Pesticidally active heterocyclic derivatives with sulfoximine-containing substituents

Abstract

Compounds having the formula (I) wherein the substituents are as defined in claim 1 are disclosed. Furthermore, the present invention relates to agrochemical compositions comprising the compounds of formula (I), to the preparation of these compositions, and to the use of said compounds or compositions in agriculture or horticulture for combating, preventing or controlling animal pests, the animal pests include arthropods and in particular representatives of insects, nematodes, mollusks or acarids. # imgabs0 #

Description

[0001] This application is a divisional application of the parent case, Chinese invention patent application 201980038081.5.

[0002] The present invention relates to pesticidally active, in particular insecticidal, heterocyclic derivatives containing sulfoximine substituents, to processes for their preparation, to compositions containing those compounds, and to their use for controlling animal pests, including arthropods and in particular insects or representatives of the order Acarina.

[0003] Pesticidal active heterobicyclic substituted cyclopropyl derivatives with sulfur-containing substituents are known and described in the literature, for example, in WO 2018 / 077565, WO 2018 / 070502, WO 2017 / 146226, WO 2017 / 089190, WO 2017 / 084879, WO 2016 / 121997, WO 2016 / 104746, WO 2016 / 096584, WO 2016 / 046071, WO 2016 / 071214, WO 2016 / 039441, WO 2016 / 026848, WO 2016 / 023954, WO 2014 / 142292 and WO 2016 / 020286. Pesticidal active heterocyclic sulfoximine derivatives have been previously described in the literature, for example in WO 2015 / 071180.

[0004] It has now surprisingly been found that certain novel bicyclic sulfoximine-containing cyclopropyl derivatives possess advantageous properties as pesticides.

[0005] The present invention therefore provides compounds of formula I,

[0006]

[0007] in

[0008] A is CH or N

[0009] R1 is C1-C4 alkyl

[0010] R2 is hydrogen, cyano, -C(O)R7, -C(O)OR8, C1-C6 alkyl or -CONR9R 10 、SO2R 11

[0011] in

[0012] R7 is hydrogen, C1-C6 alkyl or C1-C6 haloalkyl, and R8 is C1-C6 alkyl or C1-C6 haloalkyl;

[0013] R9, R 10 are independently hydrogen or C1-C6 alkyl;

[0014] R 11 is a C1-C6 alkyl group;

[0015] R3 is hydrogen, C1-C3 alkyl, C1-C3 haloalkyl, cyano, -CO2H, -CO2NH2, C1-C4 alkoxycarbonyl, C1-C4 alkylaminocarbonyl, C1-C4 dialkylaminocarbonyl

[0016] n is 0 or 1;

[0017] Q is a group selected from the group consisting of: formula Q1, Q2, Q3, Q4 and Q5

[0018]

[0019] wherein the arrow indicates the point of attachment to the ring into which the group A is incorporated;

[0020] And among them

[0021] R4 is halogen, C1-C6 haloalkyl, C1-C4 haloalkylsulfanyl, C1-C4 haloalkylsulfinyl, C1-C4 haloalkylsulfonyl or C1-C6 haloalkoxy;

[0022] X1 is O or NR5;

[0023] R5 is C1-C4 alkyl;

[0024] R6 is C1-C4 alkyl, C1-C4 haloalkyl, C1-C4 alkoxy, or C3-C6 cycloalkyl;

[0025] G1 and G2 are independently N or CH;

[0026] or an agrochemically acceptable salt, stereoisomer, enantiomer, tautomer or N-oxide of a compound of formula I.

[0027] Compounds of the formula I with at least one basic center can form, for example, acid addition salts with strong inorganic acids (e.g. mineral acids, for example perchloric acid, sulfuric acid, nitric acid, nitrose acid, phosphoric acid or hydrohalic acids), strong organic carboxylic acids (e.g. unsubstituted or, for example, halogen-substituted C1-C4-alkanecarboxylic acids, for example acetic acid, for example saturated or unsaturated dicarboxylic acids, for example oxalic acid, malonic acid, succinic acid, maleic acid, fumaric acid or phthalic acid, for example hydroxycarboxylic acids, for example ascorbic acid, lactic acid, malic acid, tartaric acid or citric acid, or for example benzoic acid), or organic sulfonic acids (e.g. unsubstituted or, for example, halogen-substituted C1-C4-alkanesulfonic acids or arylsulfonic acids, for example methanesulfonic acid or p-toluenesulfonic acid). Compounds of formula I having at least one acidic group can, for example, form salts with bases, such as mineral salts, for example alkali metal or alkaline earth metal salts, for example sodium, potassium or magnesium salts; or with ammonia or an organic amine (for example morpholine, piperidine, pyrrolidine, mono-, di- or tri-lower alkylamines, for example ethylamine, diethylamine, triethylamine or dimethylpropylamine, or mono-, di- or tri-hydroxy lower alkylamines, for example monoethanolamine, diethanolamine or triethanolamine).

[0028] As used herein, the term "C1-C n "Alkyl" refers to a saturated straight or branched hydrocarbon group having 1 to n carbon atoms attached via any of these carbon atoms, for example, any of the following groups: methyl, ethyl, n-propyl, isopropyl, n-butyl, sec-butyl, isobutyl, tert-butyl, pentyl, hexyl, and branched isomers thereof. For example, any of the following groups can also be mentioned: 1-methylbutyl, 2-methylbutyl, 3-methylbutyl, 2,2-dimethylpropyl, 1-ethylpropyl, n-hexyl, n-pentyl, 1,1-dimethylpropyl, 1,2-dimethylpropyl, 1-methylpentyl, 2-methylpentyl , 3-methylpentyl, 4-methylpentyl, 1,1-dimethylbutyl, 1,2-dimethylbutyl, 1,3-dimethylbutyl, 2,2-dimethylbutyl, 2,3-dimethylbutyl, 3,3-dimethylbutyl, 1-ethylbutyl, 2-ethylbutyl, 1,1,2-trimethylpropyl, 1,2,2-trimethylpropyl, 1-ethyl-1-methylpropyl, or 1-ethyl-2-methylpropyl. As described below, haloalkyl, haloalkylsulfanyl, haloalkylsulfinyl, haloalkylsulfonyl, alkoxy, and haloalkoxy are derived from alkyl groups.

[0029] Halogen is typically fluorine, chlorine, bromine or iodine. This also applies correspondingly to halogen in combination with other meanings, such as haloalkyl.

[0030] As used herein, the term "C1-C n "Haloalkyl" refers to a straight or branched chain saturated C1-C nalkyl (as mentioned above), wherein some or all of the hydrogen atoms in these groups may be replaced by fluorine, chlorine, bromine and / or iodine, i.e., for example, any of the following: 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 Preferably, the alkyl group is selected from the group consisting of 1,2-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.

[0031] As used herein, the term "C1-C n "Alkoxy" refers to a straight or branched saturated C1-C12 radical having 1 to n carbon atoms and attached via an oxygen atom. n Alkyl (as mentioned above), i.e., for example, any of the following radicals: methoxy, ethoxy, propoxy, isopropoxy, n-butoxy, isobutoxy, sec-butoxy, tert-butoxy, 1-methylpropoxy, 2-methylpropoxy and 1,1-dimethylethoxy and also the isomers pentoxy and hexoxy; preferably methoxy and ethoxy.

[0032] As used herein, the term "C1-C n "Haloalkoxy" refers to a radical having 1 to n carbon atoms attached via an oxygen atom (similar to C1-C n Alkoxy) straight or branched chain saturated C1-C n Haloalkyl (as mentioned above).

[0033] As used herein, the term "C1-C n "Alkylsulfanyl" refers to a straight-chain or branched saturated alkyl group having 1 to n carbon atoms (as defined above), which is attached via a sulfur atom, i.e., for example, any of methylthio, ethylthio, n-propylthio, 1-methylethylthio, butylthio, 1-methylpropylthio, 2-methylpropylthio or 1,1-dimethylethylthio.

[0034] As used herein, the term "C1-C n"Haloalkylsulfanyl" refers to a C1-C n Alkylsulfanyl which is partially or completely substituted by fluorine, chlorine, bromine and / or iodine, i.e., for example, fluoromethylthio, difluoromethylthio, trifluoromethylthio, chlorodifluoromethylthio, bromodifluoromethylthio, 2-fluoroethylthio, 2-chloroethylthio, 2-bromoethylthio, 2-iodoethylthio, 2,2-difluoroethylthio, 2,2,2-trifluoroethylthio, 2,2,2-trichloroethylthio, 2-chloro-2-fluoroethylthio, 2-chloro-2,2-difluoroethylthio, 2,2-dichloro-2-fluoroethylthio, pentafluoroethylthio, 2-fluoropropylthio, 3-fluoropropylthio any one of the following: 1-(fluoromethyl)-2-fluoroethylthio, 1-(chloromethyl)-2-chloroethylthio, 1-(bromomethyl)-2-bromoethylthio, 4-fluorobutylthio, 4-chlorobutylthio or 4-bromobutylthio.

[0035] Similar considerations apply to the term “C1-C n "Haloalkylsulfinyl" and "C1-C n "Haloalkylsulfonyl" refers to a C1-C n haloalkylsulfanyl (as mentioned above), but wherein the sulfur is in a different oxidation state, for example sulfoxide -S(O)C1-C n Halogenated alkyl or sulfone -S(O)2C1-C n Haloalkyl. Thus, for example, radicals such as trifluoromethylsulfinyl, trifluoromethylsulfonyl or 2,2,2-trifluoroethylsulfonyl.

[0036] The term "C3-C6 cycloalkyl" as used herein refers to a 3-6 membered cycloalkyl group such as cyclopropane, cyclobutane, cyclopropane, cyclopentane and cyclohexane.

[0037] The term "C1-C n "Alkoxycarbonyl" refers to a straight or branched chain saturated C1-C2-6 carbonyl radical having 1 to n carbon atoms and attached via a carbonyl group. n Alkoxy (as mentioned above).

[0038] The term "C1-C n "Alkylaminocarbonyl" refers to a straight or branched chain saturated C1-C12 aminocarbonyl radical having 1 to n carbon atoms and attached via the nitrogen atom of the aminocarbonyl radical. n Alkyl (as mentioned above).

[0039] The term "C1-C n"Dialkylaminocarbonyl" refers to a linear or branched saturated C1-C2-6 carbonyl radical having 1 to n carbon atoms (the same or different number) and two carbon atoms attached via the nitrogen atom of the aminocarbonyl radical. n Alkyl (as mentioned above).

[0040] A terminal single bond (radical) represents a methyl group in the context of a given molecular structure or a point of attachment in the context of a variable group definition.

[0041] The compounds of formula I according to the invention also include hydrates which may be formed during salt formation.

[0042] As described below, embodiments according to the present invention are provided.

[0043] Example 1 provides a compound having formula I as defined above, or an agrochemically acceptable salt, stereoisomer, enantiomer, tautomer or N-oxide thereof.

[0044] Embodiment 2 provides a compound according to embodiment 1 or an agrochemically acceptable salt, stereoisomer, enantiomer, tautomer or N-oxide thereof, wherein:

[0045] A is CH or N;

[0046] R1 is ethyl, propyl or isopropyl;

[0047] R2 is hydrogen, cyano, C1-C3 alkyl, C1-C3 alkylcarbonyl, C1-C3 alkoxycarbonyl, C1-C3 haloalkylcarbonyl;

[0048] R3 is hydrogen, C1-C3 haloalkyl, cyano, -CO2H, -CO2NH2, C1-C4 dialkylaminocarbonyl; and

[0049] n is 1.

[0050] Embodiment 3 provides a compound according to embodiment 1 or an agrochemically acceptable salt, stereoisomer, enantiomer, tautomer or N-oxide thereof, wherein:

[0051] A is CH or N;

[0052] R1 is ethyl;

[0053] R2 is hydrogen;

[0054] R3 is hydrogen, C1-C2 haloalkyl, cyano, -CO2NH2, C1-C2 dialkylaminocarbonyl; and

[0055] n is 1.

[0056] Embodiment 4 provides a compound according to embodiment 1 or an agrochemically acceptable salt, stereoisomer, enantiomer, tautomer or N-oxide thereof, wherein:

[0057] A is CH or N;

[0058] R1 is ethyl;

[0059] R2 is hydrogen;

[0060] R3 is hydrogen, cyano or CO2NH2; and

[0061] n is 1.

[0062] Embodiment 5 provides a compound according to embodiment 1 or an agrochemically acceptable salt, stereoisomer, enantiomer, tautomer or N-oxide thereof, wherein:

[0063] A is CH or N;

[0064] R1 is ethyl;

[0065] R2 is hydrogen;

[0066] R3 is hydrogen or cyano; and

[0067] n is 1.

[0068] Embodiment 6 provides a compound according to embodiment 1 or an agrochemically acceptable salt, stereoisomer, enantiomer, tautomer or N-oxide thereof, wherein:

[0069] Q is a group selected from Q1, Q2, Q4 and Q5

[0070]

[0071] wherein the arrow indicates the point of attachment to the ring into which the group A is incorporated;

[0072] And among them

[0073] R4 is C1-C2 haloalkyl, C1-C2 haloalkylsulfanyl, C1-C2 haloalkylsulfinyl or C1-C2 haloalkylsulfonyl;

[0074] X1 is oxygen or NCH3;

[0075] R6 is C1-C2 alkyl, C1-C2 haloalkyl, C1-C2 alkoxy or cyclopropyl; and

[0076] G1 and G2 are independently N or CH.

[0077] Embodiment 7 provides a compound according to embodiment 1 or an agrochemically acceptable salt, stereoisomer, enantiomer, tautomer or N-oxide thereof, wherein:

[0078] is a group selected from Q1, Q2 and Q5

[0079]

[0080] wherein the arrow indicates the point of attachment to the ring into which the group A is incorporated;

[0081] And among them

[0082] R4 is C1-C2 fluoroalkyl, trifluoromethylsulfanyl, trifluoromethylsulfinyl, trifluoromethylsulfonyl, difluoromethylsulfanyl, difluoromethylsulfinyl, or difluoromethylsulfonyl;

[0083] X1 is NCH3;

[0084] R6 is methyl, ethyl, 2,2,2-trifluoroethyl, methoxy or cyclopropyl; and

[0085] G1 and G2 are independently N or CH.

[0086] Embodiment 8 provides a compound according to embodiment 1 or an agrochemically acceptable salt, stereoisomer, enantiomer, tautomer or N-oxide thereof, wherein:

[0087] Q is a group selected from Q1 and Q5

[0088]

[0089] wherein the arrow indicates the point of attachment to the ring into which the group A is incorporated;

[0090] And among them

[0091] R4 is trifluoromethyl, pentafluoroethyl, trifluoromethylsulfanyl, trifluoromethylsulfinyl or trifluoromethylsulfonyl;

[0092] X1 is NCH3;

[0093] R6 is ethyl, methoxy or cyclopropyl; and

[0094] 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.

[0095] Embodiment 9 provides a compound according to embodiment 1 or an agrochemically acceptable salt, stereoisomer, enantiomer, tautomer or N-oxide thereof, wherein:

[0096] Q is the group Q1

[0097]

[0098] wherein the arrow indicates the point of attachment to the ring into which the group A is incorporated;

[0099] And among them

[0100] R4 is trifluoromethyl;

[0101] X1 is NCH3; and

[0102] G1 is N and G2 is CH, G1 is CH and G2 is N, or G1 and G2 are N.

[0103] Embodiment 10 provides a compound according to embodiment 1 or an agrochemically acceptable salt, stereoisomer, enantiomer, tautomer or N-oxide thereof, wherein:

[0104] A is CH or N;

[0105] R1 is ethyl, propyl or isopropyl;

[0106] R2 is hydrogen, cyano, C1-C3 alkyl, C1-C3 alkylcarbonyl, C1-C3 alkoxycarbonyl, C1-C3 haloalkylcarbonyl;

[0107] R3 is hydrogen, C1-C3 haloalkyl, cyano, CO2H, CO2NH2, C1-C4 dialkylaminocarbonyl;

[0108] n is 1;

[0109] Q is a group selected from Q1, Q2, Q4 and Q5

[0110]

[0111] wherein the arrow indicates the point of attachment to the ring into which the group A is incorporated;

[0112] And among them

[0113] R4 is C1-C2 haloalkyl, C1-C2 haloalkylsulfanyl, C1-C2 haloalkylsulfinyl or C1-C2 haloalkylsulfonyl;

[0114] X1 is oxygen or NCH3;

[0115] R6 is C1-C2 alkyl, C1-C2 haloalkyl, C1-C2 alkoxy or cyclopropyl; and

[0116] G1 and G2 are independently N or CH.

[0117] Embodiment 11 provides a compound according to Embodiment 1 or an agrochemically acceptable salt, stereoisomer, enantiomer, tautomer or N-oxide thereof, wherein:

[0118] A is CH or N;

[0119] R1 is ethyl;

[0120] R2 is hydrogen;

[0121] R3 is hydrogen, C1-C2 haloalkyl, cyano, CO2NH2, C1-C2 dialkylaminocarbonyl;

[0122] n is 1;

[0123] Q is a group selected from Q1, Q2 and Q5

[0124]

[0125] wherein the arrow indicates the point of attachment to the ring into which the group A is incorporated;

[0126] And among them

[0127] R4 is C1-C2 fluoroalkyl, trifluoromethylsulfanyl, trifluoromethylsulfinyl, trifluoromethylsulfonyl, difluoromethylsulfanyl, difluoromethylsulfinyl, or difluoromethylsulfonyl;

[0128] X1 is NCH3;

[0129] R6 is methyl, ethyl, 2,2,2-trifluoroethyl, methoxy or cyclopropyl; and

[0130] G1 and G2 are independently N or CH.

[0131] Embodiment 12 provides a compound according to embodiment 1 or an agrochemically acceptable salt, stereoisomer, enantiomer, tautomer or N-oxide thereof, wherein:

[0132] A is CH or N;

[0133] R1 is ethyl;

[0134] R2 is hydrogen;

[0135] R3 is hydrogen, cyano or CO2NH2;

[0136] n is 1;

[0137] Q is a group selected from Q1 and Q5

[0138]

[0139] wherein the arrow indicates the point of attachment to the ring into which the group A is incorporated;

[0140] And among them

[0141] R4 is trifluoromethyl, pentafluoroethyl, trifluoromethylsulfanyl, trifluoromethylsulfinyl or trifluoromethylsulfonyl;

[0142] X1 is NCH3;

[0143] R6 is ethyl, methoxy or cyclopropyl; and

[0144] 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.

[0145] Embodiment 13 provides a compound according to Embodiment 1 or an agrochemically acceptable salt, stereoisomer, enantiomer, tautomer or N-oxide thereof, wherein:

[0146] A is CH or N;

[0147] R1 is ethyl;

[0148] R2 is hydrogen;

[0149] R3 is hydrogen or cyano;

[0150] n is 1;

[0151] Q is the group Q1

[0152]

[0153] wherein the arrow indicates the point of attachment to the ring into which the group A is incorporated;

[0154] And among them

[0155] R4 is trifluoromethyl;

[0156] X1 is NCH3; and

[0157] G1 is N and G2 is CH, G1 is CH and G2 is N, or G1 and G2 are N.

[0158] Embodiment 14 provides a compound according to Embodiment 1, 2, 3, 4 or 5, or an agrochemically acceptable salt, stereoisomer, enantiomer, tautomer or N-oxide thereof, wherein:

[0159] Q is selected from Q 1-1 , Q 1-2 , Q 1-3 , Q 1-4 and Q 1-5 Group

[0160]

[0161] wherein the arrow indicates the point of attachment to the ring into which the group A is incorporated; and

[0162] R4 is trifluoromethyl, trifluoromethylsulfanyl or trifluoromethylsulfonyl.

[0163] Embodiment 15 provides the compound according to Embodiment 14 or an agrochemically acceptable salt, stereoisomer, enantiomer, tautomer or N-oxide thereof:

[0164] Where Q is selected from Q 1-2 , Q 1-3 , Q 1-4 and Q 1-5 The group.

[0165] Embodiment 16 provides a compound according to Embodiment 1, 2, 3, 4 or 5, or an agrochemically acceptable salt, stereoisomer, enantiomer, tautomer or N-oxide thereof, wherein:

[0166] Q is a group selected from Q5

[0167]

[0168] wherein the arrow indicates the point of attachment to the ring into which the group A is incorporated;

[0169] R4 is trifluoromethyl, trifluoromethylsulfanyl or trifluoromethylsulfonyl; and

[0170] R6 is OCH3, CH2CH3 or cyclopropyl.

[0171] Embodiment 17 provides a compound according to Embodiment 1, 2, 3, 4 or 5, or an agrochemically acceptable salt, stereoisomer, enantiomer, tautomer or N-oxide thereof, wherein:

[0172] Q is the group Q2

[0173]

[0174] wherein the arrow indicates the point of attachment to the ring into which the group A is incorporated;

[0175] R4 is trifluoromethyl, trifluoromethylsulfanyl or trifluoromethylsulfonyl; and

[0176] G2 is N or CH.

[0177] Embodiment 18 provides a compound according to Embodiment 1, 2, 3, 4 or 5, or an agrochemically acceptable salt, stereoisomer, enantiomer, tautomer or N-oxide thereof, wherein:

[0178] Q is Q3; and

[0179] R4 is trifluoromethyl, trifluoromethylsulfanyl or trifluoromethylsulfonyl.

[0180] Embodiment 19 provides a compound according to Embodiment 1, 2, 3, 4 or 5, or an agrochemically acceptable salt, stereoisomer, enantiomer, tautomer or N-oxide thereof, wherein:

[0181] Q is for Q4

[0182]

[0183] wherein the arrow indicates the point of attachment to the ring into which the group A is incorporated;

[0184] R4 is trifluoromethyl, trifluoromethylsulfanyl or trifluoromethylsulfonyl; and

[0185] G1 is N and G2 is CH, G1 is CH and G2 is N, G1 and G2 are CH, or G1 and G2 are N; preferably, G1 is CH and G2 is N.

[0186] In another aspect, the present invention provides a composition comprising an insecticidal, acaricidal, nematicidal or molluscicidal effective amount of a compound of formula (I) as defined in any one of the preceding embodiments 1-19, or an agrochemically acceptable salt, stereoisomer, enantiomer, tautomer or N-oxide thereof, and optionally, an adjuvant or diluent.

[0187] In another aspect, the present invention provides a method for combating and controlling insects, mites, nematodes or molluscs, the method comprising applying an insecticidal, acaricidal, nematicidal or molluscicidal effective amount of a compound of formula (I) as defined in any one of the preceding embodiments 1-19, or an agrochemically acceptable salt, stereoisomer, enantiomer, tautomer or N-oxide thereof, or a composition as defined above to the pest, a location of the pest or a plant susceptible to attack by the pest.

[0188] In yet another aspect, the present invention provides a method for protecting plant propagation material from attack by insects, acarids, nematodes or molluscs, which method comprises treating the propagation material or the locus where the propagation material is planted with a composition as defined above.

[0189] The process for preparing the compounds of formula (I) according to the invention 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. sulfilimines Ia, where R1, R2, R3, A and Q are as defined above) can be prepared by reacting the corresponding sulfide of formula II (where R1, R2, R3, A and Q are as defined above) under imination reaction conditions (step A, scheme 1). A specific subgroup of compounds of formula I (where n is 1, defined as sulfimines I, where R1, R2, R3, A and Q are as defined above) can be obtained by oxidation of sulfilimine compounds of formula Ia (where R1, R2, R3, A and Q are as defined above) (step B).

[0190] Solution 1

[0191]

[0192] Conversely, the order of these two steps can be reversed, whereby a sulfoximine compound of formula I (wherein R1, R2, R3, A and Q are as defined above) can be prepared from a sulfoxide of formula III (wherein R1, R2, R3, A and Q are as defined above) under appropriate imination conditions (step A').

[0193] Typical preparation methods and reaction conditions for obtaining compounds of formula I (whether for sulfilimine Ia (step A) or sulfoximine I (step A')) can be found in the following literature, for example, H. Okamura, C. Bolm, Org. Lett. [Organic Letters], 2004, 6, 1305-1307; H. Okamura, C. Bolm, Chem. Lett. [Chemical Letters], 2004, 33, 482-487; D. Leca, K. Song, M. Amatore, L. Fensterbank, E. M. Malacria, Chem. Eur. J. [European Journal of Chemistry] 2004, 10, 906-916; or M. Reggelin, C. Zur, Synthesis [Synthesis], 2000, 1-64. Typical imidization agents / conditions can be defined as NaN3 / H2SO4, O-mesitylenesulfonyl-hydroxylamine (MSH) or metal-catalyzed methods [see OGMancheno, C.Bolm, Chem.Eur.J., 2007, 13, 6674-6681], 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-cyano-phenyl)-oxaziridine-2-carboxylic acid tert-butyl ester).

[0194] Of particular interest are metal-free imination methods of sulfides of formula II and / or sulfoxides of formula III to prepare sulfilimines of formula Ia (step A) and / or sulfoximines of formula I (step A'). Such imination reactions involve R2-NH2 and an oxidant, 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 tert-butoxide, as described in C.Bolm et al., Synthesis 2010, No. 17, 2922-2925. Alternatively, oxidizing agents such as N-iodosuccinimide (NIS) or iodine can also be used, as described, for example, in OG Mancheno, C. Bolm, Org. Lett. [Organic Letters] 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 WO 2008 / 106006.

[0195] For the conversion of sulfilimine Ia to sulfoximine I (step B), classical oxidizing agents such as KMnO4, NaMnO4, mCPBA, NaIO4 / RuO2, NaIO4 / RuCl3, H2O2, oxone can be involved. In particular, the use of ruthenium salts in combination with alkali metal periodates and alternatively alkali metal permanganates is described in WO 2008 / 097235 and WO2008 / 106006.

[0196] Detailed preparation conditions for the synthesis of such sulfilimine and / or sulfoximine compounds of formula Ia, I, respectively, are also given, for example, in WO 2006 / 061200 or WO 2007 / 080131.

[0197] Alternatively, a subset of sulfoximine compounds having Formula I, wherein R2 is hydrogen and n is 1, and wherein R1, R3, A and Q are as defined in Formula I,

[0198] Option 1a

[0199]

[0200] It can be prepared by reacting a sulfide of formula II (wherein R1, R3, A and Q are as defined in formula I) with a suitable nitrogen source such as ammonia, ammonium carbamate or ammonium acetate (preferably ammonium carbamate) in the presence of a hypervalent iodine reagent such as diacetoxyiodobenzene in a solvent such as toluene, acetonitrile or methanol at a temperature between 0 and 100° C. (preferably around room temperature) (Scheme 1a), similar to the description found, for example, in Chem. Commun. 53, 348-351; 2017 (and references cited therein).

[0201] Compounds of formula Ib, wherein R1, R3, A and Q are as defined above and wherein n is 1 and R2 is CN, can be converted to compounds of formula Ic, wherein R1, R3, A and Q are as defined above and wherein n is 1 and R2 is C(O)CF3, by treatment with trifluoroacetic anhydride in a solvent such as dichloromethane, as described, for example, in OG Mancheno, C. Bolm, Org. Lett. [Organic Letters] 2007, 9, 3809-3811. Compounds of formula Ic, wherein R1, R3, A and Q are as defined above and wherein n is 1 and R2 is C(O)CF3, can be converted into compounds of formula I, wherein R1, R3, A and Q are as defined above and wherein n is 1 and R2 is hydrogen, by treatment with a base, such as sodium carbonate or potassium carbonate, in a polar protic solvent, such as methanol or ethanol, as described, for example, in H. Okamura, C. Bolm, Org. Lett. [Organic Letters] 2004, 6, 1305-1307. Compounds of formula Id (wherein R1, R3, A and Q are as defined above and wherein n is 1, wherein R2 is C(O)NH2) can be prepared from compounds of formula Ib (wherein R1, R3, A and Q are as defined above and wherein n is 1, wherein R2 is CN) by treatment with a strong acid (such as concentrated sulfuric acid) in an organic solvent (such as acetonitrile) as described, for example, in WO 09 / 111309. The chemistry is summarized in Scheme 2.

[0202] Solution 2

[0203]

[0204] Compounds of formula Ie, wherein R1, R3, A and Q are as defined above, and wherein n is 1 and R2 is C1-C6 alkyl, can be prepared by reacting the alkylating agent of formula LG-R2, wherein LG is a leaving group, such as a halogen, especially bromine or iodine, a sulfonate, such as OSO2R2, in an inert solvent, preferably in the presence of a suitable base, such as an alkali metal carbonate, for example sodium carbonate or potassium carbonate, or an alkali metal hydride, for example sodium hydride, or an alkali metal hydroxide, for example sodium hydroxide and potassium hydroxide, at a temperature between -20°C and 150°C, preferably between 0°C and 80°C. 12 (especially mesylate or tosylate) (where R 12is C1-C6 alkyl, C1-C6 haloalkyl or phenyl optionally substituted by nitro or C1-C3 alkyl), or sulfate (such as dimethyl sulfate) is prepared by treating a compound having formula I (wherein R1, R3, A and Q are as defined above, and wherein n is 1 and wherein R2 is hydrogen). Examples of the solvent to be used include ethers such as tetrahydrofuran, ethylene glycol dimethyl ether (1,2-dimethoxyethane), tert-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.

[0205] Compounds of formula If, wherein R1, R3, A and Q are as defined above, and wherein n is 1 and R2 is C(O)R7 and R7 is C1-C6 alkyl or C1-C6 haloalkyl, can be prepared by treatment with a reagent of formula LG1-C(O)R7 or an anhydride reagent of formula R7C(O)-OC(O)R7, wherein R7 is as defined above and LG1 is a leaving group, such as halogen (especially chlorine), at a temperature between 0°C and 50°C in an inert solvent, optionally in the presence of an acylation catalyst such as 4-dimethylaminopyridine (DMAP), preferably in the presence of a base such as triethylamine, diisopropylethylamine or pyridine. Examples of the solvent to 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. The reaction can be carried out in the presence of an excess of a base, which can then also serve as a solvent or diluent.

[0206] Compounds of formula Ig, wherein R1, R3, A and Q are as defined above and wherein n is 1, wherein R2 is C(O)OR8 and R8 is C1-C6 alkyl, C1-C6 haloalkyl, can be prepared by treating with a reagent of formula LG2-C(O)OR8, wherein R8 is as defined above and LG2 is a leaving group, such as halogen (especially chlorine), at a temperature between 0°C and 50°C in an inert solvent, optionally in the presence of an acylation catalyst such as 4-dimethylaminopyridine (DMAP), preferably in the presence of a base such as triethylamine, diisopropylethylamine or pyridine. Examples of the solvent to 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. The reaction can be carried out in the presence of an excess of a base, which can then also serve as a solvent or diluent.

[0207] A compound of formula Ih (wherein R1, R3, A and Q are as defined above and wherein n is 1, and wherein R2 is CONR9R 10 And R9, R 10 LG3-C(O)NR9R 10 Reagents (where R9 and R 10 is as defined above and LG3 is a leaving group such as halogen (especially chlorine)) by treating with a compound of formula I wherein R1, R3, A and Q are as defined above and wherein n is 1 and wherein R2 is hydrogen. Examples of solvents to 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. The reaction can be carried out in the presence of an excess of a base, which can then also serve as a solvent or diluent.

[0208] A compound of formula Ii wherein R1, R3, A and Q are as defined above and wherein n is 1, and wherein R2 is SO2R 11 And R 11is C1-C6 alkyl) can be prepared by reacting a alkyl group having the formula LG4-SO2R at a temperature between 0°C and 50°C in an inert solvent, optionally in the presence of an acylation catalyst such as 4-dimethylaminopyridine (DMAP), preferably in the presence of a base such as triethylamine, diisopropylethylamine or pyridine. 11 Reagents (where R 11 is as defined above and LG4 is a leaving group such as halogen (especially chlorine)) by treating with a compound of formula I wherein R1, R3, A and Q are as defined above and wherein n is 1 and wherein R2 is hydrogen. Examples of solvents to 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. The reaction can be carried out in the presence of an excess of a base, which can then also serve as a solvent or diluent. Compounds of formula Ij (wherein R1, R2, R3 and Q are as defined above and wherein n is 1, wherein R2 is C(O)R7 and R7 is hydrogen) can be prepared by treating with trialkyl orthoformate (such as trimethyl orthoformate) at a temperature between 0°C and 180°C, optionally in the presence of an acid activator (such as p-toluenesulfonic acid), optionally in the presence of an inert organic solvent, by compounds of formula I (wherein R1, R3, A and Q are as defined above and wherein n is 1 and R2 is hydrogen). The reaction can be carried out in the presence of an excess of trialkyl orthoformate, which can then also serve as a solvent or diluent. Such a method is shown, for example, in WO 2006 / 037945. The above-described conversion is illustrated in Scheme 3.

[0209] Solution 3

[0210]

[0211] In some cases, compounds of formula II wherein R3 is hydrogen are known, for example:

[0212] 2-(5-Cyclopropyl-3-ethylsulfanyl-2-pyridyl)-5-(trifluoromethoxy)-1,3-benzoxazole, CAS[2128705-99-5], WO 2017146226; 2-(5-Cyclopropyl-3-ethylsulfanyl-2-pyridyl)-5-(difluoromethylsulfanyl)-1,3-benzoxazole, CAS[2128706-06-7], WO 2017146226; 2-(5-Cyclopropyl-3-ethylsulfanyl-2-pyridyl)-5-(difluoromethoxy)-1,3-benzoxazole, CAS[2128706-01-2], WO 2017146226; 5-cyclopropyl-2-(5-cyclopropyl-3-ethylsulfanyl-2-pyridyl)-3-methyl-6-(trifluoromethyl)imidazo[4,5-c]pyridin-4-one, CAS[2098699-63-7], WO 2017089190; 5-cyclopropyl-2-(4-cyclopropyl-2-ethylsulfanyl-phenyl)-3-methyl-6-(trifluoromethyl)imidazo[4,5-c]pyridin-4-one, CAS[2098699-80-8], WO 2017089190; 2-(5-cyclopropyl-3-ethylsulfanyl-2-pyridyl)-5-(1,1,2,2,2-pentafluoroethyl)-1,3-benzoxazole, CAS[1975147-97-7], WO 2016121997; 2-(5-cyclopropyl-3-ethylsulfanyl-2-pyridyl)-5-(trifluoromethylsulfanyl)-1,3-benzoxazole, CAS[1975147-94-4], WO2017146226; 2-(5-cyclopropyl-3-ethylsulfanyl-2-pyridyl)-1-methyl-5-(trifluoromethyl)benzimidazole, CAS[1975147-91-1], WO 2016121997; 2-(5-cyclopropyl-3-ethylsulfanyl-2-pyridinyl)-6-(trifluoromethyl)oxazolo[5,4-b]pyridine, CAS[1975147-87-5], WO2016121997; 2-(5-cyclopropyl-3-ethylsulfanyl-2-pyridinyl)-3-methyl-6-(1,1,2,2,2-pentafluoroethyl)imidazo[4,5-b]pyridine, CAS[1975147-85-3], WO 2016121997; 6-(5-cyclopropyl-3-ethylsulfanyl-2-pyridinyl)-7-methyl-3-(2,2,2-trifluoroethoxy)imidazo[4,5-c]pyridazine, CAS[1957168-99-8], WO2016104746; 2-(5-cyclopropyl-3-ethylsulfanyl-2-pyridinyl)-3-methyl-6-(trifluoromethyl)imidazo[4,5-b]pyridine, CAS[1951416-89-9], WO 2016096584;2-(4-Cyclopropyl-2-ethylsulfanyl-phenyl)-7-(trifluoromethyl)imidazo[1,2-c]pyrimidine, CAS[1923785-41-4], WO 2016071214; 2-(5-Cyclopropyl-3-ethylsulfanyl-2-pyridinyl)-7-(trifluoromethyl)imidazo[1,2-c]pyrimidine, CAS[1923784-36-4], WO 2016071214; 2-(4-Cyclopropyl-2-ethylsulfanyl-phenyl)-5-ethyl-3-methyl-6-(trifluoromethyl)imidazo[4,5-c]pyridin-4-one, CAS[1879051-89-4], WO 2016023954; 2-(4-cyclopropyl-2-ethylsulfanyl-phenyl)-3,5-dimethyl-6-(trifluoromethyl)imidazo[4,5-c]pyridin-4-one, CAS[1879051-88-3], WO 2016023954. ;

[0213] A compound of formula II (wherein R3 is H), ie a compound of formula IIa

[0214]

[0215] Generally, it can be prepared by reacting a compound of formula IV (wherein A, Q and R1 are as defined above in formula I) with a compound of formula V, as shown in Scheme 4:

[0216] Solution 4

[0217]

[0218] More specifically, the compound having the formula IIa can be prepared by reacting the compound having the formula V (wherein X b1 may be halogen (preferably chlorine, bromine or iodine), and Y b1 It may be a boron-derived functional group such as, for example, B(OH)2 or B(OR b1 )2, where R b1 It can be a C1-C6 alkyl group or these two groups OR b1Compounds of formula IIa (as described in Scheme 4) can be prepared by reacting with a boron atom to form a five-membered or six-membered ring (such as, for example, pinacol borate) (Suzuki cross coupling, see, for example, Tetrahedron Letters, 43 (39), 6987-6990; 2002). In formula IIa, A, R1 and Q are as described in formula I. The reaction can be catalyzed by a palladium-based catalyst, such as tetrakis(triphenylphosphine)palladium(0), bis(triphenylphosphine)palladium(II) dichloride, chloro(2-dicyclohexylphosphino-2',4',6'-triisopropyl-1,1'-biphenyl)[2-(2'-amino-1,1'-biphenyl)]palladium(II) (XPhos cyclopalladium complex), (1,1'bis(diphenylphosphino)-ferrocene)palladium(II) dichloride-dichloromethane (1:1 complex) or palladium acetate plus a phosphine ligand (such as, for example, triphenylphosphine or tricyclohexylphosphine), in the presence of a base (such as sodium carbonate, tripotassium phosphate or cesium fluoride), in a solvent (such as toluene, 1,2-dimethoxyethane DME, tetrahydrofuran or dioxane) or a solvent mixture (such as, for example, a mixture of 1,2-dimethoxyethane (or dioxane, toluene, or tetrahydrofuran) and water), preferably under an inert atmosphere. The reaction temperature may preferably range from ambient temperature to the boiling point of the reaction mixture, or alternatively, heating may be carried out under microwave irradiation.

