Pesticidal Active Heterocyclic Derivatives with Sulfur-Containing Substituents - Patent application

Abstract

Formula (I) The compounds of TIFF2023523456000194.tif55157 are disclosed, the substituents of which are as defined in claim 1. Furthermore, the present invention relates to agrochemical compositions comprising compounds of formula (I), to the preparation of these compositions, and to the use of these compounds or compositions in agriculture or horticulture for combating, preventing or controlling animal pests, including arthropods, in particular insects or representatives of the order Acarina.

Description

[Technical Field]

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

[0002] Pesticidal heterocyclic derivatives containing a sulfur substituent -f+ have already been described in the literature, for example in WO 12 / 086848, WO 13 / 018928, WO 15 / 000715, WO 15 / 121136, WO 18 / 197315, WO 18 / 206348, JP 2019 / 081800 and WO 19 / 065568.

[0003] Surprisingly, it has now been found that certain novel sulfur-containing phenyl and pyridyl derivatives bearing a cyanoisopropoxy group have favorable properties as pesticides. Summary of the Invention [Means for solving the problem]

[0004] The present invention therefore provides a compound of formula I [ka] (In the formula, A is CH or N; R1 is C1-C4 alkyl or C3-C6 cycloalkyl-C1-C4 alkyl; R9 is hydrogen or C1-C4 alkyl; Q is the formula Q1 to Q7 [ka] wherein the arrow indicates the point of attachment to the ring containing group A; and X1 is O, S or NR3; R3 is C1-C4 alkyl; R2 is halogen, C1-C6 haloalkyl, C1-C4 haloalkylsulfanyl, C1-C4 haloalkylsulfinyl, C1-C4 haloalkylsulfonyl or C1-C6 haloalkoxy; G1 and G2 are, independently of each other, N or CH; R4 is C1-C4 alkyl, C1-C4 haloalkyl, C3-C6 cycloalkyl or C1-C4 alkoxy. is a group selected from the group consisting of or an agrochemically acceptable salt, stereoisomer, enantiomer, tautomer or N-oxide of a compound of formula I. DETAILED DESCRIPTION OF THE INVENTION

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

[0006] The alkyl groups in the definitions of the substituents can be linear or branched, such as methyl, ethyl, n-propyl, isopropyl, n-butyl, sec-butyl, isobutyl, t-butyl, pentyl, hexyl, and their branched isomers. The alkylsulfanyl, alkylsulfinyl, alkylsulfonyl, and alkoxy groups are derived from the alkyl groups already mentioned.

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

[0008] The haloalkyl group preferably has a chain length of 1 to 6 carbon atoms. Haloalkyl is, for example, fluoromethyl, difluoromethyl, trifluoromethyl, chloromethyl, dichloromethyl, trichloromethyl, 2,2,2-trifluoroethyl, 2-fluoroethyl, 2-chloroethyl, pentafluoroethyl, 1,1-difluoro-2,2,2-trichloroethyl, 2,2,3,3-tetrafluoroethyl, and 2,2,2-trichloroethyl; preferably trichloromethyl, difluorochloromethyl, difluoromethyl, trifluoromethyl, and dichlorofluoromethyl.

[0009] Preferably, the alkoxy group has a preferred chain length of 1 to 6 carbon atoms. Alkoxy is, for example, methoxy, ethoxy, propoxy, i-propoxy, n-butoxy, isobutoxy, sec-butoxy and t-butoxy, as well as the isomeric pentyloxy and hexyloxy groups; preferably methoxy and ethoxy.

[0010] Preferably, the alkoxyalkyl group has a chain length of 1 to 6 carbon atoms, more preferably 1 to 4 carbon atoms. Alkoxyalkyl is, for example, methoxymethyl, methoxyethyl, ethoxymethyl, ethoxyethyl, n-propoxymethyl, n-propoxyethyl, isopropoxymethyl or isopropoxyethyl.

[0011] Alkylsulfanyl is, for example, methylsulfanyl, ethylsulfanyl, propylsulfanyl, isopropylsulfanyl, butylsulfanyl, pentylsulfanyl and hexylsulfanyl.

[0012] Alkylsulfinyl is, for example, methylsulfinyl, ethylsulfinyl, propylsulfinyl, isopropylsulfinyl, butylsulfinyl, pentylsulfinyl and hexylsulfinyl.

[0013] Alkylsulfonyl is, for example, methylsulfonyl, ethylsulfonyl, propylsulfonyl, isopropylsulfonyl, butylsulfonyl, pentylsulfonyl and hexylsulfonyl.

[0014] Cycloalkyl groups preferably have 3 to 6 ring carbon atoms, for example cyclopropyl, cyclobutyl, cyclopentyl and cyclohexyl.

[0015] The haloalkylsulfanyl group preferably has a chain length of 1 to 4 carbon atoms. Haloalkylsulfanyl is, for example, difluoromethylsulfanyl, trifluoromethylsulfanyl, or 2,2,2-trifluoroethylsulfanyl. Similar considerations apply to the groups C1-C4 haloalkylsulfinyl and C1-C4 haloalkylsulfonyl, which may be, for example, trifluoromethylsulfinyl, trifluoromethylsulfonyl, or 2,2,2-trifluoroethylsulfonyl.

[0016] The compounds of formula I according to the present invention also include hydrates which may be formed during salt formation.

[0017] The embodiments of the present invention are as follows.

[0018] Embodiment 1 provides a compound of formula I, as defined above, or an agrochemically acceptable salt, stereoisomer, enantiomer, tautomer, or N-oxide thereof.

[0019] Embodiment 2 provides a compound according to embodiment 1, or an agrochemically acceptable salt, stereoisomer, enantiomer, tautomer, or N-oxide thereof, wherein: A is CH or N; R1 is ethyl, propyl, isopropyl, or -CH2cyclopropyl; R9 is hydrogen, methyl or ethyl.

[0020] Embodiment 3a provides a compound according to embodiment 1, or an agrochemically acceptable salt, stereoisomer, enantiomer, tautomer, or N-oxide thereof, wherein: A is CH or N; R1 is ethyl or -CH2cyclopropyl; preferably, R1 is ethyl; and R9 is hydrogen or methyl.

[0021] Embodiment 3b provides a compound according to embodiment 1, or an agrochemically acceptable salt, stereoisomer, enantiomer, tautomer, or N-oxide thereof, wherein: A is N; R1 is ethyl or -CH2cyclopropyl; preferably, R1 is ethyl; and R9 is hydrogen or methyl.

[0022] Embodiment 4a provides a compound according to embodiment 1, or an agrochemically acceptable salt, stereoisomer, enantiomer, tautomer, or N-oxide thereof, wherein: A is CH or N; R1 is ethyl or -CH2cyclopropyl; preferably, R1 is ethyl; and R9 is hydrogen.

[0023] Embodiment 4b provides a compound according to embodiment 1, or an agrochemically acceptable salt, stereoisomer, enantiomer, tautomer, or N-oxide thereof, wherein: A is N; R1 is ethyl or -CH2cyclopropyl; preferably, R1 is ethyl; and R9 is hydrogen.

[0024] Embodiment 5a provides a compound according to embodiment 1, or an agrochemically acceptable salt, stereoisomer, enantiomer, tautomer, or N-oxide thereof, wherein: A is CH or N; R1 is ethyl or -CH2cyclopropyl; preferably, R1 is ethyl; and R9 is methyl.

[0025] Embodiment 5b provides a compound according to embodiment 1, or an agrochemically acceptable salt, stereoisomer, enantiomer, tautomer, or N-oxide thereof, wherein: A is N; R1 is ethyl or -CH2cyclopropyl; preferably, R1 is ethyl; and R9 is methyl.

[0026] Embodiment 6 provides a compound according to embodiment 1, or an agrochemically acceptable salt, stereoisomer, enantiomer, tautomer, or N-oxide thereof, wherein: Q is Q1, Q2, Q4 and Q5 [ka] wherein the arrow indicates the point of attachment to the ring containing group A; and R2 is C1-C2 haloalkyl, C1-C2 haloalkylsulfanyl, C1-C2 haloalkylsulfinyl or C1-C2 haloalkylsulfonyl; X1 is oxygen or NCH3; R3 is C1-C2 alkyl; R4 is C1-C2 alkyl, C1-C2 haloalkyl, C1-C2 alkoxy or cyclopropyl; and G1 and G2 are, independently of each other, N or CH. is a group selected from

[0027] Embodiment 7 provides a compound according to embodiment 1, or an agrochemically acceptable salt, stereoisomer, enantiomer, tautomer, or N-oxide thereof, wherein: Q is Q1, Q2 and Q5 [ka] (wherein the arrow indicates the point of attachment to the ring containing group A; and R2 is C1-C2 fluoroalkyl, trifluoromethylsulfanyl, trifluoromethylsulfinyl, trifluoromethylsulfonyl, difluoromethylsulfanyl, difluoromethylsulfinyl, or difluoromethylsulfonyl; X1 is NCH3; R3 is methyl; R4 is methyl, ethyl, 2,2,2-trifluoroethyl, methoxy, or cyclopropyl; and G1 is N or CH is a group selected from

[0028] Embodiment 8a provides a compound according to embodiment 1, or an agrochemically acceptable salt, stereoisomer, enantiomer, tautomer, or N-oxide thereof, wherein: Q is Q1, Q2 and Q5 [ka] (wherein the arrow indicates the point of attachment to the ring containing group A; and R2 is trifluoromethyl, pentafluoroethyl, trifluoromethylsulfanyl, trifluoromethylsulfinyl, or trifluoromethylsulfonyl; X1 is NCH3; R3 is methyl; R4 is ethyl, methoxy or cyclopropyl; and G1 is CH or N is a group selected from

[0029] Embodiment 8b provides a compound according to embodiment 1, or an agrochemically acceptable salt, stereoisomer, enantiomer, tautomer, or N-oxide thereof, wherein: Q is Q1, Q2 and Q5 [ka] (wherein the arrow indicates the point of attachment to the ring containing group A; and R2 is trifluoromethyl, pentafluoroethyl, or trifluoromethylsulfanyl; X1 is NCH3; R3 is methyl; R4 is ethyl or cyclopropyl; and G1 is CH or N is a group selected from

[0030] Embodiment 8c provides a compound according to embodiment 1, or an agrochemically acceptable salt, stereoisomer, enantiomer, tautomer, or N-oxide thereof, wherein: Q is Q1, Q2, Q5 and Q7 [ka] (wherein the arrow indicates the point of attachment to the ring containing group A; and R2 is trifluoromethyl, pentafluoroethyl, or trifluoromethylsulfanyl; X1 is O or NCH3; R3 is methyl; R4 is ethyl or cyclopropyl; and G1 is CH or N is a group selected from

[0031] Embodiment 8d provides a compound according to embodiment 1, or an agrochemically acceptable salt, stereoisomer, enantiomer, tautomer, or N-oxide thereof, wherein: Q is Q1, Q2, Q5 and Q7 [ka] (wherein the arrow indicates the point of attachment to the ring containing group A; and R2 is trifluoromethyl, pentafluoroethyl, or trifluoromethylsulfanyl; X1 is NCH3; R3 is methyl; R4 is ethyl or cyclopropyl; and G1 is CH or N is a group selected from

[0032] Embodiment 9 provides a compound according to embodiment 1, or an agrochemically acceptable salt, stereoisomer, enantiomer, tautomer, or N-oxide thereof, wherein: Q is the base of Q1 [ka] (wherein the arrow indicates the point of attachment to the ring containing group A; and R2 is trifluoromethyl; X1 is NCH3; and G1 is CH or N is.

[0033] Embodiment 10a provides a compound according to embodiment 1, or an agrochemically acceptable salt, stereoisomer, enantiomer, tautomer, or N-oxide thereof, wherein: Q is the base of Q2 [ka] (wherein the arrow indicates the point of attachment to the ring containing group A; and R2 is trifluoromethyl, pentafluoroethyl, trifluoromethylsulfanyl, trifluoromethylsulfinyl or trifluoromethylsulfonyl. is.

[0034] Embodiment 10b provides a compound according to embodiment 1, or an agrochemically acceptable salt, stereoisomer, enantiomer, tautomer, or N-oxide thereof, wherein: Q is the base of Q2 [ka] (wherein the arrow indicates the point of attachment to the ring containing group A; and R2 is trifluoromethyl, pentafluoroethyl or trifluoromethylsulfanyl is.

[0035] Embodiment 11 provides a compound according to embodiment 1, or an agrochemically acceptable salt, stereoisomer, enantiomer, tautomer, or N-oxide thereof, wherein: Q is the base of Q5 [ka] (wherein the arrow indicates the point of attachment to the ring containing group A; and R2 is trifluoromethyl; R3 is methyl; and R4 is ethyl or cyclopropyl. is.

[0036] Embodiment 11a provides a compound according to embodiment 1, or an agrochemically acceptable salt, stereoisomer, enantiomer, tautomer, or N-oxide thereof, wherein: Q is the base of Q7 [ka] (wherein the arrow indicates the point of attachment to the ring containing group A; and X1 is O or NCH3 is.

