-6]+TX, fenhexamide [126833-17-8]+TX, fosetyl-aluminum [39148-24-8]+TX, himexazole [10004-44-1]+TX, iprovalicarb [140923-17-7]+TX, IKF-916 (cyazofamide) [120116-88-3]+TX, kasugamycin [6980-18-3]+TX, metasulfocarb [66952-49-6 ]+TX, Metraphenone [220899-03-6]+TX, Pencyclon [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, Pyrroquilon [57369-32-1]+TX, Quinoxifen [124495-18-7]+TX, Quintozene [82-68-8]+TX, Sulfur [7704-34-9]+TX, Thiazinil [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-naphthalene-5-yl)-amide (disclosed in International Publication No. 2007 / 048556) + TX, 3-Difluoromethyl-1-methyl-1H-pyrazole-4-carboxylic acid (3',4',5'-trifluorobiphenyl-2-yl)-amide (disclosed in International Publication No. 2006 / 087343) + TX, [(3S,4R,4aR,6S,6aS,12R,12aS,12bS)-3-[(cyclopro [Pyrcarbonyl)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,11Hnaphtho[2,1-b]pyrano[3,4-e]pyran-4-yl]methylcyclopropanecarboxylate[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 consisting of substances comprising ethyl]phenyl]-1H-pyrazole-4-carboxamide[926914-55-8]+TX, as well as lancotrione[1486617-21-3]+TX, florpyrauxifen[943832-81-3]+TX, ipufentrifluconazole[1417782-08-1]+TX, mefentrifluconazole[1417782-03-6]+TX, quinofumerine[861647-84-9]+TX, chloroprallethrin[399572-87-3]+TX, cyhalodiamide[1262 605-53-7]+TX, Fluazaidinidine [1254304-22-7]+TX, Fluxamethamide [928783-29-3]+TX, ε-Metofluthrin [240494-71-7]+TX, ε-Monfluorothrin [1065124-65-3]+TX, Pidiflumetofen [1228284-64-7]+TX, κ-Bifenthrin [439680-76-9]+TX, Brofranilide [1207727-04-5]+TX, Dichloromesothiaz [1263629-39-5]+TX, Dipimethitron [16114-35-5]+TX,Pyraziflumid [942515-63-1] + TX and κ-tefluthrin [391634-71-2] + TX, fenpicoxamide [517875-34-2] + TX; flufenpyrrolidone + TX, benzpyrimoxane [1449021-97-9] + TX; isocycloseram + TX, rescalle [64309-03-1] + TX; aminopyriphen [1531626-08-0] + TX; and, Microorganisms including the following: 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 alternate + TX, Alternaria cassiae (Alternaria 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(registered trademark)+TX, TAZO B(registered trademark))+TX, Azotobacter+TX, Azotobacter chroocuccum (Azotomeal(registered trademark))+TX, Azotobacter cyst (Bionatural Blooming Blossoms(registered trademark))+TX, Bacillus amyloliquefaciens+TX, Bacillus cereus+TX, Bacillus chitinosporus strain CM-1+TX, Bacillus 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 (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 strain Bacillus subtilis strain AQ743+TX, Bacillus subtilis strain QST3002+TX, Bacillus subtilis strain QST3004+TX, Bacillus subtilis var. amyloliquefaciens.amyloliquefaciens) strain FZB24 (Taegro(registered trademark)+TX, Rhizopro(registered trademark))+TX, Bacillus thuringiensis Cry 2Ae+TX, Bacillus thuringiensis Cry1Ab+TX, Bacillus thuringiensis aizawai GC 91 (Agree(registered trademark))+TX, Bacillus thuringiensis israelensis (BMP123(registered trademark)+TX, Aquabac(registered trademark)+TX, VectoBac(registered trademark))+TX, Bacillus thuringiensis krustaki (Bacillus thuringiensis Bacillus thuringiensis kurstaki (Javelin® + TX, Deliver® + TX, CryMax® + TX, Bondide® + 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 Bacillus thuringiensis) strain AQ52+TX, Bacillus thuringiensis var. aizawai (XenTari(registered trademark)+TX, DiPel(registered trademark))+TX, bacterial species (bacteria spp.)(GROWMEND(registered trademark)+TX, GROWSWEET(registered trademark)+TX, Shootup(registered trademark))+TX, Clavipacter michiganensis bacteriophage (AgriPhage(registered trademark))+TX, Bakflor(registered trademark)+TX, Beauveria bassiana(Beaugenic(registered trademark)+TX, Brocaril WP(registered trademark))+TX, Beauveria bassiana GHA(Mycotrol ES(registered trademark)+TX, Mycotrol O(registered trademark)+TX, BotaniGuard(registered trademark))+TX, Beauveria brongniartii(Engerlingspilz(registered trademark)+TX, Schweizer Beauveria(registered trademark)+TX, Melocont(registered trademark))+TX, Beauveria genus (Beauveria spp.)+TX, Gray mold fungus (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, . Candida 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 (Candida Candida pulcherrima)+TX, Candida reukaufii+TX, Candida saitoana (Bio-Coat®+TX, Biocure®)+TX, Candida sake+TX, Candida spp.)+TX, Candida tenius+TX, Cedecea dravisae+TX, Cellulomonas flavigena+TX, Chaetomium cochliodes (Nova-Cide®)+TX, Chaetomium globosum (Nova-Cide®)+TX, Chromobacterium subtsugae strain PRAA4-1T (Grandevo®)+TX, Cladosporium cladosporioides+TX, Cladosporium oxysporum+TX, Cladosporium chlorocephalum 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(registered trademark))+TX, Cryptococcus humicola+TX, Cryptococcus infirmo-miniatus+TX, Cryptococcus laurentii+TX, Cryptophlebia leucotreta granulovirus (Cryptex(registered trademark))+TX, Cupriavidus campinensis+TX, Codlinga granulovirus (Cydia pomonella granulovirus) (CYD-X(registered trademark))+TX, Codlinga granulovirus (Cydia pomonella Granulovirus) (Madex® + TX, Madex Plus® + TX, Madex Max / Carpovirusine®) + TX, Cylindrobasidium laeve (Stumpout®) + TX, Cylindrocladium + TX, Debaryomyces hansenii + TX, Drecslera hawaiinensis + TX, Enterobacter cloacae + TX, Enterobacteriaceae + TX, Entomophtora virulenta (Vektor®) + TX, Epicoccum nigrum + TX, Epicoccum perparasense (Epicoccum 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 WP(registered trademark))+TX, Metschnikowia fruticola (Shemer(registered trademark))+TX, Metschnikowia pulcherrima+TX, Microdochium dimerum (Antibot(registered trademark))+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 humosoroseus fumosoroseus)(PFR-97(registered trademark)+TX, PreFeRal(registered trademark))+TX, Paecilomyces linacinus(Biostat WP(registered trademark))+TX, Paecilomyces lilacinus strain 251(MeloCon WG(registered trademark))+TX, Paenibacillus polymyxa+TX, Pantoea agglomerans(BlightBan C9-1(registered trademark))+TX, Pantoea genus (Pantoea spp.)+TX, Pasteuria genus (Pasteuria spp.))(Econem(registered trademark))+TX, Pasteuria nishizawae+TX, Penicillium aurantiogriseum+TX, Penicillium billai(Jumpstart(registered trademark)+TX, TagTeam(registered trademark))+TX, Penicillium brevicompactum+TX, Penicillium frequentans+TX, Penicillium griseofulvum+TX, Penicillium purpurogenum+TX, Penicillium genus (Penicillium spp.)+TX, Penicillium viridicatum+TX, Phlebiopsis gigantean (Rotstop®)+TX, Phosphate-lysing bacteria (Phosphomeal®)+TX, Phytophthora cryptogea+TX, Phytophthora palmivora (Devine®)+TX, Pichia anomala+TX, Pichia guilermondii+TX, Pichia membranaefaciens+TX, Pichia onychis+TX, Pichia stipites+TX, Pseudomonas aeruginosa)+TX, Pseudomonas aureofasciens (Spot-Less Biofungicide®)+TX, Pseudomonas cepacia+TX, Pseudomonas chlororaphis (AtEze®)+TX, Pseudomonas corrugate+TX, Pseudomonas fluorescens strain A506 (BlightBan A506®)+TX, Pseudomonas putida+TX, Pseudomonas reactans+TX, Pseudomonas spp.)+TX, Pseudomonas syringae (Bio-Save®)+TX, Pseudomonas viridiflava+TX, fluorescent bacterium (Pseudomons fluorescens) (Zequanox®)+TX, Pseudozyma flocculosa strain PF-A22 UL (Sporodex L®)+TX, Puccinia canaliculata+TX, Puccinia thlaspeos (Wood Warrior®)+TX, Pythium paroecandrum+TX, Pythium oligandrum (Pythium oligandrum)(Polygandron(registered trademark)+TX, Polyversum(registered trademark))+TX, Pythium periplocum+TX, Rhanella aquatilis+TX, Rhanella spp.+TX, Rhizobia(Dormal(registered trademark)+TX, Vault(registered trademark))+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 glyceoplanus (Streptomyces griseoplanus)+TX, Streptomyces griseoviridis (Mycostop®)+TX, Streptomyces lydicus (Actinovate®)+TX, Streptomyces lydicus WYEC-108 (ActinoGrow®)+TX, Streptomyces violaceus+TX, Tilletiopsis minor+TX, Tilletiopsis spp.)+TX, Trichoderma asperellum (T34 Biocontrol®)+TX, Trichoderma gamsii (Tenet®)+TX, Trichoderma atroviride (Plantmate®)+TX, Trichoderma hamatum TH 382+TX, Trichoderma harzianum rifai (Mycostar®)+TX, Trichoderma harzianum T-22 (Trianum-P®)+TX, PlantShield HC®+TX, RootShield®+TX, Trichoderma-G®)+TX, Trichoderma harzianum (Trichoderma harzianum)T-39(Trichodex(registered trademark))+TX, Trichoderma inhamatum+TX, Trichoderma koningii+TX, Trichoderma genus (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 auxiliary micronutrients (Natural II®)+TX, various fungi (Millennium Microbes®)+TX, Verticillium chlamydosporium+TX, Verticillium lecani lecanii)(Mycotal(registered trademark)+TX, Vertalec(registered trademark))+TX, Vip3Aa20(VIPtera(registered trademark))+TX, Virgibaclillus marismortui+TX, Xanthomonas campestris pv.Poae(Camperico(registered trademark))+TX, Xenorhabdus bovienii+TX, Xenorhabdus nematophilus; and. Plant extracts including the following: Pine oil (Retenol®) + TX, Azadirachtin (Plasma Neem Oil® + TX, AzaGuard® + TX, MeemAzal® + TX, Molt-X® + TX), Botanical Insect Growth Regulators (Botanical IGRs) (Neemazad® + TX, Neemix®) + TX, Rapeseed oil (Lilly Miller Vegol®) + TX, American ant-grain plant (Chenopodium ambrosioides near ambrosioides) (Requiem®) + TX, Chrysanthemum extract (Crisant®) + TX, Neem oil extract (Trilogy®) + TX, Lamiaceae plant essential oil (Botania®) + TX, Clove, rosemary, peppermint and thyme oil extracts (Garden insect Killer® + TX, Glycine Betaine (Greenstim®) + TX, Garlic + TX, Lemongrass Oil (GreenMatch®) + TX, Neem Oil + TX, Catnip Oil (Nepeta cataria) + TX, Catnip Oil (Nepeta catarina) + TX, Nicotine + TX, Oregano Oil (MossBuster®) + TX, Pedaliaceae Oil (Nematon®) + TX, Pyrethrum + TX, Soap Tree (Quillaja saponaria) (NemaQ®) + TX, Japanese Knotweed (Reynoutria sachalinensis) (Regalia® + TX, Sakalia®) + TX, Rotenone (Eco Roten®) + TX, Rutaceae Extract (Soleo®) + TX, Soybean Oil (Ortho ecosense(registered trademark))+TX, tea tree oil (Timorex Gold(registered trademark))+TX, thyme oil+TX, AGNIQUE(registered trademark) MMF+TX, BugOil(registered trademark)+TX, mixture of rosemary, sesame, peppermint, thyme and cinnamon extracts (EF)300 (registered trademark)) + TX, a mixture of clove, rosemary and peppermint extracts (EF 400 (registered trademark)) + TX, a mixture of clove, peppermint, garlic oil and mint (Soil Shot (registered trademark)) + TX, kaolin (Screen (registered trademark)) + TX, brown algae storage glucan (Laminarin (registered trademark)); and Pheromones including the following: blackheaded fireworm pheromone (3M Sprayable Blackheaded Fireworm Pheromone®) + TX, codling moth pheromone (Paramount dispenser-(CM) / Isomate C-Plus®) + TX, grape berry moth pheromone (3M MEC-GBM Sprayable Pheromone®) + TX, leafroller moth pheromone (3M MEC-LR Sprayable Pheromone®) + TX, muscamone (Snip7 Fly Bait® + TX, Starbar Premium Fly Bait®) + TX, oriental fruit moth pheromone (3M oriental fruit moth sprayable pheromone®) + TX, peachtree moth pheromone (Sneezing moth) Borer pheromone (Isomate-P®) + TX, Tomato Pinworm