[0219] Alternatively, a compound of formula IV (wherein X b1 can be halogen (preferably chlorine, bromine or iodine)) and a compound of formula V (wherein Y b1 is a magnesium halide group, such as -MgBr (Kumada cross coupling)) optionally in the presence of an additive such as a zinc halide (Journal of Organic Chemistry, 75(19), 6677-6680; 2010). The reaction can be catalyzed by a palladium-based catalyst, or can involve a nickel-based catalyst such as 1,3-bis(diphenylphosphino)propane nickel dichloride (dppp) NiCl2.

[0220] Also known are compounds of formula IV and compounds of formula V (wherein Y b1is a reaction between zinc halide groups, such as -ZnBr (Negishi cross coupling), as described, for example, in Synthetic Communications, 28 (2), 225-232; 1998. The reaction can be catalyzed by a palladium-based catalyst, such as, for example, (1,1'-bis(diphenylphosphino)-ferrocene)dichloropalladium Pd(dppf)Cl2 or bis(triphenylphosphine)dichloropalladium(II), optionally in the presence of a phosphine additive, such as, for example, 2-dicyclohexyl-phosphino-2',6'-dimethoxy-biphenyl S-PHOS, in a solvent such as, for example, 1,2-dimethoxyethane, dioxane, toluene, or tetrahydrofuran, preferably under an inert atmosphere. The reaction temperature can preferably range from ambient temperature to the boiling point of the reaction mixture.

[0221] In some cases, compounds of formula II wherein R3 is cyano are known, for example:

[0222] 1-[5-ethylsulfanyl-6-[5-methoxy-3-methyl-4-oxo-6-(trifluoromethyl)imidazo[4,5-c]pyridin-2-yl]-3-pyridinyl]cyclopropanecarbonitrile, CAS[2225113-68-6], WO 2018 / 077565; 1-[3-ethylsulfanyl-4-[5-methoxy-3-methyl-4-oxo-6-(trifluoromethyl)imidazo[4,5-c]pyridin-2-yl]phenyl]cyclopropanecarbonitrile, CAS[CAS[2225113-73-3], WO 2018 / 077565; 1-[4-[5-cyclopropyl-3-methyl-4-oxo-6-(trifluoromethyl)imidazo[4,5-c]pyridin-2-yl]-3-ethylsulfanyl-phenyl]cyclopropanecarbonitrile, CAS[2098699-74-0], WO 2017 / 089190; 1-[6-[5-cyclopropyl-3-methyl-4-oxo-6-(trifluoromethyl)imidazo[4,5-c]pyridin-2-yl]-5-ethylsulfanyl-3-pyridinyl]cyclopropanecarbonitrile, CAS[2098699-59-1], WO 2017 / 089190; 1-[5-ethylsulfanyl-6-[5-(trifluoromethylsulfanyl)-1,3-benzoxazol-2-yl]-3-pyridinyl]cyclopropanecarbonitrile, CAS[1975148-53-8], WO 2016 / 121997; 1-[3-ethylsulfanyl-4-[7-(trifluoromethyl)imidazo[1,2-c]pyrimidin-2-yl]phenyl]cyclopropanecarbonitrile, CAS[1923785-47-0], WO 2016 / 071214; 1-[5-ethylsulfanyl-6-[7-(trifluoromethyl)imidazo[1,2-c]pyrimidin-2-yl]-3-pyridinyl]cyclopropanecarbonitrile, CAS[1923784-42-2], WO2016 / 071214.

[0223] Other compounds of formula II (wherein R3 is cyano and R1, A and Q are as defined in formula I), i.e. compounds of formula IIb

[0224]

[0225] It can be prepared as shown in Scheme 5:

[0226] Solution 5

[0227]

[0228] As shown in Scheme 5, compounds of formula IV, wherein R1, Q and A are as defined in formula I, and wherein Xb1 is preferably halogen (even more preferably chlorine, bromine or iodine), are treated with trimethylsilyl-acetonitrile TMSCN in the presence of zinc(II) fluoride and a palladium(0) catalyst (such as tris(dibenzylideneacetone)dipalladium(0)-chloroform adduct (Pd2(dba)3), a ligand (such as Xantphos) in an inert solvent (such as DMF) at a temperature between 100-160°C, optionally under microwave heating, to produce compounds of formula VI. Such chemistry has been described in the literature, for example, in Org. Lett. [Organic Chemistry Communications], 16(24), 6314-6317; 2014. It can be prepared in the presence of a base. A compound of formula IV is treated with a compound of formula VII (wherein Xb1 is as defined above) in the presence of an inert solvent (such as DMF, acetone, or acetonitrile) to give a compound of formula IIb. Alternatively, a compound of formula IIb can be prepared directly from a compound of formula IV by treating with a compound of formula VIII with Pd2(dba)3, a ligand (such as BINAP), a strong base (such as LiHMDS) in an inert solvent (such as THF) at a temperature of 40°C-70°C. Such chemistry has been described, for example, in J. Am. Chem. Soc., 127(45), 15824-15832; 2005.

[0229] Another method for compounds of formula IIb involves reacting a compound of formula IV (wherein A, R1 and Q are as described under formula I, and wherein Xb1 is a halogen (preferably chlorine, bromine, iodine)) with 4-isoxazoleboronic acid or 4-isoxazoleboronic acid pinacol ester (a compound of formula IX) in the presence of potassium fluoride (KF) and a palladium catalyst (such as bis(triphenylphosphine)palladium(II) dichloride (Pd(PPh3)2Cl2)) in an inert solvent (such as dimethyl sulfoxide (DMSO), optionally in a mixture with water, at a temperature between 40°C and 150°C, optionally under microwave heating to produce a compound of formula IX (wherein Q, R1 and A are as described under formula I). The compound of formula IX is reacted with aqueous potassium fluoride KF (at a concentration between 0.5 and 3 M, preferably 1 M) in an inert solvent such as dimethyl sulfoxide DMSO or methanol at a temperature between 20° C. and 150° C., optionally under microwave heating, to produce a compound of formula VI (wherein A, R1 and Q are as described under formula I). ​​The conversion of a compound of formula V to a compound of formula IIb is as described above. Such a chemical process has been described in the following literature: for example J Am Chem Soc [American Chemical Society] 2011, 133, 6948-6951.

[0230] Compounds of formula IIb can be further used to prepare compounds of formula II (Scheme 6), wherein R3 is further functionalized. In practice, compounds of formula IIb (wherein A, R1, X1 and R2 are as defined in formula I above) can be partially hydrolyzed to compounds of formula IIc, or completely hydrolyzed to compounds of formula IId, under acidic or basic conditions known to those skilled in the art. Compounds of formula IIc are treated with reagents such as SF4 or Fluolead (4-tert-butyl-2,6-dimethylphenylsulfur trifluoride), optionally in the presence of HF, to produce compounds of formula IIe (as described, for example, in Organic Letters, 16, 6314-6317; 2014).

[0231] Compounds of formula (IId) wherein R1, Q and A are as defined in formula I are activated to form activated species (IIf) by methods known to those skilled in the art and described, for example, in Tetrahedron, 2005, 61 (46), 10827-10852, wherein Q, R1 and A are as defined in formula I and wherein X0 is halogen, preferably chlorine. For example, compound (IIf) wherein X0 is halogen, preferably chlorine, is formed by treating (IId) with, for example, oxalyl chloride (COCl) 2 or thionyl chloride SOCl 2 in an inert solvent such as dichloromethane CH2Cl2 or tetrahydrofuran THF in the presence of a catalytic amount of N,N-dimethylformamide DMF at a temperature between 20° C. and 100° C., preferably 25° C. Alternatively, treatment of compounds of formula (IId) with, for example, 1-ethyl-3-(3-dimethylaminopropyl)carbodiimide EDC or dicyclohexylcarbodiimide DCC at temperatures between 50°C and 180°C, optionally in the presence of a base such as triethylamine, in an inert solvent such as pyridine or tetrahydrofuran (THF) will yield activated species (XII) (wherein X0 is X 01 or X 02 ); Such activated intermediates of formula Iif can react with nucleophiles (e.g., having formula HNR 101 R 012 Amines, where R 101 and R 102 is hydrogen or C1-C6 alkyl, or HOR 103 , wherein R103 is C1-C6 alkyl) is optionally reacted in the presence of a base (e.g. triethylamine, pyridine or DMAP) in an inert solvent (e.g. CH2Cl2, THF or acetonitrile) to give a compound of formula Iig and a compound of formula Iih, respectively. Such reactions are well known to those skilled in the art. The subsequent conversion of cyanocyclopropyl is illustrated in Scheme 6.

[0232] Solution 6

[0233]

[0234] A compound of formula II (wherein Q is Q1, defining a compound of formula II-Q1,

[0235]

[0236] wherein R1, R3, R4, X1, G1 and G2 are as defined in Formula I) can be prepared as shown in Scheme 7.

[0237] Solution 7

[0238]

[0239] As shown in Scheme 7, compounds of formula II-Q1 can be prepared by cyclizing compounds of formula (XIV) (wherein R1, R3, R4, A, X1, G1 and G2 are as defined in formula I), for example by heating in acetic acid or trifluoroacetic acid (preferably when X1 is NR5, wherein R5 is C1-C4 alkyl) at a temperature of 0°C to 180°C, preferably 20°C to 150°C, optionally under microwave irradiation. Cyclization of compounds of formula (XIV) can also be achieved at a temperature between 25°C-180°C (preferably 100°C-170°C) in an inert solvent (such as N-methylpyrrolidone, toluene or xylene) in the presence of an acid catalyst (e.g., methanesulfonic acid or p-toluenesulfonic acid p-TsOH). Such methods have been previously described, for example, in WO 2016096584. Alternatively, compounds of formula (XIV) can be converted to compounds of formula II-Q1 (preferably when X1 is O) using triphenylphosphine, diisopropyl azodicarboxylate (or diethyl azodicarboxylate) in an inert solvent such as tetrahydrofuran (THF) at a temperature between 20°C and 50°C. Such Mitsunobu reaction conditions have been previously described for these transformations (see WO 2009 / 131237 and WO2016 / 121997).

[0240] Compounds of formula (XIV) wherein R1, R3, R4, A, X1, G1 and G2 are as defined in formula I can be prepared via acylation by;

[0241] i) Activating a compound of formula (XIII) wherein R1, R3 and A are as defined in formula I by methods known to those skilled in the art and described, for example, in Tetrahedron, 2005, 61 (46), 10827-10852, to form an activated species (XII) wherein R1, R3 and A are as defined in formula I and wherein X0 is halogen, preferably chlorine. For example, compound (XII) wherein X0 is halogen, preferably chlorine, is formed by treating (XIII) with, for example, oxalyl chloride (COCl) 2 or thionyl chloride SOCl 2 in an inert solvent such as dichloromethane CH2Cl2 or tetrahydrofuran THF in the presence of a catalytic amount of N,N-dimethylformamide DMF at a temperature between 20° C. and 100° C., preferably 25° C. Alternatively, treatment of compounds of formula (XIII) with, for example, 1-ethyl-3-(3-dimethylaminopropyl)carbodiimide EDC or dicyclohexylcarbodiimide DCC at temperatures between 50°C and 180°C, optionally in the presence of a base such as triethylamine, in an inert solvent such as pyridine or tetrahydrofuran (THF) will yield activated species (XII) (wherein X0 is respectively X 01 or X 02 ); then

[0242] ii) treating the activated substance (XII) with a compound of formula (XI) (wherein X1, G1, G2 and R4 are as defined in formula I) in an inert solvent (such as dichloromethane, tetrahydrofuran, dioxane, N,N-dimethylformamide, N,N-dimethylacetamide, acetonitrile, ethyl acetate or toluene) in the presence of a base (such as triethylamine, N,N-diisopropylethylamine or pyridine) at a temperature between 0°C and 50°C to form a compound of formula (XIV). Compounds of formula XIII (wherein R3 is H, i.e. compounds where R1 is ethyl, R3 is H and A is N or CH) are known and described in WO 2017146226, or WO2016121997 (for 5-cyclopropyl-3-ethylsulfanyl-pyridine-2-carboxylic acid), CAS [1975148-58-3], and WO2016023954 (for 4-cyclopropyl-2-ethylsulfanyl-benzoic acid), CAS [1879052-58-0]. Compounds of formula XIII wherein R3 is cyano, R1 is ethyl and A is CH(4-(1-cyanocyclopropyl)-2-ethylsulfanyl-benzoic acid, CAS [2225113-79-9])) and compounds of formula XIII wherein R3 is cyano, R1 is ethyl and A is N(5-(1-cyanocyclopropyl)-3-ethylsulfanyl-pyridine-2-carboxylic acid, CAS [2225113-77-7])) are known and described in WO 2018 / 077565.

[0243] Compounds of formula (XI), wherein X1, G1, G2 and R2 are as defined in formula I, have been previously described in, for example, WO 2012 / 086848, WO 2015 / 000715 and WO 2016 / 116338.

[0244] A compound of formula II, wherein Q is Q2, defining a compound of formula II-Q2,

[0245] wherein R1, R3, R4, A and G2 are as defined in Formula I,

[0246] Solution 8

[0247]

[0248] It can be prepared by condensing a compound of formula (XVI) wherein R1, R3 and A are as defined in formula I and wherein Xc is a leaving group such as chlorine, bromine or iodine (preferably chlorine or bromine) with a compound of formula (XVI) wherein G2 and R2 are as defined in formula I in an inert solvent such as ethanol or acetonitrile, optionally in the presence of a suitable base such as sodium carbonate, potassium carbonate or cesium carbonate, at a temperature of 80° C. to 150° C., optionally under microwave heating conditions (Scheme 8). Such methods have been previously described, for example, in WO 2012 / 49280 or WO 2003 / 031587. Compounds of formula (XV) wherein G2 and R2 are as defined in formula I are either known compounds, commercially available, or can be prepared by known methods known to those skilled in the art.

[0249] A compound of formula (XVI) wherein R1, R3 and A are as defined in formula I, and wherein Xc is a leaving group, such as chlorine, bromine or iodine (preferably chlorine or bromine),

[0250] Solution 9

[0251]

[0252] The halogenating agent ("Xc + " source" (e.g., N-bromosuccinimide, N-iodosuccinimide, N-chlorosuccinimide, I2, CuBr2, Br2 / acetic acid, PhNMe3 + Br3 -) is treated with a compound of formula (XVIII) (wherein R1, R3 and A are as defined in formula I) (Scheme 9). Such methods have been previously described, for example, in WO 2016 / 071214.

[0253] Compounds of formula (XVIII) (wherein R1, R3 and A are as defined in formula I) can be prepared by reacting compounds of formula (XVII) (wherein R1 and A are as defined in formula I, and wherein 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).

[0254] Compounds of formula (XVII) (wherein R1 and A are as defined in formula I and wherein Xa is a leaving group, such as chlorine, bromine or iodine), in particular those wherein Xa is halogen (even more preferably chlorine, bromine or iodine; particularly preferred is chlorine or bromine) are known compounds, commercially available or can be prepared by known methods described in the literature (e.g. in WO 2016 / 071214).

[0255] Alternatively, a compound of formula II (wherein Q is Q5), defining a compound of formula II-Q5 (wherein R1, R3, R4, R6 and A are as defined in formula I),

[0256] Scheme 9a :

[0257]

[0258] It can be prepared by cyclizing a compound of formula (XXa) (wherein R1, R3, R4, R5, R6 and A are as defined in formula I) or a regioisomer of formula (XXb) having the same substituent definition, or a mixture thereof in any ratio under the conditions described above (see Scheme 7, conversion of compound (XIV) to II-Q1) (Scheme 9a).

[0259] Compounds of formula (XXa) (wherein R1, R3, R4, R5, R6 and A are as defined in formula I), or regioisomers of formula (XXb) having the same substituent definitions, or mixtures thereof in any ratio can be prepared by treating the above-mentioned activated substance (XII) with a compound of formula (XIX) (wherein R4, R5 and R6 are as defined in formula I) under the conditions already described above (see Scheme 7, conversion of compounds (XII) and (XIII) to compound (XIV)).

[0260] Compounds of formula (XIX), wherein R4, R5 and R6 are as defined in formula I, have been previously described in, for example, WO 2016 / 023954, WO 2016 / 142326, WO 2017 / 133994 and WO 2018077565.

[0261] Alternatively, a compound of formula II (wherein Q is Q3), defining a compound of formula II-Q3 (wherein R1, R4, R3 and A are as defined in formula I),

[0262] Solution 10

[0263]

[0264] It can be prepared by condensing the above compounds of formula (XVI) (wherein R1, R3 and A are as defined in formula I, and wherein Xc is a leaving group, such as chlorine, bromine or iodine (preferably chlorine or bromine)) with compounds of formula (XXI) (wherein R4 is as defined in formula I) in an inert solvent (e.g. ethanol, toluene or acetonitrile), optionally in the presence of a suitable base (e.g. sodium carbonate, potassium carbonate or cesium carbonate (or sodium bicarbonate or potassium bicarbonate)) or magnesium oxide at a temperature between 80 and 150° C., optionally under microwave heating conditions (Scheme 10). Such methods have been previously described, for example, in WO 2011 / 074658. Compounds of formula (XXI) (wherein R4 is as defined in formula I) are either known compounds, commercially available or can be prepared by known methods known to those skilled in the art (see, for example, WO 2011 / 074658 and WO 2010 / 083145).

[0265] A compound of formula II, wherein Q is Q4, defining a compound of formula II-Q4,

[0266]

[0267] wherein R1, R3, R4, G1, G2 and A are as defined in formula I,

[0268] Solution 11

[0269]

[0270] It can also be prepared by the N-N bond formation reaction of the azidoimine of the compound of formula (XXV) (wherein R1, R4, R7, R8, A, G1, G2 and R2 are as defined in formula I) under pyrolysis conditions that promote N2 discharge (Scheme 11). Alternatively, the reaction can be carried out in the presence of a metal catalyst (e.g., a Cu(I) catalyst such as CuI, CuBr, CuCl or CuCN), or more generally in combination with a transition metal and a ligand such as tetramethylethylenediamine, 2,2'-bipyridine or 1,10-phenanthroline. Suitable solvents may include toluene, chlorobenzene or xylene at temperatures between room temperature and 200°C, preferably between 100°C and 160°C, optionally under microwave heating conditions. Such reductive cyclization reaction conditions are described, for example, in Organic Letters, 2011, Vol. 13, No. 13, 3542-3545 and US 2017 / 0260183,

[0271] Compounds of formula (XXV) (wherein R1, R3, R4, G1, G2 and A are as defined in formula I) can be prepared by reaction between a compound of formula (XXIII) (wherein R1, R3 and A are as defined in formula I) and a compound of formula (XXIV) (wherein G1, G2 and R4 are as defined in formula I) in a suitable solvent (which may include, for example, toluene or xylene) by heating, typically at a temperature between room temperature and 200° C. (preferably between 40 and 160° C.), optionally under microwave heating conditions. The formation of compounds of formula (XXV) may require removal of water by azeotropic distillation or with a desiccant (such as, for example, TiCl4 or molecular sieves). Such formation of Schiff bases of formula (XXV) is known to those skilled in the art and is described, for example, in WO 2017 / 134066. Compounds of formula XXIV are reported in the literature (see CAS 2211908-96-0 reported in WO 2018 / 052136).

[0272] Compounds of formula XXIII can be prepared by reacting compounds of formula XXII in the presence of an acid (e.g., HCl, H2SO4, H3PO4, HNO3, TFA). Deprotection reactions of such N-linked carbamates are well known to those skilled in the art and are described, for example, in RSC Advances [Journal of the Royal Society of Chemistry], 5(5), 3200-3205; 2015.

[0273] Compounds of formula XXII can be prepared by reacting compounds of formula XIII with an organic azide or an amine derivative (e.g. NH4OH, NH3, NH2Boc) in the presence of a suitable base and in the presence or absence of a Lewis acid and a solvent at a temperature between 50°C and 200°C. Examples of organic azides include TMSN3, sodium azide, diphenylphosphoryl azide or tosyl azide and suitable solvents may be t-BuOH, toluene, xylene, THF or acetonitrile. Examples of suitable Lewis acids may include Zn(OTf)2. Such reactions for converting carboxylic acids into amines are well known to those skilled in the art under the name Curtius reaction and are reported in Org. Lett. [Organic Express], 2005, 7, 4107-4110; Journal of Medicinal Chemistry [Medicinal Chemistry Journal], 49(12), 3614-3627; 2006.

[0274] Alternatively, a compound of formula II-Q4 wherein R1, R3, R4, G1, G2 and A are as defined in formula I can be prepared by reacting a compound of formula (XXVI) wherein R4, G1, G2 are as defined in formula I and wherein L G A leaving group (e.g., such as chlorine, bromine or iodine (preferably chlorine or bromine), or an aryl-, alkyl- or halogenated alkylsulfonate (e.g., trifluoromethanesulfonate)) and a compound of formula (XXVII) (wherein G1, G2 and R4 are as defined in formula I) in the presence of a base (e.g., such as cesium carbonate, sodium carbonate, potassium carbonate or lithium carbonate, or sodium hydride), optionally in the presence of a metal catalyst (e.g., copper (I) iodide or palladium catalyst), with or without additives (e.g., L-proline, N,N'-dimethylethylenediamine or phosphorus-based ligands), in an inert solvent (e.g., acetonitrile, N,N-dimethylformamide, N-methyl-2-pyrrolidone or dimethyl sulfoxide), at a temperature between room temperature and 200° C., optionally under microwave heating conditions. Such aromatic nucleophilic substitution reaction conditions are described, for example, in WO 2017 / 134066. Compounds of formula XXVII can be obtained by Sandmeyer reaction (i.e., diazotization of compound XXIII with NaNO or tBu-ONO in an inert solvent such as t-BuOH or water followed by addition of an inorganic halide such as CuBr, CuCl, or KI). Such Sandmeyer reactions are well known in the literature (see, for example, Synthesis, 2007, 2534-2538, Org. Lett., 2008, 10, 3961-3964) and references cited therein.

[0275] The reactants may be reacted in the presence of a base. Examples of suitable bases are alkali metal or alkaline earth metal hydroxides, alkali metal or alkaline earth metal hydrides, alkali metal or alkaline earth metal amides, alkali metal or alkaline earth metal alkoxides, alkali metal or alkaline earth metal acetates, alkali metal or alkaline earth metal carbonates, alkali metal or alkaline earth metal dialkylamides or alkali metal or alkaline earth metal alkylsilylamides, alkylamines, alkylenediamines, free or N-alkylated saturated or unsaturated cycloalkylamines, basic heterocycles, ammonium hydroxides and carbocyclic amines. Examples which may be mentioned are sodium hydroxide, sodium hydride, sodium amide, sodium methoxide, sodium acetate, sodium carbonate, potassium tert-butoxide, potassium hydroxide, potassium carbonate, potassium hydride, lithium diisopropylamide, potassium bis(trimethylsilyl)amide, calcium hydride, triethylamine, diisopropylethylamine, triethylenediamine, cyclohexylamine, N-cyclohexyl-N,N-dimethylamine, N,N-diethylaniline, pyridine, 4-(N,N-dimethylamino)pyridine, quinuclidine, N-methylmorpholine, benzyltrimethylammonium hydroxide and 1,8-diazabicyclo[5.4.0]undec-7-ene (DBU).

[0276] These reactants can react with each other as is, i.e. without adding solvent or diluent. However, in most cases, it is advantageous to add an inert solvent or diluent or a mixture of these. If the reaction is carried out in the presence of a base, the base used in excess (such as triethylamine, pyridine, N-methylmorpholine or N,N-diethylaniline) can also serve as a solvent or diluent.

[0277] The reaction is advantageously carried out at a temperature of from about -80°C to about +140°C, preferably from about -30°C to about +100°C, and in many cases at a temperature between ambient temperature and about +80°C.

[0278] A compound of the formula I can be converted into another compound of the formula I in a manner known per se by replacing one or more substituents of the starting compound of the formula I with another or other substituent or substituents according to the invention in a customary manner.

[0279] Depending on the reaction conditions and the starting materials chosen which are appropriate in the respective case, it is possible, for example, to replace only one substituent with another substituent according to the invention in one reaction step or to replace several substituents with further substituents according to the invention in one and the same reaction step.

[0280] Salts of compounds of formula I can be prepared in a manner known per se. Thus, for example, acid addition salts of compounds of formula I are obtained by treatment with a suitable acid or a suitable ion exchanger reagent, and salts with bases are obtained by treatment with a suitable base or with a suitable ion exchanger reagent.

[0281] Salts of compounds of the formula I can be converted in a customary manner into the free compounds I, acid addition salts (for example by treatment with suitable basic compounds or with suitable ion exchanger reagents) and salts with bases (for example by treatment with suitable acids or with suitable ion exchanger reagents).

[0282] Salts of compounds of formula I can be converted into other salts, acid addition salts of compounds of formula I in a manner known per se, for example into other acid addition salts, for example by treating salts of inorganic acids (such as hydrochlorides) with suitable metal salts of the acid (such as sodium, barium or silver salts, for example with silver acetate) in a suitable solvent in which the inorganic salt formed (such as silver chloride) is insoluble and therefore precipitates from the reaction mixture.

[0283] Depending on the procedure or reaction conditions, those compounds of the formula I which have salt-forming properties can be obtained in free form or in the form of salts.

[0284] Depending on the number of asymmetric carbon atoms present in the molecule, the absolute and relative configuration and / or on the configuration of non-aromatic double bonds present in the molecule, the compounds of the formula I and, where appropriate, their tautomers, in each case in free form or in salt form, may be present in the form of one of the possible isomers or as a mixture of these, for example in the form of pure isomers, such as enantiomers and / or diastereomers, or as isomer mixtures, such as enantiomeric mixtures, for example racemates, diastereomeric mixtures or racemic mixtures; the invention relates to the pure isomers and also to all possible isomer mixtures, and the above and below are to be understood as such in each case, even if stereochemical details are not explicitly mentioned in each case.

[0285] Diastereomeric mixtures or racemic mixtures of compounds of formula I in free form or in salt form, which can be obtained depending on the starting materials and procedures chosen, can be separated in a known manner into the pure diastereomers or racemates on the basis of the physicochemical differences of the components, for example by fractional crystallization, distillation and / or chromatography.

[0286] Enantiomeric mixtures that can be obtained in an analogous manner (such as racemates) can be resolved into the optical antipodes by known methods, for example by recrystallization from optically active solvents; by chromatography on chiral adsorbents, such as high performance liquid chromatography (HPLC) on acetylcellulose; by cleavage with specific immobilized enzymes with the aid of suitable microorganisms; by forming containing compounds, for example using chiral crown ethers, in which only one enantiomer is complexed; or by conversion into diastereomeric salts, for example by reacting the basic end product racemate with an optically active acid (such as a carboxylic acid, such as camphoric acid, tartaric acid or malic acid, or a sulfonic acid, such as camphorsulfonic acid), and separating the diastereomeric mixture that can be obtained in this way, for example by fractional crystallization based on their different solubility, thereby obtaining the diastereomers from which the desired enantiomer can be freed by the action of a suitable reagent (such as a basic reagent).

[0287] Pure diastereomers or enantiomers can be obtained according to the invention not only by separation of the appropriate isomer mixtures but also by generally known methods of diastereoselective or enantioselective synthesis, for example by carrying out the method according to the invention with starting materials having the appropriate stereochemistry.

[0288] N-oxides can be prepared by reacting a compound of formula I with a suitable oxidizing agent (e.g. H O / urea adduct) in the presence of an anhydride (e.g. trifluoroacetic anhydride). Such oxidations are known from the literature, for example from J. Med. Chem. [Journal of Medicinal Chemistry], 32 (12), 2561-73, 1989 or WO 2000 / 15615.

[0289] If the individual components have different biological activities, it is advantageous to separate or synthesize the biologically more effective isomers, such as enantiomers or diastereomers or isomer mixtures, such as enantiomeric mixtures or diastereomeric mixtures, in each case.

[0290] If appropriate, the compounds of the formula I and, where appropriate, their tautomers (in each case in free form or in salt form) can also be obtained in the form of hydrates and / or include further solvents, such as those which can be used for crystallization of compounds present in solid form.

[0291] The following compounds of formula I according to the following groups Y-1 to Y-8, X-1 to X-8, U-1 to U-2 and V-1 to V-6 can be prepared according to the above methods. The following examples are intended to illustrate the invention and show preferred compounds of formula I.

[0292] Groups Y-1 to Y-8 refer to compounds having the following formula

[0293]

[0294] Table Z: Definition of substituents of R3 and R4:

[0295] index <![CDATA[R4]]> R3 1 <![CDATA[CF3]]> CN 2 <![CDATA[SCF3]]> CN 3 <![CDATA[SO2CF3]]> CN 4 <![CDATA[CF3]]> H 5 <![CDATA[SCF3]]> H 6 <![CDATA[SO2CF3]]> H 7 <![CDATA[CF3]]> <![CDATA[CONH2]]> 8 <![CDATA[SCF3]]> <![CDATA[CONH2]]>

[0296] Group Y-1 8 compounds Y-1.001 to Y-1.008 of formula IaY are provided, wherein A is CH, G1 is CH, G2 is CH, and R3, R4 are as defined in Table Z.

[0297] For example, compound Y-1.001 has the following structure;

[0298]

[0299] Group Y-2 8 compounds Y-2.001 to Y-2.008 of formula IaY are provided, wherein A is CH, G1 is CH, G2 is N, and R3, R4 are as defined in Table Z.

[0300] For example, compound Y-2.001 has the following structure;

[0301]

[0302] Group Y-3 provides 8 compounds Y-3.001 to Y-3.008 of formula IaY, wherein A is CH, G1 is N, G2 is CH, and R3, R4 are as defined in Table Z.

[0303] For example, compound Y-3.001 has the following structure;

[0304]

[0305] Group Y-4 Provided are 8 compounds Y-4.001 to Y-4.008 of formula IaY wherein A is CH, G1 is N, G2 is N, and R3, R4 are as defined in Table Z.

[0306] For example, compound Y-4.001 has the following structure;

[0307]

[0308] Group Y-5 8 compounds Y-5.001 to Y-5.008 of formula IaY are provided, wherein A is N, G1 is CH, G2 is CH, and R3, R4 are as defined in Table Z.

[0309] For example, compound Y-5.001 has the following structure;

[0310]

[0311] Group Y-6 Provided are 8 compounds Y-6.001 to Y-6.008 of formula IaY wherein A is N, G1 is CH, G2 is N, and R3, R4 are as defined in Table Z.

[0312] For example, compound Y-6.001 has the following structure;

[0313]

[0314] Group Y-7 Provided are 8 compounds Y-7.001 to Y-7.008 of formula IaY, wherein A is N, G1 is N, G2 is CH, and R3, R4 are as defined in Table Z.

[0315] For example, compound Y-7.001 has the following structure;

[0316]

[0317] Group Y-8 Provided are 8 compounds Y-8.001 to Y-8.008 of formula IaY, wherein A is N, G1 is N, G2 is N, and R3, R4 are as defined in Table Z.

[0318] For example, compound Y-8.001 has the following structure;

[0319]

[0320] Groups X-1 to X-8 refer to compounds having the following formula

[0321]

[0322] Group X-1 8 compounds X-1.001 to X-1.008 of formula lax are provided, wherein A is CH, G1 is CH, G2 is CH, and R3, R4 are as defined in Table Z.

[0323] For example, compound X-1.001 has the following structure;

[0324]

[0325] Group X-2 Provided are 8 compounds X-2.001 to X-2.008 of formula lax, wherein A is CH, G1 is CH, G2 is N, and R3, R4 are as defined in Table Z.

[0326] Group X-3 8 compounds X-3.001 to X-3.008 of formula lax are provided, wherein A is CH, G1 is N, G2 is CH, and R3, R4 are as defined in Table Z.

[0327] Group X-4 Provided are 8 compounds X-4.001 to X-4.008 of formula lax wherein A is CH, G1 is N, G2 is N, and R3, R4 are as defined in Table Z.

[0328] Group X-5 Provided are 8 compounds X-5.001 to X-5.008 of formula lax, wherein A is N, G1 is CH, G2 is CH, and R3, R4 are as defined in Table Z.

[0329] Group X-6 There are provided 8 compounds X-6.001 to X-6.008 of Formula Ib wherein A is N, G1 is CH, G2 is N, and R3, R4 are as defined in Table Z.

[0330] Group X-7 Provided are 8 compounds X-7.001 to X-7.008 of Formula Ib wherein A is N, G1 is N, G2 is CH, and R3, R4 are as defined in Table Z.

[0331] Group X-8 Provided are 8 compounds X-8.001 to X-8.008 of Formula Ib wherein A is N, G1 is N, G2 is N, and R3, R4 are as defined in Table Z.

[0332] The following groups V-1 to V-6 illustrate specific compounds of the invention having formula I (wherein R2 is H, and n is 1).

[0333]

[0334] Group V-1 9 compounds V-1.001 to V-1.009 having Formula I are provided, wherein A is CH, R3 is CN, and Q is as defined in Table W.

[0335] Table W: Definition of substituents for Q:

[0336]

[0337]

[0338] For example, compound V-1.002 has the following structure:

[0339]

[0340] Group V-2 Provided are 9 compounds V-2.001 to V-2.009 of Formula I wherein A is N, R3 is CN, and Q is as defined in Table W.

[0341] For example, compound V-2.005 has the following structure:

[0342]

[0343] Group V-3 9 compounds V-3.001 to V-3.009 of Formula I are provided wherein A is CH, R3 is H, and Q is as defined in Table W.

[0344] For example, compound V-3.008 has the following structure:

[0345]

[0346] Group V-4 Provided are 9 compounds V-4.001 to V-4.009 of Formula I wherein A is N, R3 is H, and Q is as defined in Table W.

[0347] For example, compound V-4.001 has the following structure:

[0348]

[0349] Group V-5 Provided are 9 compounds V-5.001 to V-5.009 of Formula I wherein A is CH, R3 is CONH2, and Q is as defined in Table W.

[0350] For example, compound V-5.007 has the following structure:

[0351]

[0352] Group V-6 Provided are 9 compounds V-6.001 to V-6.009 of Formula I wherein A is N, R3 is CONH2, and Q is as defined in Table W.

[0353] For example, compound V-6.006 has the following structure:

[0354]

[0355] Group U-1 to U-2 refer to compounds having the following formula

[0356]

[0357] Group U-1 8 compounds U-1.001 to U-1.008 of formula IaU are provided, wherein A is CH, and R3, R4 are as defined in Table Z.

[0358] For example, compound U-1.001 has the following structure;

[0359]

[0360] Group U-2 8 compounds U-2.001 to U-2.008 of formula IaU are provided, wherein A is N, and R3, R4 are as defined in Table Z.

[0361] The compounds of formula I according to the invention are active ingredients of preventive and / or therapeutic value in the field of pest control, even at low application rates, they have a very favorable biocidal spectrum and are well tolerated by warm-blooded species, fish and plants. These active ingredients according to the invention act on all or individual developmental stages of normally sensitive and also resistant animal pests (such as representatives of insects, molluscs, nematodes or Acarina). The insecticidal, molluscicidal, nematicidal or acaricidal activity of the active ingredient according to the invention can be directly displayed per se, i.e., the destruction of the pest occurs immediately or only after some time has passed (e.g., during molting); or indirectly, for example, a good activity corresponding to the destruction rate (mortality) of at least 50% to 60% is displayed, for example, by reducing the egg-laying and / or hatching rate.