[0037] Embodiment 12 provides a compound according to embodiment 1, or an agrochemically acceptable salt, stereoisomer, enantiomer, tautomer, or N-oxide thereof, wherein: A is CH or N; R1 is ethyl, propyl, isopropyl, or -CH2cyclopropyl; R9 is hydrogen, methyl or ethyl; Q is Q1, Q2, Q4 and Q5 [ka] (wherein the arrow indicates the point of attachment to the ring containing group A; and R2 is C1-C2 haloalkyl, C1-C2 haloalkylsulfanyl, C1-C2 haloalkylsulfinyl or C1-C2 haloalkylsulfonyl; X1 is oxygen or NCH3; R3 is C1-C2 alkyl; R4 is C1-C2 alkyl, C1-C2 haloalkyl, C1-C2 alkoxy or cyclopropyl; and G1 and G2 are, independently of each other, N or CH. is a group selected from

[0038] Embodiment 13 provides a compound according to embodiment 1, or an agrochemically acceptable salt, stereoisomer, enantiomer, tautomer, or N-oxide thereof, wherein: A is CH or N; R1 is ethyl or -CH2cyclopropyl; preferably, R1 is ethyl; R9 is hydrogen or methyl; Q is Q1, Q2 and Q5 [ka] (wherein the arrow indicates the point of attachment to the ring containing group A; and R2 is C1-C2 fluoroalkyl, trifluoromethylsulfanyl, trifluoromethylsulfinyl, trifluoromethylsulfonyl, difluoromethylsulfanyl, difluoromethylsulfinyl, or difluoromethylsulfonyl; X1 is NCH3; R3 is methyl; R4 is methyl, ethyl, 2,2,2-trifluoroethyl, methoxy, or cyclopropyl; and G1 is N or CH is a group selected from

[0039] Embodiment 14 provides a compound according to embodiment 1, or an agrochemically acceptable salt, stereoisomer, enantiomer, tautomer, or N-oxide thereof, wherein: A is CH or N; R1 is or -CH2cyclopropyl; preferably, R1 is ethyl; R9 is hydrogen or methyl; Q is Q1, Q2 and Q5 [ka] (wherein the arrow indicates the point of attachment to the ring containing group A; and R2 is C1-C2 fluoroalkyl, trifluoromethylsulfanyl, trifluoromethylsulfinyl, trifluoromethylsulfonyl, difluoromethylsulfanyl, difluoromethylsulfinyl, or difluoromethylsulfonyl; X1 is NCH3; R3 is methyl; R4 is methyl, ethyl, 2,2,2-trifluoroethyl, methoxy, or cyclopropyl; and G1 is N or CH is a group selected from

[0040] Embodiment 15 provides a compound according to embodiment 1, or an agrochemically acceptable salt, stereoisomer, enantiomer, tautomer, or N-oxide thereof, wherein: A is N; R1 is ethyl or -CH2cyclopropyl; preferably, R1 is ethyl; R9 is hydrogen or methyl; Q is Q1, Q2 and Q5 [ka] (wherein the arrow indicates the point of attachment to the ring containing group A; and R2 is trifluoromethyl, pentafluoroethyl, trifluoromethylsulfanyl, trifluoromethylsulfinyl, or trifluoromethylsulfonyl; X1 is NCH3; R3 is methyl; R4 is ethyl, methoxy or cyclopropyl; and G1 is CH or N is a group selected from

[0041] Embodiment 16 provides a compound according to embodiment 1, or an agrochemically acceptable salt, stereoisomer, enantiomer, tautomer, or N-oxide thereof, wherein: A is N; R1 is ethyl or -CH2cyclopropyl; preferably, R1 is ethyl; R9 is hydrogen or methyl; Q is Q1, Q2 and Q5 [ka] (wherein the arrow indicates the point of attachment to the ring containing group A; and R2 is trifluoromethyl, pentafluoroethyl, or trifluoromethylsulfanyl; X1 is NCH3; R3 is methyl; R4 is ethyl or cyclopropyl; and G1 is CH or N is a group selected from

[0042] Embodiment 16a provides a compound according to embodiment 1, or an agrochemically acceptable salt, stereoisomer, enantiomer, tautomer, or N-oxide thereof, wherein: A is N; R1 is ethyl or -CH2cyclopropyl; preferably, R1 is ethyl; R9 is hydrogen or methyl; Q is Q1, Q2, Q5 and Q7 [ka] (wherein the arrow indicates the point of attachment to the ring containing group A; and R2 is trifluoromethyl, pentafluoroethyl, or trifluoromethylsulfanyl; X1 is O or NCH3; R3 is methyl; R4 is ethyl or cyclopropyl; and G1 is CH or N is a group selected from

[0043] Embodiment 17 provides a compound according to embodiment 1, or an agrochemically acceptable salt, stereoisomer, enantiomer, tautomer, or N-oxide thereof, wherein: A is N; R1 is ethyl or -CH2cyclopropyl; preferably, R1 is ethyl; R9 is hydrogen or methyl; Q is the base of Q1 [ka] (wherein the arrow indicates the point of attachment to the ring containing group A; and R2 is trifluoromethyl; X1 is NCH3; and G1 is N or CH is.

[0044] Embodiment 18 provides a compound according to embodiment 1, or an agrochemically acceptable salt, stereoisomer, enantiomer, tautomer, or N-oxide thereof, wherein: A is N; R1 is ethyl or -CH2cyclopropyl; preferably, R1 is ethyl; R9 is hydrogen; Q is the base of Q1 [ka] (wherein the arrow indicates the point of attachment to the ring containing group A; and R2 is trifluoromethyl; X1 is NCH3; and G1 is N or CH is.

[0045] Embodiment 19 provides a compound according to embodiment 1, or an agrochemically acceptable salt, stereoisomer, enantiomer, tautomer, or N-oxide thereof, wherein: A is N; R1 is ethyl or -CH2cyclopropyl; preferably, R1 is ethyl; R9 is methyl; Q is the base of Q1 [ka] (wherein the arrow indicates the point of attachment to the ring containing group A; and R2 is trifluoromethyl; X1 is NCH3; and G1 is N or CH is.

[0046] Embodiment 20 provides a compound according to embodiment 1, or an agrochemically acceptable salt, stereoisomer, enantiomer, tautomer, or N-oxide thereof, wherein: A is N; R1 is ethyl or -CH2cyclopropyl; preferably, R1 is ethyl; R9 is hydrogen; Q is the base of Q2 [ka] (wherein the arrow indicates the point of attachment to the ring containing group A; and R2 is trifluoromethyl, pentafluoroethyl, trifluoromethylsulfanyl, trifluoromethylsulfinyl or trifluoromethylsulfonyl. is.

[0047] Embodiment 21 provides a compound according to embodiment 1, or an agrochemically acceptable salt, stereoisomer, enantiomer, tautomer, or N-oxide thereof, wherein: A is N; R1 is ethyl or -CH2cyclopropyl; preferably, R1 is ethyl; R9 is hydrogen; Q is the base of Q2 [ka] (wherein the arrow indicates the point of attachment to the ring containing group A; and R2 is trifluoromethyl, pentafluoroethyl or trifluoromethylsulfanyl is.

[0048] Embodiment 22 provides a compound according to embodiment 1, or an agrochemically acceptable salt, stereoisomer, enantiomer, tautomer, or N-oxide thereof, wherein: A is CH; R1 is ethyl or -CH2cyclopropyl; preferably, R1 is ethyl; R9 is hydrogen; Q is the base of Q2 [ka] (wherein the arrow indicates the point of attachment to the ring containing group A; and R2 is trifluoromethyl, pentafluoroethyl, trifluoromethylsulfanyl, trifluoromethylsulfinyl or trifluoromethylsulfonyl. is.

[0049] Embodiment 23 provides a compound according to embodiment 1, or an agrochemically acceptable salt, stereoisomer, enantiomer, tautomer, or N-oxide thereof, wherein: A is CH; R1 is ethyl or -CH2cyclopropyl; preferably, R1 is ethyl; R9 is hydrogen; Q is the base of Q2 [ka] (wherein the arrow indicates the point of attachment to the ring containing group A; and R2 is trifluoromethyl, pentafluoroethyl or trifluoromethylsulfanyl is.

[0050] Embodiment 24 provides a compound according to embodiment 1, or an agrochemically acceptable salt, stereoisomer, enantiomer, tautomer, or N-oxide thereof, wherein: A is N; R1 is ethyl; R9 is hydrogen; Q is the base of Q5 [ka] (wherein the arrow indicates the point of attachment to the ring containing group A; and R2 is trifluoromethyl; R3 is methyl; and R4 is ethyl or cyclopropyl. is.

[0051] Embodiment 25 provides a compound according to embodiment 1, or an agrochemically acceptable salt, stereoisomer, enantiomer, tautomer, or N-oxide thereof, wherein: A is N; R1 is ethyl; R9 is hydrogen; Q is the base of Q7 [ka] (wherein the arrow indicates the point of attachment to the ring containing group A; and X1 is O or NCH3 is.

[0052] A preferred group of compounds of formula I is the compound of formula I-1 [ka] wherein R1, R2, R3, R9 and A are as defined in Formula I above, or It is represented by an agrochemically acceptable salt, stereoisomer, enantiomer, tautomer or N-oxide of formula I-1.

[0053] In one preferred group of compounds of formula I-1, A is CH or N; R is ethyl, propyl or isopropyl or CHcyclopropyl; R is C-C haloalkyl, C-C haloalkylsulfanyl, C-C haloalkylsulfinyl or C-C haloalkylsulfonyl; R is C-C alkyl; and R is hydrogen, methyl or ethyl.

[0054] In another preferred group of compounds of formula I-1, A is CH or N; R1 is ethyl; R2 is C1-C2 fluoroalkyl, trifluoromethylsulfanyl, trifluoromethylsulfinyl, trifluoromethylsulfonyl, difluoromethylsulfanyl, difluoromethylsulfinyl or difluoromethylsulfonyl; R3 is methyl; R9 is hydrogen or methyl, preferably R9 is hydrogen.

[0055] In the compounds of formula I-1 and all preferred embodiments of the compounds of formula I-1 above, unless otherwise specified, R1, R2, R3, R9 and A are as defined in formula I above; A is CH or N, preferably A is N; R2 is trifluoromethyl, pentafluoroethyl or trifluoromethylsulfanyl or trifluoromethylsulfonyl; preferably R2 is trifluoromethyl; R3 is methyl; and R9 is hydrogen.

[0056] Another preferred group of compounds of formula I is the compounds of formula I-2 [ka] wherein R1, R2, R3, R9 and A are as defined in Formula I above, or It is represented by an agrochemically acceptable salt, stereoisomer, enantiomer, tautomer or N-oxide of formula I-2.

[0057] In one preferred group of compounds of formula I-2, A is CH or N; R is ethyl, propyl, or isopropyl or CHcyclopropyl; R is C-C haloalkyl, C-C haloalkylsulfanyl, C-C haloalkylsulfinyl, or C-C haloalkylsulfonyl; R is C-C alkyl; and R is hydrogen, methyl, or ethyl.

[0058] In another preferred group of compounds of formula I-2, A is CH or N; R1 is ethyl; R2 is C1-C2 fluoroalkyl, trifluoromethylsulfanyl, trifluoromethylsulfinyl, trifluoromethylsulfonyl, difluoromethylsulfanyl, difluoromethylsulfinyl or difluoromethylsulfonyl; R3 is methyl; R9 is hydrogen or methyl, preferably R9 is hydrogen.

[0059] In the compounds of formula I-2 and all preferred embodiments of the compounds of formula I-2 above, unless otherwise specified, R1, R2, R3, R9 and A are as defined in formula I above; preferably, A is CH or N, more preferably, A is N; R2 is trifluoromethyl, pentafluoroethyl or trifluoromethylsulfanyl or trifluoromethylsulfonyl; preferably, R2 is trifluoromethyl; R3 is methyl; and R9 is hydrogen.

[0060] Another preferred group of compounds of formula I is the compounds of formula I-3 [ka] wherein R1, R2, R3, R9 and A are as defined in Formula I above, or It is represented by an agrochemically acceptable salt, stereoisomer, enantiomer, tautomer or N-oxide of formula I-3.

[0061] In one preferred group of compounds of formula I-3, A is CH or N; R is ethyl, propyl, or isopropyl or CHcyclopropyl; R is C-C haloalkyl, C-C haloalkylsulfanyl, C-C haloalkylsulfinyl, or C-C haloalkylsulfonyl; R is C-C alkyl; and R is hydrogen, methyl, or ethyl.

[0062] In another preferred group of compounds of formula I-3, A is CH or N; R1 is ethyl; R2 is C1-C2 fluoroalkyl, trifluoromethylsulfanyl, trifluoromethylsulfinyl, trifluoromethylsulfonyl, difluoromethylsulfanyl, difluoromethylsulfinyl or difluoromethylsulfonyl; R3 is methyl; R9 is hydrogen or methyl, preferably R9 is hydrogen.

[0063] In the compounds of formula I-3 and all preferred embodiments of the compounds of formula I-3 above, unless otherwise specified, R1, R2, R3, R9, and A are as defined in formula I above; preferably, A is CH or N, more preferably, A is N; R2 is trifluoromethyl, pentafluoroethyl, or trifluoromethylsulfanyl or trifluoromethylsulfonyl; preferably, R2 is trifluoromethyl; R3 is methyl; and R9 is hydrogen.

[0064] Another preferred group of compounds of formula I is the compounds of formula I-4 [ka] wherein R1, R2, R3, R4, R9 and A are as defined in Formula I above, or It is represented by an agrochemically acceptable salt, stereoisomer, enantiomer, tautomer or N-oxide of formula I-4.

[0065] In one preferred group of compounds of formula I-4, A is CH or N; R1 is ethyl, propyl, or isopropyl or CH2cyclopropyl; R2 is C1-C2 haloalkyl, C1-C2 haloalkylsulfanyl, C1-C2 haloalkylsulfinyl, or C1-C2 haloalkylsulfonyl; R3 is C1-C2 alkyl; R4 is C1-C2 alkyl, C1-C2 haloalkyl, C1-C2 alkoxy, or cyclopropyl; and R9 is hydrogen, methyl, or ethyl.

[0066] In another preferred group of compounds of formula I-4, A is CH or N; R1 is ethyl; R2 is C1-C2 fluoroalkyl, trifluoromethylsulfanyl, trifluoromethylsulfinyl, trifluoromethylsulfonyl, difluoromethylsulfanyl, difluoromethylsulfinyl or difluoromethylsulfonyl; R3 is methyl; R4 is methyl, ethyl, methoxy or cyclopropyl; R9 is hydrogen or methyl, preferably R9 is hydrogen.

[0067] In another preferred group of compounds of formula I-4, R4 is ethyl or cyclopropyl.

[0068] In compounds of formula I-4 and all preferred embodiments of compounds of formula I-4 above, unless otherwise specified, R1, R2, R3, R4, R9, and A are as defined in formula I above; preferably, A is CH or N, more preferably, A is N; R2 is trifluoromethyl, pentafluoroethyl, or trifluoromethylsulfanyl or trifluoromethylsulfonyl; preferably, R2 is trifluoromethyl; R3 is methyl; R4 is ethyl, methoxy, or cyclopropyl; and R9 is hydrogen.

[0069] Another preferred group of compounds of formula I is the compounds of formula I-5 [ka] wherein R1, R2, R9 and A are as defined in Formula I above, or It is represented by an agrochemically acceptable salt, stereoisomer, enantiomer, tautomer or N-oxide of formula I-5.

[0070] In one preferred group of compounds of formula I-5, A is CH or N; R is ethyl, propyl, or isopropyl or CHcyclopropyl; R is C-C haloalkyl, C-C haloalkylsulfanyl, C-C haloalkylsulfinyl, or C-C haloalkylsulfonyl; and R is hydrogen, methyl, or ethyl.

[0071] In another preferred group of compounds of formula I-5, A is CH or N; R1 is ethyl; R2 is C1-C2 fluoroalkyl, trifluoromethylsulfanyl, trifluoromethylsulfinyl, trifluoromethylsulfonyl, difluoromethylsulfanyl, difluoromethylsulfinyl or difluoromethylsulfonyl; R9 is hydrogen or methyl, preferably R9 is hydrogen.

[0072] In compounds of formula I-5 and all preferred embodiments of compounds of formula I-5 above, unless otherwise specified, R1, R2, R9, and A are as defined in formula I above; preferably, A is CH or N, more preferably, A is N; R2 is trifluoromethyl, pentafluoroethyl, or trifluoromethylsulfanyl or trifluoromethylsulfonyl; preferably, R2 is trifluoromethyl; and R9 is hydrogen.

[0073] Another preferred group of compounds of formula I is the compounds of formula I-6 [ka] wherein R1, R2, R9 and A are as defined in Formula I above, or It is represented by an agrochemically acceptable salt, stereoisomer, enantiomer, tautomer or N-oxide of formula I-6.

[0074] In one preferred group of compounds of formula I-6, A is CH or N; R is ethyl, propyl or isopropyl or CHcyclopropyl; R is C-C haloalkyl, C-C haloalkylsulfanyl, C-C haloalkylsulfinyl or C-C haloalkylsulfonyl; and R is hydrogen, methyl or ethyl.