pheromone (3M Sprayable pheromone®) + TX, Entostat powder (extract from palm trees) (Exosex CM®) + TX, (E+TX,Z+TX,Z)-3+TX,8+TX,11-tetradecatrieninyl acetate + TX, (Z+TX,Z+TX,E)-7+TX,11+TX,13-hexadecatrienal + TX, (E+TX,Z)-7+TX,9-dodecadienediene-1-yl acetate + TX, 2-methyl-1-butanol + TX, calcium acetate + TX, Scenturion® + TX, Biolure® + TX, Check-Mate® + TX, Lavandulyl senecioate; and Macrobiotics including the following: Aphelinus abdominalis + TX, Aphidius ervi (Aphelinus-System®) + TX, Acerophagus papaya + TX, Adalia bipunctata (Adalia-System®) + TX, Adalia bipunctata (Adaline®) + TX, Adalia bipunctata (Aphidalia®) + TX, Ageniaspis citricola + TX, Ageniaspis fuscicollis + TX, Amblyseius andersoni andersoni) (Anderline(registered trademark)+TX, Andersoni-System(registered trademark))+TX, Amblyseius californicus (Amblyline(registered trademark)+TX, Spical(registered trademark))+TX, Amblyseius cucumeris (Thripex(registered trademark)+TX, Bugline cucumeris(registered trademark))+TX, Amblyseius fallacis (Fallacis(registered trademark))+TX, Amblyseius swirskii (Bugline swirskii(registered trademark)+TX, Swirskii-Mite(registered trademark))+TX, Amblyseius womersleyi (WomerMite(registered trademark))+TX, Amitus hesperidum hesperidum)+TX, Anagrus atomus+TX, Anagyrus fusciventris+TX, Anagyrus kamali+TX, Anagyrus roeckii (Anagyrusloecki)+TX, Anagyrus pseudococci (Citripar(registered trademark))+TX, Anicetus benefices+TX, Anisopteromalus calandrae+TX, Anthocoris nemoralis (Anthocoris-System(registered trademark))+TX, Aphelinus abdominalis (Apheline(registered trademark)+TX, Aphiline(registered trademark))+TX, Aphelinus asychis+TX, Aphidius colemani (Aphipar(registered trademark))+TX, Aphidius ervi (Ervipar(registered trademark))+TX, Aphidius gifuensis (Aphidius gifuensis)+TX, Aphidius matricariae (Aphipar-M(registered trademark))+TX, Aphidoletes aphidimyza (Aphidend(registered trademark))+TX, Aphidoletes aphidimyza (Aphidoline(registered trademark))+TX, Aphytis lingnanensis+TX, Aphytis melinus+TX, Aprostocetus hagenowii+TX, Atheta coriaria (Staphyline(registered trademark))+TX, Bombus spp.+TX, European bumblebee (Bombus terrestris) (Natupol Beehive®) + TX, European bumblebee (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 genus 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(registered trademark))+TX, Diglyphus isaea(Diminex(registered trademark))+TX, Delphastus catalinae(Delphastus(registered trademark))+TX, Delphastus pusillus+TX, Diachasmimorphakrausii)+TX, Diachasmimorpha longicaudata+TX, Diaparsis jucunda+TX, Diaphorencyrtus aligarhensis+TX, Diglyphus isaea+TX, Diglyphus isaea (Miglyphus(registered trademark)+TX, Digline(registered trademark))+TX, Dacnusa sibirica (DacDigline(registered trademark)+TX, Minex(registered trademark))+TX, Diversinervus spp.+TX, Encarsia citrina+TX, Encarsia formosa(Encarsia max(registered trademark)+TX, Encarline(registered trademark)+TX, En-Strip(registered trademark))+TX, Desert parasitic wasp (Eretmocerus eremicus) (Enermix(registered trademark))+TX, Encarsia guadeloupae+TX, Encarsia haitiensis+TX, Slender hoverfly (Episyrphus balteatus) (Syrphidend(registered trademark))+TX, Eretmoceris siphonini+TX, Eretmocerus californicus+TX, Desert parasitic wasp (Eretmocerus eremicus) (Ercal(registered trademark)+TX, Eretline e(registered trademark))+TX, Desert parasitic wasp (Eretmocerus Eretmocerus eremicus) (Bemimix (registered trademark)) + TX, Eretmocerus hayati + TX, Eretmocerus mundus (Bemipar (registered trademark) + TX, Eretline m (registered trademark)) + TX, Eretmocerus siphonini (Eretmocerussiphonini)+TX, Exochomus quadripustulatus+TX, Feltiella acarisuga (Spidend(registered trademark))+TX, Feltiella acarisuga (Feltiline(registered trademark))+TX, Fopius arisanus+TX, Fopius ceratitivorus+TX, formononetin (Wirless Beehome(registered trademark))+TX, Franklinothrips vespiformis (Vespop(registered trademark) (Tag))+TX, Galendromus occidentalis+TX, Goniozus legneri+TX, Habrobracon hebetor+TX, Harmonia axyridis (HarmoBeetle®)+TX, Heterorhabditis spp. (Lawn Patrol®)+TX, Heterorhabditis bacteriophora (NemaShield) HB(registered trademark)+TX, Nemaseek(registered trademark)+TX, Terranem-Nam(registered trademark)+TX, Terranem(registered trademark)+TX, Larvanem(registered trademark)+TX, B-Green(registered trademark)+TX, NemAttack(registered trademark)+TX, Nematop(registered trademark))+TX, Heterorhabditis megidis (Nemasys H(registered trademark)+TX, BioNem H(registered trademark)+TX, Exhibitline hm(registered trademark)+TX, Larvanem-M(registered trademark))+TX, Hippodamia convergens+TX, Hypoaspis aculeifer (Aculeifer-System(registered trademark)+TX, Entomite-A(registered trademark))+TX, Hypoaspis miles (Hypoline m(registered trademark)+TX, Entomite-M(registered trademark))+TX, Lbalia leucospoides+TX, Lecanoideus floccissimus+TX, Lemophagus errabundus+TX, Leptomastidea abnormis+TX, Leptomastix dactylopii (Leptopar(registered trademark))+TX, Leptomastix eponaepona)+TX, Lindorus lophanthae+TX, Lipolexis oregmae+TX, Lucilia caesar (Natufly(registered trademark))+TX, Lysiphlebus testaceipes+TX, Macrolophus caliginosus (Mirical-N(registered trademark)+TX, Macroline c(registered trademark)+TX, Mirical(registered trademark))+TX, Mesoseiulus longipes+TX, Metaphycus flavus+TX, Metaphycus lounsburyi+TX, Micromus angratus 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(registered trademark)+TX, Nesibug(registered trademark))+TX, Ophyra aenescens(Biofly(registered trademark))+TX, Orius insidiosus(Thripor-I(registered trademark)+TX, Oriline i(registered trademark))+TX, Orius laevigatus(Thripor-L(registered trademark)+TX, Orilinel(registered trademark))+TX, Orius majusculus (Oriline m(registered trademark))+TX, Orius strigicollis (Thripor-S(registered trademark))+TX, Pauesia juniperorum+TX, Pediobius foveolatus+TX, Phasmarhabditis hermaphrodita ((Nemaslug(registered trademark))+TX, Phymastichus coffea+TX, Phytoseiulus macropilus+TX, Phytoseiulus persimilis (Spidex(registered trademark))+TX, Phytoline p(registered trademark))+TX, Podisus maculiventris (Podisus(registered trademark))+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 lophantae lophanthae)+TX, Rodolia cardinalis+TX, Rumina decollate+TX, Semielacher petiolatus+TX, Sitobion avenaeavenae)(Ervibank(registered trademark))+TX, Steinernema carpocapsae(Nematac C(registered trademark)+TX, Millenium(registered trademark)+TX, BioNem C(registered trademark)+TX, NemAttack(registered trademark)+TX, Nemastar(registered trademark)+TX, Capsanem(registered trademark))+TX, Steinernema feltiae(NemaShield(registered trademark)+TX, Nemasys F(registered trademark)+TX, BioNem F(registered trademark)+TX, Steinernema-System(registered trademark)+TX, NemAttack(registered trademark)+TX, Nemaplus(registered trademark)+TX, Exhibitline sf(registered trademark)+TX, Scia-rid(registered trademark)+TX, Entonem(registered trademark))+TX, Steinernema kraussei(Nemasys L(registered trademark)+TX, BioNem L(registered trademark)+TX, Exhibitline srb(registered trademark))+TX, Steinernema riobrave (BioVector(registered trademark)+TX, BioVektor(registered trademark))+TX, Steinernema scapterisci (Nematac S(registered trademark))+TX, Steinernema spp.+TX, Steinernematid spp. (Guardian Nematodes(registered trademark))+TX, Stethorus punctillum (Stethorus(registered trademark))+TX, Tamarixia radiate+TX, Tetrastichus setifer)+TX, Thripobius semiluteus+TX, Torymus sinensis+TX, Egg parasitic wasp (Trichogramma brassicae) (Tricholineb(registered trademark))+TX, egg parasitic wasp (Trichogramma brassicae) (Tricho-Strip(registered trademark))+TX, armyworm egg parasitoid wasp (Trichogramma evanescens)+TX, Tricogramma minutum+TX, corn borer egg parasitoid wasp (Trichogramma ostriniae)+TX, Tricogramma platneri+TX, Tricogramma pretiosum+TX, yellow-legged flat wasp (Xanthopimpla stemmator); and Other biological products including the following: 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, Ferric phosphate (Ferramol®) + TX, Funnel Trap (Trapline y®) + TX, Gallex® + TX, Grower's Secret (registered trademark) + TX, Homo-brassonolide + TX, Iron phosphate (Lilly Miller Worry Free Ferramol Slug & Snail Bait (registered trademark)) + TX, MCP hail trap (Trapline f (registered trademark)) + TX, Microctonus hyperodae + TX, Mycoleptodiscus terrestris (Des-X (registered trademark)) + TX, BioGain (registered trademark) + TX, Aminomite (registered trademark) + TX, Zenox (registered trademark) + TX, Pheromone trap (Thripline ams(registered trademark)) + TX, potassium bicarbonate (MilStop(registered trademark)) + TX, potassium salt of fatty acid (Sanova(registered trademark)) + TX, potassium silicate solution (Sil-Matrix(registered trademark)) + TX, potassium iodide + potassium thiocyanate (Enzicur(registered trademark)) + TX, SuffOil-X(registered trademark) + TX, spider venom + TX, Nosema locustae (Semaspore Organic Grasshopper Control(registered trademark)) + TX, sticky trap (Trapline)YF(registered trademark)+TX, Rebell Amarillo(registered trademark))+TX and Trap(Takitrapline y+b(registered trademark))+TX; or Broflutrinate + TX, Diflovidazine + TX, Frometoquin + TX, Fluhexaphon + TX, Diamondback moth (Plutella xylostella) granulosis virus + TX, Codling moth (Cydia pomonella) granulosis virus + TX, Imisiafos + TX, False tobacco budworm (Heliothis virescens) nuclear polynuclear virus + TX, Heliothis punctigera nuclear polynuclear virus + TX, American tobacco budworm (Helicoverpa zea) nuclear polynuclear virus + TX, Spodoptera frugiperda nuclear polynuclear virus + TX, Diamondback moth (Plutella A bioactive ingredient or drug selected from Xylostella (nuclear multinuclear virus) + TX, p-cymene + TX, piflubmid + TX, pyrafuruprole + TX, QRD420 + TX, QRD452 + TX, QRD460 + TX, terpenoid blend + TX, terpenoid + TX, tetraniliprole + TX, and α-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 codes +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, etc.; or Quinofumelin + TX, Mefentrifluconazole + TX, Fenpicoxamide + TX, Fluindapir + TX, Impilfluxam + TX or Indiflumetpir + TX, Isoflucipram + TX, Pirapropoin + TX, Florylpicoxamide + TX, Methyltetraprole + TX, Ipupurphenoquine + TX, Pyridaclomethyl + TX or Clopyridiflu + TX, Tetrachlorantraniliprole + TX, Tetrachloraniliprole + TX, Tetoflupyrrolimeth + TX, Triflufenpyrrolidone + TX, Cyclopyrazoflor + TX, Flupyrimin + TX or Pyrifluramide + TX, Benzpyrimoxa Other biologically effective ingredients or drugs selected from n+TX, beflubutamide-M+TX, benzosphyll+TX or oxazosulfyl+TX, etopirafen+TX, acinonapir+TX or pyrinonafen+TX, oxotrione+TX, vixurozone+TX or clofenzizone+TX or dichloroxone+TX, cyclopyranil+TX or pyrazocyclonil+TX or cyclopyrazonil+TX, α-bromadiolone+TX, oxatiapiproline+TX, fluopyram+TX, penflufen+TX, fluoxopirosad+TX, fluoxapiproline+TX, and flupyradiflon+TX.