[0362] The compounds of formula (I) according to the present invention may have any number of benefits, including in particular favorable levels of biological activity for protecting plants against insects or superior properties (e.g., higher biological activity, favorable activity spectrum, increased safety, improved physico-chemical properties, or increased biodegradability or environmental profile) for use as agrochemical active ingredients. Specifically, it has been unexpectedly found that certain compounds of formula (I) show favorable safety relative to non-target organisms, such as non-target arthropods, particularly pollinators (such as honey bees, solitary bees and bumblebees). Most particularly, relative to Apis mellifera.

[0363] In this respect, certain compounds of the invention having formula (I) may be distinguished from known compounds by a greater efficacy at low application rates, which can be demonstrated by a person skilled in the art using experimental procedures similar to or adapted from those outlined in the Biological Examples, using lower application rates (if necessary) such as, for example, 50 ppm, 12.5 ppm, 6 ppm, 3 ppm, 1.5 ppm, 0.8 ppm or 0.2 ppm.

[0364] In addition, it has been unexpectedly found that compounds of formula (I) show favorable physicochemical properties for crop protection applications, in particular reduced melting point, reduced lipophilicity and increased water solubility. Such properties have been found to be advantageous for plant absorption and systemic distribution, see, for example, A. Buchholz, S. Trapp, Pest Management (PestManag Sci) 2016; 72: 929-939) to control certain pest species listed below.

[0365] Examples of the above-mentioned animal pests are:

[0366] From the order Acarina, e.g.

[0367] Acalitus spp., Aculus spp., Acaricalus spp., Aceria spp., Acarus siro, Amblyomma spp., Argas spp., Boophilus spp., Brevipalpus spp., Bryobia spp., Calipitrimerus spp., Chorioptes spp., Dermanyssusgallinae, Dermatophagoides spp., Eotetranychus spp., Eriophyes spp.), Hemitarsonemus spp., Hyalomma spp., Ixodes spp., Olygonychus spp., Ornithodoros spp., Polyphagotarsone latus, Panonychus spp., Phyllocoptruta oleivora, Phytonemus spp., Polyphagotarsonemus spp., Psoroptes spp., Rhipicephalus spp., Rhizoglyphus spp., Sarcoptes spp.), Steneotarsonemus spp., Tarsonemus spp., and Tetranychus spp.;

[0368] From the order Phthirus, e.g.

[0369] Haematopinus spp., Linognathus spp., Pediculus spp., Pemphigus spp., and Phylloxera spp.;

[0370] From the order Coleoptera, e.g.

[0371] Agriotes spp., Amphimallon majale, Anomala orientalis, Anthonomus spp., Aphodius spp., Astylus atromaculatus, Ataenius spp., Atomaria linearis, Chaetocnema tibialis, Cerotomaspp., Conoderus spp., Cosmopolites spp., Cotinis nitida, Curculio spp., Cyclocephalaspp., Dermestes spp., Diabrotica spp.), Diloboderus abderus, Epilachna spp., Eremnus spp., Heteronychus arator, Hypothenemus hampei, Lagria vilosa, Leptinotarsa ​​decemlineata, Lissorhoptrus spp., Liogenys spp., Maecolaspis spp., Maladera castanea, Megascelis spp., Melighetes aeneus, Melolontha spp., Myochrousarmatus, Orycaephilus spp., Otiorhynchus spp., Phyllophaga spp.), Phlyctinus spp., Popillia spp., Psylliodes spp., Rhyssomatus aubtilis, Rhizopertha spp., Scarabeidae, Sitophilus spp., Sitotroga spp.), Somaticus spp., Sternechus subsignatus, Tenebrio spp., Tribolium spp., and Trogoderma spp.;

[0372] From the order Diptera, e.g.

[0373] Aedes spp., Anopheles spp., Antherigonas occata., Bactrocea oleae, Bibio hortulanus, Bradysia spp., Calliphora erythrocephala, Ceratitis spp., Chrysomyia spp., Culex spp., Cuterebra spp., Dacus spp., Delia spp., Drosophilamelanogaster, Fannia spp., Gastrophilus spp., Geomyza tripunctata, Glossina spp.), Hypoderma spp., Hyppobosca spp., Liriomyza spp., Lucilia spp., Melanagromyza spp., Musca spp., Oestrus spp., Orseolia spp., Oscinella frit, Pegomyia hyoscyami, Phorbia spp., Rhagoletis spp., Rivelia quadrifasciata, Scatella spp., Sciara spp., Stomoxys spp., Tabanus spp., Tannia spp.) and Tipula spp.;

[0374] From the order Hemiptera, e.g.

[0375] Acanthocoris scabrator, Green stink bug, Alfalfa blind bug, Amblypeltanitida, Bathycoelia thalassina, Soil stink bug, Cockspur, Clavigralla tomentosicollis, Creontiades spp., Cocoa stink bug, Dichelops furcatus, Cotton red stink bug, Edessa, Euschistus spp., Eurydema pulchrum, Flat shield bug, Tea winged stink bug, Horcias nobilellus, Rice stink bug, Lygus, Tropical scale, Murgantiahistrionic, Neomegalotomus, Nesidiocoris tenuis), green stink bugs, Nysius simulans, Oebalus insularis, skin stink bugs, wall stink bugs, red assassin bugs, cocoa stink bugs, Scaptocoris castanea, black stink bugs (Scotinophara spp.), Thyanta spp., trypanosoma spp., cassava web stink bugs (Vatigailludens);

[0376] Acyrthosium pisum, Adalges species, Agallina ensigera, Targuilon vein psyllid, Aleurodicus species, Aleurocanthus species, Sugarcane hole whitefly, Aleurothrixus floccosus, Aleyrodes brassicae, Amarasca biguttula, Citrus long-spiked leafhopper, Nephrodactylus species, Aphididae, Aphid species, Aspidiotus species, Solanum grove netless aphid, Bactericera cockerelli, Aleurodicus species, Brachycaudus species, Cabbage aphid, Cavariella species, Cavariella aegopodii Scop.), wax scale species, black brown round shield scale, orange brown round shield scale, leafhopper species, large white leafhopper (Cofana spectra), Cryptomyxodon species, leafhopper species, brown soft scale, corn yellow-winged leafhopper, naked whitefly species, citrus psyllid, wheat aphid, western round tail aphid species, small green leafhopper species, apple aphid, grape leafhopper species, Gascardia species, red eucalyptus psyllid (Glycaspis brimblecombei), vegetable constriction aphid (Hyadaphispseudobrassicae), large tail aphid species (Hyalopterus spp.), hyperomyzuspallidus species (Hyperomyzuspallidus), lemon fruit green leafhopper (Idioscopus clypealis), African leafhopper, Laodelphax species, water and soil hard scale, oyster shield scale species, radish aphid (Lopaphis erysimi), Lyogenys maidis, Aphids spp., Metcalfa pruinosa, Aphids spp., Aphids spp., Neotoxoptera sp., Nilaparvata spp., Nilaparvata spp.), pear green aphid, Odonaspis ruthae, sugarcane cotton aphid, bayberry whitefly, Caulis psyllid, spp. of shield scale, spp. of gall aphid, corn wax cicada, spp. of flat horned planthopper, spp. of warty aphid, spp. of root nodule aphid, spp. of Mosella, spp. of white scale, spp. of mealybug, spp. of cotton blind bug (Pseudatomoscelis seriatus), spp. of psyllid, spp. of cotton scale (Pulvinaria aethiopica), spp. of toothed shield scale, spp. of Quesada gigas, spp. of electric light leafhopper (Reciliadorsalis), spp. of constricted tube aphid, spp. of black helmet scale, spp. of banded leafhopper, spp. of dichotomous aphid, spp. of wheat aphid (Sitobion spp.), white-backed planthopper, Spissistilus festinus, Tarophagus Proserpina), aphid species, whitefly species, Tridiscus sporoboli, Trionymus spp., African psyllids, scutellaria spp., flame leafhoppers, Zyginidia scutellaris;.

[0377] From the order Hymenoptera, e.g.

[0378] Acromyrmex, Arge spp., Atta spp., Cephus spp., Diprion spp., Diprionidae, Gilpinia polytoma, Hoplocampa spp., Lasius spp., Monomorium pharaonis, Neodiprions spp., Pogonomyrmex spp., Fire ants, Solenopsis spp., and Vespa spp.

[0379] From the order Isoptera, e.g.

[0380] Coptotermes spp., Corniternes cumulans, Incisitermes spp., Macrotermes spp., Mastotermes spp., Microtermes spp., Reticulitermes spp.; Tropical fire ant (Solenopsis geminate)

[0381] From the order Lepidoptera, for example,

[0382] Species of the genus Long-winged Tortoise, Species of the genus Brown-banded Tortoise, Species of the genus Clearwing, Species of the genus Spodoptera, Cotton leafworm, Species of the genus Amylois, Bean armyworm, Species of the genus Yellow-winged Tortoise, Species of the genus Argyresthia, Species of the genus Banded Tortoise, Species of the genus Spodoptera, Cotton miner, Corn armyworm, Powderyngium striata, Peach fruit moth, Species of the genus Graminus, Species of the genus Colored Tortoise, Chrysoteuchia topiaria, Grape fruit moth, Species of the genus Leaffolder, Species of the genus Cloud-winged Tortoise, Species of the genus Sheath moth, Colias lesbia, Cosmophila flava), Sesamia species, Greater cabbage borer, Apple anomaly, Boxwood moth, Herpetogramma species, Boxwood moth, Herpetogramma species, Sudan bollworm, Spodoptera species, Sweet potato stem borer, Alopecurus species, Epinotia spp., Estigmene acrea, Etiella zinckinella, Flower tortoise species, Ring needle tortoise, Yellow tussock species, Cutworm species, Feltia jaculiferia, Grapholitas pp., Cloudy broad-winged tortoise, Spodoptera species, Cabbage borer, Herpetogramma spp., White moth, Tomato borer, Lasmopalpus lignosellus, Leafminer, Leafminer species, Grape flower tortoise, Loxostege bifidalis, Lymantria species, Mining moth species, Malacosoma spp., Cabbage armyworm, Manduca sexta, Mythimna spp., Noctuidae species, Fall geometrid species, Orniodes indica, European corn borer, Microcotyle species, Brown tortoise species, Small-eyed moth, Stem borer, Red bell moth, Coffee leaf miner, One-star armyworm, Potato moth, Pieris rapae, Pieris species, Plutella xylostella, White nest moth species, Geometridae species, Rachiplusia nu, Richia albicosta, Scirpophaga species spp.), Spodoptera species, Cynocephala species, Spodoptera species, Cotton leaf folder, Hymenoptera species, Heteroptera species, Cynocephala species, Trichoplusia species, Liriomyza species, and Lymantria species;

[0383] From the order Mallophaga, for example,

[0384] Damalina spp. and Trichodectes spp.;

[0385] From the order Orthoptera, for example,

[0386] Blatta spp., Blattella spp., Gryllotalpa spp., Leucophaea maderae, Locusta spp., Neocurtilla hexadactyla, Periplaneta spp., Scapteriscus spp., and Schistocerca spp.;

[0387] From the order Psocoptera, for example,

[0388] Liposcelis spp.;

[0389] From the order of the Siphonaptera, for example,

[0390] Ceratophyllus spp., Ctenocephalides spp. and Xenopsylla cheopis;

[0391] From the order of the Thysanoptera, for example,

[0392] Calliothrips phaseoli, Frankliniella spp., Heliothrips spp., Hercinothrips spp., Parthenothrips spp., Scirtothrips aurantii, Sericothrips variabilis, Taeniothrips spp., Thrips spp.;

[0393] From the order of the Thysanura, for example, Lepisma saccharina.

[0394] The active ingredients according to the invention can be used for controlling, i.e. suppressing or destroying pests of the abovementioned type, which occur in particular on plants, especially on useful and ornamental plants in agriculture, in horticulture and in forestry, or on organs of these plants, such as fruits, flowers, leaves, stems, tubers or roots, and in some cases even plant organs formed at a later point in time still remain protected against these pests.

[0395] In particular, suitable target crops are cereals, such as wheat, barley, rye, oats, rice, corn or sorghum; beets, such as sugar beets or fodder beets; fruits, such as pome, drupe or soft fruit, such as apples, pears, plums, peaches, apricots, cherries or berries, such as strawberries, raspberries or blackberries; leguminous crops, such as beans, lentils, peas or soybeans; oil crops, such as rape, mustard, olives, sunflowers, coconuts, castor beans, cocoa beans or groundnuts; melon crops, such as pumpkin, cucumber or melon; fiber plants, such as cotton, flax or jute; citrus fruits, such as oranges, lemons, grapefruits or tangerines; vegetables, such as spinach, lettuce, asparagus, cabbage, carrots, onions, tomatoes, potatoes or bell peppers; Lauraceae, such as avocado, cinnamon or camphor; and also tobacco, nuts, coffee, eggplant, sugar cane, tea, pepper, grapevines, hops, plantaginaceae and latex plants.

[0396] The compositions and / or methods of the invention may also be used on any ornamental and / or vegetable crops, including flowers, shrubs, broadleaf trees and evergreen plants.

[0397] For example, the present invention can be used in any of the following ornamental plant species: Ageratum species, Alonsoa spp., Anemone species, Anisodontea capsenisis, Anthemis species, Antirrhinum species, Aster species, Begonia species (e.g., Rieger Begonia, Begonia sempervivum, Begonia tubéreux), Bougainvillea species, Brachycome spp., Brassica species (ornamental plants), Calceolaria species, Capsicum, Catharanthus roseus, Canna species, Centaurea species, Chrysanthemum species, Cineraria species (C. maritime), Coreopsis species, Crassula coccinea, Cupheaignea, Dahlia species, Delphinium species, Dicentra species, Dorotheantus species. spp.), Eustoma, Forsythia, Fuchsia, Geranium, Geranium, Geranium gnaphalium, Gerbera, Globe amaranth, Heliotropium, Hibiscus, Hydrangea, Hydrangea, Iris, Impatiens, Iresines, Kalanchoe, Lantana, March flower, Lion's ear, Lilium, Mesembryanthemum, Physalis, Monarda, Tagetes, Dianthus, Canna, Oxalis, Daisy, Geranium, Viola, Petunia, Nerium, Plecthranthus spp.), poinsettia, creeper (parthenocissus quinquefolia, Parthenocissus tricuspidata), primrose, ranunculus, azalea, rosa (rose), rudbeckia, African violet, salvia, Scaevola aemola, Schizanthus wisetonensis, sedum, Solanum, Surfinia spp., marigold, tobacco, verbena, zinnia, and other bedding plants.

[0398] For example, the present invention can be used with any of the following vegetable species: Allium species (garlic, onion, A.oschaninii, leek, shallot, scallion), fennel, celery (Apium graveolus), asparagus, beets, Brassica species (cabbage, Chinese cabbage, turnip), peppers, chickpeas, endive, chicory species (chicory, endive), watermelon (Citrillus lanatus), Cucumber species (cucumber, melon), Cucurbita species (zucchini, Indian pumpkin), Cyanara spp. (artichoke, cardoon), wild carrot, fennel, Hypericum species, lettuce, Lycopersicon species (tomato, cherry tomato), mint species, basil, parsley, Phaseolus species (bean, pea), peas, radish, edible rhubarb, Rosemary species, Sage species, black salsify (Scorzonera hispanica), eggplant, spinach, new valerian species (V. eriocarpa), and broad beans.

[0399] Preferred ornamental plant species include African violet, begonia, dahlia, gerbera, hydrangea, verbena, rose, kalanchoe, poinsettia, aster, cornflower, coreopsis, delphinium, monarda, phlox, rudbeckia, sedum, petunia, viola, impatiens, geranium, chrysanthemum, ranunculus, fuchsia, salvia, hydrangea, rosemary, sage, St. Johnswort, mint, sweet pepper, tomato and cucumber.

[0400] The active ingredients according to the invention are particularly suitable for controlling bean aphids, cucumber leaf beetles, tobacco budworm, peach aphid, diamondback moth and sea lily armyworm on cotton, vegetables, corn, rice and soybean crops. The active ingredients according to the invention are further particularly suitable for controlling cabbage armyworm (preferably on vegetables), codling moth (preferably on apples), green leafhopper (preferably on vegetables, vineyards), potato leaf beetle (Leptinotarsa) (preferably on potatoes) and striped stem borer (preferably on rice).

[0401] The active ingredients according to the invention are particularly suitable for controlling bean aphids, cucumber leaf beetles, tobacco budworm, peach aphid, diamondback moth and sea lily armyworm on cotton, vegetables, corn, rice and soybean crops. The active ingredients according to the invention are further particularly suitable for controlling cabbage armyworm (preferably on vegetables), codling moth (preferably on apples), green leafhopper (preferably on vegetables, vineyards), potato leaf beetle (Leptinotarsa) (preferably on potatoes) and striped stem borer (preferably on rice).

[0402] In another aspect, the present invention may also relate to a method for controlling damage to plants and parts thereof by plant parasitic nematodes (endoparasitic-, semiendoparasitic- and ectoparasitic nematodes), in particular the following plant parasitic nematodes, such as root knot nematodes, Meloidogyne hapla, Meloidogyne incognita, Meloidogyne javanica, Meloidogyne arenaria and other species of root knot nematodes; cyst-forming nematodes, Globodera rostochiensis and other species of Globodera; cereal cyst nematodes (Heterodera avenae), soybean cyst nematodes (Heteroderaglycines), beet cyst nematodes (Heterodera exigua) and other species of Globodera. schachtii), Heteroderatrifolii, and other Heterodera species; Seed gall nematodes, Anguina species; Stem and foliar nematodes, Aphelenchoides species; Sting nematodes, Belonolaimuslongicaudatus, and other Belonolaimus species; Pine nematodes, Bursaphelenchus xylophilus, and other Bursaphelenchus species; Ring nematodes, nematodes), Criconema species, Criconemella species, Criconemoides species, Mesocriconema species; Stemand bulb nematodes, Ditylenchus destructor, Ditylenchus dipsaci and other Ditylenchus species; Awl nematodes, Dolichodorus species;Spiral nematodes, Heliocotylenchus multicinctus and other species of the genus Helicotylenchus; Sheath and sheathoid nematodes, species of the genera Hemicycliophora and Hemicriconemoides; species of the genus Hirshmanniella; Lancenematodes, species of the genus Hoploaimus; false rootknot nematodes, species of the genus Nacobbus; Needle nematodes, Longidoruse longatus and other species of the genus Longidorus; Pin nematodes, species of the genus Pratylenchus; Lesion nematodes nematodes, Pratylenchus negletus, Pratylenchus penetrans, Pratylenchus curvitatus, Pratylenchus goodeyi, and other Pratylenchus species; Burrowing nematodes, Radopholus similis, and other Radopholus species; Reniform nematodes, Rotylenchus robustus, Rotylenchus reniformis, and other Rotylenchus species; Scutellonema species; Stubby root nematodes, Trichodorus primitivus and other species of the genus Trichodorus, species of the genus Paratrichodorus; Stunt nematodes, Tylenchorhynchus claytoni, Tylenchorhynchus dubius and other species of the genus Tylenchorhynchus;Citrus nematodes, Tylenchulus species; Dagger nematodes, Xiphinema species; and other plant parasitic nematode species, such as Subanguina spp., Hypsoperine spp., Macroposthonia spp., Melinius spp., Punctodera spp., and Quinisulcius spp.;

[0403] The compounds of the invention also have activity against molluscs. Examples include, for example, the family Pomacea; the family Arion (A. ater, A. circumscriptus, A. hortensis, A. rufus); the family Bradybaenidae (Bradybaenidae, fruticum); Cepaea (C. hortensis, C. nemoralis); Ochlodina; Deroceras (D. agrestis, D. empiricorum, D. laeve, D. reticulatum); Discus (D. rotundatus); Euomphalia; Galba (G. trunculata); Helicelia (H. itala, H. obvia); Helicigona arbustorum; Helicodiscus; Helix (H. aperta); Limax (L. cinereoniger, L. flavus, L. marginatus, L. maximus, L. tenellus); Lymnaea; Milax (M. gagates, M. marginatus, M. sowerbyi); Opeas; Pomacea (P. canaticulata); Vallonia and Zanitoides.

[0404] The term "crops" is to be understood as also including crop plants which have been transformed by the use of recombinant DNA techniques such that they are able to synthesize one or more selectively acting toxins, such as are known, for example, from toxigenic bacteria, in particular those of the genus Bacillus.

[0405] Toxins that can be expressed by such transgenic plants include, for example, insecticidal proteins, such as those from Bacillus cereus or Bacillus japonicus; or insecticidal proteins from Bacillus thuringiensis, such as delta-endotoxins, for example Cry1Ab, Cry1Ac, Cry1F, Cry1Fa2, Cry2Ab, Cry3A, Cry3Bb1, or Cry9C, or vegetative insecticidal proteins (Vips), for example Vip1, Vip2, Vip3, or Vip3A; or insecticidal proteins of bacterial colonizing nematodes, for example Photorhabdus spp. or Xenorhabdus spp., such as Photorhabdus luminescens, Xenorhabdus nematophila, or Xenorhabdus spp. nematophilus); toxins produced by animals, such as scorpion toxins, spider toxins, bee toxins and other insect-specific neurotoxins; toxins produced by fungi, such as streptomycin, plant lectins, such as pea lectin, barley lectin or snowdrop lectin; agglutinin; protease inhibitors, such as trypsin inhibitor, silk proteinase inhibitor, potato glycoprotein, cystatin, papain inhibitor; ribosome inactivating protein (RIP), such as ricin, maize-RIP, abrin, luffa seed toxin protein, saponin protein or bryophyllin; steroid metabolizing enzymes, such as 3-hydroxysteroid oxidase, ecdysteroid-UDP-glycosyl-transferase, cholesterol oxidase, ecdysone inhibitor, HMG-COA-reductase, ion channel blockers such as sodium channel or calcium channel blockers, juvenile hormone esterase, diuretic hormone receptor, stilbene synthase, bibenzyl synthase, chitinase and glucanase.

[0406] In the context of the present invention, delta-endotoxins (e.g., Cry1Ab, Cry1Ac, Cry1F, Cry1Fa2, Cry2Ab, Cry3A, Cry3Bb1 or Cry9C) or vegetative insecticidal proteins (Vips) (e.g., Vip1, Vip2, Vip3 or Vip3A) are understood to include obviously also mixed toxins, truncated toxins and modified toxins. Mixed toxins are recombinantly produced by new combinations of different domains of those proteins (see, e.g., WO 2002 / 15701). Truncated toxins, such as truncated Cry1Ab, are known. In the case of modified toxins, one or more amino acids of the naturally occurring toxin are replaced. In such amino acid replacements, it is preferred that a non-naturally occurring protease recognition sequence is inserted into the toxin, such as, for example, in the case of Cry3A055, a cathepsin-G-recognition sequence is inserted into the Cry3A toxin (see WO 2003 / 018810).

[0407] Examples of such toxins or transgenic plants capable of synthesizing such toxins are disclosed, for example, in EP-A-0 374 753, WO 1993 / 07278, WO 1995 / 34656, EP-A-0 427 529, EP-A-451 878 and WO 2003 / 052073.

[0408] Methods for preparing such transgenic plants are generally known to the person skilled in the art and are described, for example, in the publications mentioned above. CryI-type deoxyribonucleic acids and their preparation are known, for example, from WO 95 / 34656, EP-A-0 367474, EP-A-0 401 979 and WO 1990 / 13651.

[0409] The toxins included in the transgenic plants render the plants tolerant to harmful insects. Such insects can be found in any insect taxonomic group, but are particularly common among beetles (Coleoptera), two-winged insects (Diptera), and moths (Lepidoptera).

[0410] Transgenic plants comprising one or more genes encoding insecticide resistance and expressing one or more toxins are known and some of them are commercially available. Examples of such plants are: (corn variety expressing Cry1Ab toxin); YieldGard (corn variety expressing Cry3Bb1 toxin); YieldGard (corn varieties expressing Cry1Ab and Cry3Bb1 toxins); (corn variety expressing Cry9C toxin); Herculex (a corn variety expressing the Cry1Fa2 toxin and the enzyme phosphinothricin N-acetyltransferase (PAT) that confers tolerance to the herbicide glufosinate-ammonium); NuCOTN (cotton variety expressing Cry1Ac toxin); Bollgard (cotton variety expressing Cry1Ac toxin); Bollgard (cotton varieties expressing Cry1Ac and Cry2Ab toxins); (cotton varieties expressing Vip3A and Cry1Ab toxins); (potato variety, expressing Cry3A toxin); GT Advantage (GA21 glyphosate tolerance trait), CB Advantage (Bt11 corn borer (CB) trait) and

[0411] Further examples of such genetically modified crops are:

[0412] 1. Bt11 corn, from Syngenta Seeds SAS, Chemin del'Hobit 27, F-31 790 St. Sauveur, France, registration number C / FR / 96 / 05 / 10. Genetically modified maize, which is resistant to attack by European corn borer (Ostrinia nubilalis and Sesamia inermis) by transgenic expression of a truncated Cry1Ab toxin. Bt11 corn also transgenic expression of the PAT enzyme to obtain tolerance to the herbicide glufosinate ammonium.

[0413] 2. Bt176 corn, from Syngenta Seeds, 27 Hobbit Road, F-31 790 Saint-Sauveur, France, registration number C / FR / 96 / 05 / 10. Genetically modified maize, which is resistant to attack by the European corn borer (Ostrinia nubilalis and Sesamia inermis) by transgenic expression of the Cry1Ab toxin. Bt176 corn also transgenic expression of the enzyme PAT to obtain tolerance to the herbicide glufosinate ammonium.

[0414] 3. MIR604 corn, from Syngenta Seeds, 27 Rue Hobbitt, F-31 790 Saint-Sauveur, France, registration number C / FR / 96 / 05 / 10. Corn made insect-resistant by transgenic expression of a modified Cry3A toxin. This toxin is Cry3A055 modified by insertion of a cathepsin-G-protease recognition sequence. The preparation of such transgenic corn plants is described in WO 2003 / 018810.

[0415] 4. MON 863 maize, from Monsanto Europe SA, 270-272 Avenue de Tervuren, B-1150 Brussels, Belgium, registration number C / DE / 02 / 9. MON 863 expresses the Cry3Bb1 toxin and is resistant to certain coleopteran insects.

[0416] 5. IPC 531 Cotton, from Monsanto Europe NV, 270-272 Avenue Tervuren, B-1150 Brussels, Belgium, registration number C / ES / 96 / 02.

[0417] 6.1507 Maize from Pioneer Overseas Corporation, Avenue Tedesco, 7B-1160 Brussels, Belgium, registration number C / NL / 00 / 10. Genetically modified maize expressing the protein Cry1F for resistance to certain lepidopteran insects and the protein PAT for tolerance to the herbicide glufosinate ammonium.

[0418] 7. NK603×MON 810 maize, from Monsanto Europe 270-272 Avenue Tervuren, B-1150 Brussels, Belgium, registration number C / GB / 02 / M3 / 03. Made from a conventionally bred hybrid maize variety by crossing the genetically modified varieties NK603 and MON 810. NK603×MON 810 maize transgenically expresses the protein CP4 EPSPS obtained from the Agrobacterium strain CP4, rendering it tolerant to herbicides (contains glyphosate), and also Cry1Ab toxin obtained from Bacillus thuringiensis subsp. kurstakia, which confers resistance to certain lepidopteran insects, including the European corn borer.

[0419] Transgenic crops of insect-resistant plants are also described in the BATS (Zentrum für Biosicherheit und Nachhaltigkeit, Zentrum BATS, Clarastrasse 13, 4058 Basel, Switzerland) report 2003 ( http: / / bats.ch )middle.

[0420] The term "crops" is to be understood as also including crop plants which have been transformed by the use of recombinant DNA technology so that they can synthesize selectively acting antipathogenic substances, such as, for example, so-called "pathogenesis-related proteins" (PRPs, see, for example, EP-A-0 392 225). Examples of such antipathogenic substances and transgenic plants capable of synthesizing such antipathogenic substances are known, for example, from EP-A-0 392 225, WO 1995 / 33818 and EP-A-0353 191. Methods for producing such transgenic plants are generally known to the person skilled in the art and are described, for example, in the publications mentioned above.

[0421] Antipathogenic substances that can be expressed by such transgenic plants include, for example, ion channel blockers, such as blockers of sodium channels and calcium channels, for example viral KP1, KP4 or KP6 toxins; stilbene synthases; bibenzyl synthases; chitinases; glucanases; so-called "pathogenesis-related proteins" (PRPs; see, for example, EP-A-0 392 225); antipathogenic substances produced by microorganisms, such as peptide antibiotics or heterocyclic antibiotics (see, for example, WO 1995 / 33818) or proteins or polypeptide factors that are involved in plant defense against pathogens (so-called "plant disease resistance genes", as described in WO 2003 / 000906).

[0422] Further areas of use of the compositions according to the invention are the protection of stored goods and storage rooms and of raw materials, such as wood, textiles, floors or buildings, and also in the hygiene sector, in particular for the protection of humans, domestic animals and productive livestock from pests of the type mentioned.

[0423] The present invention also provides methods for controlling pests (such as mosquitoes and other disease vectors; see also http: / / www.who.int / malaria / vector_control / irs / en / ). In one embodiment, the method for controlling pests comprises applying the composition of the present invention to the target pests, their loci or surfaces or substrates by brushing, rolling, spraying, coating or dipping. By way of example, IRS (indoor residual spray) application of surfaces (such as wall, ceiling or floor surfaces) is contemplated by the methods of the present invention. In another embodiment, it is contemplated that such compositions are applied to substrates such as nonwoven or fabric materials in the form of netting, coverings, bedding, curtains and tents (or can be used in the manufacture of such articles).

[0424] In one embodiment, the method for controlling such harmful organisms comprises applying the composition of the present invention of pesticidal effective amount to the target harmful organisms, their place or surface or substrate, so as to provide effective retained pesticidal activity on the surface or substrate. Such application can be carried out by brushing, rolling, spraying, coating or dipping the pesticidal composition of the present invention. By way of example, the IRS application of surfaces (such as walls, ceilings or floor surfaces) is considered by the method of the present invention, so as to provide effective retained pesticidal activity on the surface. In another embodiment, it is considered to apply such compositions for the residual control of harmful organisms on substrates, and the substrate is a fabric material such as in the form of netting, coverings, bedding, curtains and tents (or can be used in the manufacture of these articles).

[0425] The substrate to be treated (including nonwovens, fabrics or nettings) can be made of natural fibers, such as cotton, raffia, jute, flax, sisal, burlap or wool, or synthetic fibers, such as polyamide, polyester, polypropylene, polyacrylonitrile, etc. Polyester is particularly suitable. Methods for textile treatment are known, for example WO 2008 / 151984, WO 2003 / 034823, US 5631072, WO 2005 / 64072, WO 2006 / 128870, EP 1724392, WO 2005 / 113886 or WO 2007 / 090739.

[0426] A further area of ​​use of the compositions according to the invention is in the field of tree injection / trunk treatment of all ornamental trees as well as all kinds of fruit and nut trees.

[0427] In the field of tree injection / trunk treatment, the compounds according to the invention are particularly suitable for combating wood-boring insects from the orders Lepidoptera mentioned above and from the orders Coleoptera, in particular against the wood-boring insects listed in the following Tables A and B:

[0428] Table A. Examples of exotic wood-boring insects of economic importance.

[0429]

[0430] Table B. Examples of native wood-boring insects of economic importance.

[0431]

[0432]

[0433]

[0434] The present invention can also be used to control any insect pest that may be present in turfgrass including, for example, beetles, caterpillars, fire ants, ground pearls, millipedes, woodlice, mites, mole crickets, scale insects, mealybugs, ticks, cicadas, southern wheat bugs, and grubs. The present invention can be used to control insect pests at all stages of their life cycle, including eggs, larvae, nymphs, and adults.

[0435] In particular, the present invention can be used to control insect pests that feed on the roots of turf grasses, including grubs (such as Cyclocephala spp. (e.g., labeled beetle, C. lurida), Rhizotrogus spp. (e.g., European beetle, European root-cutting gill beetle (R. majalis)), Cotinus spp. (e.g., Green June beetle, Green June flower beetle (C. nitida)), Popillia spp. (e.g., Japanese beetle, Japanese arc beetle (P. japonica)), Phyllophaga spp. (e.g., May / June beetle), Chafer spp. (e.g., Blackturfgrass ataenius, Black velvet beetle), Maladera spp. (e.g., Asiatic garden beetle (Asiatic garden beetle beetle, chestnut beetle) and Tomarus species), ground pearls (Margarodes spp.), mole crickets (tawny, southern, and short-winged; mole crickets (Scapteriscus spp., Gryllotalpa africana) and leatherjackets (European crane fly, Tipula spp.).

[0436] The present invention can also be used to control insect pests of turfgrass in thatched homes, including armyworms (such as fall armyworm, Spodoptera frugiperda, and common armyworm, Pseudaletia unipuncta), cutworms, weevils (Sphenophorus spp., such as S. venatus verstitus and S. parvulus), and grass borers (such as Crambus spp. and tropical grass borer, Herpetogramma phaeopteralis).

[0437] The present invention can also be used to control insect pests in turfgrass that live above ground and feed on turfgrass leaves, including wheat stink bugs (such as the southern wheat stink bug, Blissus insularis), Bermudagrass mite (Eriophyes cynodoniensis), Grass mealybug (Antonina graminis), Propsapia bicincta, leafhoppers, cutworms (Noctuidae), and Schizaphis graminis.

[0438] The present invention may also be used to control other pests in turfgrass, such as introduced red imported fire ants (Solenopsis invicta) which create nests in the lawn.

[0439] In the hygiene sector, the compositions according to the invention are effective against ectoparasites such as hard ticks, soft ticks, scabies, autumn mites, flies (biting and licking), parasitic fly larvae, lice, hair lice, bird lice and fleas.

[0440] Examples of such parasites are:

[0441] From the order of the Pediculus: Haematopus spp., Linognathus spp., Pediculus spp., and Phtirus spp., Phidirus spp.

[0442] From the order Trichophagus: Felicola spp., Felicola spp., Felicola spp., Felicola spp., Werneckiella spp., Lepikentron spp., Felicola spp., Felicola spp. and Felicola spp.

[0443] From the order Diptera and the suborder Nematocerina and Brachycerina, for example, Aedes spp., Anopheles spp., Culex spp., Simulium spp., Eusimulium spp., Phlebotomus spp., Lutzomyia spp., Culicoides spp., Chrysops spp., Hybomitra spp., Atylotus spp., Tabanus spp., Haematopota spp., Philipomyia spp., Braula spp. spp.), Musca spp., Hydrotaea spp., Biting flies spp., Haematobia spp., Morellia spp., Fannia spp., Glossina spp., Calliphora spp., Lucilia spp., Chrysomyia spp., Wohlfahrtia spp., Sarcophaga spp., Oestrus spp., Hypoderma spp., Gasterophilus spp., Hippobosca spp., Lipoptena spp.) and tick species (Melophagus spp.).

[0444] From the order of the Siphonapterida, for example, Pulex spp., Ctenocephalides spp., Xenopsylla spp., Ceratophyllum spp.

[0445] From the order of the Heteropterida, for example, Cimex spp., Trypanosoma spp., Echinostoma spp., Panstrongylus spp.

[0446] From the order of the Blattarida, for example, Blatta orientalis, Periplaneta americana, Blattelagermanica and Supella spp.

[0447] The subclass Acaria (family Acarida) and the orders Meta-stigmata and Meso-stigmata, for example Argas spp., Ornithodorus spp., Otobius spp., Ixodes spp., Amblyomma spp., Boophilus spp., Dermacentor spp., Haemophysalis spp., Hyalomma spp., Rhipicephalus spp., Dermanyssus spp., Raillietia spp., Pneumonyssus spp. spp.), Sternostoma spp., and Varroa spp.

[0448] From the order Actinedida (suborder Prostigmata) and Acaridida (suborder Astigmata), for example, Acarapis spp., Cheyletiella spp., Ornithocheyletia spp., Myobia spp., Psorergates spp., Demodex spp., Trombicula spp., Listrophorus spp., Acarus spp., Tyrophagus spp., Caloglyphus spp., Hypodectes spp., Pterolichus spp. spp.), Psoroptes spp., Chorioptes spp., Otodectes spp., Sarcoptes spp., Notoedress spp., Knemidocoptes spp., Cytodites spp., and Laminosioptes spp.

[0449] The compositions according to the invention are also suitable for protecting materials in the case of, for example, wood, textiles, plastics, adhesives, glues, paints, paper and card, leather, floor coverings and construction from infestation by insects.