[0075] In another preferred group of compounds of formula I-6, A is CH or N; R1 is ethyl; R2 is C1-C2 fluoroalkyl, trifluoromethylsulfanyl, trifluoromethylsulfinyl, trifluoromethylsulfonyl, difluoromethylsulfanyl, difluoromethylsulfinyl or difluoromethylsulfonyl; R9 is hydrogen or methyl, preferably R9 is hydrogen.

[0076] In the compounds of formula I-6 and all preferred embodiments of the compounds of formula I-6 above, unless otherwise specified, R1, R2, R9, and A are as defined in formula I above; preferably, A is CH or N, more preferably, A is N; R2 is trifluoromethyl, pentafluoroethyl, or trifluoromethylsulfanyl or trifluoromethylsulfonyl; preferably, R2 is trifluoromethyl; and R9 is hydrogen.

[0077] Another preferred group of compounds of formula I is the compounds of formula I-7 [ka] wherein R1, R2, R9 and A are as defined in Formula I above, or It is represented by an agrochemically acceptable salt, stereoisomer, enantiomer, tautomer or N-oxide of formula I-7.

[0078] In one preferred group of compounds of formula I-7, A is CH or N; R is ethyl, propyl, or isopropyl or CHcyclopropyl; R is C-C haloalkyl, C-C haloalkylsulfanyl, C-C haloalkylsulfinyl, or C-C haloalkylsulfonyl; and R is hydrogen, methyl, or ethyl.

[0079] In another preferred group of compounds of formula I-7, A is CH or N; R1 is ethyl; R2 is C1-C2 fluoroalkyl, trifluoromethylsulfanyl, trifluoromethylsulfinyl, trifluoromethylsulfonyl, difluoromethylsulfanyl, difluoromethylsulfinyl or difluoromethylsulfonyl; R9 is hydrogen or methyl, preferably R9 is hydrogen.

[0080] In compounds of formula I-7 and all preferred embodiments of compounds of formula I-7 above, unless otherwise specified, R1, R2, R9, and A are as defined in formula I above; preferably, A is CH or N, more preferably, A is N; R2 is trifluoromethyl, pentafluoroethyl, or trifluoromethylsulfanyl or trifluoromethylsulfonyl; preferably, R2 is trifluoromethyl; and R9 is hydrogen.

[0081] Another preferred group of compounds of formula I is the compounds of formula I-8 [ka] wherein R1, R2, R9 and A are as defined in Formula I above, or It is represented by an agrochemically acceptable salt, stereoisomer, enantiomer, tautomer or N-oxide of formula I-8.

[0082] In one preferred group of compounds of formula I-8, A is CH or N; R is ethyl, propyl, or isopropyl or CHcyclopropyl; R is C-C haloalkyl, C-C haloalkylsulfanyl, C-C haloalkylsulfinyl, or C-C haloalkylsulfonyl; and R is hydrogen, methyl, or ethyl.

[0083] In another preferred group of compounds of formula I-8, A is CH or N; R1 is ethyl; R2 is C1-C2 fluoroalkyl, trifluoromethylsulfanyl, trifluoromethylsulfinyl, trifluoromethylsulfonyl, difluoromethylsulfanyl, difluoromethylsulfinyl or difluoromethylsulfonyl; R9 is hydrogen or methyl, preferably R9 is hydrogen.

[0084] In compounds of formula I-8 and all preferred embodiments of compounds of formula I-8 above, unless otherwise specified, R1, R2, R9, and A are as defined in formula I above; preferably, A is CH or N, more preferably, A is N; R2 is trifluoromethyl, pentafluoroethyl, or trifluoromethylsulfanyl or trifluoromethylsulfonyl; preferably, R2 is trifluoromethyl; and R9 is hydrogen.

[0085] Another preferred group of compounds of formula I is the compounds of formula I-9 [ka] wherein R1, R2, R9 and A are as defined in Formula I above, or It is represented by an agrochemically acceptable salt, stereoisomer, enantiomer, tautomer or N-oxide of formula I-9.

[0086] In one preferred group of compounds of formula I-9, A is CH or N; R is ethyl, propyl, or isopropyl or CHcyclopropyl; R is C-C haloalkyl, C-C haloalkylsulfanyl, C-C haloalkylsulfinyl, or C-C haloalkylsulfonyl; and R is hydrogen, methyl, or ethyl.

[0087] In another preferred group of compounds of formula I-9, A is CH or N; R1 is ethyl; R2 is C1-C2 fluoroalkyl, trifluoromethylsulfanyl, trifluoromethylsulfinyl, trifluoromethylsulfonyl, difluoromethylsulfanyl, difluoromethylsulfinyl or difluoromethylsulfonyl; R9 is hydrogen or methyl, preferably R9 is hydrogen.

[0088] In compounds of formula I-9 and all preferred embodiments of compounds of formula I-9 above, unless otherwise specified, R1, R2, R9, and A are as defined in formula I above; preferably, A is CH or N, more preferably, A is N; R2 is trifluoromethyl, pentafluoroethyl, or trifluoromethylsulfanyl or trifluoromethylsulfonyl; preferably, R2 is trifluoromethyl; and R9 is hydrogen.

[0089] Another preferred group of compounds of formula I is the compounds of formula I-10 [ka] wherein R1, R3, R9 and A are as defined in formula I above, or It is represented by an agrochemically acceptable salt, stereoisomer, enantiomer, tautomer or N-oxide of formula I-10.

[0090] In one preferred group of compounds of formula I-10, A is CH or N; R1 is ethyl, propyl or isopropyl or CH2cyclopropyl; R3 is C1-C2 alkyl; and R9 is hydrogen, methyl or ethyl.

[0091] In another preferred group of compounds of formula I-10, A is CH or N; R1 is ethyl; R3 is methyl; R9 is hydrogen or methyl, preferably R9 is hydrogen.

[0092] In compounds of formula I-10 and all preferred embodiments of compounds of formula I-10 above, unless otherwise specified, R1, R3, R9, and A are as defined in formula I above; preferably, A is CH or N, more preferably, A is N; R3 is methyl; and R9 is hydrogen.

[0093] Another preferred group of compounds of formula I is the compounds of formula I-11 [ka] wherein R1, R9 and A are as defined in formula I above, or It is represented by an agrochemically acceptable salt, stereoisomer, enantiomer, tautomer or N-oxide of formula I-11.

[0094] In one preferred group of compounds of formula I-11, A is CH or N; R1 is ethyl, propyl or isopropyl or CH2cyclopropyl; and R9 is hydrogen, methyl or ethyl.

[0095] In another preferred group of compounds of formula I-11, A is CH or N; R1 is ethyl; and R9 is hydrogen or methyl, preferably R9 is hydrogen.

[0096] In the compounds of formula I-11 and all preferred embodiments of the compounds of formula I-11 above, unless otherwise specified, R1, R9, and A are as defined in formula I above; preferably, A is CH or N, more preferably, A is N; and R9 is hydrogen.

[0097] Another particularly preferred group of compounds of formula I are those represented by compounds of formula I-1, I-2, I-3, I-4, I-5, I-6, I-7, I-8, I-9, I-10 or I-11, wherein A is CH or N, preferably A is N; R1 is ethyl, propyl, isopropyl or CH2cyclopropyl; preferably, R1 is ethyl; R9 is hydrogen; and In the case of compounds of formula I-1, I-2, I-3, I-4, I-5, I-6, I-7, I-8 and I-9 R2 is trifluoromethyl, pentafluoroethyl, trifluoromethylsulfanyl, or trifluoromethylsulfonyl; preferably, R2 is trifluoromethyl; and In the case of compounds of formula I-1, I-2, I-3, I-4 and I-10, R3 is methyl; and in the case of compounds of formula I-4, R4 is ethyl, methoxy or cyclopropyl.

[0098] The compounds of the present invention may have any number of benefits, including, inter alia, advantageous levels of biological activity for protecting plants against insects, or excellent properties for use as agrochemical active ingredients (e.g., high biological activity, advantageous activity spectrum, high safety profile, improved physicochemical properties, or high biodegradability or environmental profile). In particular, it has been unexpectedly found that certain compounds of formula (I) may exhibit advantageous safety profiles against non-target arthropods, particularly pollinators such as honeybees, solitary bees, and bumblebees. Most particularly, the European honeybee (Apis mellifera).

[0099] In another aspect, the present invention provides a composition comprising an insecticidally, acaricidally, nematicidally or molluscicidally effective amount of a compound of formula (I), or an agrochemically acceptable salt, stereoisomer, enantiomer, tautomer or N-oxide thereof, as defined in any of embodiments 1 to 25 (above), or any of the embodiments relating to a compound of formula I-1, I-2, I-3, I-4, I-5, I-6, I-7, I-8, I-9, I-10 or I-11, and optionally an adjuvant or diluent.

[0100] In a further aspect, the present invention provides a method for the control and combating of insects, acaridae, nematodes or molluscs, comprising the step of applying to the pest, the habitat of the pest or plants susceptible to attack by the pest an insecticidally, acaricidally, nematicidally or molluscicidally effective amount of a compound of formula (I) or an agrochemically acceptable salt, stereoisomer, enantiomer, tautomer or N-oxide thereof as defined in any of embodiments 1 to 25 (above), or in any of the embodiments relating to a compound of formula I-1, I-2, I-3, I-4, I-5, I-6, I-7, I-8, I-9, I-10 or I-11 (above), or a composition as defined above.

[0101] In a further aspect, the present invention provides a method for protecting plant propagation material from attack by insects, mites, nematodes or mollusks, comprising the step of treating the propagation material or the site where the propagation material is to be planted with a composition as defined above.

[0102] The preparation process of the compound of formula I according to the present invention is carried out by methods known to those skilled in the art. The compound of formula I (wherein A, R1, R9, and Q are as defined in formula I above) can be prepared by oxidation of the compound of formula II-a (wherein A, R1, R9, and Q are as defined in formula I above) (Scheme 1). This reaction can be carried out with a reagent such as a peracid, for example, peroxyacetic acid or m-chloroperbenzoic acid (mCPBA), or a hydroperoxide, for example, hydrogen peroxide or t-butyl hydroperoxide, or an inorganic oxidizing agent, for example, monoperoxo-disulfate salt (oxone), sodium periodate, sodium hypochlorite, or potassium permanganate. Similarly, compounds of formula II-a (wherein A, R1, R9 and Q are as defined in formula I above) can be prepared by oxidation of compounds of formula II (wherein A, R1, R9 and Q are as defined in formula I above) under conditions similar to those described above.

[0103] Scheme 1: [ka] Similarly, compounds of formula II can be directly oxidized to compounds of formula I under the above conditions. The amount of oxidizing agent to be used in this reaction is generally 1 to 3 moles, preferably 1 to 1.2 moles, per mole of sulfoxide compound II-a to produce sulfone compound I. Preferably, the amount of oxidizing agent to be used in this reaction is 2 to 2.2 moles per mole of sulfide compound II to produce sulfone compound I. These reactions can be carried out in various organic or aqueous solvents that meet these conditions at temperatures below 0°C to the boiling point of the solvent system. Examples of solvents that can be used in this reaction include aliphatic halogenated hydrocarbons such as dichloromethane and chloroform; alcohols such as methanol and ethanol; acetic acid; water; and mixtures thereof.

[0104] Scheme 5: [ka] Compounds of formula II (wherein R9, R1, A and Q are as defined in formula I) are commercially available from, for example, Bioorganic & Medicinal As described in Chemistry, 20(18), 5600-5615;2012, a compound of formula III (wherein R, R, A, and Q are as defined in formula I) can be prepared by reacting, preferably at least two equivalents, a compound of formula IV (wherein Xb is a leaving group such as chlorine, bromine, or iodine (preferably iodine or bromine), or an aryl-, alkyl-, or haloalkylsulfonate such as trifluoromethanesulfonic acid) in the presence of, preferably at least two equivalents, a base such as potassium carbonate, cesium carbonate, lithium hexamethyldisilazide, or lithium diisopropylamide in a suitable solvent such as acetonitrile, tetrahydrofuran, or N,N-dimethylformamide at a temperature of −78° C. to 100° C., preferably −10° C. to 80° C. (Scheme 5). Methyl iodide, methyl bromide, or dimethyl sulfate are typical representatives of the methylating reagent CH3-Xb IV. Optionally, the compound of formula III is treated twice sequentially with about 1 equivalent (or more) each of the methylating reagent CH3-Xb IV and a base.

[0105] Compound of Formula II [ka] (wherein A, R1, R9 and Q are as defined in formula I above) are novel and have been developed specifically for the preparation of compounds of formula I according to the invention and therefore represent a further object of the present invention. The substituent preferences and preferred embodiments of compounds of formula I are also valid for compounds of formula II.

[0106] Scheme 6: [ka] A compound of formula III (wherein R9, R1, A, and Q are as defined in formula I) can be prepared, for example, as described in Tetrahedron Letters, 34(47), 7567-8; 1993, by reacting a compound of formula V (wherein R9, R1, A, and Q are as defined in formula I) with a compound of formula VI (wherein Xa is a leaving group such as, for example, chlorine, bromine, or iodine (preferably chlorine or bromine), or an aryl-, alkyl-, or haloalkylsulfonate such as trifluoromethanesulfonic acid) in the presence of a base such as potassium carbonate, cesium carbonate, or sodium hydride, optionally in the presence of a catalytic amount of an additive such as sodium or potassium iodide, in a suitable solvent such as acetone, tetrahydrofuran, acetonitrile, dimethyl sulfoxide, or N,N-dimethylformamide at a temperature of −10° C. to 100° C., preferably 0° C. to 80° C. (Scheme 6).

[0107] Scheme 7: [ka] Alternatively, compounds of formula II (wherein R9, R1, A, and Q are as defined in formula I) can be prepared by reacting compounds of formula VII (wherein R9, R1, A, and Q are as defined in formula I) with a dehydrating agent such as trifluoroacetic acid, trifluoroacetic anhydride, diphosphorus pentoxide, thionyl chloride, or phosphorus oxychloride, optionally in the presence of a base such as triethylamine or pyridine, in a suitable solvent such as dichloromethane, dioxane, or N,N-dimethylformamide, at a temperature between 0°C and 180°C, preferably between 5°C and 80°C, under dehydrating conditions, as described, for example, in U.S. Patent Application Publication No. 20100267738 (Scheme 7).

[0108] Scheme 8: [ka] A compound of formula VII (wherein R9, R1, A, and Q are as defined in formula I) can be prepared, for example, as described in WO 2014071044, by reacting a compound of formula V (wherein R9, R1, A, and Q are as defined in formula I) with a compound of formula VIII (wherein Xa is a leaving group such as, for example, chlorine, bromine, or iodine (preferably bromine), or an aryl-, alkyl-, or haloalkylsulfonate such as trifluoromethanesulfonic acid) in the presence of a base such as, for example, lithium hydroxide, sodium hydroxide, or potassium hydroxide, sodium hydride, potassium carbonate, or cesium carbonate, in a suitable solvent such as acetone, dioxane, acetonitrile, N,N-dimethylformamide, or N,N-dimethylacetamide at a temperature of −10° C. to 100° C., preferably 0° C. to 80° C. (Scheme 8).