[0292] The reference number in square brackets after the active ingredient, e.g., [3878-19-1], refers to the chemical abstract registration number. The compounds in the above mixtures are publicly known. If an active ingredient is included in “The Pesticide Manual” [The Pesticide Manual - A World Compendium; Thirteenth Edition; Editor: CDSTomlin; The British Crop Protection Council], it is listed therein with the item number indicated in parentheses above for the specific compound; for example, the compound “abamectin” is listed under item number (1). If "[CCN]" is appended to a specific compound above, the compound in question is included in the “Compendium of Pesticide Common Names,” which is accessible on the internet [A. Wood; Compendium of Pesticide Common Names, (Copyright) 1995-2004]; for example, the compound “acetoprole” is listed at the internet address: http: / / www.alanwood.net / pesticides / acetoprole.html.

[0293] In this specification, most of the active ingredients are referred to by so-called “common names,” related “ISO common names,” or other “common names” as used in the individual cases. Where a “common name” is not used, the nature of the alternative name used is indicated in parentheses for the particular compound; in this case, the IUPAC name, IUPAC / Chemical Abstracts name, “chemical name,” “customary name,” “compound name,” or “development code” is used, or if none of these names or “common names” are used, an “alternative name” is adopted. “CAS Registry Number” means Chemical Abstracts Registry Number.