[0450] The compositions according to the invention can be used, for example, against the following pests: beetles, such as Hylotrupes bajulus, Chlorophorus pilosis, Anobium punctatum, Xestobium rufovillosum, Ptilinuspecticornis, Dendrobium pertinex, Ernobius mollis, Priobium carpini, Lyctus brunneus, Lyctus africanus, Lyctus planicollis, Lyctus linearis, Lyctus pubescens, Trogoxylon aequale), Minthesrugicollis, Xyleborus spec., Tryptodendron spec., Apate monachus, Bostrychus capucins, Heterobostrychus brunneus, Sinoxylon spec. and Dinoderus minutus, as well as Hymenoptera, such as Sirex juvencus, Urocerus gigas, Urocerus gigas taignus and Urocerus augu, and termites, such as Kalotermes flavicollis, Cryptotermes brevis, Heterotermes spp. indicola), Reticulitermes flavipes, Reticulitermes santonensis, Reticulitermes lucifugus, Mastotermes darwiniensis, Zootermopsis nevadensis and Coptotermes formosanus, as well as borers such as Silverfish (Lepisma saccharina).

[0451] The compounds according to the invention can be used as pesticides in unmodified form, but they are usually formulated into compositions in various ways using formulation adjuvants such as carriers, solvents and surface-active substances. These formulations can be in different physical forms, for example in the form of dusting powders, gels, wettable powders, water-dispersible granules, water-dispersible tablets, effervescent spherical granules, emulsifiable concentrates, microemulsifiable concentrates, oil-in-water emulsions, flowable oils, aqueous dispersions, oily dispersions, suspoemulsions, capsule suspensions, emulsifiable granules, soluble liquids, water-soluble concentrates (with water or water-miscible organic solvents as carriers), impregnated polymer films or in other known forms, for example from Manual on Development and Use of FAO and WHO Specifications for Pesticides, United Nations, 1st edition, second revision (2010). Such formulations can be used directly or can be diluted before use. Dilution can be carried out with, for example, water, liquid fertilizers, micronutrients, biological organisms, oils or solvents.

[0452] These formulations can be prepared, for example, by mixing the active ingredient with a formulation adjuvant to obtain a composition in the form of a finely divided solid, granules, solution, dispersion or emulsion. The active ingredients can also be formulated with other adjuvants such as finely divided solids, mineral oils, oils of plant or animal origin, modified oils of plant or animal origin, organic solvents, water, surface-active substances or combinations thereof.

[0453] These active ingredients can also be contained in very fine microcapsules. Microcapsules contain active ingredients in porous carriers. This allows the active ingredients to be released (e.g., slowly released) into the environment in a controlled amount. Microcapsules typically have a diameter of from 0.1 to 500 microns. The amount of active ingredients they contain is about 25% to 95% of the capsule weight by weight. These active ingredients can be in the form of an integral solid, in the form of fine particles in a solid or liquid dispersion, or in the form of a suitable solution. The encapsulated membrane can include, for example, natural or synthetic rubber, cellulose, styrene / butadiene copolymers, polyacrylonitrile, polyacrylate, polyester, polyamide, polyurea, polyurethane or chemically modified polymers and starch xanthate or other polymers known to those skilled in the art. Alternatively, very fine microcapsules can be formed, in which the active ingredients are contained in the form of finely dispersed particles in a solid matrix of a base material, but these microcapsules themselves are not wrapped.

[0454] Formulation adjuvants suitable for preparing the compositions according to the invention are known per se. As liquid carriers there may be used: water, toluene, xylene, petroleum ether, vegetable oils, acetone, methyl ethyl ketone, cyclohexanone, anhydrides, acetonitrile, acetophenone, amyl acetate, 2-butanone, butylene carbonate, chlorobenzene, cyclohexane, cyclohexanol, alkyl acetates, diacetone alcohol, 1,2-dichloropropane, diethanolamine, p-diethylbenzene, diethylene glycol, diethylene glycol rosinate, diethylene glycol butyl ether, diethylene glycol ethyl ether, diethylene glycol methyl ether, N,N-dimethyl Formamide, dimethyl sulfoxide, 1,4-dioxane, dipropylene glycol, dipropylene glycol methyl ether, dipropylene glycol dibenzoate, dipropylene glycol, alkyl pyrrolidone, 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, acetic acid glyceryl, diacetic acid glyceryl, triacetin, decaglycerol Hexadecane, hexanediol, isoamyl acetate, isobornyl acetate, isooctane, isophorone, cumene, isopropyl myristate, lactic acid, laurylamine, mesityl oxide, methoxypropanol, methyl isoamyl ketone, methyl isobutyl ketone, methyl laurate, methyl octanoate, methyl oleate, dichloromethane, m-xylene, n-hexane, n-octylamine, octadecanoic acid, octylamine acetate, oleic acid, oleylamine, o-xylene, phenol, polyethylene glycol, propionic acid, propyl lactate , propylene carbonate, propylene glycol, propylene glycol methyl ether, p-xylene, toluene, triethyl phosphate, triethylene glycol, xylene sulfonic acid, paraffin, mineral oil, trichloroethylene, perchloroethylene, ethyl acetate, amyl acetate, butyl acetate, propylene glycol methyl ether, diethylene glycol methyl ether, methanol, ethanol, isopropanol and higher molecular weight alcohols such as amyl alcohol, tetrahydrofuranol, hexanol, octanol, ethylene glycol, propylene glycol, glycerol, N-methyl-2-pyrrolidone, etc.

[0455] Suitable solid carriers are, for example, talc, titanium dioxide, pyrophyllite clay, silica, attapulgite clay, diatomaceous earth, limestone, calcium carbonate, bentonite, calcium montmorillonite, cottonseed hulls, wheat flour, soybean flour, pumice, wood flour, ground walnut shells, lignin and similar substances.

[0456] Many surface-active substances can be used advantageously in both solid and liquid formulations, especially in those formulations which can be diluted with a carrier before use. Surface-active substances can be anionic, cationic, nonionic or polymeric and they can act as emulsifying agents, wetting agents or suspending agents or for other purposes. Typical surface-active substances include, for example, salts of alkyl sulfates, such as diethanolammonium dodecyl sulfate; salts of alkylarylsulfonates, such as calcium dodecylbenzenesulfonate; alkylphenol / alkylene oxide addition products, such as ethoxylated nonylphenol; alcohol / alkylene oxide addition products, such as ethoxylated tridecanol; soaps, such as sodium stearate; salts of alkylnaphthalenesulfonates, such as sodium dibutylnaphthalenesulfonate; salts of dialkylsulfosuccinates, such as sodium di(2-ethylhexyl)sulfosuccinate; sorbitol esters, such as sorbitan oleate; quaternary ammoniums, such as dodecyltrimethylammonium 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 dialkyl phosphates; and also other substances, such as are described in: McCutcheon's Detergents and Emulsifiers Annual, MC Publishing Company (MC Publishing Corp., Ridgewood New Jersey (1981).

[0457] Additional adjuvants that can be used in pesticidal formulations include crystallization inhibitors, viscosity modifiers, suspending agents, dyes, antioxidants, foaming agents, light absorbers, mixing aids, defoamers, complexing agents, substances and buffers that neutralize or change the pH, corrosion inhibitors, fragrances, wetting agents, absorption enhancers, micronutrients, plasticizers, glidants, lubricants, dispersants, thickeners, antifreeze agents, microbicides, and liquid and solid fertilizers.

[0458] The composition according to the invention may comprise an additive comprising an oil of plant or animal origin, a mineral oil, an alkyl ester of such an oil or a mixture of such an oil with an oil derivative. The amount of the oil additive in the composition according to the invention is generally from 0.01% to 10% based on the mixture to be applied. For example, the oil additive may be added to the spray tank in the desired concentration after the spray mixture has been prepared. Preferred oil additives include mineral oil or oil of plant origin, such as rapeseed oil, olive oil or sunflower oil; emulsified vegetable oils; alkyl esters of oils of plant origin, such as methyl derivatives; or oils of animal origin, such as fish oil or tallow. Preferred oil additives include C8-C 22 Alkyl esters of fatty acids, especially C 12 -C 18Methyl derivatives of fatty acids, such as the methyl esters of lauric acid, palmitic acid and oleic acid (methyl laurate, methyl palmitate and methyl oleate, respectively). Many oil derivatives are known from the Compendium of Herbicide Adjuvants, 10th edition, Southern Illinois University, 2010.

[0459] These compositions according to the invention generally comprise from 0.1% to 99% by weight, in particular from 0.1% to 95% by weight, of a compound according to the invention and from 1% to 99.9% by weight of a formulation auxiliary, which preferably comprises from 0 to 25% by weight of a surface-active substance. Whereas commercial products may preferably be formulated as concentrates, the end user will generally use dilute formulations.

[0460] The application rate varies within a wide range and depends on the nature of the soil, the application method, the crop plants, the harmful organisms to be controlled, the prevailing climatic conditions, and other factors governed by the application method, the application time and the target crop. In general, the compound can be applied at a rate of from 1 to 2000 l / ha, especially from 10 to 1000 l / ha.

[0461] Preferred formulations may have the following composition (wt%):

[0462] Emulsifiable concentrates :

[0463] Active ingredient: 1% to 95%, preferably 60% to 90%

[0464] Surfactant: 1% to 30%, preferably 5% to 20%

[0465] Liquid carrier: 1% to 80%, preferably 1% to 35%

[0466] Dusting agent :

[0467] Active ingredient: 0.1% to 10%, preferably 0.1% to 5%

[0468] Solid carrier: 99.9% to 90%, preferably 99.9% to 99%

[0469] Suspension concentrate:

[0470] Active ingredient: 5% to 75%, preferably 10% to 50%

[0471] Water: 94% to 24%, preferably 88% to 30%

[0472] Surfactant: 1% to 40%, preferably 2% to 30%

[0473] Wettable powder :

[0474] Active ingredient: 0.5% to 90%, preferably 1% to 80%

[0475] Surfactant: 0.5% to 20%, preferably 1% to 15%

[0476] Solid carrier: 5% to 95%, preferably 15% to 90%

[0477] Granules:

[0478] Active ingredient: 0.1% to 30%, preferably 0.1% to 15%

[0479] Solid carrier: 99.5% to 70%, preferably 97% to 85%

[0480] The following examples further illustrate (but do not limit) the present invention.

[0481] <![CDATA[ Wettable powder ]]> a) b) c) Active ingredients 25％ 50％ 75％ Sodium lignin sulfonate 5％ 5％ - Sodium lauryl sulfate 3％ - 5％ Sodium diisobutylnaphthalene sulfonate - 6％ 10％ Phenol polyglycol ether (7-8 mol of ethylene oxide) - 2％ - Highly dispersed silicic acid 5％ 10％ 10％ Kaolin 62％ 27％ -

[0482] The combination is thoroughly mixed with the adjuvants and the mixture is thoroughly ground in a suitable grinder to obtain wettable powders which can be diluted with water to give a suspension of the desired concentration.

[0483] <![CDATA[ Powders for dry seed treatment ]]> a) b) c) Active ingredients 25％ 50％ 75％ Light mineral oil 5％ 5％ 5％ Highly dispersed silicic acid 5％ 5％ - Kaolin 65％ 40％ - talc - 20％

[0484] The combination is thoroughly mixed with adjuvants and the mixture is thoroughly ground in a suitable grinder to obtain a dust that can be used directly for seed treatment.

[0485]

[0486]

[0487] Emulsions of any desired dilution which can be used in plant protection can be obtained from these concentrates by dilution with water.

[0488] Dusting agent a) b) c) Active ingredients 5％ 6％ 4％ talc 95％ - - Kaolin - 94％ - Mineral fillers - - 96％

[0489] Ready-to-use dusting powders are obtained by mixing the combination with a carrier and grinding the mixture in a suitable grinder. Such powders can also be used for dry seed dressing of seeds.

[0490] <![CDATA[ Extruder pellets ]]> Active ingredients 15％ Sodium lignin sulfonate 2％ Carboxymethyl cellulose 1％ Kaolin 82％

[0491] The combination is mixed and ground with the adjuvants, and the mixture is moistened with water.

[0492] The mixture is extruded and then dried in a stream of air.

[0493] Coated granules Active ingredients 8％ Polyethylene glycol (molecular weight 200) 3％ Kaolin 89％

[0494] This finely ground combination is applied uniformly in a mixer to the kaolin moistened with polyethylene glycol. In this way, non-dusting coated granules are obtained.

[0495] Suspension concentrates

[0496] Active ingredients 40％ Propylene glycol 10％ Nonylphenol polyglycol ether (15 mol of ethylene oxide) 6％ Sodium lignin sulfonate 10％ Carboxymethyl cellulose 1％ Silicone oil (in the form of a 75% emulsion in water) 1％ water 32％

[0497] The finely ground combination is intimately mixed with adjuvants to give a suspension concentrate from which any desired dilution of suspension can be obtained by dilution with water. Using such dilutions, living plants together with plant propagation materials can be treated and protected against microbial infection by spraying, pouring or immersion.

[0498] Flowable concentrate for seed treatment

[0499] Active ingredients 40％ Propylene glycol 5％ Copolymer Butanol PO / EO 2％ Tristyrylphenol, with 10-20 moles of EO 2％ 1,2-Benzisothiazolin-3-one (in the form of a 20% solution in water) 0.5％ Monoazo-pigment calcium salt 5％ Silicone oil (in the form of a 75% emulsion in water) 0.2％ water 45.3％

[0500] The finely ground combination is intimately mixed with adjuvants to give a suspension concentrate from which any desired dilution of suspension can be obtained by dilution with water. Using such dilutions, living plants together with plant propagation materials can be treated and protected against microbial infection by spraying, pouring or immersion.

[0501] Extended-release capsule suspension

[0502] 28 parts of the combination are mixed with 2 parts of an aromatic solvent and 7 parts of a toluene diisocyanate / polymethylene-polyphenyl isocyanate mixture (8:1). This mixture is emulsified in a mixture of 1.2 parts of polyvinyl alcohol, 0.05 parts of a defoamer and 51.6 parts of water until the desired particle size is reached. To this emulsion are added 2.8 parts of a 1,6-hexanediamine mixture in 5.3 parts of water. The mixture is stirred until the polymerization is complete. The obtained capsule suspension is stabilized by adding 0.25 parts of a thickener and 3 parts of a dispersant. The capsule suspension formulation contains 28% of active ingredient. The diameter of the medium capsules is 8-15 microns. The resulting formulation is applied to the seeds as an aqueous suspension in a device suitable for this purpose.

[0503] Formulation types include emulsion concentrates (EC), suspension concentrates (SC), suspoemulsions (SE), capsule suspensions (CS), water-dispersible granules (WG), emulsifiable granules (EG), emulsions, water-in-oil emulsions (EO), oil-in-water emulsions (EW), microemulsions (ME), oil dispersions (OD), oil suspensions (OF), oil-soluble liquids (OL), soluble concentrates (SL), ultra low volume suspensions (SU), ultra low volume liquids (UL), master batches (TK), dispersible concentrates (DC), wettable powders (WP), soluble granules (SG) or any technically feasible formulation in combination with agriculturally acceptable adjuvants.

[0504] Preparation Example:

[0505] "Mp" refers to the melting point in ° C. Free radical means methyl group. 1 H NMR measurements were recorded on a Brucker 400 MHz spectrometer and chemical shifts are given in ppm relative to a TMS standard. Spectra were measured in deuterated solvents as specified. The compounds were characterized using any of the following LCMS methods. Characteristic LCMS values ​​obtained for each compound are the retention time ("Rt" reported in minutes) and the measured molecular ion (M+H) + or (MH) - .

[0506] LCMS and GCMS methods:

[0507] Method 1:

[0508] Spectra were recorded on a mass spectrometer from Waters (SQD, SQDII single quadrupole mass spectrometer) equipped with an electrospray source (polarity: positive and negative ions, capillary: 3.00 kV, cone range: 30 V, extractor: 2.00 V, source temperature: 150°C, desolvation temperature: 350°C, cone gas flow: 50 l / h, desolvation gas flow: 650 l / h; mass range: 100 Da to 900 Da) and an Acquity UPLC from Waters: 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 to 500, solvent gradient: A = water + 5% MeOH + 0.05% HCOOH, B = acetonitrile + 0.05% HCOOH; gradient: 10%-100% B in 1.2 min; flow rate (ml / min) 0.85

[0509] Method 2:

[0510] Spectra were recorded on a mass spectrometer from Waters (SQD, SQDII single quadrupole mass spectrometer) equipped with an electrospray source (polarity: positive and negative ions, capillary: 3.00 kV, cone range: 30 V, extractor: 2.00 V, source temperature: 150°C, desolvation temperature: 350°C, cone gas flow: 50 l / h, desolvation gas flow: 650 l / h, mass range: 100 Da to 900 Da) and an Acquity UPLC from Waters: 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 to 500, solvent gradient: A = water + 5% MeOH + 0.05% HCOOH, B = acetonitrile + 0.05% HCOOH; gradient: 10%-100% B in 2.7 min; flow rate (ml / min) 0.85

[0511] Method 3:

[0512] Spectra were recorded on a mass spectrometer from Waters (SQD, SQDII or ZQ single quadrupole mass spectrometer) equipped with an electrospray source (polarity: positive and negative ions, capillary: 3.00 kV, cone range: 30 V, extractor: 2.00 V, source temperature: 150°C, desolvation temperature: 350°C, cone gas flow: 50 l / h, desolvation gas flow: 650 l / h, mass range: 100 Da to 900 Da) and an Acquity UPLC from Waters: 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 to 500, solvent gradient: A = water + 5% MeOH + 0.05% HCOOH, B = acetonitrile + 0.05% HCOOH; gradient: 0%-10% B in 2.5 min; flow rate (ml / min) 0.85

[0513] Method 4:

[0514] Spectra were recorded on a mass spectrometer from Waters (SQD, SQDII single quadrupole mass spectrometer) equipped with an electrospray source (polarity: positive and negative ions, capillary: 3.00 kV, cone range: 30 V, extractor: 2.00 V, source temperature: 150°C, desolvation temperature: 350°C, cone gas flow: 50 l / h, desolvation gas flow: 650 l / h, mass range: 100 Da to 900 Da) and an Acquity UPLC from Waters: 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 to 500, solvent gradient: A = water + 5% MeOH + 0.05% HCOOH, B = acetonitrile + 0.05% HCOOH; gradient: 40%-100% B in 1.2 min; flow rate (ml / min) 0.85

[0515] Method 5 :

[0516] Spectra were recorded on a mass spectrometer (Acquity SDS mass spectrometer) from Waters equipped with an electrospray source (polarity: positive and negative polarity switching, capillary: 3.00 kV, cone voltage: 41.00 V, source temperature: 150°C, desolvation gas flow: 1000 L / Hr, desolvation temperature: 500°C, cone gas flow: 50 L / hr, mass range: 110 Da-800 Da, PDA wavelength range: 210 nm-400 nm). Column: Acquity UPLC HSS T3 C18, length 30 mm, diameter 2.1 mm, particle size 1.8 μm. Column oven temperature 40°C. Solvent gradient: A = water:acetonitrile (95:5 v / v) with 0.1% formic acid. B = acetonitrile with 0.05% formic acid. Gradient = 0 min 90% A, 10% B; 0.2 min 50% A, 50% B; 0.7 min-1.3 min 0% A, 100% B; 1.4-1.6 min 90% A, 10% B. Flow rate 0.6 mL / min.

[0517] Example H1: 1-[5-(ethylsulfonylimino)-6-[7-methyl-3-(trifluoromethyl)imidazo[4,5-c]pyridazine- Preparation of 6-yl]-3-pyridyl]cyclopropanecarbonitrile (Table P, Example P10)

[0518]

[0519] Step 1: Preparation of 5-(1-cyano-2-ethoxy-2-oxo-ethyl)-3-ethylsulfanyl-pyridine-2-carboxylic acid methyl ester preparation

[0520]

[0521] 5-Bromo-3-ethylsulfanyl-pyridine-2-carboxylic acid methyl ester (32g, 115.88mmol) prepared as described in patent WO 2017 / 089190 was dissolved in dimethyl sulfoxide (350mL). Ethyl 2-cyanoacetate (18.5mL, 173.82mmol), potassium carbonate (40.442g, 289.70mmol) and tetrabutylammonium bromide (3.81g, 11.588mmol) were then added continuously at room temperature. The resulting suspension was stirred at 90°C overnight and then cooled to room temperature. Water and ethyl acetate were added, the resulting mixture was cooled at 0°C, and hydrochloric acid (2M) 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 in vacuo. The resulting crude product was heated in ethanol (250ml) at 80°C for 1 hour. The resulting solution was cooled to 0°C, stirred for 1 hour and filtered. The precipitate was washed with cold ethanol to give 5-(1-cyano-2-ethoxy-2-oxo-ethyl)-3-ethylsulfanyl-pyridine-2-carboxylic acid methyl ester.

[0522] LCMS (method 1): 309 (M+H) + ; Retention time: 0.85min.

[0523] 1H NMR (400 MHz, CHLOROFORM-D) δ ppm 1.33 (t, J = 7.15 Hz, 3H) 1.45 (t, J = 7.34 Hz, 3H) 2.98-3.05 (m, 2H) 4.04 (s, 3H) 4.28-4.35 (m, 2H) 4.84 (s, 1H) 7.83 (d, J = 1.83 Hz, 1H) 8.49 (d, J = 1.83 Hz, 1H).

[0524] Step 2: Preparation of 5-(cyanomethyl)-3-ethylsulfanyl-pyridine-2-carboxylic acid methyl ester

[0525]

[0526] 5-(1-cyano-2-ethoxy-2-oxo-ethyl)-3-ethylsulfanyl-pyridine-2-carboxylic acid methyl ester (7.3 g, 24 mmol) was dissolved in dimethyl sulfoxide (70 mL). NaCl (14 g, 240 mmol) and water (35 mL) were added sequentially thereto at room temperature. The resulting suspension was stirred at 125° C. for 3 hours. The reaction mixture was cooled to room temperature, diluted with 50 mL of water and 100 mL of ethyl acetate. The aqueous layer was extracted three times with ethyl acetate. The organic layers were combined, dried over sodium sulfate and concentrated in vacuo. The crude product was purified on silica gel to give 5-(cyanomethyl)-3-ethylsulfanyl-pyridine-2-carboxylic acid methyl ester.

[0527] LCMS (method 1): 237 (M+H)+ ; Retention time: 0.72min.

[0528] 1H NMR (400 MHz, CHLOROFORM-D) δ ppm 1.45 (t, J = 7.52 Hz, 3H) 3.01 (q, J = 7.34 Hz, 2H) 3.87 (s, 2H) 4.04 (s, 3H) 7.72 (d, J = 1.83 Hz, 1H) 8.35-8.41 (m, 1H).

[0529] Step 3: Preparation of 5-(1-cyanocyclopropyl)-3-ethylsulfanyl-pyridine-2-carboxylic acid methyl ester

[0530]

[0531] 5-(Cyanomethyl)-3-ethylsulfanyl-pyridine-2-carboxylic acid methyl ester (5 g, 21.16 mmol) was dissolved in acetonitrile (170 mL) and treated with cesium carbonate (20.7 g, 63.48 mmol) and 1,2-dibromoethane (2.19 mL, 25.39 mmol) at room temperature. The resulting mixture was stirred at 80 ° C for 3 h 30 hours and then stirred at room temperature overnight. The reaction mixture was diluted with water and ethyl acetate. The aqueous layer was extracted 3 times with ethyl acetate. The combined organic layers were washed with brine, dried over sodium sulfate, filtered and concentrated in vacuo to give a crude product, which was purified by chromatography to give 5-(1-cyanocyclopropyl)-3-ethylsulfanyl-pyridine-2-carboxylic acid methyl ester.

[0532] LCMS (method 1): 263 (M+H) + ; Retention time: 0.85min.

[0533] 1H NMR (400 MHz, CHLOROFORM-D) δ ppm 1.45 (t, J = 7.34 Hz, 3H) 1.54-1.62 (m, 2H) 1.89-1.96 (m, 2H) 3.01 (q, J = 7.34 Hz, 2H) 4.02 (s, 3H) 7.74 (d, J = 2.20 Hz, 1H) 8.17 (d, J = 1.83 Hz, 1H).

[0534] Step 4: Preparation of 5-(1-cyanocyclopropyl)-3-ethylsulfanyl-pyridine-2-carboxylic acid

[0535]

[0536] 5-(1-Cyanocyclopropyl)-3-ethylsulfanyl-pyridine-2-carboxylic acid methyl ester (2.63 g, 10.0 mmol) was dissolved in tetrahydrofuran (50 mL) and water (15 mL). Lithium hydroxide (0.375 g, 15.0 mmol) was then added and the reaction was stirred at room temperature overnight. After this time, another portion of lithium hydroxide (0.160 g, 7.0 mmol) was added and the reaction was stirred at room temperature for another 2 hours. The reaction mixture was concentrated in vacuo and the residue was dissolved in dichloromethane. 1 M aqueous HCl solution was added and the aqueous layer (pH 1) was extracted 3 times with dichloromethane. The combined organic layers were dried over sodium sulfate, filtered and concentrated in vacuo to give 5-(1-Cyanocyclopropyl)-3-ethylsulfanyl-pyridine-2-carboxylic acid.

[0537] LCMS (method 1): 249 (M+H) + ; Retention time: 0.67min.

[0538] 1H NMR (400 MHz, DMSO-d solvent) δ ppm 1.26 (t, J = 7.34 Hz, 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 = 2.20 Hz, 1H) 8.37 (d, J = 1.83 Hz, 1H) 13.16-13.40 (m, 1H).

[0539] Step 5. 5-(1-Cyanocyclopropyl)-3-ethylsulfanyl-N-[3-(methylamino)-6-(trifluoromethyl)pyridazine- Preparation of 4-amino-pyridine-2-carboxamide

[0540]

[0541] 5-(1-Cyanocyclopropyl)-3-ethylsulfanyl-pyridine-2-carboxylic acid (200 mg, 0.8055 mmol) was dissolved in dichloromethane (10 mL) and N,N-dimethylformamide (10.0 μL) was added. To this suspension, oxalyl chloride (0.118 mL, 1.369 mmol) was added dropwise via syringe. The resulting light yellow suspension was stirred at room temperature. After 1.5 h, the reaction mixture was concentrated in vacuo to give 5-(1-Cyanocyclopropyl)-3-ethylsulfanyl-pyridine-2-carbonyl chloride. Fresh 5-(1-cyanocyclopropyl)-3-ethylsulfanyl-pyridine-2-carbonyl chloride (250 mg, 0.9370 mmol) was dissolved in tetrahydrofuran (12 mL) and N,N-diethylethylamine (0.27 mL, 1.933 mmol) was added dropwise, followed by N3-methyl-6-(trifluoromethyl)pyridazine-3,4-diamine (651 mg, 3.222 mmol) in tetrahydrofuran (12 mL) at 0°C. The resulting mixture was stirred at room temperature for 12 hours. The reaction mixture was then poured into water (20 ml) and extracted with dichloromethane (3 x 20 ml). The combined extracts were washed with brine (30 ml), dried over sodium sulfate, filtered and concentrated in vacuo. The crude product was purified by silica gel chromatography to give N-[4-amino-6-(trifluoromethyl)pyridazin-3-yl]-5-(1-cyanocyclopropyl)-3-ethylsulfanyl-N-methyl-pyridine-2-carboxamide

[0542] LCMS (method 2): retention time: 1.04 min, 423 (M+H) + .

[0543] Step 6: 1-[5-ethylsulfanyl-6-[7-methyl-3-(trifluoromethyl)imidazo[4,5-c]pyridazin-6-yl]- Preparation of 3-pyridyl]cyclopropanecarbonitrile

[0544]

[0545] 5-(1-cyanocyclopropyl)-3-ethylsulfanyl-N-[3-(methylamino)-6-(trifluoromethyl)pyridazine-4-yl]pyridine-2-carboxamide (240 mg, 0.5682 mmol) and glacial acetic acid (3 mL) were mixed and stirred under reflux overnight and then cooled to room temperature. Acetic acid was removed under reduced pressure, and the obtained residue was dissolved in ethyl acetate and basified with aqueous bicarbonate solution. The aqueous layer was extracted with ethyl acetate (3 x 20 ml), and the combined organic layers were dried over sodium sulfate, filtered and concentrated in vacuo. The crude product was purified by silica gel chromatography to provide 1-[5-ethylsulfanyl-6-[7-methyl-3-(trifluoromethyl)imidazo[4,5-c]pyridazine-6-yl]-3-pyridyl]cyclopropanecarbonitrile.

[0546] LCMS (method 2): retention time: 1.05 min, (M+H) + 405.

[0547] 1H NMR (400 MHz, CHLOROFORM-d) d ppm 1.34-1.46 (m, 1H) 1.38 (s, 2H) 1.62-1.66 (m, 2H) 1.89-2.02 (m, 2H) 2.97-3.10 (m, 2H) 4.26 (s, 3H) 7.76-7.84 (m, 1H) 8.22-8.27 (m, 1H) 8.34-8.41 (m, 1H).

[0548] Step 7: 1-[5-(ethylsulfonylimino)-6-[7-methyl-3-(trifluoromethyl)imidazo[4,5-c]pyridazine- Preparation of 6-yl]-3-pyridyl]cyclopropanecarbonitrile (Table P, Example P10)

[0549]

[0550] 1-[5-ethylsulfanyl-6-[7-methyl-3-(trifluoromethyl)imidazo[4,5-c]pyridazine-6-yl]-3-pyridyl]cyclopropanecarbonitrile (120 mg, 0.2967 mmol) was dissolved in methanol (6 mL). Ammonium carbamate (46 mg, 0.5935 mmol) and (diacetoxyiodo)benzene (243 mg, 0.7418 mmol) were then added at room temperature. The obtained suspension became a solution after a few minutes and was stirred at room temperature for 2 hours. The reaction mixture was quenched with water (20 ml) and extracted with dichloromethane (3 x 20 ml). The combined organic layers were washed with brine (30 ml), dried over anhydrous sodium sulfate, filtered and concentrated in vacuo. The residue was purified by silica gel chromatography using methanol and dichloromethane to give 1-[5-(ethylsulfonylimino)-6-[7-methyl-3-(trifluoromethyl)imidazo[4,5-c]pyridazin-6-yl]-3-pyridinyl]cyclopropanecarbonitrile.

[0551] LCMS (method 2): retention time: 0.85 min, 436.36 (M+H) + .

[0552] 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)

[0553] Example H2. 1-[5-(ethylsulfonylimino)-6-[3-methyl-6-(trifluoromethyl)imidazo[4,5-b]pyridine- Preparation of 2-[2-yl]-3-pyridyl]cyclopropanecarbonitrile (Example P6, Table P)

[0554]

[0555] Step 1: 5-(1-cyanocyclopropyl)-3-ethylsulfanyl-N-[2-(methylamino)-5-(trifluoromethyl)-3-pyrrolidone Preparation of [[(2-[(2-pyridyl)pyridine-2-carboxamide)]]

[0556]

[0557] 5-(1-cyanocyclopropyl)-3-ethylsulfanyl-pyridine-2-carboxylic acid (2.4g, 9.7mmol) was dissolved in dichloromethane (100mL). N,N-dimethylformamide (10.0μL) was added, and then oxalyl chloride (1mL, 12mmol) was added dropwise via a syringe. The resulting light yellow suspension was stirred at room temperature for 1 hour, and then the solvent was concentrated in vacuo. The resulting solid was dissolved in tetrahydrofuran (30ml) and added to a solution of N2-methyl-5-(trifluoromethyl)pyridine-2,3-diamine (1.8g, 9.7mmol) and N,N-diethylethylamine (3.3mL, 23mmol) in tetrahydrofuran (75mL) at 0°C. The resulting mixture was stirred at 0°C for 30' and then stirred at room temperature for 2 hours. The reaction mixture was treated with a saturated solution of NH4Cl and diluted with ethyl acetate. The aqueous layer was extracted 3 times with ethyl acetate. The combined organic layers were washed with brine, dried over Na2SO4, filtered and concentrated in vacuo to give 5-(1-cyanocyclopropyl)-3-ethylsulfanyl-N-[2-(methylamino)-5-(trifluoromethyl)-3-pyridinyl]pyridine-2-carboxamide as a crude product which was used in the next step without further purification.

[0558] LCMS (method 1): 422 (M+H) + ; Retention time: 1.03min.

[0559] 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).

[0560] Step 2: 1-[5-ethylsulfanyl-6-[3-methyl-6-(trifluoromethyl)imidazo[4,5-b]pyridin-2-yl]- Preparation of 3-pyridyl]cyclopropanecarbonitrile

[0561]

[0562] 5-(1-Cyanocyclopropyl)-3-ethylsulfanyl-N-[2-(methylamino)-5-(trifluoromethyl)-3-pyridinyl]pyridine-2-carboxamide (4.2 g, 10 mmol) was dissolved in acetic acid (100 mL) and the resulting solution was stirred for 18 hours at 110° C. The acetic acid was removed in vacuo and the crude product was purified by silica gel chromatography to give 1-[5-ethylsulfanyl-6-[3-methyl-6-(trifluoromethyl)imidazo[4,5-b]pyridin-2-yl]-3-pyridinyl]cyclopropanecarbonitrile, Mp 142-144° C.

[0563] LCMS (method 1): 404 (M+H) + ; Retention time: 1.07min.

[0564] 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).

[0565] Step 3: 1-[5-(ethylsulfonylimino)-6-[3-methyl-6-(trifluoromethyl)imidazo[4,5-b]pyridine- Preparation of 2-[2-yl]-3-pyridyl]cyclopropanecarbonitrile (Example P6, Table P)

[0566]

[0567] The formation of the sulfoximine is analogous to Example H1, Step 7.

[0568] LCMS (method 1): 435 (M+H)+ ; Retention time: 0.87min.

[0569] 1 H NMR (400 MHz, chloroform) δ ppm 1.44 (t, J = 7.34 Hz, 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 = 1.47 Hz, 1H) 8.39 (d, J = 2.20 Hz, 1H) 8.79 (d, J = 1.47 Hz, 1H) 9.06-9.09 (m, 1H).

[0570] Example H3: 1-[5-(ethylsulfonylimino)-6-[5-methoxy-3-methyl-4-oxo-6-(trifluoromethyl)imidazole Preparation of oxazolo[4,5-c]pyridin-2-yl]-3-pyridinyl]cyclopropanecarbonitrile (Example P8, Table P)

[0571]

[0572] Step 1: N-[4-bromo-6-(difluoromethyl)-1-methoxy-2-oxo-3-pyridinyl]-2,2,2-trifluoro-N-methyl Preparation of 2-amino-acetamide

[0573]

[0574] At room temperature, trifluoroacetic anhydride (7.09mL, 49.82mmol) is added to a solution of 4-bromo-1-methoxy-3-(methylamino)-6-(trifluoromethyl)pyridine-2-one (5.0g, 16.61mmol) in dichloromethane (100mL). The reaction mixture is stirred at room temperature for 30 minutes, and then concentrated in vacuo. Water (100mL) is added, followed by saturated potassium carbonate aqueous solution (50mL), and the water layer is extracted with ethyl acetate (100mL). The organic layer is washed with salt water (100mL), dried over sodium sulfate, filtered, and concentrated in vacuo. The crude product is purified on silica gel to obtain pure N-[4-bromo-6-(difluoromethyl)-1-methoxy-2-oxo-3-pyridyl]-2,2,2-trifluoro-N-methyl-acetamide.

[0575] This material was used in the next step without further purification.

[0576] LCMS (method 5): 397 / 399 (M+H + ), retention time: 0.96min. 1 H NMR (400MHz, CDCl3) δppm3.27 (s, 3H), 4.16 (s, 3H), 6.84 (s, 1H).

[0577] Step 2: N-[4-azido-1-methoxy-2-oxo-6-(trifluoromethyl)-3-pyridinyl]-2,2,2-trifluoro- Preparation of N-methyl-acetamide

[0578]

[0579] To a solution of N-[4-bromo-1-methoxy-2-oxo-6-(trifluoromethyl)-3-pyridinyl]-2,2,2-trifluoro-N-methyl-acetamide (11.8 g, 29.7 mmol) in N,N-dimethylformamide (110 mL) was added sodium azide (2.9 g, 44.6 mmol) at room temperature. The reaction mixture was stirred overnight at room temperature. The above reaction was repeated separately, and then the combined reaction mixture was diluted with cold water (500 mL) and extracted with ethyl acetate (3 x 150 mL). The combined organic layers were washed with water (100 mL) and brine, dried over sodium sulfate, filtered and concentrated in vacuo below 40 °C to give N-[4-azido-1-methoxy-2-oxo-6-(trifluoromethyl)-3-pyridinyl]-2,2,2-trifluoro-N-methyl-acetamide. This material was used in the next step without further purification.