[0109] Scheme 9: [ka] A compound of formula V, wherein R, R, A and Q are as defined in formula I, can be reacted with a compound of formula IX, wherein R, R, A and Q are as defined in formula I and X is a leaving group such as, for example, chlorine, bromine or iodine (preferably bromine), or an aryl-, alkyl- or haloalkylsulfonate such as trifluoromethanesulfonic acid, with, for example, benzaldoxime PhC=NOH, preferably ( and E)-benzaldehyde oxime in the presence of a base such as potassium carbonate or cesium carbonate, optionally in the presence of a palladium catalyst such as RockPhos-G3-palladacycle ([(2-di-t-butylphosphino-3-methoxy-6-methyl-2',4',6'-triisopropyl-1,1'-biphenyl)-2-(2-aminobiphenyl)]palladium(II) methanesulfonate), in an aprotic solvent such as acetonitrile or N,N-dimethylformamide (DMF) at a temperature of 0 to 100°C, preferably room temperature to 80°C (Scheme 9).

[0110] Alternatively, a compound of formula V (wherein R9, R1, A and Q are as defined in formula I) can be prepared from a compound of formula IX (wherein R9, R1, A and Q are as defined in formula I and X is a leaving group such as, for example, chlorine, bromine or iodine (preferably bromine), or an aryl-, alkyl- or haloalkylsulfonate such as trifluoromethanesulfonic acid) by sequentially: 1) Borylation Reaction: Typically, a compound of Formula IX is reacted with bispinacoldiborane (Bpin)2 under palladium catalysis. The introduction of such a pinacolborate functional group can be carried out in an aprotic solvent such as dioxane, preferably in the presence of a weak base such as potassium acetate (KOAc). [1,1'-bis(diphenylphosphino)ferrocene]dichloropalladium(II), also known as palladium dichloride dppf or Pd(dppf)Cl2, is a common catalyst for this type of reaction. Other palladium source / ligand combinations include, for example, tris(dibenzylideneacetone)dipalladium and tricyclohexylphosphine. The reaction temperature is preferably between 0°C and the boiling point of the reaction mixture, or the reaction may be carried out under microwave irradiation. The intermediate product of this borylation reaction is then further described below. 2) Oxidation Step: Typically, the intermediate product is treated with hydrogen peroxide HO, for example, 30% HO in water, in an inert solvent such as tetrahydrofuran or dioxane, at a temperature between 0 and 100° C., preferably at about room temperature. The above process for preparing a compound of formula V from a compound of formula IX may include isolation and purification of the boronated intermediate; however, this process is also advantageously carried out by combining the crude intermediate with oxidation step 2.

[0111] Compounds of formula IX, where R, R, A and Q are as defined in formula I and X is a leaving group, particularly where X is a halogen, are known compounds or can be prepared by known methods or can be synthesized by methods similar to those already described and found in the literature. In particular WO 2016 / 071214 (Q is Q2 and G2 is N) and WO 2015 / 000715 (Q is Q2 and G2 is CH), WO 2016 / 026848 and WO 2016 / 005263 (Q is Q1, G1 is CH and G2 is N), WO 2016 / 059145 (Q is Q1, G1 is N and G2 is N), WO 2016 / 020286 and WO 2017 / 134066 (Q is Q 4である ), WO 2017 / 089190, WO 2017 / 084879 and WO 2016 / 023954 (Q is Q5), WO 2015 / 000715 (Q is Q3), and WO 2012 / 086848, WO 2013 / 018928 (Q is Q1, G1 is N or CH, and G2 is CH).

[0112] A compound of formula IV, wherein Xb is a leaving group such as chlorine, bromine or iodine (preferably iodine or bromine), or an aryl-, alkyl- or haloalkylsulfonate such as trifluoromethanesulfonic acid; and A compound of formula VI, wherein Xa is a leaving group such as, for example, chlorine, bromine, or iodine (preferably bromine), or an aryl-, alkyl-, or haloalkylsulfonate such as trifluoromethanesulfonic acid; and Compounds of formula VIII, wherein Xa is a leaving group such as, for example, chlorine, bromine or iodine (preferably bromine), or an aryl-, alkyl- or haloalkylsulfonate such as trifluoromethanesulfonic acid. are all known compounds, commercially available, or can be prepared by known methods described in the literature.

[0113] Scheme 10: [ka] A subgroup of compounds of formula V where R is C-C alkyl, defining compounds of formula Vc (where R, A, and Q are as defined in formula I), can be prepared from compounds of formula Vb (where R, A, and Q are as defined in formula I, and X is a halogen, preferably chlorine, bromine, or iodine), typically by a C-C bond-forming reaction under palladium-catalyzed (alternatively, nickel-catalyzed) cross-coupling conditions (Scheme 10). Such Suzuki-Miyaura cross-coupling reactions of compounds of formula Vb with C-C alkylboronic acids of formula R9B(OH)2 (where R is as defined in formula I), or the corresponding C-C alkylboronate ester derivatives, or the corresponding 6-membered tri(C-C alkyl)boroxine derivatives of formula (R9BO)3 (where R is as defined in formula I), are well known to those skilled in the art. In the specific situation where R9 is methyl, the compound of formula Vb can be reacted with, for example, trimethylboroxine (also known as 2,4,6-trimethyl-1,3,5,2,4,6-trioxatriborinane) in the presence of a palladium catalyst such as tetrakis(triphenylphosphine)-palladium(0) or [1,1'-bis(diphenylphosphino)ferrocene]palladium(II) dichloride dichloromethane complex and a base such as sodium carbonate or potassium carbonate in a solvent such as N,N-dimethylformamide, dioxane, or a dioxane-water mixture at a temperature between room temperature and 160°C, optionally under microwave heating conditions, and preferably under an inert atmosphere. Such conditions are described, for example, in Tetrahedron Letters (2000), 41(32), 6237-6240.

[0114] Compounds of formula Vb (wherein R, A, and Q are as defined in formula I, and Xb is a halogen, preferably chlorine, bromine, or iodine) can be prepared, for example, by a halogenation reaction comprising reacting a subgroup of compounds of formula V (wherein R is hydrogen) that defines compounds of formula Va (wherein R, A, and Q are as defined in formula I) with a halogenating agent such as N-chlorosuccinimide (NCS), N-bromosuccinimide (NBS), or N-iodosuccinimide (NIS), or alternatively chlorine, bromine, or iodine, optionally in the presence of a base such as sodium carbonate, potassium carbonate, or cesium carbonate. Such halogenation reactions are carried out in inert solvents such as chloroform, carbon tetrachloride, 1,2-dichloroethane, acetic acid, ether, N,N-dimethylformamide, acetonitrile, or acetonitrile-water mixtures, at temperatures between 20 and 200°C, preferably between room temperature and 100°C.

[0115] Scheme 11: [ka] Alternatively, compounds of formula II (wherein Q is Q1) defining compounds of formula II-Q1 (wherein R1, R9, A, X1, G1, and R2 are as defined in formula I) can be prepared by cyclization of compounds of formula (XX) (wherein R1, R9, A, X1, G1, and R2 are as defined in formula I) via heating in, for example, acetic acid or trifluoroacetic acid (preferably when X1 is NR3 and R3 is C1-C4 alkyl) at temperatures between 0 and 180°C, preferably between 20 and 150°C, optionally under microwave irradiation (Scheme 11). Cyclization of compounds of formula (XX) can also be achieved in the presence of an acid catalyst, such as methanesulfonic acid or p-toluenesulfonic acid p-TsOH, in an inert solvent such as N-methylpyrrolidone, toluene, or xylene, at temperatures between 25 and 180°C, preferably between 100 and 170°C. Such a process has been previously described, for example, in WO 2010 / 125985. Alternatively, compounds of formula (XX) 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 of 20-50° C. Such Mitsunobu conditions have been previously described for these conversions (see WO 2009 / 131237).

[0116] Compounds of formula (XX) (wherein R1, R9, A, X1, G1 and R2 are as defined in formula I) may be prepared via acylation by: i) by methods known to those skilled in the art and described, for example, in Tetrahedron, 2005, 61(46), 10827-10852, the activation species (XXII) (wherein R, R and A are as defined in formula I, and X 00 is a halogen, preferably chlorine), to form a compound of formula (XXIII) (wherein R, R and A are as defined in formula I). ​​For example, by activating a compound of formula (XXII) (wherein X is a halogen, preferably chlorine), 00is a halogen, preferably chlorine, is formed by treatment of (XXIII) with, for example, oxalyl chloride (COCl) or thionyl chloride SOCl in the presence of a catalytic amount of N,N-dimethylformamide (DMF) in an inert solvent such as methylene chloride CHCl or tetrahydrofuran (THF) at a temperature of 20-100° C., preferably 25° C. Alternatively, treatment of compounds of formula (XXIII) with, for example, 1-ethyl-3-(3-dimethylaminopropyl)carbodiimide (EDC) or dicyclohexylcarbodiimide (DCC) in an inert solvent such as pyridine or tetrahydrofuran (THF), optionally in the presence of a base such as triethylamine, at a temperature of 50-180° C., gives activated species (XXII) (wherein X 00 are X 01 or X 02 This leads to ii) Treatment of activated species (XXII) with a compound of formula (XI) (wherein X1, G1 and R2 are as defined in formula I) in the presence of a base such as triethylamine, N,N-diisopropyl-ethyl-amine or pyridine in an inert solvent such as dichloromethane, tetrahydrofuran, dioxane, N,N-dimethylformamide, N,N-dimethylacetamide, acetonitrile, ethyl acetate or toluene at a temperature of 0-50°C to form a compound of formula (XX).

[0117] Scheme 11a: [ka] Alternatively, compounds of formula II (wherein Q is Q6) defining compounds of formula II-Q6 (wherein R1, R9, A, X1 and R2 are as defined in formula I) can be prepared by cyclization of compounds of formula (XX-N) (wherein R1, R9, A, X1 and R2 are as defined in formula I) under conditions similar to those described above (see description in Scheme 11) (Scheme 11a).

[0118] Compounds of formula (XX-N), where R, R, A, X, and R are as defined in formula I, can be prepared by reacting the activated species (XXII) with compounds of formula (XI-N), where X and R are as defined in formula I, under conditions similar to those described above (see description in Scheme 11).

[0119] Scheme 12: [ka] Compounds of formula (XXIII), where R, R, and A are as defined in formula I, can be converted to compounds of formula (XXIV), where R, R, and A are as defined in formula I, and R, under conditions known to those skilled in the art (e.g., using conditions such as aqueous sodium hydroxide, potassium hydroxide, or lithium hydroxide in methanol, ethanol, tetrahydrofuran, or dioxane at room temperature or up to reflux conditions). 00 is a C1-C6 alkyl) (Scheme 12).

[0120] A compound of formula (XXIV) wherein R, R and A are as defined in formula I, and R 00 is C1-C6 alkyl) can be prepared by the synthesis of a compound of formula (XXV-b) (wherein R9, R1 and A are as defined in formula I, and R 00 is C1-C6 alkyl) with a compound of formula IV, where Xb is a leaving group such as, for example, chlorine, bromine or iodine (preferably iodine or bromine), or an aryl-, alkyl- or haloalkylsulfonate such as trifluoromethanesulfonic acid, under the conditions already described above (see Scheme 5 for the conversion of compound III to II).

[0121] A compound of formula (XXV-b) (wherein R, R and A are as defined in formula I, and R 00is C1-C6 alkyl) can be prepared by reacting a compound of formula (XXV-a) (wherein R1, R9 and A are as defined in formula I, and R 00 is C1-C6 alkyl) with a compound of formula VI, where Xa is a leaving group such as, for example, chlorine, bromine or iodine (preferably chlorine or bromine), or an aryl-, alkyl- or haloalkylsulfonate such as trifluoromethanesulfonic acid, under the conditions already described above (see Scheme 6 for the conversion of compound V to III).

[0122] Alternatively, a compound of formula (XXIV) wherein R, R and A are as defined in formula I, and R 00 is C1-C6 alkyl) can be prepared by reacting a compound of formula (XXV-c) (wherein R1, R9 and A are as defined in formula I, and R 00 is C1-C6 alkyl) to the dehydration conditions already described above (see Scheme 7 for the conversion of compound VII to II).

[0123] A compound of formula (XXV-c) (wherein R, R and A are as defined in formula I, and R 00 is C1-C6 alkyl) can be prepared by reacting a compound of formula (XXV-a) (wherein R1, R9 and A are as defined in formula I, and R 00 is C1-C6 alkyl) with a compound of formula VIII, where Xa is a leaving group such as, for example, chlorine, bromine or iodine (preferably bromine), or an aryl-, alkyl- or haloalkylsulfonate such as trifluoromethanesulfonic acid, under the conditions already described above (see Scheme 8 for the conversion of compound V to VII).

[0124] A compound of formula (XXV-a) (wherein R, R and A are as defined in formula I, and R 00is C1-C6 alkyl) can be prepared by reacting a compound of formula (XXV) 00 is C1-C6 alkyl and Xc is a leaving group such as, for example, chlorine, bromine or iodine (preferably bromine), or an aryl-, alkyl- or haloalkyl-sulfonate such as trifluoromethanesulfonic acid) with, for example, benzaldoxime PhC=NOH, preferably (E)-benzaldehyde oxime, under the conditions already described above (see Scheme 9 for the conversion of compound IX to V). Alternatively, the process for preparing compounds of formula (XXV-a) from compounds of formula (XXV) can also comprise the boronation / oxidation conditions also already described in Scheme 9.

[0125] A compound of formula (XXV) wherein R, R and A are as defined in formula I, and R 00 is C1-C6 alkyl and Xc is a leaving group such as, for example, chlorine, bromine or iodine, or an aryl-, alkyl- or haloalkylsulfonate such as trifluoromethanesulfonic acid), in particular compounds where Xc is a halogen (even more preferably chlorine, bromine or iodine) are known compounds, commercially available or may be prepared by known methods as described in the literature, for example, in WO 2016 / 005263, WO 2016 / 023954, WO 2016 / 026848 and WO 2016 / 104746.

[0126] Scheme 13: [ka] Alternatively, compounds of formula II (wherein Q is Q2) defining compounds of formula II-Q2 (wherein R1, R9, A, and R2 are as defined in formula I) can be prepared by condensing a compound of formula (XXVI) (wherein R1, R9, and A are as defined in formula I, and Xd is a leaving group such as, for example, chlorine, bromine, or iodine (preferably chlorine or bromine)) with a compound of formula (XXVII) (wherein R2 is as defined in formula I) in an inert solvent such as, for example, ethanol or acetonitrile, optionally in the presence of a suitable base such as sodium carbonate, potassium carbonate, or cesium carbonate, or magnesium oxide, at a temperature of 50 to 150 °C, optionally under microwave heating conditions (Scheme 13). Such processes have been previously described, for example, in WO 2012 / 49280 or WO 2003 / 031587. Compounds of formula (XXVII), wherein R2 is as defined in formula I, are known compounds, commercially available, or can be prepared by known methods known to those skilled in the art (see in particular WO 2016 / 071214).