[0294] The active ingredient mixture of 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 the above active ingredient, is preferably a mixture of the compound 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 above active ingredient in a mixing ratio of preferably 100:1 to 1:6000, particularly 50:1 to 1:50, more particularly 20:1 to 1:20, even more particularly 10:1 to 1:10, very particularly 5:1 and 1:5 (a ratio of 2:1 to 1:2 is particularly preferred, and a ratio of 4:1 to 2:1 is equally preferred), especially 1:1, or 5: It contains in a ratio of 1, or 5:2, or 5:3, or 5:4, or 4:1, or 4:2, or 4:3, or 3:1, or 3:2, or 2:1, or 1:5, or 2:5, or 3:5, or 4:5, or 1:4, or 2:4, or 3:4, or 1:3, or 2:3, or 1:2, or 1:600, or 1:300, or 1:150, or 1:35, or 2:35, or 4:35, or 1:75, or 2:75, or 4:75, or 1:6000, or 1:3000, or 1:1500, or 1:350, or 2:350, or 4:350, or 1:750, or 2:750, or 4:750. These mixing ratios are based on weight.

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

[0296] A mixture 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 of the above-mentioned active ingredients, can be applied in combination with a single active ingredient, for example, as a single ready-mix form, or as a combined spray mixture consisting of separate formulations of a single active ingredient such as a "tank mix," and applied sequentially, i.e., over a fairly short period of time such as a few hours or a few days. The order in which the compounds 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 above-mentioned active ingredients are applied is not important for carrying out the present invention.