[0580] LCMS (method 5): 360 (M+H) + , retention time: 0.90min. 1 H NMR (400MHz, CDCl3) δppm 3.23 (s, 3H), 4.15 (s, 3H), 6.40 (s, 1H).

[0581] Step 3: Preparation of 4-azido-1-methoxy-3-(methylamino)-6-(trifluoromethyl)pyridin-2-one

[0582]

[0583] To a solution of N-[4-azido-1-methoxy-2-oxo-6-(trifluoromethyl)-3-pyridinyl]-2,2,2-trifluoro-N-methyl-acetamide (4.6 g, 13.0 mmol) in methanol (100 mL) was added potassium carbonate (4.7 g, 33.0 mmol). The reaction mixture was stirred at room temperature overnight and then diluted with water (150 mL). The aqueous layer was extracted with ethyl acetate (2 x 75 mL), the combined organic layers were washed with brine (150 mL), dried over sodium sulfate, filtered and concentrated in vacuo. The crude product was purified on silica gel (40% ethyl acetate in cyclohexane) to obtain 4-azido-1-methoxy-3-(methylamino)-6-(trifluoromethyl)pyridin-2-one (2.2 g, 8.4 mmol).

[0584] LCMS (Method E): 264 (M+H) + , retention time 0.94min. 1 H NMR (400MHz, CDCl3) δppm 3.18 (s, 3H), 4.11 (s, 3H), 6.46 (s, 1H).

[0585] Step 4: Preparation of 4-amino-1-methoxy-3-(methylamino)-6-(trifluoromethyl)pyridin-2-one

[0586]

[0587] At room temperature, triphenylphosphine (5.1g, 19mmol) was added to 4-azido-1-methoxy-3-(methylamino)-6-(trifluoromethyl)pyridine-2-one (1.7g, 6.5mmol) in tetrahydrofuran (50mL) and (5mL) solution, and the resulting mixture was stirred at room temperature for 2 hours. 2M aqueous hydrochloric acid solution (9mL, 18mmol, 2mol / L) was added and continued to stir overnight at room temperature. The reaction mixture was concentrated and quenched with saturated potassium carbonate aqueous solution (20mL). The water layer was extracted with ethyl acetate (2x75 mL), the organic layer was washed with brine (100mL) combined, dried over sodium sulfate, filtered and concentrated in vacuo. The residue was purified on silica gel (50%-60% ethyl acetate in cyclohexane) to obtain 4-amino-1-methoxy-3-(methylamino)-6-(trifluoromethyl)pyridine-2-one.

[0588] LCMS (method 5): 238 (M+H) + , retention time: 0.18min. 1 H NMR (400MHz, d6-DMSO) δppm 2.60 (s, 3H), 3.98 (s, 3H), 5.75 (s, 2H), 6.42 (s, 1H).

[0589] Step 5: 5-(1-cyanocyclopropyl)-3-ethylsulfanyl-N-[1-methoxy-3-(methylamino)-2-oxo- 6-(trifluoromethyl)-4-pyridinyl]pyridine-2-carboxamide and N-[4-amino-1-methoxy-2-oxo-6-(trifluoromethyl)- 3-pyridyl]-5-(1-cyanocyclopropyl)-3-ethylsulfanyl-N-methyl-pyridine-2-carboxamide (mixture of isomers) preparation

[0590]

[0591] To a suspension of 5-(1-cyanocyclopropyl)-3-ethylsulfanyl-pyridine-2-carboxylic acid (400 mg, 1.61 mmol) in dichloromethane (16 mL) was added a catalytic amount of N,N-dimethylformamide (2 drops) and oxalyl chloride (3.22 mmol, 0.287 mL) was added dropwise. The reaction was stirred at room temperature for 6 hours and the solvent was removed in vacuo to give 5-(1-cyanocyclopropyl)-3-ethylsulfanyl-pyridine-2-carbonyl chloride.

[0592] A solution of the above 5-(1-cyanocyclopropyl)-3-ethylsulfanyl-pyridine-2-carbonyl chloride (428 mg, 1.60 mmol) in dry tetrahydrofuran (20 mL) was slowly added to a mixture of 4-amino-1-methoxy-3-(methylamino)-6-(trifluoromethyl)pyridin-2-one (456.6 mg, 1.92 mmol) and triethylamine (0.678 mL, 4.81 mmol) in tetrahydrofuran (9.6 mL). The reaction mixture was stirred at room temperature for 2 hours, then quenched with water and extracted with dichloromethane (100 ml). The combined organic layers were washed with water and brine, dried over anhydrous sodium sulfate and concentrated in vacuo to give the desired isomeric mixture of 5-(1-cyanocyclopropyl)-3-ethylsulfanyl-N-[1-methoxy-3-(methylamino)-2-oxo-6-(trifluoromethyl)-4-pyridinyl]pyridine-2-carboxamide and N-[4-amino-1-methoxy-2-oxo-6-(trifluoromethyl)-3-pyridinyl]-5-(1-cyanocyclopropyl)-3-ethylsulfanyl-N-methyl-pyridine-2-carboxamide (750 mg, 1.60 mmol). This material was used in the next step without further purification.

[0593] LCMS (method 5): 468 (M+H) + , retention time: 0.86min.

[0594] Step 6: 1-[5-ethylsulfanyl-6-[5-methoxy-3-methyl-4-oxo-6-(trifluoromethyl)imidazo[4, Preparation of 5-c]pyridin-2-yl]-3-pyridinyl]cyclopropanecarbonitrile

[0595]

[0596] A solution of the above isomeric mixture of 5-(1-cyanocyclopropyl)-3-ethylsulfanyl-N-[1-methoxy-3-(methylamino)-2-oxo-6-(trifluoromethyl)-4-pyridinyl]pyridine-2-carboxamide and N-[4-amino-1-methoxy-2-oxo-6-(trifluoromethyl)-3-pyridinyl]-5-(1-cyanocyclopropyl)-3-ethylsulfanyl-N-methyl-pyridine-2-carboxamide (750 mg, 1.60 mmol) in acetic acid (4.8 mL) was heated to 100° C. for 48 hours. After cooling to room temperature, the reaction mixture was concentrated in vacuo. The residue was poured into water and extracted with ethyl acetate (3×100 mL), and the combined organic layers were washed with brine, dried over sodium sulfate and concentrated in vacuo. The crude product was purified by silica gel chromatography (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-pyridinyl]cyclopropanecarbonitrile (350 mg) as a solid. LCMS (Method E): 450 (M+H)+ , retention time 1.03min. 1 H NMR (400MHz, CDCl3) δppm 1.37(t,3H),1.59(m,2H),1.93(m,2H),3.01(q,2H),4.20(s,3H),4.21(s,3H),7.25(s,1H),7.76(d,J=2.0Hz,1H),8.32(d,J=2.0Hz,1H).

[0597] Step 7: 1-[5-(ethylsulfonylimino)-6-[5-methoxy-3-methyl-4-oxo-6-(trifluoromethyl)imidazole Preparation of oxazolo[4,5-c]pyridin-2-yl]-3-pyridinyl]cyclopropanecarbonitrile (Example P8, Table P)

[0598]

[0599] The formation of the sulfoximine is analogous to Example H1, Step 7.

[0600] LCMS (method 5): 481 (M+H) + ; Retention time: 0.85min.

[0601] 1H NMR(400MHz,DMSO-d6)δppm 1.14(t,J=7.40Hz,3H)1.83-1.94(m,2H)1.97-2.06(m,2H)3.44-3.66(m,2H)3.86(s, 3H) 4.12 (s, 3H) 4.56 (s, 1H) 7.41 (s, 1H) 8.38 (d, J = 2.20Hz, 1H) 8.90 (d, J = 2.20Hz, 1H).

[0602] Example H4. 1-[3-(ethylsulfonylimino)-4-[3-methyl-6-(trifluoromethylsulfanyl)imidazo[4,5- Preparation of [c]pyridin-2-yl]phenyl]cyclopropanecarbonitrile (Example P9, Table P)

[0603]

[0604] Step 1: N-[4-amino-6-(trifluoromethylsulfanyl)-3-pyridinyl]-4-bromo-2-ethylsulfanyl-N-methyl Preparation of 2-amino-benzamide

[0605]

[0606] Under argon, 4-bromo-2-ethylsulfanyl-benzoic acid (prepared as described in patent WO 2016 / 120182, (1.96 g, 7.51 mmol)) was suspended in dichloromethane (30 mL), and 2 drops of DMF were added, oxalyl dichloride (1.24 g, 0.851 mL, 9.76 mmol) was added dropwise, and gas evolution was observed. The mixture was stirred at room temperature for 4 hours, and then concentrated in vacuo to give 4-bromo-2-ethylsulfanyl-benzoyl chloride as the first step product. Under argon, 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 patent WO2016 / 169886 was added. The resulting mixture was stirred at room temperature overnight and then at 70°C for 8 hours. After cooling at room temperature, sodium bicarbonate and water were added. The aqueous layer was extracted twice with ethyl acetate. The combined organic layers were dried over sodium sulfate, filtered and concentrated in vacuo to give a mixture containing N-[4-amino-6-(trifluoromethylsulfanyl)-3-pyridinyl]-4-bromo-2-ethylsulfanyl-N-methyl-benzamide.

[0607] LCMS (method 1): 450 (M+H) + ; Retention time: 1.14min.

[0608] Step 2: 2-(4-Bromo-2-ethylsulfanyl-phenyl)-3-methyl-6-(trifluoromethylsulfanyl)imidazo[4,5- Preparation of pyridine

[0609]

[0610] N-[4-amino-6-(trifluoromethylsulfanyl)-3-pyridinyl]-4-bromo-2-ethylsulfanyl-N-methyl-benzamide (3.4 g, 5.1 mmol) was dissolved in acetic acid (51 mL). The resulting solution was stirred at 120° C. overnight and then cooled at room temperature. The acetic acid was removed under reduced pressure and the crude product was purified by silica gel chromatography.

[0611] The resulting mixture was dissolved in ethyl acetate, washed with bicarbonate, dried over sodium sulfate, filtered and concentrated in vacuo to give 2-(4-bromo-2-ethylsulfanyl-phenyl)-3-methyl-6-(trifluoromethylsulfanyl)imidazo[4,5-c]pyridine.

[0612] LCMS (method 1): 450 (M+H) + ; Retention time: 1.14min.

[0613] 1H NMR (400 MHz, chloroform) δ ppm 1.29 (t, J = 7.34 Hz, 3H) 2.92 (q, J = 7.34 Hz, 2H) 3.79 (s, 3H) 7.32 (d, J = 8.07 Hz, 1H) 7.50 (dd, J = 8.07, 1.83 Hz, 1H) 7.61 (d, J = 1.83 Hz, 1H) 8.15-8.17 (m, 1H) 8.90 (d, J = 1.10 Hz, 1H).

[0614] Step 3: 4-[3-ethylsulfanyl-4-[3-methyl-6-(trifluoromethylsulfanyl)imidazo[4,5-c]pyridine- Preparation of 2-aminophenylisoxazole

[0615]

[0616] Under argon, DMSO (1.11 mL) and water (0.53 mL) were added to a microwave vial, and the solution was purged with argon for 5 min. 2-(4-bromo-2-ethylsulfanyl-phenyl)-3-methyl-6-(trifluoromethylsulfanyl)imidazo[4,5-c]pyridine (0.2 g, 0.446 mmol), 4-isoxazole boronic acid pinacol ester (0.104 g, 0.535 mmol) and potassium fluoride (0.077 g, 1.33 mmol) were then added. Dichloropalladium; triphenylphosphine (0.0031 g, 0.0044 mmol) were added, and the resulting mixture was purged with argon for 5 min, stirred in a microwave system at 90 ° C for 40 min, cooled at room temperature and then poured into ice water. The water layer was extracted 3 times with dichloromethane. The milky water layer was then filtered and the obtained solid was dissolved in dichloromethane and added to the organic layer. The combined organic layers were dried over sodium sulfate, filtered and concentrated in vacuo. The obtained oil was washed with water. The precipitate formed in water was filtered, then redissolved in dichloromethane, and the solvent was concentrated in vacuo to give 4-[3-ethylsulfanyl-4-[3-methyl-6-(trifluoromethylsulfanyl)imidazo[4,5-c]pyridin-2-yl]phenyl]isoxazole, which was used as is in the next step.

[0617] LCMS (method 1): 437 (M+H) + ; Retention time: 0.95min.

[0618] Step 4: 2-[3-ethylsulfanyl-4-[3-methyl-6-(trifluoromethylsulfanyl)imidazo[4,5-c]pyridine- Preparation of 2-methyl]phenyl]acetonitrile

[0619]

[0620] 4-[3-Ethylsulfanyl-4-[3-methyl-6-(trifluoromethylsulfanyl)imidazo[4,5-c]pyridin-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 dark red reaction mixture (suspension) was filtered, washed with dichloromethane and concentrated in vacuo. The crude product was purified by silica gel chromatography column to give 2-[3-ethylsulfanyl-4-[3-methyl-6-(trifluoromethylsulfanyl)imidazo[4,5-c]pyridin-2-yl]phenyl]acetonitrile.

[0621] LCMS (method 1): 409 (M+H) + ; Retention time: 0.98min.

[0622] 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).

[0623] Step 5: 1-[3-ethylsulfanyl-4-[3-methyl-6-(trifluoromethylsulfanyl)imidazo[4,5-c]pyridine- Preparation of 2-methyl]phenyl]cyclopropanecarbonitrile

[0624]

[0625] 1-[3-Ethylsulfanyl-4-[3-methyl-6-(trifluoromethylsulfanyl)imidazo[4,5-c]pyridin-2-yl]phenyl]cyclopropanecarbonitrile (0.108 g, 0.2644 mmol) was dissolved in acetonitrile (1.322 mL). Then cesium carbonate (0.2584 g, 0.7931 mmol) and 1,2-dibromoethane (0.1490 g, 0.0683 mL, 0.7931 mmol) were added. The reaction mixture was stirred at 100 ° C for 2 hours under a microwave system. The reaction mixture was concentrated in vacuo. The residue was dissolved in ethyl acetate and washed several times with water and brine. The organic layer was dried over sodium sulfate, filtered and concentrated in vacuo. The crude product was purified by silica gel chromatography to obtain 1-[3-ethylsulfanyl-4-[3-methyl-6-(trifluoromethylsulfanyl)imidazo[4,5-c]pyridin-2-yl]phenyl]cyclopropanecarbonitrile.

[0626] LCMS (method 1): 435 (M+H) +; Retention time: 1.04min.

[0627] 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).

[0628] Step 6: 1-[3-(ethylsulfonylimino)-4-[3-methyl-6-(trifluoromethylsulfanyl)imidazo[4,5-c] Synthesis of [2-pyridinyl]phenyl]cyclopropanecarbonitrile (Example P9, Table P)

[0629]

[0630] Sulfoximine formation was performed as described in Example H1, Step 7.

[0631] LCMS (method 1): 466 (M+H) + ; Retention time: 0.86min.

[0632] Example H5: 1-[3-(ethylsulfonylimino)-4-[3-methyl-6-(trifluoromethyl)imidazo[4,5-c]pyridine- Synthesis of 2-methyl]phenyl]cyclopropanecarbonitrile (Example P13, Table P)

[0633]

[0634] Step 1: 1-[3-ethylsulfanyl-4-[3-methyl-6-(trifluoromethyl)imidazo[4,5-c]pyridin-2-yl]benzene Preparation of cyclopropanecarbonitrile

[0635]

[0636] To a mixture of 2-(4-bromo-2-ethylsulfanyl-phenyl)-3-methyl-6-(trifluoromethyl)imidazo[4,5-c]pyridine (prepared as described in patent WO 2016 / 030229) (0.5 g, 1.201 mmol), Pd2dba3 (0.056 g, 0.060 mmol) and BINAP (0.077 g, 0.120 mmol) in tetrahydrofuran (1.2 mL) was added cyclopropanecarbonitrile (0.090 g, 1.32 mmol) and cyclopropyl methyl ether (1.20 mL) under argon atmosphere at room temperature. The mixture was cooled at -25 °C and

[0637] At -25 ° C, under an argon atmosphere, bis(trimethylsilyl)amide lithium (1.3 mL, 1.321 mmol) was added dropwise. The mixture was stirred at 80 ° C for 2 hours. After cooling at room temperature, the mixture was filtered through a celite pad washed with ethyl acetate. The filtrate was washed with water. The aqueous layer was separated and extracted twice with ethyl acetate. The organic layers were combined, dried over anhydrous sodium sulfate, filtered and concentrated in vacuo. The crude product was purified by silica gel chromatography to obtain 1-[3-ethylsulfanyl-4-[3-methyl-6-(trifluoromethyl)imidazo[4,5-c]pyridin-2-yl]phenyl]cyclopropanecarbonitrile.

[0638] LCMS (method 1): 403 (M+H) + ; Retention time: 1.00min.

[0639] 1H NMR (400 MHz, chloroform) δ ppm 1.27 (t, J = 7.34 Hz, 3H) 1.52-1.57 (m, 2H) 1.86-1.91 (m, 2H) 2.91 (q, J = 7.46 Hz, 2H) 3.82 (s, 3H) 7.18 (dd, J = 8.07, 1.83 Hz, 1H) 7.46 (d, J = 8.07 Hz, 1H) 7.52 (d, J = 1.83 Hz, 1H) 8.14 (d, J = 0.73 Hz, 1H) 8.95 (s, 1H).

[0640] Step 2: 1-[3-(ethylsulfonylimino)-4-[3-methyl-6-(trifluoromethyl)imidazo[4,5-c]pyridine- Synthesis of 2-methyl]phenyl]cyclopropanecarbonitrile (Example P13, Table P)

[0641]

[0642] The desired product was prepared using the standard procedure described in Step 7, Example H1.

[0643] LCMS (method 1): 434 (M+H) + ; Retention time: 0.83min.

[0644] 1H NMR (400 MHz, chloroform) δ ppm 1.28 (t, J = 7.34 Hz, 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 = 8.07 Hz, 1H) 7.89 (dd, J = 7.89, 2.02 Hz, 1H) 8.05 (d, J = 1.83 Hz, 1H) 8.10 (d, J = 0.73 Hz, 1H) 8.93-8.96 (m, 1H).

[0645] Example H5: 1-[3-(ethylsulfonylimino)-4-[3-methyl-6-(trifluoromethyl)imidazo[4,5-b]pyridine- Synthesis of 2-methyl]phenyl]cyclopropanecarbonitrile (Example P15, Table P)

[0646]

[0647] Step 1: Synthesis of 2-ethylsulfanyl-4-isoxazol-4-yl-benzoic acid methyl ester

[0648]

[0649] Water (4mL), 4-isoxazole boronic acid pinacol ester (213mg, 1.09mmol) and potassium fluoride (158mg, 2.73mmol) are added to a solution of 4-bromo-2-ethylsulfanyl-benzoic acid methyl ester (WO 2016 / 023954) (250mg, 0.91mmol) in dimethyl sulfoxide (8mL) under argon. The concentrated reaction mixture is purged with argon for 5 minutes, followed by the addition of bis(triphenylphosphine)palladium dichloride (II) (6.4mg, 0.009mol). The vial is sealed, and the mixture is stirred in a microwave at 90 ° C for 40 minutes. The reaction mixture is poured into ice water, and the resulting light yellow suspension is filtered and washed with cold water. The solid is dissolved in dichloromethane, and the solution is dried over sodium sulfate and reduced to dryness under vacuum to obtain 2-ethylsulfanyl-4-isoxazole-4-yl-benzoic acid methyl ester as a light yellow solid. The substance is used in the next step without further purification.

[0650] LCMS (method 1): 262 (MH) - , retention time 0.88min.

[0651] Step 2: Synthesis of 4-(cyanomethyl)-2-ethylsulfanyl-benzoic acid methyl ester

[0652]

[0653] To a solution of 2-ethylsulfanyl-4-isoxazol-4-yl-benzoic acid methyl ester (760 mg, 2.89 mmol) in methanol (15 mL) was added a 1 M solution of potassium fluoride in water (8.66 mL, 8.66 mmol). The reaction mixture was stirred at reflux for 3 hours. After cooling, the suspension was filtered and the filtrate was concentrated in vacuo. The residue was purified by Combiflash on silica gel to give 4-(cyano-methyl)-2-ethylsulfanyl-benzoic acid methyl ester as a gum.

[0654] LCMS (method 5): 236 (M+H) + , retention time: 0.90min.

[0655] 1H 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).

[0656] Step 3: Synthesis of 4-(1-cyanocyclopropyl)-2-ethylsulfanyl-benzoic acid methyl ester

[0657]

[0658] To a solution of 4-(cyano-methyl)-2-ethylsulfanyl-benzoic acid methyl ester (300 mg, 1.275 mmol) in acetonitrile (15 mL) was added cesium carbonate (1.24 g, 3.825 mmol) and 1,2-dibromoethane (719 mg, 3.825 mmol). The reaction mixture was stirred at reflux for 90 minutes. After cooling, the suspension was filtered and the filtrate was concentrated in vacuo. The residue was purified on silica gel by Combiflash to give 4-(cyano-methyl)-2-ethylsulfanyl-benzoic acid methyl ester as an oil.

[0659] LCMS (method 1): 262 (M+H) + , retention time: 0.98min. 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).

[0660] Step 4: Synthesis of 4-(1-cyanocyclopropyl)-2-ethylsulfanyl-benzoic acid

[0661]

[0662] To a solution of 4-(1-cyanocyclopropyl)-2-ethylsulfanyl-benzoic acid methyl ester (198 mg, 0.758 mmol) in a mixture of tetrahydrofuran (9 mL) and water (3 mL) was added lithium hydroxide (1.5 eq., 1.137 mmol) at 0-5°C and the reaction mixture was stirred overnight at room temperature. The solution was concentrated in vacuo, the residue was diluted with tert-butyl methyl ether (10 mL), and acidified with 1M aqueous hydrochloric acid solution (10 mL). The organic layer was separated, the aqueous layer was extracted with tert-butyl methyl ether, the combined organic layers were washed with water and brine, dried over sodium sulfate, filtered and concentrated in vacuo to give 4-(1-cyanocyclopropyl)-2-ethylsulfanyl-benzoic acid as a solid. The material was used in the next step without further purification.

[0663] LCMS (method 5): 246 (MH) - , retention time 0.83min. 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).

[0664] Step 5 1-[3-ethylsulfanyl-4-[3-methyl-6-(trifluoromethyl)imidazo[4,5-b]pyridin-2-yl]benzene Preparation of cyclopropanecarbonitrile

[0665]

[0666] 4-(1-cyanocyclopropyl)-2-ethylsulfanyl-benzoic acid (1.7 g, 6.9 mmol) was dissolved in nitrobenzene (14 mL), and N2-methyl-5-(trifluoromethyl)pyridine-2,3-diamine (WO 2017 / 043342) (1.6 g, 1.2 equiv) was added, followed by the slow addition of phosphorus oxychloride (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 mass was quenched with 30% sodium hydroxide solution, and water (100 mL) was added. The aqueous layer was extracted with ethyl acetate (3 x 100 ml). The combined organic layers were dried over sodium sulfate, filtered and concentrated in vacuo. The crude product was purified by chromatography to obtain 1-[3-ethylsulfanyl-4-[3-methyl-6-(trifluoromethyl)imidazo[4,5-b]pyridin-2-yl]phenyl]cyclopropanecarbonitrile.

[0667] LCMS (method 2): 403 (M+H) + ; Retention time: 1.18min.

[0668] 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).

[0669] Step 6: 1-[3-(ethylsulfonylimino)-4-[3-methyl-6-(trifluoromethyl)imidazo[4,5-b]pyridine- Preparation of 2-methyl]phenyl]cyclopropanecarbonitrile (Example P15, Table P)

[0670]

[0671] The desired product was prepared using the standard procedure described in Example H1, Step 7.

[0672] LCMS (method 1): 434 (M+H) + ; Retention time: 0.88min.

[0673] 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).

[0674] Example H6: [5-Cyclopropyl-2-[7-(trifluoromethyl)imidazo[1,2-b]pyridazin-2-yl]-3-pyridinyl]-ethyl Imido-oxy-λ 6 -Synthesis of sulfane (Example P16, Table P).

[0675]

[0676] Step 1. Preparation of 2-bromo-1-(5-bromo-3-ethylsulfanyl-2-pyridyl)ethanone

[0677]

[0678] A sample of 1-(5-bromo-3-ethylsulfanyl-2-pyridyl)ethanone (prepared as described in WO 2016 / 071214) (1 g, 3.8439 mmol) was suspended in acetonitrile (3 mL) and chloroform (3 mL). Dibromocopper (1.7171 g, 7.6879 mmol) was added and the reaction mixture was heated to 70 °C and stirred for 22 hours, after which time LC-MS showed the reaction was complete. The reaction mixture was passed through celite and filtered with dichloromethane. The filtrate was concentrated in vacuo and the obtained residue was purified by silica gel chromatography to give 2-bromo-1-(5-bromo-3-ethylsulfanyl-2-pyridyl)ethanone.

[0679] LCMS (method 1): retention time: 1.10 min; 339 / 341 (M+H) + .

[0680] 1 H 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).

[0681] Step 2: Preparation of 2-(5-bromo-3-ethylsulfanyl-2-pyridyl)-7-(trifluoromethyl)imidazo[1,2-b]pyridazine preparation

[0682]

[0683] In a three-necked flask equipped with a reflux condenser, 2-bromo-1-(5-bromo-3-ethylsulfanyl-2-pyridyl)ethanone (0.50 g, 1.5 mmol) and 5-(trifluoromethyl)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 in vacuo. The resulting solid was dissolved in ethyl acetate and washed once with a saturated solution of NaHCO3. The organic layer was pre-dried with brine, dried over sodium sulfate, filtered and concentrated in vacuo. The crude product was purified by silica gel chromatography to give 2-(5-bromo-3-ethylsulfanyl-2-pyridyl)-7-(trifluoromethyl)imidazo[1,2-b]pyridazine.

[0684] LCMS (method 1): retention time: 1.15 min; 403 / 405 (M+H) + .

[0685] 1H NMR (400 MHz, chloroform) δ ppm 1.44 (t, J = 7.34 Hz, 3H) 3.04 (q, J = 7.34 Hz, 2H) 7.82 (d, J = 1.83 Hz, 1H) 8.33-8.39 (m, 1H) 8.57 (dd, J = 3.85, 2.02 Hz, 2H) 8.81-8.86 (m, 1H).

[0686] Step 3: 2-(5-cyclopropyl-3-ethylsulfanyl-2-pyridyl)-7-(trifluoromethyl)imidazo[1,2-b]pyridinium Preparation of oxazine

[0687]

[0688] Toluene (14mL) and water (0.69mL) were placed in a 100ml-3-necked flask and flushed with argon for 5min. Under argon, 2-(5-bromo-3-ethylsulfanyl-2-pyridyl)-7-(trifluoromethyl)imidazo[1,2-b]pyridazine (0.30g, 0.74mmol), cyclopropylboric acid (0.087g, 0.97mmol), tripotassium phosphate (0.58g, 2.6mmol), tricyclohexylphosphane (0.022g, 0.074mmol) and palladium acetate (II) (0.0084g, 0.050eq, 0.037mmol) were added. The brown reaction mixture was heated to 110°C and stirred overnight. The mixture was then cooled at room temperature and water and ethyl acetate were added. The resulting mixture was filtered through diatomaceous earth, and the diatomaceous earth cake was washed with ethyl acetate. The organic layer was separated, dried over sodium sulfate, filtered and concentrated under vacuum. The crude product was purified by silica gel chromatography to give 2-(5-cyclopropyl-3-ethylsulfanyl-2-pyridinyl)-7-(trifluoromethyl)imidazo[1,2-b]pyridazine.

[0689] LCMS (method 1): retention time: 1.08 min; 365 (M+H) + .

[0690] 1H NMR (400 MHz, chloroform) δ ppm 0.81-0.86 (m, 2H) 1.09-1.16 (m, 2H) 1.39 (t, J = 7.34 Hz, 3H) 1.94-2.03 (m, 1H) 3.00 (q, J = 7.34 Hz, 2H) 7.36-7.39 (m, 1H) 8.33 (d, J = 1.83 Hz, 1H) 8.33 (s, 1H) 8.54 (d, J = 2.20 Hz, 1H) 8.83-8.86 (m, 1H).

[0691] Step 4: [5-cyclopropyl-2-[7-(trifluoromethyl)imidazo[1,2-b]pyridazin-2-yl]-3-pyridinyl]-ethyl Imido-oxy-λ 6 - Preparation of sulfane ((Example P16, Table P))

[0692]

[0693] 2-(5-cyclopropyl-3-ethylsulfanyl-2-pyridinyl)-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 quenched with ice water and sodium thiosulfate after 45 min. 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]pyridazine-2-yl]-3-pyridinyl]-ethyl-imino-oxo-λ 6 -sulfane.

[0694] LCMS (method 1): retention time: 0.87 min; 396 (M+H) + .

[0695] 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).

[0696] Example H7: [5-Cyclopropyl-2-[6-(trifluoromethyl)pyrazolo[4,3-c]pyridin-2-yl]-3-pyridinyl]-ethyl Imido-oxy-λ 6 -Synthesis of sulfane (Example P7, Table P)

[0697]

[0698] Step 1: Preparation of 2,5-dibromo-3-ethylsulfanyl-pyridine

[0699]

[0700] A solution of diethyl disulfide (7.76 g, 63.5 mmol, 2.00 equiv) and tert-butyl nitrite (4.91 g, 47.6 mmol, 1.50 equiv) in DCE (60 mL) and DCM (40 mL) was heated to 40 °C. A solution of 2,5-dibromopyridin-3-amine (8.00 g, 31.7 mmol, 1.00 equiv) in dichloroethane (200 mL) was slowly added to the mixture over 90 min and the reaction mixture was stirred at 40 °C for another 1 h. After the reaction was complete, the reaction mass was cooled, diluted with water (100 mL) and extracted with dichloromethane (2 x 100 mL). The organic layer was separated and the combined organic layer was dried over sodium sulfate, filtered and concentrated in vacuo. The crude product was purified by column chromatography (silica gel, 5%-15% ethyl acetate / cyclohexane) to give 2,5-dibromo-3-ethylsulfanyl-pyridine.

[0701] LCMS (method 4): 296 (M+H) + , retention time: 1.16min.

[0702] 1 H NMR (400MHz, CDCl3) δ / ppm: 1.32 (t, 3H), 2.98 (m, 2H), 7.52 (s, 1H) 8.19 (s, 1H).

[0703] Step 2: Preparation of (5-bromo-3-ethylsulfanyl-2-pyridyl)hydrazine

[0704]

[0705] To a solution of 2,5-dibromo-3-ethylsulfanyl-pyridine (1 g, 3.3669 mmol) in 1,4-dioxane (10.34 g) was added hydrazine monohydrate (1.0113 g, 20.201 mmol) and the resulting mixture was stirred at 120° C. for 10 hours. After completion of the reaction, the mixture was diluted with water (30 ml) and extracted with ethyl acetate. The combined organic layers were washed with water (20 ml), dried over sodium sulfate, filtered and concentrated in vacuo to give (5-bromo-3-ethylsulfanyl-2-pyridyl)hydrazine.

[0706] LCMS: 250 (M+H) + , retention time 0.6min.

[0707] 1H NMR (400 MHz, CHLOROFORM-d) d ppm 1.26 (t, 3H) 2.81 (q, 2H) 3.10 (br 2H) 6.67 (br s, 1H) 7.65 (d, 1H) 8.15 (d, 1H).

[0708] Step 3: 4-[2-(5-Bromo-3-ethylsulfanyl-2-pyridinyl)hydrazine]-6-(trifluoromethyl)pyridine-3-carboxylic acid Preparation

[0709]

[0710] 4-Chloro-6-(trifluoromethyl)pyridine-3-carboxylic acid (CAS [1060810-66-3]) (20 g, 88.672 mmol), (5-bromo-3-ethylsulfanyl-2-pyridinyl)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 completion of the reaction, the mixture was concentrated in vacuo to remove all the pentanol. The obtained residue was co-evaporated with toluene. The crude product was diluted with water (100 ml), brine (100 ml) and extracted with ethyl acetate (3 x 200 ml). The combined organic layers were dried over sodium sulfate, filtered and concentrated in vacuo. The obtained solid was triturated with cyclohexane to give 4-[2-(5-bromo-3-ethylsulfanyl-2-pyridinyl)hydrazinyl]-6-(trifluoromethyl)pyridine-3-carboxylic acid.

[0711] LCMS (method 5): retention time 1.50 min, 439 (M+2) + .

[0712] 1H NMR(400MHz,DMSO-d6)d 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).

[0713] Step 4: 2-(5-Bromo-3-ethylsulfanyl-2-pyridinyl)-3-chloro-6-(trifluoromethyl)pyrazolo[4,3-c]pyrrolidone Preparation of pyridine

[0714]

[0715] 4-[2-(5-bromo-3-ethylsulfanyl-2-pyridinyl)hydrazine]-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 was refluxed at 110° C. for 50 min. After completion of the reaction, the mixture was concentrated (phosphorus oxychloride was distilled off under reduced pressure) and the reactant was diluted with dichloromethane (110 ml) and poured into ice water (200 mL). The aqueous layer was extracted with dichloromethane (2 x 100 ml). The combined organic layers were washed with water (200 ml), dried over sodium sulfate, filtered, and concentrated in vacuo. The crude product was purified by silica gel chromatography to obtain 2-(5-bromo-3-ethylsulfanyl-2-pyridinyl)-3-chloro-6-(trifluoromethyl)pyrazolo[4,3-c]pyridine.

[0716] LCMS: 437 (M+H) + , retention time 1.21min.

[0717] 1H NMR (400 MHz, CHLOROFORM-d) d ppm 1.34 (m, 3H) 2.85 (m, 2H) 7.92 (s, 2H) 8.02 (m, 1H) 8.60 (m, 1H) 9.32 (m, 1H).

[0718] Step 5: Preparation of 2-(5-bromo-3-ethylsulfanyl-2-pyridinyl)-6-(trifluoromethyl)pyrazolo[4,3-c]pyridine preparation

[0719]

[0720] 2-(5-bromo-3-ethylsulfanyl-2-pyridinyl)-3-chloro-6-(trifluoromethyl)pyrazolo[4,3-c]pyridine (0.2mmol, 0.1g) was dissolved in acetic acid (2mL), and zinc (0.5mmol, 0.03g) was slowly added to the mixture. The reaction mass was stirred at 55°C for 40min. The reaction was monitored by LCMS and TLC. After completion, the reaction mixture was poured into water (30ml), and the resulting solution was extracted with ethyl acetate (20ml x 3). The combined organic layers were washed with aqueous saturated sodium chloride solution (30ml), dried over anhydrous sodium sulfate, filtered and concentrated in vacuo. The residue was subjected to silica gel column chromatography to obtain 2-(5-bromo-3-ethylsulfanyl-2-pyridinyl)-6-(trifluoromethyl)pyrazolo[4,3-c]pyridine.

[0721] H NMR (400 MHz, CHLOROFORM-d) d ppm 1.29 (m, 4H) 2.95 (m, 2H) 7.85 (m, 1H) 8.35 (m, 1H) 8.38 (d, 1H) 8.95 (m, 1H) 9.44 (m, 1H).

[0722] LCMS: retention time 1.6 min, 403 (M+H) + .

[0723] Step 6: 2-(5-cyclopropyl-3-ethylsulfanyl-2-pyridinyl)-6-(trifluoromethyl)pyrazolo[4,3-c]pyrrolidone Preparation of pyridine

[0724]

[0725] In a microwave vial, 2-(5-bromo-3-ethylsulfanyl-2-pyridyl)-6-(trifluoromethyl)pyrazolo[4,3-c]pyridine (0.1 g, 0.2 mmol), cyclopropylboronic acid (0.03 g, 0.3 mmol), tripotassium phosphate (0.2 g, 0.9 mmol), tricyclohexylphosphane (0.007 g, 0.02 mmol) were added in toluene (2 mL) and water (1 mL). The reaction mass was purged with nitrogen for 30 min. Palladium(II) acetate (0.003 g, 0.01 mmol) was then added thereto and the reaction mixture was stirred at 150 °C under microwave 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 in vacuo. The compound was separated by silica gel chromatography to give 2-(5-cyclopropyl-3-ethylsulfanyl-2-pyridinyl)-6-(trifluoromethyl)pyrazolo[4,3-c]pyridine.

[0726] LCMS: 365 (M+H) + , retention time 1.12min.

[0727] 1H NMR (400 MHz, CHLOROFORM-d) d ppm 0.86 (m, 2H) 1.13 (br, 2H) 1.23 (m, 4H) 2.90 (q, 2H) 7.47 (d, 1H) 8.13 (m, 2H) 8.94 (s, 1H) 9.40 (m, 1H).