[0127] Scheme 14: [ka] A compound of formula (XXVI) (wherein R1, R9 and A are as defined in formula I, and Xd is a leaving group such as chlorine, bromine or iodine (preferably chlorine or bromine)) can be reacted with a halogenating agent ("Xd") in acetic acid at a temperature between 0°C and 150°C, preferably between room temperature and 120°C, optionally under microwave heating conditions. + " sources), such as N-bromosuccinimide, N-iodosuccinimide, N-chlorosuccinimide, I2, CuBr2, Br2, or trimethyl(phenyl)ammonium tribromide PhNMe3, typically in a solvent such as methanol, acetonitrile, tetrahydrofuran, ethyl acetate, chloroform, or dichloromethane, or a mixture thereof. + Br3 -Compounds of formula (XXVIII) can be prepared by treating a compound of formula (XXVIII) (wherein R, R and A are as defined in formula I) with (Scheme 14). Such processes have already been described, for example, in WO 2016 / 071214.

[0128] Compounds of formula (XXVIII), in which R, R and A are as defined in formula I, may be prepared by reacting compounds of formula (XXIX-b), in which R, R and A are as defined in formula I, with compounds of formula IV, in which X is a leaving group such as, for example, chlorine, bromine or iodine (preferably iodine or bromine), or an aryl-, alkyl- or haloalkylsulfonate, such as trifluoromethanesulfonic acid, under the conditions already described above (see Scheme 5 for the conversion of compounds III to II).

[0129] Compounds of formula (XXIX-b), in which R, R and A are as defined in formula I, can be prepared by reacting compounds of formula (XXIX-a), in which R, R and A are as defined in formula I, with compounds of formula VI, in which X is a leaving group such as, for example, chlorine, bromine or iodine (preferably chlorine or bromine), or an aryl-, alkyl- or haloalkylsulfonate such as trifluoromethanesulfonic acid, under the conditions already described above (see Scheme 6 for the conversion of compounds V to III).

[0130] Alternatively, compounds of formula (XXVIII) (wherein R1, R9 and A are as defined in formula I) can be prepared by subjecting compounds of formula (XXIX-c) (wherein R1, R9 and A are as defined in formula I) to the dehydration conditions already described above (see Scheme 7 for the conversion of compounds VII to II).

[0131] Compounds of formula (XXIX-c), in which R, R and A are as defined in formula I, can be prepared by reacting compounds of formula (XXIX-a), in which R, R and A are as defined in formula I, with compounds of formula VIII, in which Xa is a leaving group such as, for example, chlorine, bromine or iodine (preferably bromine), or an aryl-, alkyl- or haloalkylsulfonate such as trifluoromethanesulfonic acid, under the conditions already described above (see Scheme 8 for the conversion of compounds V to VII).

[0132] Compounds of formula (XXIX-a), where R, R and A are as defined in formula I, can be prepared by reacting a compound of formula (XXIX), where R, R and A are as defined in formula I and Xf is a leaving group such as, for example, chlorine, bromine or iodine (preferably bromine), or an aryl-, alkyl- or haloalkyl-sulfonate, such as trifluoromethanesulfonic acid, with, for example, benzaldoxime PhC=NOH, preferably (E)-benzaldehyde oxime, under the conditions already described above (see Scheme 9, conversion of compound IX to V). Alternatively, the process for preparing compounds of formula (XXIX-a) from compounds of formula (XXIX) can also comprise the boronation / oxidation conditions also already described in Scheme 9.

[0133] Compounds of formula (XXIX) in which R, R and A are as defined in formula I and X is a leaving group such as, for example, chlorine, bromine or iodine, or an aryl-, alkyl- or haloalkylsulfonate, such as trifluoromethanesulfonic acid, in particular compounds in which X is a halogen (even more preferably chlorine, bromine or iodine; particularly preferably chlorine or bromine) are known compounds, commercially available or can be prepared by known methods as described in the literature, for example in WO 2016 / 071214.

[0134] Scheme 15: [ka] Alternatively, compounds of formula II (wherein Q is Q5) defining compounds of formula II-Q5 (wherein R1, R9, A, R3, R4 and R2 are as defined in formula I) can be prepared by cyclization of compounds of formula (XXXa) (wherein R1, R9, A, R3, R4 and R2 are as defined in formula I) or positional isomers of formula (XXXb) with equivalent substituent definitions, or mixtures thereof in any ratio, under the conditions already described above (see Scheme 11, conversion of compound (XX) to II-Q1) (Scheme 15).

[0135] Compounds of formula (XXXa) (wherein R1, R9, A, R3, R4 and R2 are as defined in formula I) or positional isomers of formula (XXXb) with equivalent substituent definitions, or mixtures thereof in any ratio, can be prepared by treatment of the above activated species (XXII) with compounds of formula (XXXI) (wherein R3, R4 and R2 are as defined in formula I) under the conditions already described above (see Scheme 11, conversion of compounds (XXII) and (XI) to compound (XX)).

[0136] Compounds of formula (XXXI), wherein R, R and R are as defined in formula I, have already been described, for example, in WO 2016 / 023954, WO 2016 / 142326 and WO 2017 / 133994.

[0137] Scheme 16: [ka] Alternatively, compounds of formula II (wherein Q is Q3) defining compounds of formula II-Q3 (wherein R1, R9, A, and R2 are as defined in formula I) can be prepared by condensing a compound of formula (XXVI) (wherein R1, R9, and A are as defined in formula I, and Xd is a leaving group such as, for example, chlorine, bromine, or iodine (preferably, chlorine or bromine)) with a compound of formula (XXXII) (wherein R2 is as defined in formula I) in an inert solvent such as, for example, ethanol, toluene, or acetonitrile, optionally in the presence of a suitable base such as sodium carbonate, potassium carbonate, or cesium carbonate (or sodium bicarbonate or potassium bicarbonate) at a temperature of 50 to 150 °C, optionally under microwave heating conditions (Scheme 16). Such a process has already been described, for example, in WO 2011 / 074658. Compounds of formula (XXXII), where R2 is as defined in formula I, are 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).

[0138] Scheme 17: [ka] Alternatively, compounds of formula II (wherein Q is Q4) defining compounds of formula II-Q4 (wherein R, R, A, G, G, and R are as defined in formula I) can be prepared by reductive cyclization of compounds of formula (XXXIII) (wherein R, R, A, G, G, and R are as defined in formula I) in the presence of a reducing agent such as trialkyl phosphite (more specifically, for example, triethyl phosphite), trialkylphosphine, or triphenylphosphine (Scheme 17). The principle of this reductive cyclization is similar to the well-known Cadogan reaction. Alternatively, this reaction can be carried out in the presence of a molybdenum(VI) catalyst, such as MoOCl(dmf) [molybdenyl chloride-bis(dimethylformamide)], or more generally, a metal catalyst, such as one involving a transition metal complex, in combination with a reducing agent such as triethyl phosphite, triphenylphosphine, or CO. Suitable solvents may include the use of an excess amount of a reducing agent (such as triethyl phosphite) or, for example, toluene or xylene, at a temperature between room temperature and 200° C., preferably between 50 and 160° C., optionally under microwave heating conditions. Such reduction cyclization reaction conditions were described, for example, in WO 2017 / 134066.

[0139] Compounds of formula (XXXIII) (wherein R1, R9, A, G1, G2, and R2 are as defined in formula I) can be prepared by reacting a compound of formula (XXXIV) (wherein R1, R9, and A are as defined in formula I) with a compound of formula (XXXV) (wherein G1, G2, and R2 are as defined in formula I) by heating, typically at temperatures between room temperature and 200°C, preferably between 40 and 160°C, optionally under microwave heating conditions, in a suitable solvent which may include, for example, toluene or xylene. Formation of compounds of formula (XXXIII) may require removal of water by azeotropic distillation or by a drying agent such as TiCl4 or molecular sieves. The formation of such Schiff bases of formula (XXXIII) is known to those skilled in the art and has been described, for example, in WO 2017 / 134066.

[0140] Compounds of formula (XXXV), wherein G1, G2 and R2 are as defined in formula I, are known compounds, commercially available, or can be prepared by known methods known to those skilled in the art.

[0141] Scheme 18: [ka] Compounds of formula (XXXIV) (wherein R, R, and A are as defined in formula I) can be prepared by subjecting compounds of formula (XXIII) above (or their corresponding activated species (XXII), also described above) to Curtius rearrangement / decomposition conditions known to those skilled in the art (Scheme 18). Such conditions are described, for example, in WO 2009099086 and Journal of Medicinal Chemistry, 55(22), 9589-9606; 2012.

[0142] Scheme 19: [ka] Alternatively, compounds of formula II (wherein Q is Q7 and X1 is NR3) defining compounds of formula II-Q7-a (wherein R1, R9, A and R3 are as defined in formula I) can be prepared by cyclization of compounds of formula (XX-a) (wherein R1, R9, A and R3 are as defined in formula I) under the conditions already described above (see Scheme 11, conversion of compound (XX) to II-Q1) (Scheme 19).

[0143] Compounds of formula (XX-a), where R, R, A, and R are as defined in formula I, can be prepared by reacting the activated species (XXII) with compounds of formula (XI-a), or salts thereof, where R is as defined in formula I, under the same acylation conditions as described above (see description in Scheme 11).

[0144] Alternatively, the compound of formula (XX-a) (wherein R, R, A, and R are as defined in formula I) can also be prepared by the reaction of 4-dimethylamino-pyridine (DMAP) with propanephosphonic anhydride (T3P), carbodiimides (such as dicyclohexylcarbodiimide (DCC), diisopropylcarbodiimide (DIC), and 1-ethyl-3-(3-dimethylamino-propyl)carbodiimide (EDC)), optionally in the presence of a suitable base such as triethylamine, diisopropylethylamine, or pyridine. The compound of formula (XXIII) can be prepared by reacting the compound of formula (XI-a) or a salt thereof (wherein R3 is as defined in formula I) in the presence of an acylation catalyst such as dichloromethane, tetrahydrofuran, 2-methyltetrahydrofuran, dioxane, N,N-dimethylformamide, N,N-dimethylacetamide, N-methyl-pyrrolidone, acetonitrile, ethyl acetate, toluene, xylene, chlorobenzene, or a mixture of any of these, at a temperature of 0°C to about 80°C.

[0145] Alternatively, a compound of formula II-Q7-a (wherein R, R, A and R are as defined in formula I) can be converted into a compound of formula R-X in the presence of a base such as, for example, potassium carbonate, cesium carbonate, lithium hexamethyldisilazane or lithium diisopropylamide in a suitable solvent such as acetonitrile, tetrahydrofuran or N,N-dimethylformamide at a temperature of −78° C. to 100° C., preferably −10° C. to 80° C. g wherein R3 is as defined in formula I, and X gcan be prepared by alkylation reaction of compounds of formula II-Q7-a-1 (where R, R and A are as defined in formula I) with, for example, a leaving group such as chlorine, bromine or iodine (preferably iodine or bromine), or an aryl-, alkyl- or haloalkylsulfonate such as trifluoromethanesulfonic acid. In the particular situation where R is CH, methyl iodide, methyl bromide or dimethyl sulfate can be used as the alkylating reagent R-X. g This is a typical example of

[0146] Compounds of formula II-Q7-a-1, where R1, R9 and A are as defined in formula I, can be prepared by cyclization of compounds of formula (XX-a-1), where R1, R9 and A are as defined in formula I, under the conditions already described above (see Scheme 19, conversion of compound (XX-a) to II-Q7-a).

[0147] The compound of formula (XX-a-1) (wherein R, R, and A are as defined in formula I) can be prepared by reacting the activated species (XXII) with the compound of formula (XI-a-1) or a salt thereof under the same acylation conditions as described above (see Scheme 19, which is the conversion of compound (XI-a) to (XX-a)). Alternatively, the compound of formula (XX-a-1) (wherein R, R, and A are as defined in formula I) can also be prepared by reacting the compound of formula (XXIII) with the compound of formula (XI-a-1) or a salt thereof under the same acylation conditions as described above (see Scheme 19, which is the conversion of compound (XI-a) to (XX-a)).

[0148] As a further alternative, compounds of formula II-Q7-a-1 (wherein R1, R9 and A are as defined in formula I) may be prepared by direct condensation of compounds of formula (XI-a-1) or salts thereof with compounds of formula (XXII) or (XXIII) above, for example under conditions similar to those described in WO 20 / 013147.

[0149] Scheme 20: [ka] Alternatively, compounds of formula II (wherein Q is Q7 and X1 is O) defining compounds of formula II-Q7-b (wherein R1, R9 and A are as defined in formula I) can be reacted with a base such as sodium carbonate, potassium carbonate or cesium carbonate or potassium t-butoxide in the presence of a metal catalyst, for example a copper catalyst, such as copper(I) iodide, optionally with a diamine ligand (for example N,N'-dimethylethylenediamine or trans-cyclohexyldiamine). In the presence of a ligand such as benzophenone (DBA), dibenzylideneacetone (dba), or 1,10-phenanthroline, in a solvent such as toluene, N,N-dimethylformamide (DMF), N-methylpyrrolidone (NMP), dimethyl sulfoxide (DMSO), dioxane, or tetrahydrofuran (THF), at a temperature of 30 to 180° C., optionally under microwave irradiation, a compound of formula (XX-b) (wherein R1, R9, A, and R3 are as defined in formula I, and X f can be prepared by cyclizing a halogen leaving group such as, for example, chlorine, bromine, or iodine (preferably chlorine or bromine) (Scheme 20).

[0150] A compound of formula (XX-b) (wherein R1, R9, A and R3 are as defined in formula I, and X f is a halogen leaving group such as, for example, chlorine, bromine or iodine (preferably, chlorine or bromine), can be reacted with the activated species (XXII) described above under the same acylation conditions as above (see description in Scheme 11) to react with a compound of formula (XI-b) or a salt thereof (wherein X f can be prepared by reacting with a halogen leaving group such as, for example, chlorine, bromine or iodine (preferably chlorine or bromine).

[0151] Alternatively, the compound of formula (XX-b) (wherein R, R, A and R are as defined in formula I) can also be prepared by the reaction of 4-amino-2-(2-methyl-2-phenylpropan-1-yl)-2-propan-1-yl with 4-methyl-2-propan-1-yl ... In the presence of an acylation catalyst such as N,N-dimethylamino-pyridine (DMAP), in a suitable solvent such as dichloromethane, tetrahydrofuran, 2-methyltetrahydrofuran, dioxane, N,N-dimethylformamide, N,N-dimethylacetamide, N-methyl-pyrrolidone, acetonitrile, ethyl acetate, toluene, xylene, or chlorobenzene, or a mixture thereof, at a temperature of 0°C to about 80°C, the compound of formula (XXIII) above and the compound of formula (XI-b) or a salt thereof (wherein X f can be prepared by reacting with a halogen leaving group such as, for example, chlorine, bromine or iodine (preferably chlorine or bromine).

[0152] The reactants can be reacted in the presence of a base. Examples of suitable bases are alkali metal or alkaline earth metal hydroxides, alkali metal or alkaline earth metal hydrides, alkali metal or alkaline earth metal amides, alkali metal or alkaline earth metal alkoxides, alkali metal or alkaline earth metal acetates, alkali metal or alkaline earth metal carbonates, alkali metal or alkaline earth metal dialkylamides or alkali metal or alkaline earth metal alkylsilylamides, alkylamides, alkylenediamides, free or N-alkylated saturated or unsaturated cycloalkylamines, basic heterocycles, ammonium hydroxide 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).