[0297] The compositions according to the present invention may also include further solid or liquid additives such as stabilizers, e.g., non-epoxidized or epoxidized vegetable oils (e.g., epoxidized coconut oil, rapeseed oil, or soybean oil), defoamers, e.g., silicone oils, preservatives, viscosity modifiers, binders and / or tackifiers, fertilizers, or other active ingredients for obtaining specific effects, e.g., fungicides, fungicides, nematicides, plant activators, molluscicides, or herbicides.

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

[0299] Methods of application for this composition, i.e., spraying, atomizing, scattering, brushing, powdering, diffusion, or pouring (these should be selected according to the intended purpose in general situations), methods for controlling the above-mentioned types of pests, and the use of the composition for controlling the above-mentioned types of pests are also subjects of the present invention. Typical concentration ratios are 0.1 to 1000 ppm, preferably 0.1 to 500 ppm of the active ingredient. The application rate per hectare is generally 1 to 2000 g of the active ingredient per hectare, particularly 10 to 1000 g / ha, preferably 10 to 600 g / ha.

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

[0301] The compounds and compositions of the present invention are also suitable for protecting plant propagation materials, such as seeds or seedlings of fruits, tubers, or grains, from the above-mentioned types of pests. The propagation material may be treated with the compound before planting; for example, seeds may be treated before sowing. Alternatively, the compound may be applied to seed kernels by immersion in a liquid composition or by coating with a layer of a solid composition. If the propagation material is to be planted at the application site, the composition may also be applied between the rows, for example, during drill sowing. These treatment methods for plant propagation materials and the plant propagation materials 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 1 to 200 grams per 100 kg of seeds, preferably 5 to 150 grams per 100 kg of seeds (e.g., 10 to 100 grams per 100 kg of seeds).

[0302] The term "seed" encompasses all kinds of seeds and plant bulbils, including but not limited to true seeds, seed flakes, suckers, corn kernels, bulbs, fruits, tubers, grains, rhizomes, cuttings, and grafts, and in a preferred embodiment, it means true seeds.

[0303] The present invention also includes seeds that are coated or treated with or contain a compound of formula I. The term "coated or treated with and / or contain" generally indicates that the active ingredient is, in most cases, on the surface of the seed at the time of application, but depending on the method of application, some of the ingredient may penetrate into the seed material to varying degrees. The active ingredient may be absorbed when the seed product is (re)planted. In one embodiment, the present invention makes available plant propagation material to which a compound of formula (I) has been attached. Furthermore, this makes available a composition containing 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 powdering, seed coating, seed spraying, seed dipping, and seed pelleting. Seed treatment application of the compound of formula (I) may be carried out by any known method, such as by spraying or scattering seeds before sowing or at the time of sowing / planting.

[0305] Biological examples Example B1: Activity against Bemisia tabaci (cotton whitefly) Cotton leaf fragments were placed on agar in a 24-well microtiter plate and sprayed with a test aqueous solution prepared from a 10,000 ppm DMSO stock solution. After drying, adult whiteflies were inoculated onto the leaf fragments. After 6 days of incubation, the mortality rate of the samples was examined.

[0306] The following compounds resulted in at least an 80% mortality rate at doses of 00 ppm: Pages 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 a 24-well microtiter plate were treated by spraying with a test aqueous solution prepared from a 10,000 ppm DMSO stock solution. After drying, L2 larvae (6-10 per well) were exoparasitized onto the plate. Four days after exoparasitism, the samples were evaluated for mortality and growth inhibition compared to untreated samples.

[0308] The following compounds demonstrated at least an 80% effect at a 200 ppm application rate in at least one of two categories (mortality or growth inhibition): 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 a 24-well microtiter plate were sprayed with a test aqueous solution prepared from a 10,000 ppm DMSO stock solution. After drying, these leaves were exoparasitized with N2 nymphs. Five days after exoparasitism, the samples were evaluated against untreated samples for mortality and growth inhibition.

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

[0311] Example B4: Activity against the peach aphid (Myzus persicae): Sunflower leaf fragments were placed on agar in a 24-well microtiter plate and sprayed with a test aqueous solution prepared from a 10,000 ppm DMSO stock solution. After drying, aphid populations of various ages were exoparasitized on these leaf fragments. Six days after exoparasitism, the mortality rate of the samples was evaluated.

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

[0313] Example B5: Activity against the peach aphid (Myzus persicae). The roots of pea seedlings infested with aphid populations of various ages were directly placed into a test aqueous solution prepared from a 10,000 ppm DMSO stock solution. Six days after placing the seedlings in the test solution, the mortality rate of the samples was evaluated.

[0314] The following compounds resulted in at least an 80% mortality rate 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 diamondback moth (Plutella xylostella) 24-well microtiter plates containing artificial feed were treated with a test aqueous solution prepared from a 10,000 ppm DMSO stock solution using a pipette. After drying, L2 larvae (10-15 per well) were exocaristated onto the plates. Five days after exocaristation, the samples were evaluated for mortality and growth inhibition compared to untreated samples.

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

[0317] Example B7: Activity against the Egyptian armyworm (Spodoptera littoralis) Cotton leaf fragments were placed on agar in a 24-well microtiter plate and sprayed with a test aqueous solution prepared from a 10,000 ppm DMSO stock solution. After drying, five L1 larvae were ectopraistically attached to the leaf fragments. Three days after ectopraist, the samples were evaluated against untreated samples for mortality, feeding inhibition, and growth inhibition. If at least one of the categories (mortality, feeding inhibition, and growth inhibition) was higher than that of the untreated samples, the test samples were considered to have achieved control of the Egyptian armyworm (Spodoptera littoralis).

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

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

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

[0321] Example B10: Activity against spider mites (Tetranychus urticae) (two-spotted spider mite): A test aqueous solution prepared from a 10,000 ppm DMSO stock solution was sprayed onto kidney bean leaf fragments on agar in a 24-well microtiter plate. After drying, mite populations of various ages were exoparasitized onto these leaf fragments. Eight days after exoparasitism, the mortality rate of the mixed populations (mobile) was evaluated.

[0322] The following compounds resulted in at least an 80% mortality rate at a dose of 200 ppm: P3.

[0323] Example B11: Activity against diamondback moth (Plutella xylostella) 24-well microtiter plates containing artificial feed were treated with a test aqueous solution prepared from 10,000 ppm DMSO stock solution using a pipette. After drying, diamondback moth eggs were pipetteed onto gel blotting paper via a plastic stencil, and the plates were closed. Eight days after ectoparasitism, the samples were evaluated against untreated samples for mortality and growth inhibition.

[0324] The following compounds demonstrated at least an 80% effect at a 200 ppm application rate in at least one of two categories (mortality or growth inhibition): Pages 16, 17, 18, and 19.

[0325] Example B12: Activity against beet cyst nematode (Heterodera schachtii), in vitro profiling of larval mobility in a 96-well plate. Test solutions were prepared using 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 solutions. Three replicates were performed for each concentration. 80 μL of nematode solution containing 100–150 freshly collected second-stage larvae of the beet cyst nematode (Heterodera schachtii) was added to each well. The plate was covered and incubated in the dark at room temperature for 48 hours. The mobility of the exposed larvae in the treated wells was measured using an imaging tool and compared to the mean of 12 untreated replicates.