[0728] Step 7: [5-cyclopropyl-2-[6-(trifluoromethyl)pyrazolo[4,3-c]pyridin-2-yl]-3-pyridinyl]-ethyl Imido-oxy-λ 6 -Synthesis of sulfane (Example P7, Table P)

[0729]

[0730] The desired product was prepared using the standard procedure described in Example H1, Step 7.

[0731] LCMS (method 5): retention time 0.94 min, 396 (M+H) + .

[0732] 1H NMR (400 MHz, CHLOROFORM-d) d ppm 1.25 (m, 4H) 1.44 (m, 3H) 2.16 (m, 1H) 3.87 (m, 2H) 8.06 (s, 1H) 8.29 (d, 1H) 8.56 (d, 1H) 8.87 (d, 1H) 9.40 (s, 1H).

[0733] Example H8: [5-cyclopropyl-2-[5-(trifluoromethylsulfanyl)-1,3-benzoxazol-2-yl]-3-pyridinyl]- Ethyl-imino-oxy-λ 6 -Synthesis of sulfane (Example P18, Table P)

[0734]

[0735] The desired product was prepared using the standard procedure described in Example H1, Step 7 starting from 2-(5-cyclopropyl-3-ethylsulfanyl-2-pyridyl)-5-(trifluoromethylsulfanyl)-1,3-benzoxazole (known from WO 19 / 009307).

[0736] LCMS (method 5): 428 (M+H) + , retention time: 1.03min.

[0737] Additional compounds of the invention can be prepared analogously to the above methods. Table P lists compounds prepared to further illustrate the invention.

[0738]

[0739]

[0740]

[0741] By adding other insecticidal, acaricidal and / or fungicidal active ingredients, the activity of the composition according to the present invention can be significantly widened and adapted to prevailing conditions. Mixtures with compounds of formula I and other insecticidal, acaricidal and / or fungicidal active ingredients can also have other unexpected advantages, which can also be described as synergistic activities in a wider sense. For example, better tolerance of plants, reduced phytotoxicity, insects can be controlled at their different developmental stages, or better behavior during their production (e.g., during grinding or mixing, during their storage or during their use).

[0742] Here, suitable active ingredients to be added are, for example, representatives of the following classes of active ingredients: organophosphorus compounds, nitrophenol derivatives, thioureas, juvenile hormones, formamidines, benzophenone derivatives, ureas, pyrrole derivatives, carbamates, pyrethroids, chlorinated hydrocarbons, acylureas, pyridylmethyleneamino derivatives, macrolides, neonicotinoids and Bacillus thuringiensis preparations.

[0743] The following mixtures of a compound of formula I with an active ingredient are preferred (the abbreviation "TX" means "a compound selected from the group consisting of Group Y-1 to Y-8, X-1 to X-8, U-1 to U-2 and V-1 to V-6 and the compounds of the present invention in Table P”):

[0744] An auxiliary agent selected from the group consisting of: petroleum (alias) (628) + TX;

[0745] Acaricide selected from the group consisting of: 1,1-bis(4-chlorophenyl)-2-ethoxyethanol (IUPAC name) (910) + TX, 2,4-dichlorophenylbenzenesulfonate (IUPAC / Chemical Abstracts name) (1059) + TX, 2-fluoro-N-methyl-N-1-naphthylacetamide (IUPAC name) (1295) + TX, 4-chlorophenylphenyl sulfone (IUPAC name) (981) + TX, avermectin (1) + TX, acetamipridone (3) + T X, acetothionil [CCN] + TX, flumethrin (9) + TX, aldicarb (16) + TX, aldicarb (863) + TX, α-cypermethrin (202) + TX, cypermethrin (870) + TX, sulfamethoxam [CCN] + TX, aminothioate (872) + TX, amitriptyline (875) + TX, amitriptyline hydrogen oxalate (875) + TX, amitraz (24) + TX, cypermethrin (881) + TX, arsenic trioxide (882) + TX, AVI 382 (compound code) + TX, AZ 60541 (compound code) + TX, azinphos-methyl (44) + TX, azinphos-methyl (45) + TX, azobenzene (IUPAC name) (888) + TX, azacyclotin (46) + TX, azothoate (889) + TX, benomyl (62) + TX, benoxafos (alias) [CCN] + TX, benzoximate (71) + TX, benzyl benzoate (IUPAC name) [CCN] + TX, bifenazate (74) + TX, bifenthrin (76) + TX, binacarb (907) + TX, bromethrin (alias) + TX, bromocyclene (918) + TX, bromophos (920) + TX, ethyl bromophos (921) + TX, bromopropylate (94) + TX, buprofezin (99) + TX, butanone (103) + TX, butanone sulfone (104) + TX, butylpyridaben (alias) + TX, lime sulfur (calcium polysulfide)(IUPAC name)(111)+TX、campheechlor(941)+TX、carbanolate(943)+TX、carbaryl(115)+TX、carbofuran(118)+TX、carbothion(947)+TX、CGA 50'439(research code)(125)+TX、chinomethionat(126)+TX、chlorbenside(959)+TX、chlordimeform(964)+TX、Chlorpheniramine hydrochloride (964) + TX, chlorfenapyr (130) + TX, chlorfenapyr (968) + TX, chlorfenson (970) + TX, chlorfensulfide (971) + TX, chlorfenphos (131) + TX, chlorobenzilate (975) + TX, chloromebuform (977) + TX, chloromethiuron (978) + TX, chloropropylate (983) + TX, chlorpyrifos (145) + TX, methyl chlorpyrifos (146 )+TX, chlorthiophos (994)+TX, cinerin I (696)+TX, cinerin II (696)+TX, cinerins (696)+TX, clofenac (158)+TX, closantel (alias) [CCN]+TX, kumaphos (174)+TX, crotamiton (alias) [CCN]+TX, crotoxyphos (1010)+TX, thiophene (1013)+TX, cyanthoate (1020)+TX, fluazifop (CAS registration number: 400882-07-7)+TX, trichlorofluoro Cypermethrin (196) + TX, Cyclohexan (199) + TX, Cypermethrin (201) + TX, DCPM (1032) + TX, DDT (219) + TX, Demephion (1037) + TX, Demephion-O (1037) + TX, Demephion-S (1037) + TX, Demeton (1038) + TX, Demeton-methyl (224) + TX, Demeton-O (1038) + TX, Demeton-methyl (224) + TX, Demeton-S (1038) + TX, Demeton-S (224) + TX, Demeton-S-methylsulfonyl fon)(1039)+TX, dimethoate(226)+TX, dimpropyridaz+TX, dialifos(1042)+TX, diazinon(227)+TX, benzylfluanid(230)+TX, dichlorvos(236)+TX, dicliphos(alias)+TX, chlorpyrifos(242)+TX, dicrotophos(243)+TX, pendimethalin(1071)+TX, dimefox(1081)+TX, dimethoate(262)+TX, dinacti(alias)(653)+TX, dinex(1089)+TX,Dinex-diclexine (1089) + TX, dinobuton (269) + TX, dinocap (270) + TX, dinocap-4 [CCN] + TX, dinocap-6 [CCN] + TX, dinitropropene (1090) + TX, dinopenton (1092) + TX, dinosulfon (1097) + TX, dinoterbon (1098) + TX, dioxafos (1102) + TX, diphenyl sulfone (IUPAC name) (1103) + TX, disulfiram (alias) [CCN] + TX, disulfothion (278) + TX, DNO C(282)+TX, dofenapyn(1113)+TX, doramectin(alias)[CCN]+TX, endosulfan(294)+TX, endothion(1121)+TX, EPN(297)+TX, eprinomectin(alias)[CCN]+TX, ethion(309)+TX, ethoate-methyl(1134)+TX, etoxazole(320)+TX, etrimfos(1142)+TX, fenazaflor(1147)+TX, fenazaquin(328)+TX, fenbutatin oxide)(330)+TX, fenothiocarb(337)+TX, cypermethrin(342)+TX, fenpyrad(alias)+TX, fenpyroximate(345)+TX, fenson(1157)+TX, fentrifanil(1161)+TX, cypermethrin(349)+TX, fipronil(354)+TX, fluacrypyrim(360)+TX 、flubenzimine (1166) + TX、flubenzimine (1167) + TX、flufenuron (366) + TX、flucythrinate (367) + TX、fluenetil (1169) + TX、flufenuron (370) + TX、flumethrin (372) + TX、fluorbenside (1174) + TX、fluvalinate (1184) + TX、FMC 1137 (research code) (1185) + TX、fenapyr (405) + TX、fenapyr hydrochloride (405) + TX、formothion (1192) + TX、Formparanate (1193) + TX, γ-HCH (430) + TX, glyodin (1205) + TX, halfenprox (424) + TX, heptenophos (432) + TX, hexadecylcyclopropanecarboxylate (IUPAC / Chemical Abstracts name) (1216) + TX, hexathiazolin (441) + TX, iodomethane (IUPAC name) (542) + TX, isocarbophos (alias) (473) + TX, isopropyl O-(methoxyaminothiophosphoryl) salicylate (IUPAC name) (473) + TX, ivermectin (alias) [CCN] + TX, jasmolin I (696) + TX, jasmolin II (696) + TX, jodfenphos ( phos)(1248)+TX, lindane(430)+TX, chlorfenuron(490)+TX, malathion(492)+TX, malonoben(1254)+TX, mecarbam(502)+TX, mephosfolan(1261)+TX, methylthiophene (alias)[CCN]+TX, methacrifos( 1266) + TX, methamidophos (527) + TX, methidathion (529) + TX, methiocarb (530) + TX, methomyl (531) + TX, methyl bromide (537) + TX, metolcarb (550) + TX, metolcarb (556) + TX, mexacarbate (1290) + TX, mitoxantrone (557) + TX, milbemycin oxime (alias) [CCN] + TX, mipafox (1293) + TX, monocrotophos (561) + TX, morphothion (1300) + TX, moxidectin (alias) [CCN] + TX, naled (567) + TX, NC-184 (compound code) + TX, NC-512 (compound code) + TX, nifluridide (1309) + TX, nicotin 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, oxydeprofos (1324) + TX,Oxydisulfoton (1325) + TX, pp'-DDT (219) + TX, parathion (615) + TX, permethrin (626) + TX, petroleum oil (alias) (628) + TX, fenthion (1330) + TX, fenthion (631) + TX, phorate (636) + TX, phosalone (637) + TX, phosfolan (1338) + TX, phosmet (638) + TX, phosphamidon (639) + TX, phoxim (642) + TX, methylpirimphos (652) + TX, polychloroterpenes (traditional name) (1347) + TX 、polynactins (alias) (653) + TX, proclonol (1350) + TX, probromophos (662) + TX, promacyl (1354) + TX, propetamphos (671) + TX, propetamphos (673) + TX, propoxur (678) + TX, prothidathion (1360) + TX, prothoate (1362) + TX, pyrethrin I (696) + TX, pyrethrin II (696) + TX, pyrethrins (696) + TX, pyridaben (699) + TX, pyridazinethio Pyridaphenthion (701) + TX, pyrimidifen (706) + TX, pyrimidophos (1370) + TX, quinalphos (711) + TX, quintiofos (1381) + TX, R-1492 (research code) (1382) + TX, RA-17 (research code) (1383) + TX, rotenone (722) + TX, schradan (1389) + TX, sebufos (alias) + TX, selamectin (alias) [CCN] + TX, SI-0009 (chemical Compound code) + TX, sophamide (1402) + TX, spirodiclofen (738) + TX, spiromesiclofen (739) + TX, SSI-121 (research code) (1404) + TX, sulfilam (alias) [CCN] + TX, sulfluramid (750) + TX, sulfotep (753) + TX, sulfur (754) + TX, SZI-121 (research code) (757) + TX, τ-fluvalinate (398) + TX, tebufenpyrad (763) + TX, TEPP (1417) + TX, terbufen (terbam) (alias) + TX, stirofos (777) + TX,Tetradifon (786) + TX, Tetranactin (alias) (653) + TX, Tetrasul (1425) + TX, Thiafenox (alias) + TX, Thiocarboxime (1431) + TX, Thiofanox (800) + TX, Thiometon (801) + TX, Thiofanox (1436) + TX, Thuringiensin (alias) [CCCN ]+TX, triamiphos (1441)+TX, triarathene (1443)+TX, triazophos (820)+TX, triazuron (alias)+TX, trichlorfon (824)+TX, trifenofos (1455)+TX, trinactin (alias) (653)+TX, aphidazole (847)+TX, vaniliprole [CCN] and YI-5302 (compound code)+TX,

[0746] an algaecide selected from the group consisting of bethoxazin [CCN] + TX, copper dioctanoate (IUPAC name) (170) + TX, copper sulfate (172) + TX, cybutryne [CCN] + TX, dichlone (1052) + TX, dichlorophen (232) + TX, endosylamine (295) + TX, fentin (347) + TX, slaked lime [CCN] + TX, nabam (566) + TX, quinoclamine (714) + TX, quinonamid (1379) + TX, simazine (730) + TX, triphenyltin acetate (IUPAC name) (347) and triphenyltin hydroxide (IUPAC name) (347) + TX,

[0747] An anthelmintic selected from the group consisting of: avermectin (1) + TX, fusulin (1011) + TX, doramectin (alias) [CCN] + TX, emamectin (291) + TX, emamectin benzoate (291) + TX, eprinomectin (alias) [CCN] + TX, ivermectin (alias) [CCN] + TX, milbemycin oxime (alias) [CCN] + TX, moxidectin (alias) [CCN] + TX, piperazine [CCN] + TX, selamectin (alias) [CCN] + TX, spinosad (737) and thiophanate (1435) + TX,

[0748] Avicides selected from the group consisting of chloralose (127) + TX, endrin (1122) + TX, fenthion (346) + TX, pyridin-4-amine (IUPAC name) (23) and strychnine (745) + TX,

[0749] Bactericides selected from the group consisting of: 1-hydroxy-1H-pyridine-2-thione (IUPAC name) (1222) + TX, 4-(quinoxalin-2-ylamino)benzenesulfonamide (IUPAC name) (748) + TX, 8-hydroxyquinoline sulfate (446) + TX, bronopol (97) + TX, copper dioctanoate (IUPAC name) (170) + TX, copper hydroxide (IUPAC name) (169) + TX, cresol [CCN] + TX, dichlorophen (232) + TX, dipyrithione (1105) + TX, dodesine (1112) + TX, fenaminosulf (1144) + TX, formaldehyde (404) + TX, mercaptophenone ( alias) [CCN] + TX, kasugamycin (483) + TX, kasugamycin hydrochloride hydrate (483) + TX, nickel bis(dimethyldithiocarbamate) (IUPAC name) (1308) + TX, nitrapyrin (580) + TX, octhilinone (590) + TX, oxolinic acid (606) + TX, oxytetracycline (611) + TX, potassium hydroxyquinoline sulfate (446) + TX, probenazole (658) + TX, streptomycin (744) + TX, streptomycin sesquisulfate (744) + TX, chlorphenamine (766) + TX, and thimerosal (alias) [CCN] + TX,

[0750] A biological agent selected from the group consisting of: GV of cotton brown banded moth (alias) (12) + TX, Agrobacterium radiobacterium (alias) (13) + TX, Amblyseius spp. (alias) (19) + TX, Spodoptera exigua NPV (alias) (28) + TX, Anagrus atomus (alias) (29) + TX, Aphelinus abdominalis (alias) (33) + TX, Aphidius colemani (alias) (34) + TX, Aphidoletes aphidimyza (alias) (35) + TX, Spodoptera exigua NPV (alias) (38) + TX, Bacillus firmus (alias) (48) + TX, Bacillus sphaericus Neide)(scientific name)(49)+TX、Bacillus thuringiensis Berliner)(scientific name)(51)+TX、Bacillus thuringiensis subsp.aizawai)(scientific name)(51)+TX、Bacillus thuringiensis subsp.israelensis)(scientific name)(51)+TX、Bacillus thuringiensis subsp.japonensis)(scientific name)(51)+TX、Bacillus thuringiensis subsp.kurstaki)(scientific name)(51)+TX、Bacillus thuringiensis subsp.tenebrionis (scientific name) (51) + TX, Beauveria bassiana (alias) (53) + TX, Beauveria brongniartii (alias) (54) + TX, Chrysoperla carnea (alias) (151) + TX, Cryptolaemus montrouzieri (alias) (178) + TX, Codling moth GV (alias) (191) + TX, Dacnusa sibirica (alias) (212) + TX, Diglyphus isaea (alias) (254) + TX, Encarsia formosa (scientific name) (293) + TX, Eretmocerus eremicus) (alias) (300) + TX, Spodoptera exigua NPV (alias) (431) + TX, Heterorhabditis bacteriophora and H. megidis (alias) (433) + TX, Hippodamia convergens (alias) (442) + TX, Leptomastix dactylopii (alias) (488) + TX, Macrolophus caliginosus (alias) (491) + TX, Cabbage armyworm NPV (alias) (494) + TX, Metaphycus helvolus (alias) (522) + TX, Metarhizium anisopliae var.acridum)(scientific name)(523)+TX, Metarhizium anisopliae var.anisopliae)(scientific name)(523)+TX, Neodiprionsertifer NPV and Neodiprionsertifer rubrum NPV.lecontei)NPV(alias)(575)+TX、Phytoseiulus species(alias)(596)+TX、Paecilomyces fumosoroseus(alias)(613)+TX、Phytoseiulus persimilis(alias)(644)+TX、Spodopteraexigua multicapsid nuclear polyhedrosis virus(scientific name)(741)+TX、Steinernema bibionis(alias)(742)+TX、Steinernema carpocapsae(alias)(742)+TX、Steinernema glaseri(alias)(742)+TX、Steinernema riobrave)(alias)(742)+TX, Steinernema riobravis(alias)(742)+TX, Steinernema scapterisci(alias)(742)+TX, Steinernema spp.(alias)(742)+TX, Trichogramma species(alias)(826)+TX, Typhlodromus occidentalis(alias)(844) and Verticillium lecanii(alias)(848)+TX,.

[0751] Soil disinfectant selected from the group consisting of methyl iodide (IUPAC name) (542) and methyl bromide (537) + TX,

[0752] A chemical sterilant selected from the group consisting of apholanate [CCN] + TX, bis(aziridine) methylaminophosphine sulfide (bisazir) (alias) [CCN] + TX, busulfan (alias) [CCN] + TX, diflubenzuron (250) + TX, dimatif (alias) [CCN] + TX, hemel [CCN] + TX, hempa [CCN] + TX, metepa [CCN] + TX, methylsulfonate Methotepa [CCN] + TX, methylapholate [CCN] + TX, morzid [CCN] + TX, penfluron (alias) [CCN] + TX, tepa [CCN] + TX, thiohempa (alias) [CCN] + TX, thiotepa (alias) [CCN] + TX, trothamide (alias) [CCN] and urethaneimide (alias) [CCN] + TX,

[0753] An insect pheromone selected from the group consisting of (E)-dec-5-en-1-yl acetate and (E)-dec-5-en-1-ol (IUPAC name) (222) + TX, (E)-tridec-4-en-1-yl acetate (IUPAC name) (829) + TX, (E)-6-methylhept-2-en-4-ol (IUPAC name) (541) + TX, (E,Z)-tetradec-4,10-dien-1-yl acetate (IUPAC name) (779) + TX, (Z)-dodec-7-en-1-yl acetate (IUPAC name) (285) + TX, (Z)-hexadec-11-enal (IUPAC name) (436) + TX, (Z)-hexadec-11-en-1-yl acetate (IUPAC name) (437) + TX X, (Z)-hexadec-13-en-11-yn-1-yl acetate (IUPAC name) (438) + TX, (Z)-eicos-13-en-10-one (IUPAC name) (448) + TX, (Z)-tetradec-7-en-1-al (IUPAC name) (782) + TX, (Z)-tetradec-9-en-1-ol (IUPAC name) (783) + TX, (Z)-tetradec-9-en-1-yl acetate (IUPAC name) (784) + TX, (7E,9Z)-dodec-7,9-dien-1-yl acetate (IUPAC name) (283) + TX, (9Z,11E)-tetradec-9,11-dien-1-yl acetate (IUPAC name) (780) + TX, (9Z,12E)-tetradec-9,12-Dien-1-yl acetate (IUPAC name) (781) + TX, 14-methyloctadec-1-ene (IUPAC name) (545) + TX, 4-methylnonan-5-ol and 4-methylnonan-5-one (IUPAC name) (544) + TX, alpha-multistriatin (alias) [CCN] + TX, western pine beetle gathering pheromone (brevicomin) (alias) [CCN] + TX, codlelure (alias) [CCN] + TX, codle mone)(alias)(167)+TX、cuelure(alias)(179)+TX、disparlure(277)+TX、1-dodecyl acetate(IUPAC name)(286)+TX、1-dodecyl acetate(IUPAC name)(287)+TX、10-1-dodecyl acetate(IUPAC name)(284)+TX、dominicalure(alias)[CCN]+TX、ethyl 4-methyloctanoate(IUPAC name) C name) (317) + TX, eugenol (alias) [CCN] + TX, southern pine beetle aggregation pheromone (frontalin) (alias) [CCN] + TX, gossyplure (alias) (420) + TX, grandlure (421) + TX, grandlure I (alias) (421) + TX, grandlure II (alias) (421) + TX, grandlure III (alias) (421) + TX, grandlure IV (alias) (421) + TX, hexalure )[CCN]+TX、ipsdienol (alias)[CCN]+TX、ipsenol (alias)[CCN]+TX、japonilure (alias)(481)+TX、lineatin (alias)[CCN]+TX、litlure (alias)[CCN]+TX、looplure (alias)[CCN]+TX、medlure[CCN]+TX、megatomoic acid (alias)[CCN]+TX、methyl eugenol (alias)(540)+TX、muscalure (563)+TX、octadecene-2,13-diene-1-yl acetate (IUPAC name)(588)+TX、octadecene-3,13-Dien-1-yl acetate (IUPAC name) (589) + TX, orfralure (alias) [CCN] + TX, oryctalure (alias) (317) + TX, ostramone (alias) [CCN] + TX, siglure [CCN] + TX, sordidin (alias) (736) + TX, sulcatol )(Other name)[CCN]+TX, tetradec-11-en-1-yl acetate (IUPAC name) (785)+TX, Mediterranean fruit fly attractant (839)+TX, Mediterranean fruit fly attractant A (Other name) (839)+TX, Mediterranean fruit fly attractant B1 (Other name) (839)+TX, Mediterranean fruit fly attractant B2 (Other name) (839)+TX, Mediterranean fruit fly attractant C (Other name) (839) and trunc-call (Other name)[CCN]+TX,

[0754] An insect repellent selected from the group consisting of 2-(octylthio)ethanol (IUPAC name) (591) + TX, butopyronoxyl (933) + TX, butoxy(polypropylene glycol) (936) + TX, dibutyl adipate (IUPAC name) (1046) + TX, dibutyl phthalate (1047) + TX, dibutyl succinate (IUPAC name) (1048) + TX, DEET [CCN] + TX, dimethyl carbate [CCN] + TX, dimethyl phthalate [CCN] + TX, ethyl hexanediol (1137) + TX, hexylurea [CCN] + TX, methoquin-butyl (1276) + TX, methyl neodecylamide [CCN] + TX, oxamate [CCN] and picaridin [CCN] + TX,

[0755] Insecticide selected from the group consisting of: 1-dichloro-1-nitroethane (IUPAC / Chemical Abstracts name) (1058) + TX, 1,1-dichloro-2,2-di(4-ethylphenyl)ethane (IUPAC name) (1056) + TX, 1,2-dichloropropane (IUPAC / Chemical Abstracts name) (1062) + TX, 1,2-dichloropropane with 1,3-dichloropropene (IUPAC name) (1063) + TX, 1-bromo-2-chloroethane (IUPAC / Chemical Abstracts name) (916) + TX, 2,2,2-trichloro-1-(3,4-dichlorophenyl)ethyl acetate (IUPAC name) (1451) + TX, 2,2-dichlorovinyl acetate (IUPAC name) (1460) + TX, 2-Ethylsulfinylethyl methyl phosphate (IUPAC name) (1066) + TX, 2-(1,3-dithiolan-2-yl)phenyl dimethylcarbamate (IUPAC / Chemical Abstracts name) (1109) + TX, 2-(2-butoxyethoxy)ethyl thiocyanate (IUPAC / Chemical Abstracts name) (935) + TX, 2-(4,5-dimethyl-1,3-dioxolan-2-yl)phenyl methylcarbamate (IUPAC / Chemical Abstracts name) (1084) + TX, 2-(4-chloro-3,5-xylyloxy)ethanol (IUPAC name) (986) + TX, 2-chlorovinyl diethyl phosphate (IUPAC name) (984) + TX, 2-imidazolidinone (IUPAC name) (1225) + TX, 2-isovalerylindan-1,3-dione (IUPAC name) (1246) + TX, 2-methyl (prop-2-ynyl) aminophenyl methylcarbamate (IUPAC name) (1284) + TX, 2-thiocyanatoethyl laurate (IUPAC name) (1433) + TX, 3-bromo-1-chloroprop-1-ene (IUPAC name) (917) + TX, 3-methyl-1-phenylpyrazol-5-yl dimethylcarbamate (IUPAC name) (1283) + TX, 4-methyl (prop-2-ynyl) amino-3,5-xylyl methylcarbamate (IUPAC name) (1285 )+TX, 5,5-dimethyl-3-oxocyclohex-1-enyl dimethylcarbamate (IUPAC name) (1085)+TX, avermectin (1)+TX, acephate (2)+TX, acetamiprid (4)+TX, domesticaphos (alias) [CCN]+TX, acetothrin [CCN]+TX, flumethrin (9)+TX, acrylonitrile (IUPAC name) (861)+TX, cotton bell carb (15)+TX, aldicarb (16)+TX, aldicarb (863)+TX, chloronaphthalene (864)+TX, allethrin (17)+TX, alomycin (alias) [CCN]+TX, chlorpyrifos (866)+TX, α-cypermethrin (202)+TX,α-Ecdysone (alias) [CCN] + TX, aluminum phosphide (640) + TX, thiophos (870) + TX, thioamide (872) + TX, cypermethrin (873) + TX, cypermethrin (875) + TX, cypermethrin hydrogen oxalate (875) + TX, amitraz (24) + TX, neonicotinoid (877) + TX, ethyl cypermethrin (883) + TX, AVI 382 (compound code) + TX, AZ 60541 (compound code) + TX, azadirachtin (alias) (41) + TX, methyl pyriphos (42) + TX, azinphos-ethyl (44) + TX, azinphos-methyl (45) + TX, azophos (889) + TX, Bacillus thuringiensis delta endotoxins (alias) (52) + TX, barium hexafluorosilicate (alias) [CCN] + TX, barium polysulfide (IUPAC / Chemical Abstracts name) (892) + TX, fumonisin [CCN] + TX, Bayer 22 / 190 (research code) (893) + TX, Bayer 22408 (research code) (894) + TX, benfuracarb (58) + TX, benfuracarb (60) + TX, sulfamethoxazole (66) + TX, β-cyfluthrin (194) + TX, β-cypermethrin (203) + TX, bifenthrin (76) + TX, bio-allethrin (78) + TX, bio-allethrin S-cyclopentenyl isomer (alias) (79) + TX, pentaerythrin Cyclomethrin (bioethanomethrin) [CCN] + TX, biopermethrin (908) + TX, pyrethrin (80) + TX, bis (2-chloroethyl) ether (IUPAC name) (909) + TX, bistrifluan (83) + TX, borax (86) + TX, bromethrin (alias) + TX, bromophenazone (914) + TX, bromomethoxine (918) + TX, bromo-DDT (alias) [CCN] + TX, bromothioate (920) + TX, bromothion-ethyl (921) + TX, chlorpyrifos (924) + TX, thiamethoxam (99) + TX, chlorpyrifos (926) + TX, demethyl butylpyrimidinphos (butathiofos) (927) + TX, butanone carbendazim (103) + TX, butyl ester phosphine (932) + TX, butanone sulfone carbendazim (104) + TX, butyl pyridaben (alias) + TX, sulfamethoxam (109) + TX, calcium arsenate [CCN] + TX, calcium cyanide ( 444)+TX, calcium polysulfide (IUPAC name) (111)+TX, toxaphene (941)+TX, chlorfenapyr (943)+TX, carbaryl (115)+TX, carbofuran (118)+TX, carbon disulfide (IUPAC / Chemical Abstracts name) (945)+TX, carbon tetrachloride (IUPAC name) (946)+TX, trithion (947)+TX, carbofuran butyrate (119)+TX, cartap (123)+TX,Cartap hydrochloride (123) + TX, Veratrum alkaloid (alias) (725) + TX, Borneol (960) + TX, Chlordane (128) + TX, Chlordecone (963) + TX, Chlordane (964) + TX, Chlordane hydrochloride (964) + TX, Chloroxyphos (129) + TX, Chlorfenapyr (130) + TX, Chlorfenapyr (131) + TX, Chlorfluazuron (132) + TX, Chloroform (136) + TX, Chloroform [CCN] + TX, Chloropicrin (141) + TX, Chlornithine oxime (989) + TX, Chlorprazophos (990) + TX, Chlorpyrifos (145) + TX, Chlorpyrifos-methyl (146) + TX, Chlorfenapyr (9 94)+TX, cyclomethrin (150)+TX, chrysanthemumin I (696)+TX, chrysanthemumin II (696)+TX, chrysanthemuminoids (696)+TX, cis-resmethrin (cis-resmethrin) (alternative name)+TX, cis-resmethrin (cismethrin) (80)+TX, cypermethrin (alternative name)+TX, cypermethrin (999)+TX, closantelamide (alternative name) [CCN]+TX, clothianidin (165)+TX, copper acetylarensite [CCN]+TX, copper arsenate [CCN]+TX, copper oleate [CCN]+TX, coumaphos (174)+TX, cypermethrin (1006)+TX, crotamiton (alternative name) [CCN]+TX, Baclofos (1010)+TX, Cluofos (1011)+TX, Cryolite (alternative name) (177)+TX, CS708 (research code) (1012)+TX, Benzophos (1019)+TX, Fenpyraclostrobin (184)+TX, Fructofos (1020)+TX, Cypermethrin [CCN]+TX, Cypermethrin (188)+TX, Cyfluthrin (193)+TX, Cyhalothrin (196)+TX, Cypermethrin (201)+TX, Cypermethrin (206)+TX, Cypromazine (209)+TX, Cyclomethrin (alternative name) [CCN]+TX, d-Limonene (alternative name) [CCN]+TX, d-Tetramethrin Ester (alternative name) (788) + TX, DAEP (1031) + TX, dazomet (216) + TX, DDT (219) + TX, decarbofuran (1034) + TX, cypermethrin (223) + TX, tanafon (1037) + TX, tanafon-O (1037) + TX, tanafon-S (1037) + TX, entafon (1038) + TX, entafon-methyl (224) + TX, entafon-O (1038) + TX, entafon-O-methyl (224) + TX, entafon-S (1038) + TX, entafon-S-methyl (224) + TX, entafon-S-methyl sulfone (1039) + TX,Difenothuron (226) + TX, chlormethinol (1042) + TX, diamidophos (1044) + TX, diazinon (227) + TX, isochlorophos (1050) + TX, dichlorvos (1051) + TX, dichlorvos (236) + TX, dicliphos (alternative name) + TX, dicresyl (alternative name) [CCN] + TX, dicrotophos (243) + TX, dicynilide (244) + TX, dieldrin (1070) + TX, diethyl 5-methylpyrazol-3-yl phosphate (IUPAC name) (1076) + TX, diflubenzuron (250) + TX, dilor (alternative name) )[CCN]+TX, tetrafluthrin [CCN]+TX, methylfluthrin (1081)+TX, dimethoate (1085)+TX, dimethoate (262)+TX, pyrethrin (1083)+TX, methyl chlorpyrifos (265)+TX, dichlorvos (1086)+TX, chlorpyrifos (1089)+TX, chlorpyrifos (1089)+TX, chlorpyrifos (1093)+TX, chlorpyrifos (1094)+TX, danoic acid (1095)+TX, dimethoate (271)+TX, benzylpezil (1099)+TX, vegetable phosphorus (1100)+TX, dimethoate (1101)+TX, dimethoate (1102)+TX, ethyl Amitrophos (278) + TX, dithiocarb (1108) + TX, DNOC (282) + TX, doramectin (alternative name) [CCN] + TX, DSP (1115) + TX, ecdysone (alternative name) [CCN] + TX, EI1642 (research code) (1118) + TX, avermectin (291) + TX, avermectin benzoate (291) + TX, EMPC (1120) + TX, fenthrin (292) + TX, endosulfan (294) + TX, fenthion (1121) + TX, endrin (1122) + TX, EPBP (1123) + TX, EPN (297 )+TX, cypermethrin (1124)+TX, eprinomectin (alternative name) [CCN]+TX, cypermethrin (302)+TX, etaphos (alternative name) [CCN]+TX, ethiofencarb (308)+TX, ethiofencarb (309)+TX, ethiprole (310)+TX, methyl thiosulfate (1134)+TX, ethoxyproline (312)+TX, ethyl formate (IUPAC name) [CCN]+TX, ethyl-DDD (alias) (1056)+TX, ethylene dibromide (316)+TX, ethylene dichloride (chemical name) (1136)+TX, ethylene oxide [CCN]+TX, ethomethrin (319)+TX,Ethiophos (1142) + TX, EXD (1143) + TX, thiophos (323) + TX, fenamiphos (326) + TX, anti-mite azole (1147) + TX, pyrifos (1148) + TX, fenthiocarb (1149) + TX, fenfluramide (1150) + TX, cypermethrin (335) + TX, fenthiocarb (336) + TX, fenoxacrim (1153) + TX, fenoxycarb (340) + TX, cypermethrin (1155) + TX, cypermethrin (342) + TX, fenpyrad (alias) + TX, fensulfuron (1158) + TX )+TX, fenthion (346)+TX, fenthion-ethyl [CCN]+TX, cypermethrin (349)+TX, fipronil (354)+TX, flonicamid (358)+TX, flubendiamide (CAS registration number: 272451-65-7)+TX, flufenicol (1168)+TX, flufenamide (366)+TX, flucythrinate (367)+TX, fluazifop (1169)+TX, flufenicol [CCN]+TX, flufenicol (370)+TX, trifluthrin (1171)+TX, flumethrin (372)+TX, cypermethrin (1184)+TX, FMC 1137 (research code) (1185) + TX, fenthion (1191) + TX, fluazifop (405) + TX, cypermethrin hydrochloride (405) + TX, angolan (1192) + TX, formparanate (1193) + TX, fenthion (1194) + TX, pyraclostrobin (1195) + TX, thiamethoxam (408) + TX, thiophanate (1196) + TX, furathiocarb (412) + TX, pyrethroid (1200) + TX, γ-cyhalothrin (197) + TX, γ-HCH (430) + TX, cypermethrin (422) + TX, cypermethrin acetate (422) + TX, GY-81 (research code) (423) + TX, benzylfenthion (424) + TX, chlorfenapyr ( 425)+TX、HCH(430)+TX、HEOD(1070)+TX、Heptachlor(1211)+TX、Heptylphos(432)+TX、Cetirizine[CCN]+TX、Hexaflumuron(439)+TX、HHDN(864)+TX、Hydrazine(443)+TX、Hydrogen cyanide(444)+TX、Methoprene(445)+TX、Hyquincarb(1223)+TX、Imidazolyl(458)+TX、Imidazolyl(460)+TX、Indoxacarb(465)+TX、Methyl iodide(IUPAC name)(542)+TX、IPSP(1229)+TX、Chlorfenapyr(1231)+TX、Carbochlorin(1232)+TX、Isopropylamine(473)+TX、Isodrin (1235) + TX, isothiophos (1236) + TX, transplanting agent (1237) + TX, leaf cicada powder (472) + TX, isopropyl O-(methoxyaminothiophosphoryl) salicylate (IUPAC name) (473) + TX, rice blast (474) + TX, isothiophos (1244) + TX, oxazoline (480) + TX, ivermectin (alias) [CCN] + TX, jasmonate I (696) + TX, jasmonate II (696) + TX, iodine (1248) + TX, juvenile hormone I (alias) [CCN] + TX, juvenile hormone II (alias) [CCN] + TX, juvenile hormone III (alias) [CCN] + TX, chlorfenapyr (12 49) + TX, methoprene (484) + TX, λ-cyfluthrin (198) + TX, lead arsenate [CCN] + TX, lepidomicil (CCN) + TX, bromophenphos (1250) + TX, lindane (430) + TX, acetamiprid (lirimfos) (1251) + TX, chlorfenuron (490) + TX, thiathion (1253) + TX, m-isopropyl methyl carbamate (IUPAC name) (1014) + TX, magnesium phosphide (IUPAC name) (640) + TX, malathion (492) + TX, cyprodinil (1254) + TX, phosphorus azide (1255) + TX, cyprodinil (502) + TX, methyl cyprodinil (1258) +TX, chlorpyrifos (1260) +TX, dithiophos (1261) +TX, mercurous chloride (513) +TX, methyl sulfoxide (1263) +TX, metaflumizone (CCN) +TX, metamizole (519) +TX, metamizole potassium salt (alias) (519) +TX, metamizole sodium salt (519) +TX, acarbamide (1266) +TX, methylamidophos (527) +TX, methylsulfonyl fluoride (IUPAC / Chemical Abstracts name) (1268) +TX, methamidophos (529) +TX, methiocarb (530) +TX, butenyl amine (methocrotophos) (1273) +TX, methomyl (531) +TX, methoprene (532) +TX, Mequindine (1276) + TX, methoxythrin (alias) (533) + TX, methoxychlor (534) + TX, methoxyfenozide (535) + TX, methyl bromide (537) + TX, methyl isothiocyanate (543) + TX, methyl chloroform (alias) [CCN] + TX, dichloromethane [CCN] + TX, metofluthrin [CCN] + TX, cypermethrin (550) + TX, chlorpyrifos (1288) + TX, cypermethrin (556) + TX, cypermethrin (1290) + TX, mitoxantrone (557) + TX, milbemycin (alias) [CCN] + TX, propylamine (1293) + TX, anticide (1294) + TX, monocrotophos (561) + TX,Maoguo (1300) + TX, Moxidectin (alias) [CCN] + TX, Naphthophos (alias) [CCN] + TX, Dibromophos (567) + TX, Naphthalene (IUPAC / Chemical Abstracts name) (1303) + TX, NC-170 (research code) (1306) + TX, NC-184 (compound code) + TX, Nicotine (578) + TX, Nicotine sulfate (578) + TX, Fluorine (1309) + TX, Nitenpyram (579) + TX, Nithiothiazide (13 11) + TX, valcarb (1313) + TX, valcarb 1:1 zinc chloride complex (1313) + TX, NNI-0101 (compound code) + TX, NNI-0250 (compound code) + TX, orthonicotine (traditional name) (1319) + TX, flubendiamide (585) + TX, flubendiamide (586) + TX, O-5-dichloro-4-iodophenyl O-ethylethylphosphonothioate (IUPAC name) (1057) + TX, O,O-diethyl O-4- Methyl-2-oxo-2H-benzopyran-7-yl phosphorothioate (IUPAC name) (1074) + TX, O,O-diethyl O-6-methyl-2-propylpyrimidin-4-yl phosphorothioate (IUPAC name) (1075) + TX, O,O,O',O'-tetrapropyl dithiodiphosphate (IUPAC name) (1424) + TX, oleic acid (IUPAC name) (593) + TX, omethoate (594) + TX, oxamyl (602) + TX, isothiocarb Sulfon (609) + TX, isothiophos (1324) + TX, sulfonylphos (1325) + TX, pp'-DDT (219) + TX, p-dichlorobenzene [CCN] + TX, parathion (615) + TX, methyl parathion (616) + TX, flubendiamide (alias) [CCN] + TX, pentachlorophenol (623) + TX, pentachlorophenyl laurate (IUPAC name) (623) + TX, permethrin (626) + TX, petroleum oil (628) + TX, PH 60-38 (research code) (1328) + TX, fenthion (1330) + TX, phenthrin (630) + TX, fenthion (631) + TX, phorate (636) + TX, phosalone (637) + TX, thiophanate (1338) + TX, phosmet (638) + TX, parathion (1339) + TX, phosphamidon (639) + TX, phosphine (IUPAC name) (640) + TX, phoxim (642) + TX, phoxim-methyl (1340) + TX, methylpirimetaphos (1344) + TX, pirimetaphos (651) + TX, ethylpirimitaphos (1345) + TX, methylpirimitaphos (652) + TX, polychlorodicyclopentadiene isomers (IUPAC name) (1346) + TX,Chlorinated turpentine (polychloroterpenes) (traditional name) (1347) + TX, potassium arsenite [CCN] + TX, potassium thiocyanate [CCN] + TX, phyllotoxin (655) + TX, precocious oxadiazine I (alias) [CCN] + TX, precocious oxadiazine II (alias) [CCN] + TX, precocious oxadiazine III (alias) [CCN] + TX, acetophenone (primidophos) (1349) + TX, bromophos (66 2) + TX, flumethrin [CCN] + TX, flumethrin (1354) + TX, fenthion (1355) + TX, propanil (1356) + TX, fenthion (673) + TX, propoxur (678) + TX, ethidium (1360) + TX, prothiophene (686) + TX, thiophene (1362) + TX, protrifenbute [CCN] + TX, pymetrozine (688) + TX, pyraclostrobin (6 89) + TX, pyrethrin (693) + TX, pyresmethrin (1367) + TX, pyrethrin I (696) + TX, pyrethrin II (696) + TX, pyrethrins (696) + TX, pyrethrin (699) + TX, pyridalyl (700) + TX, pyridazine (701) + TX, pyrimidine (706) + TX, pyrimidine (1370) + TX, pyriproxyfen (708) + TX, quassia extract Quassia (alias) [CCN] + TX, quinalphos (711) + TX, quinalphos-methyl (1376) + TX, quinalphos (1380) + TX, quintiofos (1381) + TX, R-1492 (research code) (1382) + TX, rafoxanide (alias) [CCN] + TX, resmethrin (719) + TX, rotenone (722) + TX, RU 15525 (research code) (723) + TX, RU 25475 (research code) (1386) + TX, ryania (alias) (1387) + TX, ryanodine (traditional name) (1387) + TX, sabah (alias) (725) + TX, octamethrin (1389) + TX, cadusin (alias) + TX, selamectin (alias) [CCN] + TX, SI-0009 (compound code) + TX, SI-0205 (compound code) + TX, SI-0404 (compound code) + TX, SI-0405 (compound code) + TX, flusilate (728) + TX, SN72129 (research code) (1397) + TX, sodium arsenite [CCN] + TX, sodium cyanide (444) + TX, sodium fluoride (IUPAC / Chemical Abstracts name) (1399) + TX, sodium hexafluorosilicate (1400) + TX,Sodium pentachlorophenol (623) + TX, sodium selenate (IUPAC name) (1401) + TX, sodium thiocyanate [CCN] + TX, thiothion (1402) + TX, spinosad (737) + TX, spiromesifen (739) + TX, spirotetramat (CCN) + TX, sulcofuron (746) + TX, sulcofuron-sodium (746) + TX, sulfluramid (750) + TX, thiophanate (753) + TX, sulfonyl fluoride (756) + TX, thiopromide (1408) + TX, tar (alias) (758) + TX, τ-fluvalinate (398) + TX, thiamethoxam (14 12) + TX, TDE (1414) + TX, tebufenoxad (762) + TX, tebufenpyrad (763) + TX, butylpyrimidophos (764) + TX, flubendiamide (768) + TX, tefluthrin (769) + TX, tebufos (770) + TX, TEPP (1417) + TX, cypermethrin (1418) + TX, terbuthion (773) + TX, tetrachloroethane [CCN] + TX, cypermethrin (777) + TX, tetramethrin (787) + TX, theta-cypermethrin (204) + TX, thiacloprid (791) + TX, thiafenox (alias) + TX, thiamethoxam Azine (792) + TX, thicrofos (1428) + TX, carbofuran (1431) + TX, thiocarb (798) + TX, thiocarb hydrogen oxalate (798) + TX, thiodicarb (799) + TX, long-acting carb (800) + TX, methyl sulfamethoxam (801) + TX, thiosulfuron (1434) + TX, thiosultap (803) + TX, thiosultap-sodium (803) + TX, thuringin (alias) [CCN] + TX, tolfenpyrad (809) + TX, tralomethrin (812) + TX, transfluthrin (813) + TX, trans-permethrin ( transpermethrin)(1440)+TX、vinphos(1441)+TX、triazophos(818)+TX、triazophos(820)+TX、trichlorfon(824)+TX、trichlormetaphos-3)(alias)[CCN]+TX、tolufosinate(1452)+TX、trichlorfos(1455)+TX、thiocarb(835)+TX、mixed thiocarb(840)+TX、methoxam(1459)+TX、aphidoxam(847)+TX、vaniliprole[CCN]+TX、veratridine(alias)(725)+TX、Veratrine (alias) (725) + TX, XMC (853) + TX, cypermethrin (854) + TX, YI-5302 (compound code) + TX, ζ-cypermethrin (205) + TX, zetamethrin (alias) + TX, zinc phosphide (640) + TX, zolaprofos (1469) and ZXI8901 (research code) (858) + TX, cyantraniliprole [736994-63-19] + TX, chlorantraniliprole [500008-45-7] + TX, cyenopyrafen [560121-52-0] + TX, fluazifop [400882-07-7] + TX, pyrifluquinazon [33 7458-27-2] + TX, spinetoram [187166-40-1 + 187166-15-0] + TX, spirotetramat [203313-25-1] + TX, sulfoxaflor [946578-00-3] + TX, flufiprole [704886-18-0] + TX, chlorfluthrin [915288-13-0] + TX, tetramethylfluthrin [84937-88-2] + TX, triflumezopyrim (disclosed in WO2012 / 092115) + TX, fluxametamide (WO 2007 / 026965)+TX, ε-methofluthrin [240494-71-7]+TX, ε-momfluorothrin [1065124-65-3]+TX, fluazaindolizine [1254304-22-7]+TX, chlor-alkali propylthrin [399572-87-3]+TX, fluxametamide [928783-29-3]+TX, cyhalothrin odiamide) [1262605-53-7] + TX, tioxazafen [330459-31-9] + TX, broflanilide [1207727-04-5] + TX, flufiprole [704886-18-0] + TX, cyclobromobendan [1031756-98-5] + TX, flucyantamide [1229654-66-3] + TX, pyraclostrobin (described in WO 2010 / 060231) + TX, cyclohexidine (described in WO 2005 / 077934) + TX, Spiropidion + TX, Afidopyropen + TX, flupyrimin + TX,Momfluorothrin+TX, kappa-bifenthrin+TX, kappa-tefluthrin+TX, Dichloromezotiaz+TX, Tetrachloraniliprole+TX, benzpyrimoxan+TX;