[0153] Compound of Formula XXXVI [ka] (In the formula, R1, R9 and A are as defined above in Formula I, and R 100 is OH, chloro or C1-C4 alkoxy) are novel and have been developed specifically for the preparation of compounds of formula I according to the invention and therefore represent a further object of the present invention. The substituent preferences and preferred embodiments of compounds of formula I are also valid for compounds of formula XXXVI.

[0154] The reactants can be reacted with each other as they are, i.e., without the addition of a solvent or diluent. However, in most cases, it is advantageous to add an inert solvent or diluent or a mixture thereof. When the reaction is carried out in the presence of a base, the base used in excess, such as triethylamine, pyridine, N-methylmorpholine, or N,N-diethylaniline, can also serve as the solvent or diluent.

[0155] The reaction is advantageously carried out in the temperature range of about -80°C to about +140°C, preferably about -30°C to about +100°C, and in many cases in the range of ambient temperature to about +80°C.

[0156] Compounds of formula I can be converted into other compounds of formula I in a manner known per se by replacing one or more substituents of the starting compound of formula I by other substituents according to the invention in a conventional manner.

[0157] Depending on the respective suitable reaction conditions and the choice of starting materials, it is possible, for example, to simply replace one substituent with another substituent according to the invention in one reaction step, or multiple substituents can be replaced with other substituents according to the invention in the same reaction step.

[0158] Salts of compounds of formula I can be prepared in a manner known per se: thus, for example, acid addition salts of compounds of formula I can be obtained by treatment with a suitable acid or with a suitable ion exchange reagent, and base salts can be obtained by treatment with a suitable base or with a suitable ion exchange reagent.

[0159] Salts of compounds of formula I can be converted in a customary manner into acid addition salts of the free compounds I, for example by treatment with suitable basic compounds or suitable ion exchange reagents, and into salts with bases, for example by treatment with suitable acids or suitable ion exchange reagents.

[0160] Salts of compounds of formula I may be converted into other salts, such as acid addition salts, of compounds of formula I in a manner known per se, for example by treating the inorganic acid salt, such as the hydrochloride, with a suitable metal salt, such as the sodium, barium or silver salt of the acid, for example silver acetate, in a suitable solvent in which the inorganic salt that forms silver chloride is insoluble and therefore precipitates from the reaction mixture.

[0161] Depending on the procedure or reaction conditions, compounds of formula I having salt-forming properties may be obtained in free form or in salt form.

[0162] The compounds of formula I and, where appropriate, their tautomers, in each free or salt form, can exist in the form of pure isomers, such as enantiomers and / or diastereomers, or as isomeric mixtures, such as enantiomeric mixtures, such as racemates, diastereomeric mixtures or racemic mixtures, depending on the number, absolute and relative configuration of asymmetric carbon atoms occurring in the molecule and / or depending on the configuration of non-aromatic double bonds occurring in the molecule; the invention relates to the pure isomers and also to all possible isomeric mixtures, and is to be understood in this sense above and below, respectively, even if details of the stereochemistry are not specifically stated in each case.

[0163] Diastereomeric or racemic mixtures of compounds of formula I, in free or salt form, obtained depending on which starting materials and procedures are selected, can be separated in known manner into pure diastereomers or racemates on the basis of the physical chemical differences of the components, for example, by fractional crystallization, distillation, and / or chromatography.

[0164] Enantiomeric mixtures, such as racemates, obtained in a similar manner can be resolved into their optical antipodes by known methods, for example by recrystallization from optically active solvents, by chromatography on chiral adsorbents, for example by high-performance liquid chromatography (HPLC) on acetylcellulose using suitable microorganisms, by cleavage with specific immobilized enzymes via the formation of inclusion compounds, for example with chiral crown ethers, in which only one enantiomer is complexed, or by conversion to diastereomeric salts, for example by reacting the basic final product racemate with an optically active acid, such as a carboxylic acid, for example camphoric acid, tartaric acid or malic acid, or a sulfonic acid, for example camphorsulfonic acid, and separating the diastereomeric mixtures thus obtained, for example by fractional crystallization based on their different solubilities, to give diastereomers from which the desired enantiomer can be released by the action of a suitable substance, for example a basic substance.

[0165] Pure diastereomers or enantiomers can be obtained according to the present invention not only by separating the appropriate isomeric mixtures, but also by generally known methods of diastereoselective or enantioselective synthesis, e.g. by carrying out the process according to the present invention using stereochemically characterized starting materials.

[0166] The N-oxides can be prepared by reacting the compounds of formula I with a suitable oxidizing agent, such as the H2O2 / urea adduct, in the presence of an acid anhydride, such as trifluoroacetic anhydride. Such oxidations are known from the literature, for example, J. Med. Chem., 32(12), 2561-73, 1989 or WO 00 / 15615.

[0167] Compounds in which R2 is C1-C4 haloalkylsulfinyl or C1-C4 haloalkylsulfonyl may be prepared from the corresponding compounds in which R2 is C1-C4 haloalkylsulfanyl by suitable oxidation methods, for example as described in WO 19 / 008115.

[0168] When the individual components have different biological activities, it may be advantageous to isolate or synthesize the respective more biologically active isomer, e.g., enantiomer or diastereomer, or mixture of isomers, e.g., mixture of enantiomers or diastereomers.

[0169] The compounds of formula I and, where appropriate, their tautomers, may also be obtained in free or salt form, optionally in the form of hydrates, and / or contain other solvents, such as solvents that may have been used for the crystallization of compounds present in solid form.

[0170] The compounds of formula I according to the following Tables X, A-1 to A-22, and B-1 to B-4 can be prepared according to the above methods. The following examples are intended to illustrate the invention and to show preferred compounds of formula I.

[0171] The following Tables A-1 to A-22 illustrate specific compounds of the present invention. [ka]

[0172] Table A-1 provides four compounds A-1.001 to A-1.004 of formula I, in which R1 is ethyl and A and R9 are as defined in Table X, and Q is a group of formula Q6 [ka] It is said that.

[0173] [Table 1]

[0174] For example, compound A-1.004 has the following structure: [ka] It has.

[0175] Table A-2 provides four compounds A-2.001 to A-2.004 of formula I, where R1 is ethyl and A and R9 are as defined in Table X, and Q is a group of formula Q6 [ka] It is said that.

[0176] Table A-3 provides four compounds A-3.001 to A-3.004 of formula I, where R1 is ethyl and A and R9 are as defined in Table X, and Q is a group of formula Q1 [ka] It is said that.

[0177] Table A-4 provides four compounds A-4.001 to A-4.004 of formula I, where R1 is ethyl and A and R9 are as defined in Table X, and Q is a group of formula Q1 [ka] It is said that.

[0178] Table A-5 provides four compounds A-5.001 to A-5.004 of formula I, where R1 is ethyl and A and R9 are as defined in Table X, and Q is a group of formula Q2 [ka] It is said that.

[0179] Table A-6 provides four compounds A-6.001 to A-6.004 of formula I, where R1 is ethyl and A and R9 are as defined in Table X, and Q is a group of formula Q3 [ka] It is said that.

[0180] Table A-7 provides four compounds A-7.001 to A-7.004 of formula I, where R1 is ethyl and A and R9 are as defined in Table X, and Q is a group of formula Q1 [ka] It is said that.

[0181] Table A-8 provides four compounds A-8.001 to A-8.004 of formula I, where R1 is ethyl and A and R9 are as defined in Table X, and Q is a group of formula Q1 [ka] It is said that.

[0182] Table A-9 provides four compounds A-9.001 to A-9.004 of formula I, where R1 is ethyl and A and R9 are as defined in Table X, and Q is a group of formula Q4 [ka] It is said that.

[0183] Table A-10 provides four compounds A-10.001 to A-10.004 of formula I, where R1 is ethyl and A and R9 are as defined in Table X, and Q is a group of formula Q4 [ka] It is said that.

[0184] Table A-11 provides four compounds A-11.001 to A-11.004 of formula I, where R1 is ethyl and A and R9 are as defined in Table X, and Q is a group of formula Q5 [ka] It is said that.

[0185] Table A-12 provides four compounds A-12.001 to A-12.004 of formula I, where R1 is ethyl and A and R9 are as defined in Table X, and Q is a group of formula Q5 [ka] It is said that.

[0186] Table A-13 provides four compounds A-13.001 to A-13.004 of formula I, where R1 is ethyl and A and R9 are as defined in Table X, and Q is a group of formula Q5 [ka] It is said that.

[0187] Table A-14 provides four compounds A-14.001 to A-14.004 of formula I, where R1 is ethyl and A and R9 are as defined in Table X, and Q is a group of formula Q5 [ka] It is said that.

[0188] Table A-15 provides four compounds A-15.001 to A-15.004 of formula I, where R1 is ethyl and A and R9 are as defined in Table X, and Q is a group of formula Q1 [ka] It is said that.

[0189] Table A-16 provides four compounds A-16.001 to A-16.004 of formula I, where R1 is ethyl, and A and R9 are as defined in Table X, and Q is a group of formula Q1 [ka] It is said that.

[0190] Table A-17 provides four compounds A-17.001 to A-17.004 of formula I, where R1 is ethyl and A and R9 are as defined in Table X, and Q is a group of formula Q1 [ka] It is said that.

[0191] Table A-18 provides four compounds A-18.001 to A-18.004 of formula I, where R1 is ethyl, and A and R9 are as defined in Table X, and Q is a group of formula Q1 [ka] It is said that.

[0192] Table A-19 provides four compounds A-19.001 to A-19.004 of formula I, where R1 is ethyl, and A and R9 are as defined in Table X, and Q is a group of formula Q1 [ka] It is said that.

[0193] Table A-20 provides four compounds A-20.001 to A-20.004 of formula I, where R1 is ethyl, and A and R9 are as defined in Table X, and Q is a group of formula Q2 [ka] It is said that.

[0194] Table A-21 provides four compounds A-21.001 to A-21.004 of formula I, where R1 is ethyl, and A and R9 are as defined in Table X, and Q is a group of formula Q7 [ka] It is said that.

[0195] Table A-22 provides four compounds A-22.001 to A-22.004 of formula I, where R1 is ethyl, and A and R9 are as defined in Table X, and Q is a group of formula Q7 [ka] It is said that.

[0196] The following Tables B-1 to B-4 further illustrate specific compounds of the present invention.

[0197] Table B-1 provides four compounds B-1.001 to B-1.004 of formula I, where R1 is —CH2cyclopropyl, and A and R9 are as defined in Table X, and Q is a group of formula Q6 [ka] It is said that.

[0198] Table B-2 provides four compounds B-2.001 to B-2.004 of formula I, where R1 is -CH2cyclopropyl, and A and R9 are as defined in Table X, and Q is a group of formula Q1 [ka] It is said that.

[0199] Table B-3 provides four compounds B-3.001 to B-3.004 of formula I, where R1 is -CH2cyclopropyl, and A and R9 are as defined in Table X, and Q is a group of formula Q2 [ka] It is said that.

[0200] Table B-4 provides four compounds B-4.001 to B-4.004 of formula I, where R1 is -CH2cyclopropyl, and A and R9 are as defined in Table X, and Q is a group of formula Q1 [ka] It is said that.

[0201] The compounds of formula I according to the invention are active ingredients of great preventive and / or therapeutic value in the field of pest control, even at low application rates, which have a very favorable biocidal spectrum and are well tolerated by warm-blooded species, fish, and plants. The active ingredients according to the invention act against all or each of the developmental stages of normally susceptible but resistant insects or animal pests, such as representatives of the order Acarina, nematodes, or molluscs. The insecticidal, nematicidal, molluscicidal, or acaricidal activity of the active ingredients according to the invention can be manifested directly (i.e., by mortality or control of the pest, which occurs immediately or only after a certain period of time (e.g., during molting)) or indirectly (e.g., by a reduction in egg-laying and / or hatching rate, an antifeedant effect, and / or growth inhibition).

[0202] The compounds of formula (I) according to the present invention may have any number of benefits, including, inter alia, advantageous levels of biological activity for protecting plants against insects or advantageous levels of superior properties for use as agrochemical active ingredients (e.g., high biological activity, advantageous spectrum of activity, high safety profile, improved physicochemical properties, or high biodegradability or environmental profile). In particular, it has been unexpectedly found that certain compounds of formula (I) exhibit advantageous safety profiles against non-target organisms, such as non-target arthropods, particularly pollinators such as honeybees, solitary bees, and bumblebees. More specifically, the European honeybee (Apis mellifera).

[0203] In this regard, certain compounds of formula (I) of the present invention are distinguishable from known compounds by their high efficacy at low application rates, which can be verified by one skilled in the art using experimental procedures similar to or adapted from those outlined in the biological examples, using lower application rates as needed, for example, 50 ppm, 12.5 ppm, 6 ppm, 3 ppm, 1.5 ppm, 0.8 ppm or 0.2 ppm.

[0204] Furthermore, it has been unexpectedly found that the compounds of formula (I) of the present invention exhibit advantageous physicochemical properties for use in crop protection, in particular low melting point, low lipophilicity and high water solubility.These properties have been found to be advantageous for plant uptake and systemic distribution, and for controlling certain pest species listed below (see, for example, A. Buchholz, S. Trapp, Pest Manag Sci 2016;72:929-939).

[0205] Putative metabolites of compounds of formula I that may be formed in the practice of the present invention in connection with one or more of the methods, pests, crops and / or targets described below are amide compounds of formula I-M1 and acid compounds of formula I-M2, which correspond to the parent nitrile compounds of formula I, respectively: [ka] wherein Q, R1, R2, R3, R4, R9, X1, G1, G2, and A are as defined in Formula I above, or an agrochemically acceptable salt, stereoisomer, enantiomer, tautomer, or N-oxide thereof. Specific putative metabolites may include: (1) amide compounds of Formula I-M1 corresponding to a parent nitrile selected from the group consisting of the compounds set forth in Tables A-1 to A-22, B-1 to B-4, and Table P; and (2) acid compounds of Formula I-M2 corresponding to a parent nitrile selected from the group consisting of the compounds set forth in Tables A-1 to A-22, B-1 to B-4, and Table P.