[0326] The following compounds achieved at least 60% control at 100 ppm after 48 hours: Pages 10 and 15. Another aspect of the present invention may be as follows: [1] Equation (I) [C1] JPEG0007861054000120.jpg63170 (In the formula, A is either CH or N, R 1 C 1 ~C 4 It is alkyl, R 2 C is hydrogen, cyano, -C(O)R7, -C(O)OR8, C 1 ~C 6 Alkyl or -CONR 9 R 10 , SO 2 R 11 And here, R 7 is hydrogen, C 1 ~C 6 Alkyl or C 1 ~C 6 It is a haloalkyl, R 8 C 1 ~C 6 Alkyl or C 1 ~C 6 It is a haloalkyl; R 9 、R 10 These are, independently of each other, hydrogen or C 1 ~C 6 It is alkyl; R 11 C 1 ~C 6 It is alkyl; R 3 is hydrogen, C 1 ~C 3 Alkyl, C 1 ~C 3 Haloalkyl, cyano, -CO 2 H, -CO 2 NH 2 、C 1 ~C 4 Alkoxycarbonyl, C 1 ~C 4 Alkylaminocarbonyl, C 1 ~C 4 It is a dialkylaminocarbonyl, n is either 0 or 1; Q is the formula Q 1 、Q 2 、Q 3 、Q 4 and Q 5 [Case 2] JPEG0007861054000121.jpg69161 (In the formula, the arrows indicate the bonding points to the ring incorporating base 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 It is a haloalkoxy; X 1 is O or NR 5 and; R 5 C 1 ~C 4 It is alkyl; R 6 C 1 ~C 4 Alkyl, C 1 ~C 4 Haloalkyl, C 1 ~C 4 Alkoxy or C 3 ~C 6 It is a cycloalkyl; G 1 and G 2 (These are N or CH, independently of each other.) (A group selected from the group consisting of these elements.) Agrochemically acceptable salts, stereoisomers, enantiomers, tautomers, or N-oxides of the compound of formula I. [2] A is CH or N; R 1 These are 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 It is a haloalkylcarbonyl; R 3 is hydrogen, C 1 ~C 3 Haloalkyl, cyano, -CO 2 H, -CO 2 NH 2 、C 1 ~C 4 It is a dialkylaminocarbonyl; and n is 1. The compound described in [1] above. [3] A is CH or N; R 1 It is ethyl; R 2 is hydrogen; R 3 is hydrogen, C 1 ~C 2 Haloalkyl, cyano, -CO 2 NH 2 、C 1 ~C 2 It is a dialkylaminocarbonyl; and n is 1. The compound described in [1] above. [4] A is CH or N; R 1 It is ethyl; R 2 is hydrogen; R 3 is hydrogen, cyano or CO 2 NH 2 and n is 1. The compound described in [1] above. [5] A is CH or N; R 1 It is ethyl; R 2 is hydrogen; R 3 is hydrogen or cyano; and n is 1. The compound described in [1] above. [6] Q is Q 1 、Q 2 、Q 4 and Q 5 [C3] JPEG0007861054000122.jpg101131 (In the formula, the arrows indicate the bonding points to the ring incorporating base A; R 4 C 1 ~C 2 Haloalkyl, C 1 ~C 2 Haloalkylsulfanyl, C 1 ~C 2 Haloalkylsulfinyl or C 1 ~C 2 It is a haloalkylsulfonyl; X 1 is oxygen or NCH 3 and; R 6 C 1 ~C 2 Alkyl, C 1 ~C 2 Haloalkyl, C 1 ~C 2 It is alkoxy or cyclopropyl; and G 1 and G 2 (These are N or CH, independently of each other.) A compound according to any one of the above [1] to [5], wherein the group is selected from the above. 〔7〕Q 1 、Q 2 and Q 5 [C4] JPEG0007861054000123.jpg36163 (In the formula, the arrows indicate the bonding points to the ring incorporating base A; R 4 C 1 ~C 2 These are fluoroalkyl, trifluoromethylsulfanyl, trifluoromethylsulfinyl, trifluoromethylsulfonyl, difluoromethylsulfanyl, difluoromethylsulfinyl, or difluoromethylsulfonyl; X 1 NCH 3 and; R 6 is methyl, ethyl, 2,2,2-trifluoroethyl, methoxy, or cyclopropyl; and G 1 and G 2 (These are N or CH, independently of each other.) A compound according to any one of the above [1] to [5], wherein the group is selected from the above. [8] Q is Q 1 and Q 5 [5] JPEG0007861054000124.jpg42132 (In the formula, the arrows indicate the bonding points to the ring incorporating base A; R 4 These are trifluoromethyl, pentafluoroethyl, trifluoromethylsulfanyl, trifluoromethylsulfinyl, or trifluoromethylsulfonyl; X 1 NCH 3 and; R 6 is ethyl, methoxy, or cyclopropyl; and G 1 is N and G 2 Is it CH, or G 1 is CH and G 2 Is it N, or G? 1 and G 2 Is it N, or G? 1 and G 2 (is CH) A compound according to any one of the above [1] to [5], wherein the group is selected from the above. [9] Q is radical Q 1 [6] JPEG0007861054000125.jpg4869 (In the formula, the arrows indicate the bonding points to the ring incorporating base A; R 2 It is trifluoromethyl; X 1 NCH 3 and G 1 is N and G 2 Is it CH, or G 1 is CH and G 2 Is it N, or G? 1 and G 2 (is N) The compound described in any one of the above items [1] to [5].

[10] A is CH or N; R 1 These are 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 It is a haloalkylcarbonyl; R 3 is hydrogen, C 1 ~C 3 Haloalkyl, cyano, CO 2 H, CO 2 NH 2 、C 1 ~C 4 It is a dialkylaminocarbonyl; n is 1; Q is Q 1 、Q 2 、Q 4 and Q 5 [7] JPEG0007861054000126.jpg100131 (In the formula, the arrows indicate the bonding points to the ring incorporating base A; R 4 C 1 ~C 2 Haloalkyl, C 1 ~C 2 Haloalkylsulfanyl, C 1 ~C 2 Haloalkylsulfinyl or C 1 ~C 2 It is a haloalkylsulfonyl; X 1 is oxygen or NCH 3 and; R 6 C 1 ~C 2 Alkyl, C 1 ~C 2 Haloalkyl, C 1 ~C 2 It is alkoxy or cyclopropyl; and G 1 and G 2 (These are N or CH, independently of each other.) The compound described in [1] above, which is a group selected from the above.

[11] A is CH or N; R 1 It is ethyl; R 2 is hydrogen; R 3 is hydrogen, C 1 ~C 2 Haloalkyl, cyano, CO 2 NH 2、C 1 ~C 2 It is a dialkylaminocarbonyl; n is 1; Q is Q 1 、Q 2 and Q 5 [8] JPEG0007861054000127.jpg36160 (In the formula, the arrows indicate the bonding points to the ring incorporating base A; R 4 C 1 ~C 2 These are fluoroalkyl, trifluoromethylsulfanyl, trifluoromethylsulfinyl, trifluoromethylsulfonyl, difluoromethylsulfanyl, difluoromethylsulfinyl, or difluoromethylsulfonyl; X 1 NCH 3 and; R 6 is methyl, ethyl, 2,2,2-trifluoroethyl, methoxy, or cyclopropyl; and G 1 and G 2 (These are N or CH, independently of each other.) The compound described in [1] above, which is a group selected from the above.