[0756] Molluscicide selected from the group consisting of di(tributyltin) oxide (IUPAC name) (913) + TX, bromoacetamide [CCN] + TX, calcium arsenate [CCN] + TX, chloranil (999) + TX, copper acetyl arsenite [CCN] + TX, copper sulfate (172) + TX, triphenyltin (347) + TX, iron phosphate (IUPAC name) (352) + TX, metaldehyde (518) + TX, methiocarb (530) + TX, niclosamide (576) + TX, niclosamide-ethanolamine (576) + TX, pentachlorophenol ( 623)+TX, sodium pentachlorophenoxide (623)+TX, tazimcarb (1412)+TX, thiodicarb (799)+TX, tributyltin oxide (913)+TX, trifenmorph (1454)+TX, trimethacarb (840)+TX, triphenyltin acetate (IUPAC name) (347) and triphenyltin hydroxide (IUPAC name) (347)+TX, pyriprole [394730-71-3]+TX,

[0757] A nematicide selected from the group consisting of: AKD-3088 (compound code) + TX, 1,2-dibromo-3-chloropropane (IUPAC / Chemical Abstracts name) (1045) + TX, 1,2-dichloropropane (IUPAC / Chemical Abstracts name) (1062) + TX, 1,2-dichloropropane and 1,3-dichloropropene (IUPAC name) (1063) + TX, 1,3-dichloropropene (233) + TX, 3,4-dichlorotetrahydrothiophene 1,1-dioxide (IUPAC / Chemical Abstracts name) + TX, 1,2-dichloropropane and 1,3-dichloropropene (IUPAC name) + TX, 1,3-dichloropropene (233) + TX, 1,2 ...3-dichloropropene (233) + TX, 1,3-dichloropropene (233) + TX, 1,3-dichloropropene (233) + TX Abstract name) (1065) + TX, 3-(4-chlorophenyl)-5-methylrhodanine (IUPAC name) (980) + TX, 5-methyl-6-thioxo-1,3,5-thiadiazin-3-yl acetic acid (IUPAC name) (1286) + TX, 6-isopentenylaminopurine (alias) (210) + TX, avermectin (1) + TX, acetofenamide [CCN] + TX, cotton bell carb (15) + TX, aldicarb (16) + TX, aldicarb (863) + TX, AZ60541 (compound code) + TX, benclothiaz [CCN] + TX, benomyl (62) + TX, butylpyridaben (alias) + TX, carbofuran (109) + TX, carbofuran (118) + TX, carbon disulfide (945) + TX, carbofuran (119) + TX, chloropicrin (141) + TX, chlorpyrifos (145) + TX, chlorpyrifos (999) + TX, cytokinin (alias) (210) + TX , dazomethane (216) + TX, DBCP (1045) + TX, DCIP (218) + TX, diamidafos (1044) + TX, dimethoate (1051) + TX, dicliphos (alias) + TX, dimethoate (262) + TX, doramectin (alias) [CCN] + TX, emamectin (291) + TX, emamectin benzoate (291) + TX, eprinomectin (alias) [CCN] + TX, ethoprophos (312 )+TX, ethylene dibromide (316)+TX, fenamiphos (326)+TX, fenpyrad (alias)+TX, fenthiophos (1158)+TX, thiathiophene (408)+TX, butyric acid cyclophosphate (1196)+TX, furfural (alias) [CCN]+TX, GY-81 (research code) (423)+TX, cypermethrin [CCN]+TX, iodomethane (IUPAC name) (542)+TX, isamidophos (1230)+TX, chloramine Azophos (1231) + TX, ivermectin (alias) [CCN] + TX, kinetin (alias) (210) + TX, methyl aphidazole (1258) + TX, metamectin (519) + TX, metamectin potassium salt (alias) (519) + TX, metamectin sodium salt (519) + TX, methyl bromide (537) + TX, methyl isothiocyanate (543) + TX, milbemycin oxime (alias) [CCN] + TX, moxidectin (alias) [CCN] + TX, Myrotheciumverrucaria) combination (alias) (565) + TX, NC-184 (compound code) + TX, oxamyl (602) + TX, phorate (636) + TX, phosphamidon (639) + TX, phosphamidon [CCN] + TX, clomiphene (alias) + TX, selamectin (alias) [CCN] + TX, spinosad (737) + TX, terbufos (alias) + TX, terbufos (773) + TX, tetrachlorothiophene (IUPAC / Chemical Abstract name) (1422) + TX, thiafenox (alias) + TX, cypermethrin (1434) + TX, triazophos (820) + TX, triazuron (alias) + TX, dimethylol [CCN] + TX, YI-5302 (compound code) and zeatin (alias) (210) + TX, fluensulfone [318290-98-1] + TX, fluopyram + TX,

[0758] A nitrification inhibitor selected from the group consisting of potassium ethylxanthate [CCN] and nitrapyrin (580) + TX,

[0759] A plant activator selected from the group consisting of acibenzolar (6) + TX, acibenzolar-S-methyl (6) + TX, probenazole (658) and Reynoutria sachalinensis extract (alias) (720) + TX,

[0760] A rodenticide selected from the group consisting of: 2-isovaleryl indane-1,3-dione (IUPAC name) (1246) + TX, 4-(quinoxalin-2-ylamino)benzenesulfonamide (IUPAC name) (748) + TX, α-chlorohydrin [CCN] + TX, aluminum phosphide (640) + TX, antoquinol (880) + TX, arsenic trioxide (882) + TX, barium carbonate (891) + TX, bifenthrin (912) + TX, brodifacoum (89) + TX, bromodiolone (91) + TX, bromodipine (92) + TX, calcium cyanide (444) + TX, chloralose (127) + TX, chlordipine (140) + TX, cholecalciferol (alias) (850) + TX, chlordimethoate (1004) + TX, chlordimethoate (1005) + TX, naphthalene (175) + TX, cypermethrin (1009) + TX, cypermethrin (246) + TX, thiazolin (249) + TX, difacoum (273) + TX, calciferol (301) + TX, fluoxetine , fluoroacetamide (379) + TX, fluridine (1183) + TX, fluridine hydrochloride (1183) + TX, γ-HCH (430) + TX, HCH (430) + TX, hydrogen cyanide (444) + TX, iodomethane (IUPAC name) (542) + TX, lindane (430) + TX, magnesium phosphide (IUPAC name) (640) + TX, methyl bromide (537) + TX, thiamethoxam (1318) + TX, thiamethoxam (13 36) + TX, phosphine (IUPAC name) (640) + TX, phosphorus [CCN] + TX, warfarin (1341) + TX, potassium arsenite [CCN] + TX, cypermethrin (1371) + TX, scilla glycoside (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,

[0761] A synergist selected from the group consisting of 2-(2-butoxyethoxy)ethyl piperate (IUPAC name) (934) + TX, 5-(1,3-benzodioxol-5-yl)-3-hexylcyclohex-2-enone (IUPAC name) (903) + TX, farnesol with nerolidol (alias) (324) + TX, MB-599 (research code) (498) + TX, MGK 264 (research code) (296) + TX, piperonyl butoxide (649) + TX, pipertal (1343) + TX, propyl isomer (1358) + TX, S421 (research code) (724) + TX, sesamex (1393) + TX, sesasmolin (1394) and sulfoxide (1406) + TX,

[0762] An animal repellent selected from the group consisting of anthraquinone (32) + TX, chloralose (127) + TX, copper cyclohexane [CCN] + TX, copper oxychloride (171) + TX, diazinon (227) + TX, dicyclopentadiene (chemical name) (1069) + TX, guazatine (422) + TX, guazatine acetate (422) + TX, methiocarb (530) + TX, pyridin-4-amine (IUPAC name) (23) + TX, salam (804) + TX, trimethacarb (840) + TX, zinc cyclohexane [CCN] and ziram (856) + TX,

[0763] A virucidal agent selected from the group consisting of: imipenem (alias) [CCN] and ribavirin (alias) [CCN] + TX,

[0764] A wound protection agent selected from the group consisting of mercuric oxide (512) + TX, octhilinone (590) and thiophanate methyl (802) + TX,

[0765] and a biologically active compound selected from the group consisting of: azaconazole [60207-31-0] + TX, bifenthrin [70585-36-3] + TX, oxadiazol [116255-48-2] + TX, cyproconazole [94361-06-5] + TX, difenoconazole [119446-68-3] + TX, diniconazole [83657-24-3] + TX, fluoxepinazole [106325-08-0] + TX, fenbuconazole [114369-43-6] + TX, fluquinconazole [136426-54-5] + TX, flusilazole [85509-19-9] + TX, flutriafol [76674-21-0] + TX, hexaconazole [ 79983-71-4]+TX, imazalil[35554-44-0]+TX, imidazole[86598-92-7]+TX, piclonil[125225-28-7]+TX, metconazole[125116-23-6]+TX, myclobutanil[88671-89-0]+TX, pyrifenox[88283-41-4]+TX, prochloraz[67747-09-5]+TX, propiconazole[60207-90-1]+TX, silanazole meconazole) [149508-90-7] + TX, tebuconazole [107534-96-3] + TX, fluconazole [112281-77-3] + TX, triadimefon [43121-43-3] + TX, triadimefon [55219-65-3] + TX, triflumuron [99387-89-0] + TX, trichlorfon [131983-72-7] + TX, tricyclamide [12771-68-5] + TX, chlorfenapyr [60168-88-9] + TX, fluchlorapyramide [63284-71-9] + TX, bupirimate [41483-43-6] + TX, meconazole dimethirimol [5221-53-4] + TX, ethirimol [23947-60-6] + TX, dodecacyclic morpholine [1593-77-7] + TX, fenpropidine [67306-00-7] + TX, fenpropimorph [67564-91-4] + TX, spiroxafil [118134-30-8] + TX, tridecafil [81412-43-3] + TX, cyprodinil [121552-61-2] + TX, pyrimidine [110235-47-7] + TX, pyrimethanil [53112-28-0] + TX,Seed dressing [74738-17-3] + TX, fludioxonil [131341-86-1] + TX, benalaxyl [71626-11-4] + TX, furalaxyl [57646-30-7] + TX, metalaxyl [57837-19-1] + TX, R metalaxyl [70630-17-0] + TX, furamide [58810-48-3] + TX, oxadixyl [77732-09-3] + TX, benomyl [17804-35-2] + TX, carbendazim [10605-21-7] + TX, debacar b) [62732-91-6] + TX, oxadiazine [3878-19-1] + TX, thiabendazole [148-79-8] + TX, chlozolinate [84332-86-5] + TX, dichlozoline [24201-58-9] + TX, Iprodione [36734-19-7] + TX, myclozoline [54864-61-8] + TX, procymidone [32809-16-8] + TX, vinclozoline [50471-44-8] + TX, boscalid ( boscalid)[188425-85-6]+TX、carboxin[5234-68-4]+TX、furoxanilide[24691-80-3]+TX、flutolanil[66332-96-5]+TX、mefenoxam[55814-41-0]+TX、oxycarboxin[5259-88-1]+TX、penthiopyrad[183675-82-3]+TX、thiopyrad[130000-40-7]+TX、biguanide[108173-90-6]+TX、dodine[2439-10-3][112-65-2](free bond) +TX, iminoctadine [13516-27-3] +TX, azoxystrobin [131860-33-8] +TX, doxystrobin [149961-52-4] +TX, enoxastrobin {Glasgow British Crop Protection Committee International Conference (Proc. BCPC, Int. Congr., Glasgow.) 2003, 1, 93} +TX, fluoxastrobin [361377-29-9] +TX, doxystrobin [143390-89-0] +TX, fenoxystrobin [133408-50-1] +TX, trifloxystrobin [141517-21-7] +TX, trifloxystrobin [248593-16-0] +TX,Picoxystrobin [117428-22-5] + TX, pyraclostrobin [175013-18-0] + TX, ferram [14484-64-1] + TX, mancozeb [8018-01-7] + TX, maneb [12427-38-2] + TX, methanamide [9006-42-2] + TX, propineb [12071-83-9] + TX, ceram [137-26-8] + TX, mancozeb [12122-67-7] + TX, ferram [137-30-4] + TX, captafol [2425-06-1] + TX, captan [133-06-2] + TX, Bacillus[1085-98-9]+TX, fluoroimide[41205-21-4]+TX, folpet[133-07-3]+TX, tolylfluanid[731-27-1]+TX, Bordeaux mixture[8011-63-0]+TX, copper hydroxide(copperhydroxid)[20427-59-2]+TX, copper chloride(copperoxychlorid)[1332-40-7]+TX, copper sulfate(coppersulfat)[7758-98-7]+TX, copper oxide(copperoxid)[1317-39-1]+TX, mancozeb(mancopper) ncopper [53988-93-5] + TX, oxine-copper [10380-28-6] + TX, dinocap [131-72-6] + TX, nitrothal-isopropyl [10552-74-6] + TX, kewensan [17109-49-8] + TX, iprobenphos [26087-47-8] + TX, isoprothiol [50512-35-1] + TX, phosdiphen [36519-00-3] + TX, pyraclostrobin [10552-74-6] + TX, oxadiazine [10380-28-6] + TX, oxadiazine [10380-28-6] + TX, dinocap [131-72-6] + TX, nitrothal-isopropyl [10552-74-6] + TX, kewensan [17109-49-8] + TX, iprobenphos [26087-47-8] + TX, isoprothiol [50512-35-1] + TX, phosdiphen [36519-00-3] + TX, pyraclostrobin [10552-74-6] + TX, razophos)[13457-18-6]+TX、tolclofos-methyl[57018-04-9]+TX、acibenzolar-S-methyl[135158-54-2]+TX、dichlorvos[101-05-3]+TX、benthiopyrad[413615-35-7]+TX、blasticidin-S[2079-00-7]+TX、chinomethionat[2439-01-2]+TX、chloroneb[2675-77-6]+TX、Chlorothalonil [1897-45-6] + TX, cyfluanid [180409-60-3] + TX, cymoxanil [57966-95-7] ​​+ TX, dichlone [117-80-6] + TX, diclocymet [139920-32-4] + TX, diclomezine [62865-36-5] + TX, dicloran [99-30-9] + TX, diethofencarb [87130-20-9] + TX, oxadiazine [110488-70-5] + TX, SYP-LI90 (flumorph TX, fenoxanil [115852-48-7] + TX, fentin [668-34-8] + TX, ferimzone [89269-64-7] + TX, oxadiazole [211867-47-9] + TX, dithianon [3347-22-6] + TX, ethaboxam [162650-77-3] + TX, etridiazole [2593-15-9] + TX, oxadiazole [131807-57-3] + TX, fenamidone [161326-34-7] + TX, fenoxanil [115852-48-7] + TX, fentin [668-34-8] + TX, ferimzone [89269-64 -7]+TX, fluazinam [79622-59-6]+TX, fluopicolide [239110-15-7]+TX, flusulfamide [106917-52-6]+TX, fenacet [126833-17-8]+TX, fosetyl-aluminium [39148-24-8]+TX, hymexazol [10004-44-1]+TX, propineb [140923-17-7]+TX, IKF-916 (Cyazofamid) [12 0116-88-3]+TX, kasugamycin [6980-18-3]+TX, methasulfocarb [66952-49-6]+TX, mefenamic acid [220899-03-6]+TX, pencycuron [66063-05-6]+TX, phthalide [27355-22-2]+TX, polyoxins [11113-80-7]+TX, probenazole [27605-76-1]+TX, propamocarb [25606-41-1]+TX,Iodoquinazolone (proquinazid) [189278-12-4] + TX, pyroquilon [57369-32-1] + TX, quinoxyfen [124495-18-7] + TX, pentachloronitrobenzene [82-68-8] + TX, sulfur [7704-34-9] + TX, thiazolamide [223580-51-6] + TX, triazoxide [72459-58-6] + TX, tricyclazole [41814-78-2] + TX, quinazoline [26644-46-2] + TX, validamycin [3724 8-47-8] + TX, zoxamide (RH7281) [156052-68-5] + TX, mandipropamid [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-methylene-naphthalene-5-yl)-amide (disclosed in WO 2007 / 048556) + TX, 3-difluoromethyl-1-methyl-1H-pyrazole-4-carboxylic acid (3',4',5'-trifluoro-biphenyl-2-yl)-amide (disclosed in WO 2006 / 087343) + TX, [(3S,4R,4aR,6S,6aS,12R,12aS,12bS)-3-[(cyclopropylcarbonyl)oxy]-1,3,4,4a,5,6,6a,12,12a,12b-decahydro-6,12-dihydroxy-4,6a,12b-trimethyl-11-oxo-9-(3-pyridyl)-2H,11H naphtho[2,1-b]pyrano[3,4-e]pyran-4-yl]methyl-cyclopropanecarboxylate [915972-17-7] + TX and 1,3,5-trimethyl-N-(2-methyl-1-oxypropyl)-N-[3-(2-methylpropyl)-4-[2, 2,2-Trifluoro-1-methoxy-1-(trifluoromethyl)ethyl]phenyl]-1H-pyrazole-4-carboxamide [926914-55-8] + TX, lancotrione [1486617-21-3] + TX, cloflupyridin [943832-81-3] + TX, ipfentrifluconazole [1417782-08-1] + TX, mefentrifluconazole [1417782-03-6] + TX, quinofumelin [861647-84-9] + TX, right-rotating trans-chlorpromazine [399572-87-3] + TX,Cyanocarb[1262605-53-7]+TX、trifluthrin[1254304-22-7]+TX、fluxametamide[928783-29-3]+TX、ε-Methiofluthrin[240494-71-7]+TX、ε-momfluorothrin[1065124-65-3]+TX、pydiflumetofen[1228284-64-7]+TX、κ-Bifenthrin[439680-76-9]+TX、broflanilide[1207727-04-5]+TX、dicloromezotia z[1263629-39-5]+TX, dipymetitrone[16114-35-5]+TX, pyraziflumid[942515-63-1]+TX and kappa-tefluthrin[391634-71-2]+TX, fenpicoxamid[517875-34-2]+TX; fluphenazine+TX, benzpyrimoxan[1449021-97-9]+TX; isocycloseram+TX, rescalure[64309-03-1]+TX; aminopyrifen[1531626-08-0]+TX; and,

[0766] Microorganisms, including: Acinetobacter lwoffii + TX, Acremonium protrusion + TX + TX, Acremonium cephalosporin + TX + TX, Acremonium diospyri + TX, Acremonium oblique club + TX, AdoxGV +TX, Agrobacterium radioactive strain K84 +TX, Alternaria destruens +TX, Alternaria cassia seed +TX, Alternaria destruens +TX, Psoralea corylifolia +TX, Aspergillus flavus AF36 +TX, Aspergillus flavus NRRL 21882 +TX, Aspergillus +TX, Adenophora +TX, Azospirillum +TX, ( +TX、TAZO )+TX, Azotobacter+TX, Azotobacter chroocuccum +TX, Azotobacter cysts (BionaturalBlooming )+TX, Bacillus amyloliquefaciens+TX, Bacillus cereus+TX, Bacillus chitinosporus strain CM-1+TX, Bacillus chitinosporus strain AQ746+TX, Bacillus licheniformis strain HB-2 (Biostart TM )+TX, Bacillus licheniformis strain 3086 ( +TX、Green )+TX, Bacillus circulans+TX, Bacillus firmus( +TX, +TX, )+TX, Bacillus firmus strain I-1582+TX, Bacillus megaterium+TX, Bacillus megaterium+TX, Bacillus mycoides strain AQ726+TX, Bacillus papillomavirus (Milky Spore )+TX, Bacillus pumilus+TX, Bacillus pumilus strain GB34 (Yield )+TX, Bacillus pumilus strain AQ717+TX, Bacillus pumilus strain QST 2808( +TX, Ballad )+TX, Bacillus spahericus +TX, Bacillus +TX, Bacillus strain AQ175 +TX, Bacillus strain AQ177 +TX, Bacillus strain AQ178 +TX, Bacillus subtilis strain QST 713 ( +TX, +TX, )+TX, Bacillus subtilis strain QST 714 +TX, Bacillus subtilis strain AQ153+TX, Bacillus subtilis strain AQ743+TX, Bacillus subtilis strain QST3002+TX, Bacillus subtilis strain QST3004+TX, Bacillus subtilis variant Bacillus amyloliquefaciens strain FZB24 ( +TX, )+TX, Bacillus thuringiensis Cry 2Ae+TX, Bacillus thuringiensis Cry1Ab+TX, Bacillus thuringiensis aizawai GC 91 +TX, Bacillus thuringiensis israelensis ( +TX, +TX, )+TX, Bacillus thuringiensiskurstaki ( +TX, +TX, +TX, +TX, Scutella +TX, Turilav +TX, +TX、Dipel +TX, +TX, )+TX, Bacillus thuringiensis subsp. Kurstaki BMP 123 +TX, Bacillus thuringiensis subsp. Kurstaki HD-1 (Bioprotec-CAF / )+TX, Bacillus thuringiensis strain BD#32+TX, Bacillus thuringiensis strain AQ52+TX, Bacillus thuringiensis strain Ayuzawa var. +TX, )+TX, Bacteria( +TX, +TX, )+TX, Clavipacter michiganensis phage +TX, +TX, Beauveria bassiana ( +TX, Brocaril )+TX, Beauveria bassiana GHA (Mycotrol +TX, Mycotrol +TX, )+TX, Beauveria bassiana ( +TX, Schweizer +TX, )+TX, Beauveria bassiana+TX, Botrytis cinerea+TX, Bradyrhizobium sojae +TX, Bacillus brevis +TX, Bacillus thuringiensis tenebrionis +TX, BtBooster+TX, Burkholderia cepacia ( +TX, +TX、Blue )+TX, Burkholderia gladii+TX, Burkholderia gladiolus+TX, Burkholderia spp.+TX, CBH Canadian thistle )+TX, Candida cheese+TX, Candida anonymus+TX, Candida fructus+TX, Candida glabrata+TX, Candida guilliermondii+TX, Candida orijin+TX, Candida olive strain O+TX, Candida parapsilosis+TX, Candida mycofilm+TX, Candida ferruginosa+TX, Candida reukaufii+TX, Candida saitoana( +TX, )+TX, Candida sakei+TX, Candida spp.+TX, Candida gracilis+TX, Cedecea dravisae+TX, Xanthomonas luteus+TX, Chaetocystis spiralis +TX, Chaetomium globosum +TX, Chromobacterium subtsugae strain PRAA4-1T +TX, Cladosporium cladosporium+TX, Cladosporium oxysporum+TX, Cladosporium chlorocephalum+TX, Cladosporium+TX, Cladosporium tenuissima+TX, Gliocladium roseum +TX, Colletotrichum acutatum +TX, Cotans )+TX, Conchoderma+TX, Cryptococcus albidus +TX, Cryptococcus terrestris +TX, Cryptococcus infirmo-miniatus +TX, Cryptococcus laurentii +TX, Apple trilobite granulovirus +TX, Cupriavidus campinensis +TX, Cydia pomatia granulosis virus +TX, Cydia pomatia granulosis virus ( +TX, Madex +TX, Madex Max / )+TX、Cylindrobasidium laeve +TX, Cylindrocladium+TX, Debaryomyces hansenii+TX, Drechslera hawaiinensis+TX, Enterobacter cloacae+TX, Enterobacteriaceae+TX, Entomophtora virulenta +TX, Epicoccum nigrum +TX, Epicoccum purpurascens +TX, Epicoccum species +TX, Filobasidium floriforme +TX, Fusarium acuminate +TX, Fusarium thunbergii +TX, Fusarium oxysporum / Biofox )+TX, Fusarium sp.+TX, Fusarium spp.+TX, Galactomyces geotrichum+TX, Gliocladium catenulatum ( +TX, )+TX, Gliocladium roseum+TX, Gliocladium species +TX, Gliocladium virens +TX, Granulovirus +TX, Halobacillus halophilus +TX, Halobacillus litoralis +TX, Halobacillus trueperi +TX, Halomonas species +TX, Halomonas subglaciescola +TX, Halovibrio variabilis +TX, Hansenula vitis +TX, Helicoverpa armigera nuclear polyhedrosis virus +TX, Spodoptera exigua nuclear polyhedrosis virus +TX, isoflavone-formononetin +TX, Kloeckner's yeast +TX, Kloeckner's yeast species +TX, Lagenidium giganteum +TX, Lecanicillium longisporum +TX, Lecanicillium muscarium +TX, Lymantria dispar nuclear polyhedrosis virus +TX, Halococcus halophilus +TX, Meira geulakonigii +TX, Metarhizium anisopliae +TX, Metarhizium anisopliae )+TX, Metschnikowia fruticola +TX, Metschnikowia pulcherrima+TX, Microdochium dimerum +TX, Micromonospora coerulea +TX, Microsphaeropsis ochracea +TX, Muscodor albus 620 +TX, Muscodor roseus strain A3-5+TX, Mycorrhizae spp. ( +TX、Root )+TX, Myrotheca verrucosa strain AARC-0255 +TX、BROS +TX, Ophiostoma piliferum strain D97 +TX, Paecilomyces farinosus +TX, Paecilomyces fumosorum +TX, )+TX, Paecilomyces lilacinus (Biostat )+TX, Paecilomyces lilacinus strain 251 (MeloCon )+TX, Paenibacillus polymyxa+TX, BlightBan )+TX, Pantoea species+TX, Pasteurella species +TX, Pasteuria nishizawae +TX, Penicillium chrysogenum +TX, Penicillium billai ( +TX, )+TX, Penicillium breviscomplexum+TX, Penicillium affine+TX, Penicillium purpurogenum+TX, Penicillium species+TX, Pure green Kentella+TX, Phlebiopsis gigantean +TX, phosphate-solubilizing bacteria +TX, Phytophthora cryptogenomica +TX, Phytophthora palmi +TX, Pichia anomala +TX, Pichia guilermondii +TX, Pichia membranaceus +TX, Pichia nail +TX, Pichia stipitis +TX, Pseudomonas aeruginosa +TX, Pseudomonas aureofasciens (Spot-Less )+TX, Pseudomonas cepacia+TX, Pseudomonas chlororaphis +TX, Pseudomonas corrugate +TX, Pseudomonas fluorescens strain A506 (BlightBan )+TX, Pseudomonas putida+TX, Pseudomonas reactans+TX, Pseudomonas species+TX, Pseudomonas syringae +TX, Pseudomonas aureus+TX, Pseudomonas fluorescens +TX, Pseudozyma flocculosa strain PF-A22 UL (Sporodex )+TX、Puccinia canaliculata+TX、Puccinia thlaspeos(Wood )+TX, Pythium oligandrum+TX, Pythium oligandrum +TX, )+TX, Pythium entangled +TX, Rhanella aquatilis +TX, Rhanella spp. +TX, Rhizobia ( +TX, )+TX, Rhizoctonia+TX, Rhodococcus globerulus strain AQ719+TX, Rhodosporidiumdiobovatum+TX, Rhodosporidium toruloides+TX, Rhodotorula spp.+TX, Rhodotorula glutinis+TX, Rhodotorula graminis+TX, Rhodotorula mucilagnosa+TX, Rhodotorula rubra+TX, Saccharomyces cerevisiae+TX, Salinococcus roseus+TX, Sclerotinia minor+TX, Sclerotinia minor +TX, Scytalidium spp.+TX, Scytalidium uredinicola+TX, Spodoptera exigua nuclear polyhedrosisvirus( +TX, )+TX, Serratia marcescens+TX, Serratia plymuthica+TX, Serratia spp.+TX, Sordaria fimicola+TX, Spodoptera littoralisnucleopolyhedrovirus +TX, Sporobolomyces roseus +TX, Stenotrophomonas maltophilia +TX, Streptomyces ahygroscopicus +TX, Streptomyces albaduncus +TX, Streptomyces exfoliates +TX, Streptomyces galbus +TX, Streptomyces griseoplanus +TX, Streptomyces griseoviridis +TX, Streptomyces lydicus +TX, Streptomyces lydicus WYEC-108 +TX, Streptomyces violaceus +TX, Tilletiopsis minor +TX, Tilletiopsis spp. +TX, Trichoderma asperellum (T34 )+TX, Trichoderma gamsii +TX, Trichoderma atroviride +TX, Trichoderma hamatum TH 382+TX, Trichoderma harzianum rifai +TX, Trichoderma harzianum T-22( +TX, PlantShield +TX, +TX, )+TX, Trichoderma harzianum T-39 +TX, Trichoderma mainhamatum +TX, Trichoderma koningii +TX, Trichoderma spp. LC 52 +TX, Trichoderma lignorum +TX, Trichoderma longibrachiatum +TX, Trichoderma polysporum (Binab )+TX, Trichoderma taxi+TX, Trichoderma virens+TX, Trichoderma virens (formerly known as Gliocladium virens GL-21) +TX, Trichoderma viride +TX, Trichoderma viride strain ICC 080 +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 ( +TX, Ustilago maydis +TX, various bacteria and supplemental micronutrients (Natural )+TX, various fungi (Millennium )+TX, Verticillium chlamydosporium+TX, Verticillium lecanii ( +TX, )+TX、Vip3Aa20 +TX, Virgibaclillus marismortui +TX, Xanthomonas campestris pv.Poae +TX, Xenorhabdus burnetii +TX, Xenorhabdus nematophila; and