[0206] Examples of the above animal pests are: From the order Acarina, for example: Acalitus spp., Aculus spp., Acaricalus spp., Aceria spp., Acarus siro, Amblyomma spp., Argas spp., Boophilus spp., Brevipalpus spp., Bryobia spp., Calipitrimerus spp., Chorioptes spp., Dermanyssus gallinae, Dermatophagoides spp., Eotetranychus spp. spp., Eriophyes spp., Hemitarsonemus spp., Hyalomma spp., Ixodes spp., Olygonychus spp., Ornithodoros spp., Polyphagotarsone latus, Panonychus spp., Phyllocoptruta oleivora, Phytonemus spp., Polyphagotarsonemus spp., Psoroptes spp., Rhipicephalus spp.), Rhizoglyphus spp., Sarcoptes spp., Steneotarsonemus spp., Tarsonemus spp. and Tetranychus spp.; From the order Anoplura, for example: Haematopinus spp., Linognathus spp., Pediculus spp., Pemphigus spp. and Phylloxera spp.; From the order Coleoptera, for example: Agriotes spp., Amphimallon majale, Anomala orientalis, Anthonomus spp., Aphodius spp., Astylus atromaculatus, Ataenius spp., Atomaria linearis, Chaetocnema tibialis, Cerotoma spp., Conoderus spp., Cosmopolites spp., Cotinis nitida, Curculio spp., Cyclocephala spp.), Dermestes spp., Diabrotica spp., Diloboderus abderus, Epilachna spp., Eremnus spp., Heteronychus arator, Hypothenemus hampei, Lagria vilosa, Leptinotarsa ​​decemLineata, Lissorhoptrus spp., Liogenys spp., Maecolaspis spp., Maladera castanea, Megascelis spp. spp., Melighetes aeneus, Melolontha spp., Myochrous armatus, Orycaephilus spp., Otiorhynchus spp., Phyllophaga spp., Phlyctinus spp., Popillia spp.), Psylliodes spp., Rhyssomatus aubtilis, Rhizopertha spp., Scarabaeidae, Sitophilus spp., Sitotroga spp., Somaticus spp., Sphenophorus spp., Sternechus subsignatus, Tenebrio spp., Tribolium spp. and Trogoderma spp.;. From the order Diptera, for example: Aedes spp., Anopheles spp., Antherigona soccata, Bactrocea oleae, Bibio hortulanus, Bradysia spp., Calliphora erythrocephala, Ceratitis spp., Chrysomyia spp., Culex spp., Cuterebra spp., Dacus spp., Delia spp., Drosophila melanogaster, Fannia spp. spp.), Gastrophilus spp., Geomyza tripunctata, Glossina spp., Hypoderma spp., Hyppobosca spp., Liriomyza spp., Lucilia spp., Melanagromyza spp., Musca spp., Oestrus spp., Orseolia spp., Oscinella frit, Pegomyia hyoscyami, Phorbia spp. spp.), Rhagoletis spp., Rivelia quadrifasciata, Scatella spp., Sciara spp., Stomoxys spp., Tabanus spp., Tannia spp. and Tipula spp.; From the order Hemiptera, for example: Acanthocoris scabrator, Acrosternum spp., Adelphocoris lineolatus, Aleurodes spp., Amblypelta nitida, Bathycoelia thalassina, Blissus spp., Cimex spp., Clavigrella tomentosicollis, Creontiades spp., Distantiella theobroma, Dichelops furcatus, Dysdercus spp., Edessa spp., Euchistus spp., Eurydema pulchrum, Eurygaster spp., Halyomorpha halys, Horcias nobilellus, Leptocorisa spp., Lygus spp., Margarodes spp., Murgantia histrionic, Neomegalotomus spp., Nesidiocoris tenuis, Nezara spp., Nysius simulans, Oebalus insularis insularis, Piesma spp., Piezodorus spp., Rhodnius spp., Sahlbergella singularis, Scaptocoris castanea, Scotinophara spp.), Thyanta spp., Triatoma spp., Vatiga illudens;. Acyrthosium pisum, Adalges spp., Agalliana ensigera, Agonoscena targionii, Aleurodicus spp., Aleurocanthus spp., Aleurolobus barodensis, Aleurothrixus floccosus, Aleyrodes brassicae, Amarasca biguttula, Amritodus atkinsoni, Aonidiella spp. spp.), Aphididae, Aphis spp., Aspidiotus spp., Aulacorthum solani, Bactericera cockerelli, Bemisia spp., Brachycaudus spp., Brevicoryne brassicae, Cacopsylla spp., Cavariella aegopodii Scop., Ceroplaster spp.), Chrysomphalus aonidium, Chrysomphalus dictyospermi, Cicadella spp., Cofana spectra, Cryptomyzus spp., Cicadulina spp., Coccus hesperidum, Dalbulus maidis, Dialeurodes spp., Diaphorina citri, Diuraphis noxia, Dysaphis spp., Empoasca spp., Eriosoma larigerum, Erythroneura spp., Gascardia spp., Glycaspis brimblecombei, Hyadaphis pseudobrassicae, Hyalopterus spp., Hyperomyzus pallidus, Idioscopus clypealis, Jacobiasca lybica, Laodelphax spp., Lecanium corni, Lepidosaphes spp., Lopaphis erysimi, Lyogenys maidis, Macrosiphum spp., Mahanarva spp., Metcalfa pruinosa, Metopolophium dirhodum, Myndus crudus, Myzus spp.), Neotoxoptera spp., Nephotettix spp., Nilaparvata spp., Nippolachnus piri Mats, Odonaspis ruthae, Oregma lanigera Zehnter, Bayberry whitefly (Parabemisia myricae), Paratrioza cockerelli, Parlatoria spp., Pemphigus spp., Corn planthopper (Peregrinus maidis), Perkinsiella spp., Hop wart aphid (Phorodon humuli, Phylloxera spp., Planococcus spp., Pseudaulacaspis spp., Pseudococcus spp., Pseudatomoscelis seriatus, Psylla spp., Pulvinaria aethiopica, Quadraspidiotus spp., Quesada gigas, Recilia dorsalis, Rhopalosiphum spp., Saissetia spp., Scaphoideus spp. spp.), Schizaphis spp., Sitobion spp.), Sogatella furcifera, Spisstilus festinus, Tarophagus Proserpina, Toxoptera spp., Trialeurodes spp., Tridiscus sporoboli, Trionymus spp., Trioza erytreae, Unaspis citri, Zygina flammigera, Zyginidia scutellaris; From the order Hymenoptera, for example: Acromyrmex ants, Arge spp., Atta spp., Cephus spp., Diprion spp., Diprionidae, Gilpinia polytoma, Hoplocampa spp., Lasius spp., Monomorium pharaonis ants, Neodiprion spp., Pogonomyrmex spp., Slenopsis invicta, Solenopsis spp. and Vespa spp.; From the order Isoptera, for example: Coptotermes spp., Corniternes cumulans, Incisitermes spp., Macrotermes spp., Mastotermes spp., Microtermes spp., Reticulitermes spp.; Solenopsis geminate From the order Lepidoptera, for example: Acleris spp., Adoxophyes spp., Aegeria spp., Agrotis spp., Alabama argillaceae, Amylois spp., Anticarsia gemmatalis, Archips spp., Argyresthia spp., Argyrotaenia spp., Autographa spp., Bucculatrix thurberiella, Busseola fusca, Cadra cautella, Carposina nipponensis, Chilo spp., Choristoneura spp., Chrysoteuchia topiaria, Clysia ambiguella, Cnaphalocrocis spp., Cnephasia spp., Cochylis spp., Coleophora spp., Colias lesbia, Cosmophila flava, Crambus spp., Crocidolomia binotalis, Cryptophlebia leucotreta, Cydalima perspectalis perspectalis, Cydia spp., Diaphania perspectalis, Diatraea spp., Diparopsis castanea, Earias spp.), Elasmopalpus lignosellus, Eldana saccharina, Ephestia spp., Epinotia spp., Estigmene acrea, Etiella zinckinella, Eucosma spp., Eupoecilia ambiguella, Euproctis spp., Euxoa spp., Feltia jaculiferia, Grapholita spp., Hedya nubiferana, Heliothis spp. spp.), Hellula undalis, Herpetogramma spp., Hyphantria cunea, Keiferia lycopersicella, Lasmopalpus lignosellus, Leucoptera scitella, Lithocollethis spp., Lobesia botrana, Loxostege bifidalis, Lymantria spp., Lyonetia spp., Malacosoma spp., Mamestra brassicae, Manduca sexta, Mythimna spp., Noctua spp., Operophtera spp., Orniodes indica, Ostrinia nubilalis, Pammene spp., Pandemis spp.), pine sawyer moth (Panolis flammea), Papaipema nebris, pink bollworm (Pectinophora gossypiela), coffee leafminer (Perileucoptera coffeella), Pseudaletia unipuncta, potato tuber moth (Phthorimaea operculella), cabbage white butterfly (Pieris rapae), Pieris spp., diamondback moth (Plutella xylostella), Prays spp., Pseudoplusia spp., Rachiplusia nu, Richia albicosta, Scirpophaga spp., Sesamia spp.), Sparganothis spp., Spodoptera spp., Sylepta derogate, Synanthedon spp., Thaumetopoea spp., Tortrix spp., Trichoplusia ni, Tuta absoluta and Yponomeuta spp.;. From the order Mallophaga, for example: Damalinea spp. and Trichodectes spp.; From the order Orthoptera, for example: Blatta spp., Blattella spp., Gryllotalpa spp., Leucophaea maderae, Locusta spp., Neocurtilla hexadactyla, Periplaneta spp., Scapteriscus spp. and Schistocerca spp.; From the order Psocoptera, for example: Liposcelis spp.; From the order Siphonaptera, for example: Ceratophyllus spp., Ctenocephalides spp. and Xenopsylla cheopis; From the order Thysanoptera, for example: Calliothrips phaseoli, Frankliniella spp., Heliothrips spp., Hercinothrips spp., Parthenothrips spp., Scirtothrips aurantii, Sericothrips variabilis, Taeniothrips spp., Thrips spp.; From the order Thysanura, for example, Lepisma saccharina.

[0207] The active ingredients according to the invention can be used to control, i.e. suppress or destroy, pests of the above-mentioned types occurring in particular on plants, in particular on useful plants and ornamental plants in agriculture, horticulture and forestry, or on organs such as the fruits, flowers, leaves, stems, tubers or roots of such plants, in some cases even plant organs formed at a later time remaining protected from these pests.

[0208] Suitable target crops are, in particular, cereals such as wheat, barley, rye, oats, rice, maize or sorghum; beets such as sugar beet or fodder beet; fruits, such as pome fruits, stone fruits or soft fruits, for example apples, pears, plums, peaches, almonds, cherries or berries, for example strawberries, raspberries or blackberries; legumes, such as beans, lentils, peas or soybeans; rapeseed, mustard, poppy, olive, sunflower, palm, castor, cocoa or groundnut. citrus fruits such as oranges, lemons, grapefruits or tangerines; vegetables such as spinach, lettuce, asparagus, cabbage, carrots, onions, tomatoes, potatoes or peppers; plants of the Lauraceae family such as avocado, cinnamon or camphor; and also tobacco, tree nuts, coffee, eggplant, sugarcane, tea, pepper, grapes, hops, plantains and latex plants.

[0209] The compositions and / or methods of the present invention may be used on any ornamental and / or vegetable crop, including flowers, shrubs, broadleaf trees and evergreen trees.

[0210] For example, the present invention relates to the use of the following ornamental species: Ageratum spp., Alonsoa spp., Anemone spp., Anisodontea capsenisis, Anthemis spp., Antirrhinum spp., Aster spp., Begonia spp. (e.g., B. elatior, B. semperflorens, B. tubereux), Bougainvillea spp., Brachycome spp. spp.), Brassica spp. (ornamental), Calceolaria spp., Capsicum annuum, Catharanthus roseus, Canna spp., Centaurea spp., Chrysanthemum spp., Cineraria spp. (C. maritime), Coreopsis spp., Crassula coccinea, Cuphea ignea, Dahlia spp., Delphinium spp., Bleeding hearts spectabilis, Dorotheantus spp., Lisianthus (Eustoma grandiflorum), Forsythia spp., Fuchsia spp., Geranium gnaphalium, Gerbera spp., Globetrotter (Gomphrena globosa), Heliotropium spp., Helianthus spp., Hibiscus spp.), Hortensia spp., Hydrangea spp., Hypoestes phyllostachya, Impatiens spp. (I. Walleriana), Iresines spp., Kalanchoe spp., Lantana camara, Lavatera trimestris, Leonotis leonurus, Lilium spp., Mesembryanthemum spp., Mimulus spp., Monarda spp. spp.), Nemesia spp., Tagetes spp., Dianthus spp. (carnations), Canna spp., Oxalis spp., Bellis spp., Pelargonium spp. (ivy geranium (P. peltatum), P. Zonale), Viola spp. (pansies), Petunia spp., Phlox spp., Plecthranthus spp., Poinsettia spp. spp.), Parthenocissus spp. (American Creeper (P. quinquefolia), Ivy (P. tricuspidata)), Primula spp., Ranunculus spp., Rhododendron spp., Rosa spp. (roses), Rudbeckia spp., Saintpaulia spp., Salvia spp.), Scaevola aemola, Schizanthus wisetonensis, Sedum spp., Solanum spp., Surfinia spp., Tagetes spp., Nicotinia spp., Verbena spp., Zinnia spp., and other bedding plants.

[0211] For example, the present invention relates to the use of the following vegetable species: Allium spp. (garlic (A. sativum), onion (A. cepa), shallot (A. oschaninii), leek (A. porrum), scallion (A. ascalonicum), green onion (A. fistulosum)), chervil (Anthriscus cerefolium), celery (Apium graveolus), asparagus (Asparagus officinalis), beet (Beta vulgarus), Brassica spp. (B. oleracea, Chinese cabbage (B. pekinensis), turnip (B. rapa)), chili pepper (Capsicum annuum), chickpea (Cicer arietinum), endive (Cichorium endivia), Cichorum spp. spp.) (chicory (C. intybus), endive (C. endivia)), watermelon (Citrillus lanatus), Cucumis spp. (saffron (C. sativus), melon (C. melo)), Cucurbita spp. (Cucurbita pepo, Cucurbita maxima), Cyanara spp. (artichoke (C. scolymus), cardoon (C. cardunculus)), carrot (Daucus carota), fennel (Foeniculum vulgare), Hypericum spp., lettuce (Lactuca sativa), tomato spp. spp.) (tomato (L. esculentum), tomato (L. lycopersicum)), mint species (Mentha spp.), basil (Ocimum basilicum), parsley (Petroselinum crispum), Phaseolus species (Phaseolus spp.) (P. vulgaris, runner bean (P.The present invention may be used in any of the following plants: pea (Pisum sativum), radish (Raphanus sativus), rhubarb (Rheum rhaponticum), rosemary (Rosemarinus spp.), salvia (Salvia spp.), yellow rosemary (Scorzonera hispanica), eggplant (Solanum melongena), spinach (Spinacea oleracea), Valerianella spp. (V. locusta, V. eriocarpa), and broad bean (Vicia faba).

[0212] Preferred ornamental species include Saintpaulia, Begonia, Dahlia, Gerbera, Hydrangea, Vervain, Rosa, Kalanchoe, Poinsettia, Aster, Centaurea, Coreopsis, Delphinium, Monarda, Phlox, Rudbeckia, Sedum, Petunia, Viola, Impatiens, Geranium, Chrysanthemum, Ranunculus, Fuchsia, Salvia, Hydrangea, Rosemary, Sage, St. John's Wort, Mint, Bell Pepper, Tomato, and Cucumber.

[0213] The active ingredients according to the invention are particularly suitable for controlling Aphis craccivora, Diabrotica balteata, Heliothis virescens, Myzus persicae, Plutella xylostella and Spodoptera littoralis in cotton, vegetables, corn, rice and soybean crops. The active ingredients according to the invention are particularly suitable for controlling Mamestra (preferably on vegetables), codling moth (Cydia pomonella) (preferably on apple), Empoasca (preferably on vegetables and vineyards), Leptinotarsa ​​(preferably on potato) and Chilo supressalis (preferably on rice).