[12] A is CH or N; R 1 It is ethyl; R 2 is hydrogen; R 3 is hydrogen, cyano or CO 2 NH 2 and; n is 1; Q is Q 1 and Q 5 [9] JPEG0007861054000128.jpg50154 (In the formula, the arrows indicate the bonding points to the ring incorporating base A; R 4 These are trifluoromethyl, pentafluoroethyl, trifluoromethylsulfanyl, trifluoromethylsulfinyl, or trifluoromethylsulfonyl; X 1 NCH 3 and; R 6 is ethyl, methoxy, or cyclopropyl; and G 1 is N and G 2 Is it CH, or G 1 is CH and G 2 Is it N, or G? 1 and G 2 Is it N, or G? 1 and G 2 (is CH) The compound described in [1] above, which is a group selected from the above.

[13] A is CH or N; R 1 It is ethyl; R 2 is hydrogen; R 3 is hydrogen or cyano; n is 1; Q is the base Q 1 [C10] JPEG0007861054000129.jpg5071 (In the formula, the arrows indicate the bonding points to the ring incorporating base A; R 2 It is trifluoromethyl; X 1 NCH 3 and G 1 is N and G 2 Is it CH, or G 1 is CH and G 2 Is it N, or G? 1 and G 2 (is N) The compound described in [1] above.

[14] Q is Q 1-1 、Q 1-2 、Q 1-3 、Q 1-4 and Q 1-5 [C11] JPEG0007861054000130.jpg76160 (In the formula, the arrows indicate the bonding points to the ring incorporating base A; and R 4 (These are trifluoromethyl, trifluoromethylsulfanyl, or trifluoromethylsulfonyl.) A base selected from; preferably, Q is Q 1-2 、Q 1-3 、Q 1-4 and Q 1-5 A compound according to any one of the above [1] to [5], wherein the group is selected from the above.

[15] Q is Q 5 [C12] JPEG0007861054000131.jpg60170 (In the formula, the arrows indicate the bonding points to the ring incorporating base A; R 4 is trifluoromethyl, trifluoromethylsulfanyl or trifluoromethylsulfonyl; and R 6 OCH 3 CH 2 CH 3 (or cyclopropyl) A compound according to any one of the above [1] to [5], wherein the group is selected from the above.

[16] Q is Q 4 [C13] JPEG0007861054000132.jpg59150 (In the formula, the arrows indicate the bonding points to the ring incorporating base A; R 4 is trifluoromethyl, trifluoromethylsulfanyl or trifluoromethylsulfonyl; and G 1 is N and G 2 Is it CH, or G 1 is CH and G 2 Is it N, or G 1 and G 2 Is it CH, or G 1 and G 2 is N; preferably, G 1 is CH and G 2 (is N) A compound according to any one of the above [1] to [5], wherein the group is selected from the above.

[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]pyridine-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-λ 6 -Sulfane (compound P3); [5-Cyclopropyl-2-[3-Methyl-6-(trifluoromethylsulfanyl)imidazo[4,5-c]pyridin-2-yl]-3-pyridyl]-ethyl-imino-oxo-λ 6 -Sulfane (compound P4); [5-Cyclopropyl-2-[3-methyl-6-(trifluoromethyl)imidazo[4,5-c]pyridin-2-yl]-3-pyridyl]-ethyl-imino-oxo-λ 6 -Sulfane (compound P5); 1-[5-(ethylsulfonimidoyl)-6-[3-methyl-6-(trifluoromethyl)imidazo[4,5-b]pyridin-2-yl]-3-pyridyl]cyclopropanecarbonitric (compound P6); [5-Cyclopropyl-2-[6-(trifluoromethyl)pyrazolo[4,3-c]pyridin-2-yl]-3-pyridyl]-ethyl-imino-oxo-λ 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]cyclopropanecarbonitric (compound P8); 1-[3-(ethylsulfonimidoyl)-4-[3-methyl-6-(trifluoromethylsulfanyl)imidazo[4,5-c]pyridine-2-yl]phenyl]cyclopropanecarbonitric (compound P9); 1-[5-(ethylsulfonimidoyl)-6-[7-methyl-3-(trifluoromethyl)imidazo[4,5-c]pyridazin-6-yl]-3-pyridyl]cyclopropanecarbonitric (compound P10); [5-Cyclopropyl-2-[7-Methyl-3-(trifluoromethyl)imidazo[4,5-c]pyridazin-6-yl]-3-pyridyl]-ethyl-imino-oxo-λ 6 -Sulfane (compound P11); [5-Cyclopropyl-2-[3-methyl-6-(trifluoromethyl)imidazo[4,5-b]pyridin-2-yl]-3-pyridyl]-ethyl-imino-oxo-λ 6 -Sulfane (compound P12); 1-[3-(ethylsulfonimidoyl)-4-[3-methyl-6-(trifluoromethyl)imidazo[4,5-c]pyridine-2-yl]phenyl]cyclopropanecarbonitric (compound P13); 1-[6-[5-ethyl-3-methyl-4-oxo-6-(trifluoromethyl)imidazo[4,5-c]pyridin-2-yl]-5-(ethylsulfonimidoyl)-3-pyridyl]cyclopropanecarbonitric (compound P14); 1-[3-(ethylsulfonimidoyl)-4-[3-methyl-6-(trifluoromethyl)imidazo[4,5-b]pyridine-2-yl]phenyl]cyclopropanecarbonitric (compound P15); [5-Cyclopropyl-2-[7-(trifluoromethyl)imidazo[1,2-b]pyridazin-2-yl]-3-pyridyl]-ethyl-imino-oxo-λ 6 -Sulfane (compound P16); 1-[5-(ethylsulfonimidoyl)-6-[6-(trifluoromethyl)pyrazolo[4,3-c]pyridin-2-yl]-3-pyridyl]cyclopropanecarbonitric (compound P17); [5-Cyclopropyl-2-[5-(trifluoromethylsulfanyl)-1,3-benzoxazole-2-yl]-3-pyridyl]-ethyl-imino-oxo-λ 6 -Sulfane (compound P18); and [5-Cyclopropyl-2-[5-(trifluoromethylsulfonyl)-1,3-benzoxazole-2-yl]-3-pyridyl]-ethyl-imino-oxo-λ 6 - Sulfane (compound P19) A compound of formula (I) described above, selected from the group consisting of the above.

[18] A composition comprising an amount effective in insecticidal, acaricidal, nematicidal, or molluscicidal of a compound of formula (I) described in any one of the above items [1] to

[17] or an agriculturally acceptable salt, stereoisomer, enantiomer, tautomer, or N-oxide thereof, and optionally comprising an auxiliary agent or diluent.

[19] A method for controlling and eliminating insects, mites, nematodes, or mollusks, comprising the step of applying an insecticidal, acaricidal, nematodetic, or molluscicidal amount of a compound of formula (I) described in any one of the above items [1] to

[17] or an agriculturally acceptable salt, stereoisomer, enantiomer, tautomer, or N-oxide thereof to a pest, a habitat of a pest, or a plant susceptible to attack by a pest, or the composition described in the above item

[18] .