[0767] Plant extracts, including: pine oil +TX, Plasma Neem +TX, +TX, +TX, +TX, Plant IGR( +TX, )+TX, canola oil (Lilly Miller )+TX, Chenopodium ambrosioides near ambrosioides +TX, chrysanthemum extract +TX, neem oil extract +TX, Labiatae essential oil +TX, clove-rosemary-peppermint and thyme oil extract (Garden insect )+TX, betaine +TX, garlic +TX, lemongrass oil +TX, neem oil +TX, catnip (Nepeta cataria) (catnip oil) +TX, Nepeta catarina +TX, nicotine +TX, oregano oil +TX, Pedaliaceae oil +TX, Pyrethrum+TX, Soapbark Tree (Quillaja saponaria) +TX, Reynoutria sachalinensis ( +TX, )+TX, rotenone (Eco )+TX, Rutaceae plant extract +TX, soybean oil (Ortho )+TX, tea tree oil (Timorex )+TX, thyme oil+TX, MMF+TX, +TX, Rosemary-Sesame-Peppermint-Thyme and Cinnamon Extract Blend (EF )+TX, clove-rosemary and peppermint extract blend (EF )+TX, Clove-Peppermint-Garlic Oil and Mint Blend (Soil )+TX, kaolin +TX, storage glucan of brown algae as well as

[0768] Pheromones, including: 3M Sprayable Blackheaded Fireworm )+TX, Codling moth pheromone (Paramount dispenser-(CM) / Isomate )+TX, Grape leaf roller pheromone (3MMEC-GBM Sprayable )+TX, leaf roller pheromone (3MMEC-LR Sprayable )+TX, Muscamone (Snip7Fly +TX、Starbar Premium Fly )+TX, 3M oriental fruit mothsprayable )+TX, Peachtree Borer pheromone +TX, Tomato Pinworm pheromone (3M Sprayable )+TX, Entostat powder (Exosex )+TX、(E+TX,Z+TX,Z)-3+TX,8+TX,11-tetradecatriene acetate+TX、(Z+TX,Z+TX,E)-7+TX,11+TX,13-hexadecadienal+TX、(E+TX,Z)-7+TX,9-dodecadien-1-yl acetate+TX、2-methyl-1-butanol+TX、calcium acetate+TX、 +TX, +TX, +TX, Lavandulyl senecioate; and

[0769] Macrobial agents, including: Aphidius ervi + TX, Aphidius ervi +TX, Acerophagus papaya+TX, Coccinella bispotata +TX, Coccinella bispotata +TX, Coccinella bispotata +TX, Ageniaspis citricola +TX, Polyembryonic wasp +TX, Amblyseius andersoni ( +TX, )+TX, Amblyseius californicus ( +TX, )+TX, Cucumber mite ( +TX, Bugline )+TX, Pseudoseiidae +TX, Bugline +TX, )+TX, Amblyseius ostreatus +TX, Amitus hesperidum+TX, Anagrus atomus+TX, Anagyrus fusciventris+TX, Anagyrus kamali+TX, Anagyrus loecki+TX, Anagyrus pseudococci +TX, Anicetus benefices +TX, Anisopteromalus calandrae +TX, Anthocoris nemoralis +TX, Short-spurred Aphid Wasp ( +TX, )+TX, Aphelinus asychis+TX, Aphidius colemani +TX, Alphididae +TX, Aphidida cirrhosa +TX, Aphidida serrata +TX, Aphid midge +TX, Aphid midge +TX, Lingnan yellow aphid wasp +TX, Indian yellow aphid wasp +TX, Aprostocetus hagenowii +TX, Atheta coriaria +TX, Bombus species +TX, European bumblebee (Natupol )+TX, European Bumblebee ( +TX, )+TX, Cephalonomiastephanoderis+TX, Chilocorus nigritus+TX, Chrysoperlacarnea +TX, Common lacewing +TX, Chrysoperlarufilabris+TX, Cirrospilus ingenuus+TX, Cirrospilusquadristriatus+TX, Citrostichus phyllocnistoides+TX, Closterocerus chamaeleon+TX, Closterocerus species+TX, Coccidoxenoides perminutus +TX, Coccophagus cowperi+TX, Coccophagus lycimnia+TX, Coccophagus luteola+TX, Coccophagus rapae+TX, Coccophagus monticola+TX +TX, )+TX、Japanese square-headed beetle+TX、Siberian jawed braconid wasp+TX、Siberian jawed braconid wasp +TX, Pea leafminer +TX, small black ladybug (Delphastuscatalinae) +TX, Delphastus pusillus+TX, Diachasmimorpha krausii+TX, Long-tailed fly miner+TX, Diaparsis jucunda+TX, Diaphorencyrtusaligarhensis+TX, Pea leafminer+TX, Pea leafminer +TX, )+TX, Siberian Braconidia ( +TX, )+TX, species of the genus Encarsia+TX, Aphididae spp.+TX, Encarsia spp. +TX, +TX, )+TX, Eretmocerus eremicus +TX, Encarsia guadeloupae +TX, Encarsia haitiensis +TX, Syrphididae +TX, Eretmoceris siphonini+TX, Eretmocerus californicus+TX, Eretmocerus eremicus( +TX, Eretline )+TX, Eretmocerus eremicus +TX, Eretmocerus mundus ( +TX, Eretline )+TX, Eretmocerussiphonini+TX, Exochomus quadripustulatus+TX, Feltiellaacarisuga +TX, Feltiella acarisuga +TX, Alishan fly miner (Fopius arisanus) +TX, Fopius ceratitivorus +TX, Formononetin (Wirless )+TX, Franklinothrips vespiformis +TX, Galendromus occidentalis +TX, Goniozus legneri +TX, Habrobracon hebetor +TX, Harmonia axyridis +TX, Heterorhabditis spp. (Lawn )+TX, Heterorhabditis bacteriophora (NemaShield +TX, +TX, +TX, +TX, +TX, +TX, +TX, )+TX, Heterorhabditis megidis (Nemasys +TX, BioNem +TX、Exhibitline +TX, )+TX, Hippodamia convergens+TX, Hypoaspis aculeifer ( +TX, )+TX、Hypoaspis miles +TX, )+TX、Lbalialeucospoides+TX、Lecanoideus floccissimus+TX、Lemophagus errabundus+TX、Leptomastidea abnormis+TX、Leptomastix dactylopii +TX, Leptomastix epona+TX, Lindorus lophanthae+TX, Lipolexis oregmae+TX, Lucilia caesar +TX, Lysiphlebus testaceipes +TX, Macrolophus caliginosus ( +TX、Macroline +TX, )+TX、Mesoseiulus longipes+TX、Metaphycus flavus+TX、Metaphycus lounsburyi+TX、Micromusangulatus +TX, Microterys flavus +TX, Muscidifurax raptorellus and Spalangia cameroni +TX, Neodryinustyphlocybae+TX, Neoseiulus californicus+TX, Neoseiuluscucumeris +TX, Neoseiulus fallacis +TX, Nesideocoris tenuis ( +TX, )+TX, bronze black fly (Ophyraaenescens) +TX, Orius insidiosus( +TX, Oriline )+TX, Orius laevigatus ( +TX, Oriline )+TX、Orius majusculus(Oriline )+TX, Orius strigicollis +TX, Pauesia juniperorum+TX, Pediobius foveolatus+TX, Phasmarhabditis hermaphrodita +TX, Phymastichuscoffea+TX, Phytoseiulus macropilus+TX, Phytoseiulus persimilis ( +TX、Phytoline )+TX, Podisus maculiventris +TX、Pseudacteon curvatus+TX、Pseudacteon obtusus+TX、Pseudacteontricuspis+TX、Pseudaphycus maculipennis+TX、Pseudleptomastix mexicana+TX、Psyllaephagus pilosus+TX、Psyttalia concolor(complex)+TX、Quadrastichus spp.+TX、Rhyzobius lophanthae+TX、Rodolia cardinalis+TX、Rumina decollate+TX、Semielacher petiolatus+TX、Sitobion avenae +TX, Steinernema carpocapsae (Nematac +TX, +TX, BioNem +TX, +TX, +TX, )+TX, Steinernema carinata ( +TX, Nemasys +TX, BioNem +TX, +TX, +TX, +TX、Exhibitline +TX, +TX, )+TX, Steinernema kraussei (Nemasys +TX, BioNem +TX、Exhibitline )+TX, Steinernema riobrave ( +TX, )+TX, Steinernema scapterisci (Nematac )+TX, Steinernema spp.+TX, Steinernematid spp. )+TX, Stethorus punctillum +TX, Tamarixia radiate+TX, Tetrastichussetifer+TX, Thripobius semiluteus+TX, Torymus sinensis+TX, Trichogramma brassicae(Tricholine )+TX, Trichogramma brassicae +TX, Trichogramma evanescens +TX, Trichogramma minutum +TX, Trichogramma ostriniae +TX, Trichogramma platneri +TX, Trichogramma retiosum +TX, Xanthopimpla stemmator; and

[0770] Other biological agents, including: abscisic acid + TX, +TX, Chondrostereum purpureum (Chontrol )+TX, Discosporium +TX, copper octanoate +TX, Delta trap (Trapline )+TX, Erwinia amylovora (Harpin) ( +TX、Ni-HIBIT Gold )+TX, ferric phosphate +TX, Funnel trap )+TX, +TX, Grower's +TX, Homo-brassonolide +TX, iron phosphate (Lilly Miller Worry Free Ferramol Slug & Snail )+TX、MCP hail trap )+TX、parasitic insect Microctonus hyperodae+TX、Mycoleptodiscus terrestris +TX, +TX, +TX, +TX, Pheromone Net (Thripline )+TX, potassium bicarbonate +TX, potassium salt of fatty acids +TX, potassium silicate solution +TX, potassium iodide + potassium thiocyanate +TX, +TX, spider venom +TX, locust microsporidia (Semaspore Organic Grasshopper )+TX, Trapline +TX, Rebell )+TX and the captured object (Takitrapline y+ )+TX;

[0771] or a biologically active compound or agent selected from the group consisting of flumethrin + TX, diflovidazine + TX, flometoquin + TX, fluhexafon + TX, diamondback moth granulovirus + TX, codling moth granulovirus + TX, imiphos + TX, tobacco budworm nuclear polyhedrosis virus + TX, Heliothis punctigera nuclear polyhedrosis virus + TX, zea worm nuclear polyhedrosis virus + TX, fall armyworm nuclear polyhedrosis virus + TX, diamondback moth nuclear polyhedrosis virus + TX, para-cymene + TX, pyflubumide + TX, pyrafluprole + TX, QRD 420 + TX, QRD 452 + TX, QRD 460 + TX, terpenoid mixture + TX, terpenoid + TX, tetranilide + TX, and alpha-terpinene + TX;

[0772] Or active substances mentioned by code + TX, such as code AE ​​1887196 (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-A9955+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;

[0773] or other biologically active compounds or agents selected from the group consisting of Quinofumelin+TX, mefentrifluconazol+TX, fenpicoxamid+TX, fluindapyr+TX, inpyrfluxam+TX or indiflumetpyr+TX, isoflurane+TX, pyrapropoyne+TX, florylpicoxamid+TX, metyltetraprole+TX, ipflufenoquin+TX, pyridachlometyl+TX or chlopyridiflu+TX, tetrachlorantraniliprole+TX, tetrachloraniliprole+TX, Tetflupyrolimet+TX, Triflufenpyrrolidone+TX, Tyclopyrazoflor+TX, fl upyrimin+TX or pyrifluramide+TX, benzpyrimoxan+TX, beflubutamid-M+TX, Benzosufyl+TX or oxazosulfyl+TX, etpyrafen+TX, acynonapyr+TX or pyrinonafen+TX, oxotrione+TX, bixlozone+TX or clofendizone+TX or dicloroxizone+TX, cyclopyranil+TX or pyrazocyclonil+TX or cyclopyrazonil+TX, α-bromadiolone+TX, Oxathiapiprolin+TX, Fluopyram+TX, Penflufen+TX, Fluoxopyrosad+TX, fluoxapiprolin+TX and Flupyradifurone+TX.

[0774] References in brackets after the active ingredients, e.g. [3878-19-1] refer to Chemical Abstracts Registry Numbers. The mixed compatibilities described above are known. When the active ingredients are included in "The Pesticide Manual" [The Pesticide Manual - A World Compendium; 13th edition; editor: CDSTomLin; The British Crop Protection Coimcil], they are described therein by the entry number given in parentheses above for the specific compound; e.g. the compound "avermectin" is described by entry number (1). In the case where "[CCN]" is added above to a specific compound, the compound in question is included in the "Compendium of Pesticide Common Names", which can be found on the Internet [A.Wood; CompendiumofPesticide CommonNames , 1995-2004]; for example, the compound "acetoprole" is described on the Internet at http: / / www.alanwood.net / pesticides / acetoprole.html.

[0775] Most active ingredients are referred to by what are referred to above as "common names", with the corresponding "ISO common name" or other "common names" being used in different cases. If a name is not a "common name", the kind of name used is replaced by the name given in parentheses for the specific compound; in this case, the IUPAC name, IUPAC / Chemical Abstracts name, "Chemical Name", "Traditional Name", "Compound Name" or "Research Code" is used, or if neither one of those names nor the "common name" is used, the "synonym" is used. "CAS Registry Number" means the Chemical Abstracts Registry Number.

[0776] Selected from Group Active ingredient mixtures of compounds of formula I of Y-1 to Y-8, X-1 to X-8, U-1 to U-2 and V-1 to V-6 and Table P with the above active ingredients comprise the active ingredients selected from GroupThe compounds of Y-1 to Y-8, X-1 to X-8, U-1 to U-2 and V-1 to V-6 and Table P and the active ingredients as described above, they are preferably in a mixing ratio of from 100:1 to 1:6000, especially from 50:1 to 1:50, more especially in a ratio of from 20:1 to 1:20, even more especially from 10:1 to 1:10, very especially from 5:1 and 1:5, particularly preferably in a ratio of from 2:1 to 1:2, and likewise preferably in a ratio of from 4:1 to 2:1, especially 1:1, or 5:1, or 5:2, or 5:3, or 5:4, or or 1:600, or 1:300, or 1:150, or 1:35, or 2:35, or 4:35, or 1:75, or 2:75, or 4:75, or 1:6000, or 1:3000, or 1:1500, or 1:350, or 2:350, or 4:350, or 1:750, or 2:750, or 4:750. Those mixing ratios are by weight.

[0777] The mixtures as described above can be used in a method for controlling pests which comprises applying a composition containing a mixture as described above to the pests or their environment, except for methods for treating the human or animal body by surgery or therapy and diagnostic methods performed on the human or animal body.

[0778] Included selected from Group Mixtures of compounds of formula I of Y-1 to Y-8, X-1 to X-8, U-1 to U-2 and V-1 to V-6 and Table P and one or more active ingredients as described above can be applied, for example, in a single "ready-to-use" form, in a combined spray mixture consisting of separate formulations of the single active ingredient components, such as a "tank mix", and in combination with these single active ingredients when applied in a sequential manner (i.e., one after the other within a reasonably short period of time, such as a few hours or days). Application selected from Group The order in which the compounds of formula I of Y-1 to Y-8, X-1 to X-8, U-1 to U-2 and V-1 to V-6 and Table P and the active ingredients as described above is not essential for working the present invention.

[0779] The compositions according to the invention may also contain other solid or liquid adjuvants, such as stabilizers, for example non-epoxidized or epoxidized vegetable oils (for example epoxidized coconut oil, rapeseed oil or soybean oil), defoamers (for example silicone oils), preservatives, viscosity regulators, adhesives and / or tackifiers, fertilizers or other active ingredients for obtaining specific effects, such as bactericides, fungicides, nematicides, plant activators, molluscicides or herbicides.

[0780] The compositions according to the invention are prepared in a manner known per se, in the absence of auxiliaries, for example by grinding, screening and / or compressing the solid active ingredient; and in the presence of at least one auxiliary, for example by intimately mixing the active ingredient with one or more auxiliary agents and / or grinding the active ingredient with one or more auxiliary agents. These methods for preparing the compositions and the use of compound I for preparing these compositions are also the subject matter of the present invention.

[0781] The application methods of these compositions, i.e. the methods for controlling the above-mentioned types of harmful organisms, such as spraying, atomizing, dusting, brushing, coating, broadcasting or pouring - they are selected to be suitable for the intended purpose of the prevailing situation - and the use of these compositions for controlling the above-mentioned types of harmful organisms are other subjects of the present invention. Typical concentration ratios are between 0.1 and 1000 ppm, preferably between 0.1 and 500 ppm of active ingredient. The application rate per hectare is generally 1 g to 2000 g of active ingredient per hectare, especially 10 g / ha to 1000 g / ha, preferably 10 g / ha to 600 g / ha.

[0782] In the field of crop protection, the preferred method of application is application to the leaves of these plants (foliar application), it being possible to choose the frequency and rate of application to correspond to the risk of infestation by the harmful organism in question. Alternatively, the active ingredient can reach the plants via the root system (systemic action), this being achieved by soaking the locus of these plants with a liquid composition or by introducing the active ingredient in solid form into the locus of the plants, for example into the soil, for example in the form of granules (soil application). In the case of rice crops, such granules can be metered into flooded rice fields.

[0783] Compound of the present invention and composition thereof are also suitable for the protection of plant propagation materials (e.g. seeds, such as fruits, tubers or grains, or nursery plants) to resist the harmful organisms of the above-mentioned type. The propagation material can be treated with the compound before planting, for example, seeds can be treated before sowing. Alternatively, the compound can be applied to seed grains (coating), which is achieved by dipping the grains into a liquid composition or by applying a solid composition layer. It is also possible to apply these compositions when the propagation material is planted in the application site, for example, these compositions are applied to the seed furrow during drilling. These treatment methods for plant propagation materials and the plant propagation materials so treated are other themes of the present invention. Typical treatment ratios will depend on plants to be controlled and harmful organisms / fungi, and usually between 1 gram and 200 grams per 100kg seeds, preferably between 5 grams and 150 grams per 100kg seeds, such as between 10 grams and 100 grams per 100kg seeds.

[0784] The term seed includes all kinds of seeds and plant propagules including but not limited to true seeds, seed pieces, suckers, kernels, bulbs, fruits, tubers, grains, rhizomes, cuttings, cuttings and the like and in preferred embodiments means true seeds.

[0785] The present invention also includes seeds coated or treated with compounds of formula I or seeds containing compounds of formula I. Although more or less parts of the ingredients can penetrate into the seed material, depending on the method of application, the term "coating or treatment and / or containing" generally means that at the time of application, in most cases, the active ingredient is on the surface of the seed. When the seed product is (re)planted, it can absorb the active ingredient. In an embodiment, the present invention makes it possible to use plant propagation materials with compounds of formula (I) adhered thereto. In addition, the composition comprising plant propagation materials treated with compounds of formula (I) is thus made available.

[0786] Seed treatment includes all suitable seed treatment techniques known in the art, such as seed coating, seed coating, seed dusting, seed soaking and seed pelleting. Seed treatment application with the compound of formula (I) can be carried out by any known method, such as spraying or dusting the seeds before sowing or during sowing / planting.

[0787] Biological Examples

[0788] Example B1: Bemisia tabaci Activity of (cotton whitefly)

[0789] Cotton leaf discs were placed on agar in 24-well microtiter plates and sprayed with an aqueous test solution prepared from a 10'000 ppm DMSO stock solution. After drying, the leaf discs were infested with adult whiteflies. After 6 days of incubation, the samples were checked for mortality.

[0790] The following compounds produced at least 80% mortality at an application rate of 200 ppm:

[0791] P3, P4, P6, P8, P10, P13, P14 and P15.

[0792] Example B2: Active against cucumber leaves (corn rootworm) activity

[0793] Corn sprouts placed on agar layers in 24-well microtiter plates were treated by spraying with an aqueous test solution prepared from a 10,000 ppm DMSO stock solution. After drying, the plates were infested with L2 larvae (6 to 10 / well). After infestation for 4 days, these samples were evaluated for mortality and growth inhibition compared to untreated samples.

[0794] The following compounds gave an effect of at least 80% in at least one of the two categories (mortality or growth inhibition) at an application rate of 200 ppm:

[0795] P3, P4, P5, P7, P8, P10, P11, P12, P13, P14, and P16.

[0796] Example B3: Euschistusheros Activity of the Neotropical brown stink bug

[0797] Soybean leaves on agar in 24-well microtiter plates were sprayed with aqueous test solutions prepared from a 10'000 ppm DMSO stock solution. After drying, the leaves were infested with N2 stage nymphs. After 5 days of infestation, the samples were evaluated for mortality and growth inhibition compared to untreated samples.

[0798] The following compounds gave an effect of at least 80% in at least one of the two categories (mortality or growth inhibition) at an application rate of 200 ppm:

[0799] P3, P4, P8, P9, P10, P13, P14 and P15.

[0800] Example B4: Pseudocercus persicae (Green peach aphid) activity:

[0801] Sunflower leaf disks were placed on agar in 24-well microtiter plates and sprayed with an aqueous test solution prepared from a 10'000 ppm DMSO stock solution. After drying, the leaf disks were infested with a population of mixed-age aphids. Six days after infestation, the samples were evaluated for mortality.

[0802] The following compounds produced at least 80% mortality at an application rate of 200 ppm:

[0803] P3, P4, P5, P6, P7, P8, P9, P10, P11, P12, P13, P14, P15, P16, and P17.

[0804] Example B5: Pseudocercus persicae (green peach aphid) activity.

[0805] The roots of pea seedlings infested with a population of mixed-age aphids were placed directly into an aqueous test solution prepared from a 10'000 DMSO stock solution. After the seedlings were placed in the test solution for 6 days, the samples were evaluated for mortality.

[0806] The following compounds produced at least 80% mortality at a 24 ppm test rate:

[0807] P3, P4, P5, P6, P7, P8, P9, P10, P11, P12, P13, P14, P15, P16, and P17.

[0808] Example B6: Plutella xylostella Activity of Diamond back moth

[0809] 24-well microtiter plates with artificial diet were treated by pipetting with aqueous test solutions prepared from 10'000ppm DMSO stock solutions. After drying, the plates were infested with L2 larvae (10 to 15 / well). After 5 days of infestation, the samples were evaluated for mortality and growth inhibition compared to untreated samples.

[0810] The following compounds gave an effect of at least 80% in at least one of the two categories (mortality or growth inhibition) at an application rate of 200 ppm:

[0811] P3, P4, P5, P6, P7, P8, P11, P12, P14, and P15.

[0812] Example B7: Spodoptera littoralis Activity of Egyptian cotton leafworm

[0813] Cotton leaf disk is placed on the agar in 24 hole microtiter plates and sprayed with the aqueous test solution prepared from 10'000ppm DMSO stock solution.After drying, leaf disk is infested with five L1 stage larvae.After infesting 3 days, compared to untreated sample, these samples are assessed for mortality rate, antifeedant effect and growth inhibition.When at least one of these classifications (mortality rate, antifeedant effect and growth inhibition) was higher than untreated sample, realize the control of test sample to Spodoptera littoralis.

[0814] The following compounds produced at least 80% control at a 200 ppm application rate:

[0815] P3, P4, P5, P7, P8, P11, P12, P14, P15, and P16.

[0816] Example B8: Brown planthopper (Nilaparvatalugens) (Brown plant hopper) activity

[0817] Rice plants were treated with the diluted test solutions in a spray chamber. After drying, the plants were infested with about 20 N3 stage nymphs. Seven days after treatment, the samples were evaluated for mortality and growth regulation.

[0818] P6, P10, P11, P12, P13, and P15

[0819] Example B9: Brown planthopper (Nilaparvatalugens) (Brown plant hopper) activity

[0820] Rice plants cultured in nutrient solution were treated with diluted test solutions into a nutrient culture system. One day after application, the plants were infested with about 20 N3 stage nymphs. Seven days after infestation, samples were evaluated for mortality and growth regulation.

[0821] P6, P10, P11, P12, P13, and P15

[0822] Example B10: against Tetranychus urticae Activity of (two-spotted spider mite):

[0823] Bean leaf discs on agar in 24-well microtiter plates were sprayed with aqueous test solutions prepared from a 10'000 ppm DMSO stock solution. After drying, the leaf discs were infested with a mixed age population of mites. The samples were evaluated for mortality of the mixed population (active stage) 8 days after infestation.

[0824] The following compounds caused at least 80% mortality at an application rate of 200 ppm:

[0825] P3.

[0826] Example B11: Plutella xylostella Activity of Diamond back moth

[0827] 24-well microtiter plates with artificial diets were treated by pipetting with aqueous test solutions prepared from 10,000 ppm DMSO stock solutions. After drying, Plutella xylostella eggs were pipetted through a plastic template onto gel blotting paper and the plates were sealed with it. After 8 days of infestation, these samples were evaluated for mortality and growth inhibition compared to untreated samples.

[0828] The following compounds gave an effect of at least 80% in at least one of the two categories (mortality or growth inhibition) at an application rate of 200 ppm:

[0829] P16, P17, P18, and P19.

[0830] Example B12: Activity against Heteroderaschachtii In vitro characterization of larval mobility in 96-well plates

[0831] Test solutions were prepared from 10'000ppm DMSO stock solutions with a TECAN robot to obtain 20 μL of 500ppm, 100ppm, 50ppm, 25ppm, 12.5ppm and 6.25ppm. Three replicates were produced for each concentration. 80 μL of nematode solution containing 100 to 150 newly harvested second-stage larvae of beet cyst nematodes was added to each well. The plates were covered and stored and incubated for 48 hours in the dark at room temperature. The mobility of the exposed larvae in the treated wells was measured using an imaging tool and compared with the average of 12 untreated replicates.

[0832] The following compounds achieved at least 60% control after 48 hours at 100 ppm:

[0833] P10, P15.

Claims

1. A compound having formula (I) in A is CH or N R1 is C1-C4 alkyl R2 is hydrogen, cyano, -C(O)R7, -C(O)OR8, C1-C6 alkyl or -CONR9R 10 、SO2R 11 in R7 is hydrogen, C1-C6 alkyl or C1-C6 haloalkyl, and R8 is C1-C6 alkyl or C1-C6 haloalkyl; R9, R 10 are independently hydrogen or C1-C6 alkyl; R 11 is a C1-C6 alkyl group; R3 is hydrogen, C1-C3 alkyl, C1-C3 haloalkyl, cyano, -CO2H, -CO2NH2, C1-C4 alkoxycarbonyl, C1-C4 alkylaminocarbonyl, C1-C4 dialkylaminocarbonyl n is 0 or 1; Q is a group selected from the group consisting of: formula Q1, Q2, Q3, Q4 and Q5 wherein the arrow indicates the point of attachment to the ring into which the group A is incorporated; And among them R4 is halogen, C1-C6 haloalkyl, C1-C4 haloalkylsulfanyl, C1-C4 haloalkylsulfinyl, C1-C4 haloalkylsulfonyl or C1-C6 haloalkoxy; X1 is O or NR5; R5 is C1-C4 alkyl; R6 is C1-C4 alkyl, C1-C4 haloalkyl, C1-C4 alkoxy, or C3-C6 cycloalkyl; G1 and G2 are independently N or CH; or an agrochemically acceptable salt, stereoisomer, enantiomer, tautomer or N-oxide of a compound of formula I.

2. The compound according to claim 1, wherein: A is CH or N; R1 is ethyl, propyl or isopropyl; R2 is hydrogen, cyano, C1-C3 alkyl, C1-C3 alkylcarbonyl, C1-C3 alkoxycarbonyl, C1-C3 haloalkylcarbonyl; R3 is hydrogen, C1-C3 haloalkyl, cyano, -CO2H, -CO2NH2, C1-C4 dialkylaminocarbonyl; and n is 1.

3. The compound according to claim 1, wherein: A is CH or N; R1 is ethyl; R2 is hydrogen; R3 is hydrogen, C1-C2 haloalkyl, cyano, -CO2NH2, C1-C2 dialkylaminocarbonyl; and n is 1.

4. The compound according to claim 1, wherein: A is CH or N; R1 is ethyl; R2 is hydrogen; R3 is hydrogen, cyano or CO2NH2; and n is 1.

5. The compound according to claim 1, wherein: A is CH or N; R1 is ethyl; R2 is hydrogen; R3 is hydrogen or cyano; and n is 1.

6. A compound according to any one of claims 1 to 5, wherein: Q is a group selected from Q1, Q2, Q4 and Q5 wherein the arrow indicates the point of attachment to the ring into which the group A is incorporated; And among them R4 is C1-C2 haloalkyl, C1-C2 haloalkylsulfanyl, C1-C2 haloalkylsulfinyl or C1-C2 haloalkylsulfonyl; X1 is oxygen or NCH3; R6 is C1-C2 alkyl, C1-C2 haloalkyl, C1-C2 alkoxy or cyclopropyl; and G1 and G2 are independently N or CH.

7. A compound according to any one of claims 1 to 5, wherein: is a group selected from Q1, Q2 and Q5 wherein the arrow indicates the point of attachment to the ring into which the group A is incorporated; And among them R4 is C1-C2 fluoroalkyl, trifluoromethylsulfanyl, trifluoromethylsulfinyl, trifluoromethylsulfonyl, difluoromethylsulfanyl, difluoromethylsulfinyl, or difluoromethylsulfonyl; X1 is NCH3; R6 is methyl, ethyl, 2,2,2-trifluoroethyl, methoxy or cyclopropyl; and G1 and G2 are independently N or CH.

8. A compound according to any one of claims 1 to 5, wherein: Q is a group selected from Q1 and Q5 wherein the arrow indicates the point of attachment to the ring into which the group A is incorporated; And among them 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.

9. A compound according to any one of claims 1 to 5, wherein: Q is the group Q1 wherein the arrow indicates the point of attachment to the ring into which the group A is incorporated; And among them R2 is trifluoromethyl; X1 is NCH3; and G1 is N and G2 is CH, G1 is CH and G2 is N, or G1 and G2 are N.

10. The compound according to claim 1, wherein: A is CH or N; R1 is ethyl, propyl or isopropyl; R2 is hydrogen, cyano, C1-C3 alkyl, C1-C3 alkylcarbonyl, C1-C3 alkoxycarbonyl, C1-C3 haloalkylcarbonyl; R3 is hydrogen, C1-C3 haloalkyl, cyano, CO2H, CO2NH2, C1-C4 dialkylaminocarbonyl; n is 1; Q is a group selected from Q1, Q2, Q4 and Q5 wherein the arrow indicates the point of attachment to the ring into which the group A is incorporated; And among them R4 is C1-C2 haloalkyl, C1-C2 haloalkylsulfanyl, C1-C2 haloalkylsulfinyl or C1-C2 haloalkylsulfonyl; X1 is oxygen or NCH3; R6 is C1-C2 alkyl, C1-C2 haloalkyl, C1-C2 alkoxy or cyclopropyl; and G1 and G2 are independently N or CH.

11. The compound according to claim 1, wherein: A is CH or N; R1 is ethyl; R2 is hydrogen; R3 is hydrogen, C1-C2 haloalkyl, cyano, CO2NH2, C1-C2 dialkylaminocarbonyl; n is 1; Q is a group selected from Q1, Q2 and Q5 wherein the arrow indicates the point of attachment to the ring into which the group A is incorporated; And among them R4 is C1-C2 fluoroalkyl, trifluoromethylsulfanyl, trifluoromethylsulfinyl, trifluoromethylsulfonyl, difluoromethylsulfanyl, difluoromethylsulfinyl, or difluoromethylsulfonyl; X1 is NCH3; R6 is methyl, ethyl, 2,2,2-trifluoroethyl, methoxy or cyclopropyl; and G1 and G2 are independently N or CH.

12. The compound according to claim 1, wherein: A is CH or N; R1 is ethyl; R2 is hydrogen; R3 is hydrogen, cyano or CO2NH2; n is 1; Q is a group selected from Q1 and Q5 wherein the arrow indicates the point of attachment to the ring into which the group A is incorporated; And among them 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.

13. The compound according to claim 1, wherein: A is CH or N; R1 is ethyl; R2 is hydrogen; R3 is hydrogen or cyano; n is 1; Q is the group Q1 wherein the arrow indicates the point of attachment to the ring into which the group A is incorporated; And among them R2 is trifluoromethyl; X1 is NCH3; and G1 is N and G2 is CH, G1 is CH and G2 is N, or G1 and G2 are N.

14. A compound according to any one of claims 1 to 5, wherein: Q is selected from Q 1-1 , Q 1-2 , Q 1-3 , Q 1-4 and Q 1-5 Preferably Q is selected from Q 1-2 , Q 1-3 , Q 1-4 and Q 1-5 Group wherein the arrow indicates the point of attachment to the ring into which the group A is incorporated; and R4 is trifluoromethyl, trifluoromethylsulfanyl or trifluoromethylsulfonyl.

15. A compound according to any one of claims 1 to 5, wherein: Q is a group selected from Q5 wherein the arrow indicates the point of attachment to the ring into which the group A is incorporated; R4 is trifluoromethyl, trifluoromethylsulfanyl or trifluoromethylsulfonyl; and R6 is OCH3, CH2CH3 or cyclopropyl.

16. A compound according to any one of claims 1 to 5, wherein: Q is a group selected from Q4 wherein the arrow indicates the point of attachment to the ring into which the group A is incorporated; R4 is trifluoromethyl, trifluoromethylsulfanyl or trifluoromethylsulfonyl; and G1 is N and G2 is CH, G1 is CH and G2 is N, G1 and G2 are CH, or G1 and G2 are N; preferably, G1 is CH and G2 is N.

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

18. A composition comprising an insecticidal, acaricidal, nematicidal or molluscicidal effective amount of a compound of formula (I) as defined in any one of claims 1 to 17, or an agrochemically acceptable salt, stereoisomer, enantiomer, tautomer or N-oxide thereof, and optionally, an adjuvant or diluent.

19. A method for combating and controlling insects, mites, nematodes or molluscs, the method comprising applying an insecticidal, acaricidal, nematicidal or molluscicidal effective amount of a compound of formula (I) as defined in any one of claims 1 to 17, or an agrochemically acceptable salt, stereoisomer, enantiomer, tautomer or N-oxide thereof, or a composition as defined in claim 18 to the pest, the location of the pest, or a plant susceptible to attack by the pest.

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

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