[20] A method for protecting plant propagation material from attacks by insects, mites, nematodes or mollusks, comprising the step of treating the propagation material or the place where the propagation material is planted with the composition described in

[17] .

Claims

1. Equation (I) 【Chemistry 1】 (In the formula, A is CH or N, R 1 C 1 ~C 4 It is alkyl, R 2 is hydrogen, cyano, -C(O)R 7 -C(O)OR 8 C 1 to C 6 alkyl, -CONR 9 R 10 or SO 2 R 11 wherein R 7 is hydrogen, C 1 ~C 6 Alkyl or C 1 ~C 6 It is a haloalkyl, R 8 C 1 ~C 6 Alkyl or C 1 ~C 6 It is a haloalkyl; R 9 , R 10 These are, independently of each other, hydrogen or C 1 ~C 6 It is alkyl; R 11 C 1 ~C 6 It is alkyl; R 3 is hydrogen, C 1 ~C 3 Alkyl, C 1 ~C 3 Haloalkyl, cyano, -CO 2 H, -CONH 2 , C 1 ~C 4 Alkoxycarbonyl, C 1 ~C 4 Alkylaminocarbonyl, or C 1 ~C 4 It is a dialkylaminocarbonyl, n is either 0 or 1; Q is the formula Q 1 【Chemistry 2】 (In the formula, the arrows indicate the bonding points to the ring incorporating the base A; G 1 is N and G 2 Is it CH or G 1 is CH and G 2 Is N, or G 1 is CH and G 2 CH is; R 4 These are trifluoromethyl, trifluoromethylsulfanyl, or trifluoromethylsulfonyl; X 1 NR 5 And; R 5 C 1 ~C 4 (It is alkyl.) (It is the basis of) Agrochemically acceptable salts, stereoisomers, enantiomers, tautomers, or N-oxides of the compound of formula I.

2. A is either CH or N; R 1 These are ethyl, propyl, or isopropyl; R 2 is hydrogen, cyano, C 1 ~C 3 Alkyl, C 1 ~C 3 Alkylcarbonyl, C 1 ~C 3 Alkoxycarbonyl, or C 1 ~C 3 It is a haloalkylcarbonyl; R 3 is hydrogen, C 1 ~C 3 Haloalkyl, cyano, -CO 2 H, -CONH 2 , or C 1 ~C 4 It is a dialkylaminocarbonyl; and n is 1. The compound according to claim 1.

3. A is either CH or N; R 1 It is ethyl; R 2 is hydrogen; R 3 is hydrogen, C 1 ~C 2 Haloalkyl, cyano, -CONH 2 , or C 1 ~C 2 It is a dialkylaminocarbonyl; and n is 1. The compound according to claim 1.

4. A is either CH or N; R 1 It is ethyl; R 2 is hydrogen; R 3 is hydrogen, cyano, or CONH 2 and n is 1. The compound according to claim 1.

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

6. A is either CH or N; R 1 It is ethyl; R 2 is hydrogen; R 3 is hydrogen or cyano; n is 1, Q is, Q 1 【Transformation 3】 (In the formula, the arrows indicate the bonding points to the ring incorporating the base A; R 4 It is trifluoromethyl; X 1 NCH 3 And; G 1 is N and G 2 is CH, or G 1 is CH and G 2 is N) The compound according to claim 1, which is the base of.

7. A is CH, G 1 CH is CH, and G 2 The compound according to claim 1, wherein is CH.

8. A is CH, G 1 CH is CH, and G 2 The compound according to claim 1, wherein is N.

9. A is CH, G 1 is N, and G 2 The compound according to claim 1, wherein is CH.

10. A is N, G 1 CH is CH, and G 2 The compound according to claim 1, wherein is CH.

11. A is N, G 1 CH is CH, and G 2 The compound according to claim 1, wherein is N.

12. A is N, G 1 is N, and G 2 The compound according to claim 1, wherein is CH.

13. Q is, Q 1-1 Q 1-2 , and Q 1-3 (In the formula, the arrows indicate the bonding points to the ring incorporating radical A.) A compound according to any one of claims 1 to 5, which is a radical selected from the above.

14. (Compound Y-1.001), (Compound Y-2.001), (Compound Y-3.001), (Compound Y-5.001), (Compound Y-6.001), and (Compound Y-7.001), A compound according to claim 1, selected from the group consisting of the following.

15. 1-[3-(ethylsulfonimidoyl)-4-[3-methyl-6-(trifluoromethyl)imidazo[4,5-b]pyridine-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-λ 6 - Sulfane (compound P3); [5-Cyclopropyl-2-[3-Methyl-6-(Trifluoromethylsulfanyl)imidazo[4,5-c]pyridin-2-yl]-3-pyridyl]-ethyl-imino-oxo-λ 6 - Sulfane (compound P4); [5-Cyclopropyl-2-[3-methyl-6-(trifluoromethyl)imidazo[4,5-c]pyridin-2-yl]-3-pyridyl]-ethyl-imino-oxo-λ 6 - Sulfane (compound P5); 1-[5-(ethylsulfonimidoyl)-6-[3-methyl-6-(trifluoromethyl)imidazo[4,5-b]pyridin-2-yl]-3-pyridyl]cyclopropanecarbonitric (compound P6); 1-[3-(ethylsulfonimidoyl)-4-[3-methyl-6-(trifluoromethylsulfanyl)imidazo[4,5-c]pyridine-2-yl]phenyl]cyclopropanecarbonitric (compound P9); [5-Cyclopropyl-2-[3-methyl-6-(trifluoromethyl)imidazo[4,5-b]pyridin-2-yl]-3-pyridyl]-ethyl-imino-oxo-λ 6 - Sulfane (compound P12); 1-[3-(ethylsulfonimidoyl)-4-[3-methyl-6-(trifluoromethyl)imidazo[4,5-c]pyridine-2-yl]phenyl]cyclopropanecarbonitric (compound P13); and 1-[3-(ethylsulfonimidoyl)-4-[3-methyl-6-(trifluoromethyl)imidazo[4,5-b]pyridine-2-yl]phenyl]cyclopropanecarbonitric (compound P15) A compound according to claim 1, selected from the group consisting of the following.

16. A composition comprising an amount effective in insecticidal, acaricidal, nematicidal, or molluscicidal of a compound of formula (I) according to any one of claims 1 to 15, or an agriculturally acceptable salt, stereoisomer, enantiomer, tautomer, or N-oxide thereof, and optionally comprising an auxiliary agent or diluent.

17. A method for controlling and eliminating insects, mites, nematodes, or mollusks, comprising the step of applying an insecticidal, acaricidal, nematodetic, or molluscicidal amount of a compound of formula (I) according to any one of claims 1 to 15 or an agriculturally acceptable salt, stereoisomer, enantiomer, tautomer, or N-oxide thereof to a harmful organism, a habitat of a harmful organism, or a plant susceptible to attack by a harmful organism, or to a plant susceptible to attack by a harmful organism, or applying the composition according to claim 16.

18. A method for protecting plant propagation material from attacks by insects, mites, nematodes, or mollusks, comprising the step of treating the propagation material or the place where the propagation material is planted with the composition according to claim 16.

Images