[0214] The active ingredients according to the invention are particularly suitable for controlling Aphis craccivora, Diabrotica balteata, Heliothis virescens, Myzus persicae, Plutella xylostella and Spodoptera littoralis in cotton, vegetables, corn, rice and soybean crops. The active ingredients according to the invention are particularly suitable for controlling Mamestra (preferably on vegetables), codling moth (Cydia pomonella) (preferably on apple), Empoasca (preferably on vegetables and vineyards), Leptinotarsa ​​(preferably on potato) and Chilo supressalis (preferably on rice).

[0215] In a further aspect, the present invention also relates to plant parasitic nematodes (endoparasitic, semi-endoparasitic and ectoparasitic nematodes), in particular the root-knot nematode Meloidogyne hapla, Meloidogyne incognita, Meloidogyne javanica, Meloidogyne arenaria and other Meloidogyne species; cyst-forming nematodes Globodera rostochiensis and other Globodera species; wheat cyst nematode Heterodera avenae, soybean cyst nematode Heterodera glycines, sugar beet cyst nematode Heterodera schachtii, clover cyst nematode Heterodera trifolii and other cyst nematodes (Heterodera species); seed gall nematodes, Anguina species; stem and peel nematodes, Aphelenchoides species; sting nematodes, Belonolaimus longicaudatus and other Belonolaimus species; pine wood nematode, Bursaphelenchus xylophilus and other Bursaphelenchus species; ring nematodes, Criconema species, Criconemella species, Criconemoides species, Mesocriconema species; stem and bulb nematodes, Ditylenchus destructor, Ditylenchus dipsaci and other Ditylenchus species; fire nematodes, Dolichodorus species;Screw nematodes, Heliocotylenchus multicinctus and other Helicotylenchus species; Sheath and sheathoid nematodes, Hemicycliophora species and Hemicriconemoides species; Hirshmanniella species; Spear nematodes, Hoploaimus species; False root-knot nematodes, Nacobbus species; Tylenchidae, Longidorus elongatus elongatus and other Longidorus species; pin nematodes, Pratylenchus species; root-lesion nematodes, Pratylenchus neglectus, Pratylenchus penetrans, Pratylenchus curvitatus, Pratylenchus goodeyi and other Pratylenchus species; root-lesion nematodes, Radopholus similis and other Radopholus species; false nematodes, Rotylenchus robustus, Rotylenchus reniformis and other Rotylenchus species; Scutellonema species; Trichodorus primitivus and other Trichodorus species, Paratrichodorus species;plant-parasitic nematodes such as the claytonid nematode, Tylenchorhynchus claytoni, Tylenchorhynchus dubius and other Tylenchorhynchus species; the burrowing nematode, Tylenchulus species; plant-parasitic nematodes such as the giant sting nematode, Xiphinema species; and plant-parasitic nematodes such as Subanguina species, Hypsoperine species, Macroposthonia species, Melinius species, Punctodera species and Quinisulcius species. The present invention may also relate to a method for preventing damage to plants and parts thereof by other plant-parasitic nematode species, such as Pseudomonas spp.;

[0216] The compounds of the present invention may also have activity against mollusks, such as, for example, species of the family Ampullariidae; Arion (A. ater, A. circumscriptus, A. hortensis, A. rufus); Bradybaenidae (Bradybaena fruticum); Cepaea (C. hortensis, C. rufus); Nemoralis); Ochlodina; Deroceras (D. agrestis, D. empiricorum, D. laeve, D. reticulatum); Discus (D. rotundatus); Euomphalia; Galba (G. trunculata); Helicelia (H. itala, H. obvia); Helicidae (Helicigona albustrum) arbustorum); Helicodiscus; Helix (H. aperta); Limax (L. cinereoniger, L. flavus, L. marginatus, L. maximus, L. tenellus); Monoa These include the genera Lymnaea; Milax (M. gagates, M. marginatus, M. sowerbyi); Opeas; Pomacea (P. canaticulata); Vallonia and Zanitoides.

[0217] The term "crop plant" should also be understood to include crop plants that have been transformed by the use of recombinant DNA techniques so as to be capable of synthesizing one or more selectively acting toxins, such as those known to be derived from toxin-producing bacteria, particularly bacteria of the genus Bacillus.

[0218] Toxins that can be expressed by such transgenic plants include, for example, insecticidal proteins from Bacillus cereus or Bacillus popilliae; or δ-endotoxins, such as Cry1Ab, Cry1Ac, Cry1F, Cry1Fa2, Cry2Ab, Cry3A, Cry3Bb1 or Cry9C, insecticidal proteins from Bacillus thuringiensis or plant insecticidal proteins (Vip), such as Vip1, Vip2, Vip3 or Vip3A; or bacterial-colonizing nematodes, such as Photorhabdus spp. or Xenorhabdus spp., such as Photorhabdus luminescens, Xenorhabdus nematophilus, etc. insecticidal proteins of Azotoxins; toxins produced by animals, such as scorpion toxins, arachnid toxins, wasp toxins and neurotoxins specific to other insects; toxins produced by fungi, such as Streptomycetes toxins, plant lectins, such as pea lectin, barley lectin or snowdrop lectin; agglutinins; proteinase inhibitors, such as trypsin inhibitors, serine protease inhibitors, patatin, cystatin and papain inhibitors; ricin, corn-RIP, abrin, rufin, saporin ribosome-inactivating proteins (RIPs) such as erythrin or bryodin; steroid metabolic enzymes such as 3-hydroxysteroid oxidase, ecdysteroid-UDP-glycosyl-transferase, cholesterol oxidase, ecdysone inhibitors, HMG-COA-reductase, ion channel blockers such as blockers of sodium channels or calcium channels, juvenile hormone esterase, diuretic hormone receptor, stilbene synthase, bibenzyl synthase, chitinase and glucanase.

[0219] In the context of the present invention, delta-endotoxins are understood to mean, for example, Cry1Ab, Cry1Ac, Cry1F, Cry1Fa2, Cry2Ab, Cry3A, Cry3Bb1, or Cry9C, or plant insecticidal proteins (Vip), such as Vip1, Vip2, Vip3, or Vip3A, and also specifically hybrid toxins, truncated toxins, and modified toxins. Hybrid toxins are produced recombinantly by combining different domains of these proteins (see, for example, WO 02 / 15701). Truncated toxins, such as truncated Cry1Ab, are known. In the case of modified toxins, one or more amino acids of the native toxin are replaced. In such amino acid substitutions, preferably a non-naturally occurring protease recognition sequence is inserted into the toxin, for example, in the case of Cry3A055, a cathepsin-G recognition sequence is inserted into the Cry3A toxin (see WO 03 / 018810).

[0220] Examples of such toxins or transgenic plants capable of synthesizing such toxins are disclosed, for example, in EP 0 374 753, WO 93 / 07278, WO 95 / 34656, EP 0 427 529, EP 451 878 and WO 03 / 052073.

[0221] Methods for the preparation of such transgenic plants are generally known to those skilled in the art and are described, for example, in the publications mentioned above. Deoxyribonucleic acids of the CryI type and their preparation are known, for example, from WO 95 / 34656, EP 0 367 474, EP 0 401 979 and WO 90 / 13651.

[0222] The toxins contained in the transgenic plants confer resistance to pests found in a range of insect taxa, but are particularly common in beetles (Coleoptera), two-winged insects (Diptera), and moths (Lepidoptera).

[0223] Transgenic plants containing one or more genes encoding insecticide resistance and expressing one or more toxins are known, and some of them are commercially available. Examples of such plants include YieldGard® (a corn variety expressing the Cry1Ab toxin); YieldGard Rootworm® (a corn variety expressing the Cry3Bb1 toxin); YieldGard Plus® (a corn variety expressing the Cry1Ab and Cry3Bb1 toxins); Starlink® (a corn variety expressing the Cry9C toxin); Herculex I® (a corn variety expressing the Cry1Fa2 toxin and the enzyme phosphinothricin N-acetyltransferase (PAT) for tolerance to the herbicide glufosinate ammonium); NuCOTN 33B® (a cotton variety expressing the Cry1Ac toxin); Bollgard I® (a cotton variety expressing the Cry1Ac toxin); Bollgard II® (a cotton variety expressing Cry1Ac and Cry2Ab toxins); VipCot® (a cotton variety expressing Vip3A and Cry1Ab toxins); NewLeaf® (a potato variety expressing Cry3A toxin); NatureGard®, Agrisure® GT Advantage (GA21 glyphosate tolerance trait), Agrisure® CB Advantage (Bt11 corn borer (CB) trait), and Protecta®.

[0224] Further examples of such transgenic crops are: 1. Bt11 maize, registration number C / FR / 96 / 05 / 10, manufactured by Syngenta Seeds SAS (Chemin de l'Hobit 27, F-31 790 St. Sauveur, France). This genetically modified maize is resistant to attack by the European corn borer (Ostrinia nubilalis and Sesamia nonagrioides) through the transgenic expression of a truncated Cry1Ab toxin. Bt11 maize also genetically expresses the enzyme PAT to confer tolerance to the herbicide glufosinate ammonium.

[0225] 2. Bt176 maize, registration number C / FR / 96 / 05 / 10, manufactured by Syngenta Seeds SAS (Chemin de l'Hobit 27, F-31 790 St. Sauveur, France). This genetically modified maize is resistant to attack by the European corn borer (Ostrinia nubilalis and Sesamia nonagrioides) through transgenic expression of the Cry1Ab toxin. Bt176 maize also genetically expresses the enzyme PAT to confer tolerance to the herbicide glufosinate ammonium.

[0226] 3. MIR604 maize, registration number C / FR / 96 / 05 / 10, manufactured by Syngenta Seeds SAS (Chemin de l'Hobit 27, F-31 790 St. Sauveur, France). This maize has been made insect-resistant by transgenic expression of a modified Cry3A toxin. The toxin is Cry3A055, modified by the insertion of a cathepsin-G-protease recognition sequence. The preparation of such transgenic maize plants is described in WO 03 / 018810.

[0227] 4. MON 863 maize, registration number C / DE / 02 / 9, manufactured by Monsanto Europe SA (270-272 Avenue de Tervuren, B-1150 Brussels, Belgium). MON 863 expresses the Cry3Bb1 toxin and confers resistance to certain Coleoptera insects.

[0228] 5. IPC 531 cotton, registration number C / ES / 96 / 02, manufactured by Monsanto Europe SA (270-272 Avenue de Tervuren, B-1150 Brussels, Belgium).

[0229] 6. 1507 Maize, registration number C / NL / 00 / 10, manufactured by Pioneer Overseas Corporation, Avenue Tedesco, 7 B-1160 Brussels, Belgium. Genetically modified maize for expression of the protein Cry1F for resistance to certain Lepidoptera insects and the protein PAT for resistance to the herbicide glufosinate ammonium.

[0230] 7. NK603 x MON 810 maize, registration number C / GB / 02 / M3 / 03, manufactured by Monsanto Europe SA (270-272 Avenue de Tervuren, B-1150 Brussels, Belgium). This maize consists of a conventionally bred hybrid maize variety by crossing the genetically modified varieties NK603 and MON 810. NK603 x MON 810 maize also genetically expresses the protein CP4 EPSPS, obtained from Agrobacterium sp. strain CP4, which confers resistance to the herbicide Roundup® (containing glyphosate), and the Cry1Ab toxin, obtained from Bacillus thuringiensis subsp. kurstaki, which confers resistance to certain Lepidoptera, including the European corn borer.

[0231] 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).

[0232] The term "crop plant" should also be understood to include crop plants that have been transformed by the use of recombinant DNA technology so as to be able to synthesize antipathogenic substances with selective action, such as, for example, so-called "pathogenicity-related proteins" (PRPs, see, for example, EP-A-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 95 / 33818 and EP-A-0 353 191. Methods for producing such transgenic plants are generally known to those skilled in the art and are described, for example, in the above-mentioned publications.

[0233] Crops can also be improved to increase resistance to fungal (e.g., Fusarium, anthracnose, or Phytophthora), bacterial (e.g., Pseudomonas), or viral (e.g., potato leaf curl virus, tomato spotted wilt virus, cucumber mosaic virus) pathogens.

[0234] Crops also include those that have a high resistance to nematodes, such as the soybean cyst nematode.

[0235] Crops that are tolerant to abiotic stress include those that have increased tolerance to drought, high salinity, high temperature, low temperature, frost, or light due to, for example, expression of NF-YB or other proteins known in the art.

[0236] Antipathogenic substances that can be expressed by such transgenic plants include, for example, ion channel blockers, such as blockers of sodium or calcium channels, e.g., viral KP1, KP4 or KP6 toxins; stilbene synthases; bibenzyl synthases; chitinases; glucanases; so-called "pathogenesis-related proteins" (PRPs; see, for example, EP 0 392 225); antipathogenic substances produced by microorganisms, such as peptide or heterocyclic antibiotics (see, for example, WO 95 / 33818) or proteins or polypeptide factors involved in plant pathogen defense (the so-called "plant disease resistance genes" described in WO 03 / 000906).

[0237] Further fields 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 and textiles), floor coverings and buildings, and in the hygiene sector, in particular the protection of humans, domestic animals and productive livestock from pests of the above-mentioned types.

[0238] 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 a composition of the present invention to the target pest, its habitat, or a surface or substrate by brushing, rolling, spraying, painting, or dipping. By way of example, IRS (indoor residual spray) application of surfaces such as walls, ceilings, or floors is contemplated by the method of the present invention. In another embodiment, it is contemplated to apply such compositions to substrates such as nonwoven or woven materials in the form of (or in a form that can be used to manufacture) netting, clothing, bedding, curtains, and tents.

[0239] In one embodiment, a method for controlling such pests comprises applying a pesticidally effective amount of a composition of the present invention to a target pest, its habitat, or a surface or substrate to provide effective, residual pest control activity to the surface or substrate. Such application may be by brushing, rolling, spraying, painting, or dipping the pesticidal composition of the present invention. For example, IRS application to surfaces such as walls, ceilings, or floors is contemplated by the method of the present invention to provide effective, residual pest control activity to the surface. In another embodiment, the application of such compositions for residual pest control on substrates such as fabric materials in the form of (or in the form that can be used to manufacture) netting, clothing, bedding, curtains, and tents is contemplated.

[0240] The substrates to be treated, including nonwovens, fabrics, or nets, can be made of natural fibers such as cotton, raffia, jute, flax, sisal, hemp, or wool, or synthetic fibers such as polyamide, polyester, polypropylene, or polyacrylonitrile. Polyesters are particularly suitable. Methods for treating textiles are known, for example, from WO 2008 / 151984, WO 2003 / 034823, U.S. Pat. No. 5,631,072, WO 2005 / 64072, WO 2006 / 128870, EP 1 724 392, WO 2005 113 886, or WO 2007 / 090739.

[0241] A further field of use for the compositions according to the invention is that of trunk injection / trunk treatment of all ornamental trees and all kinds of fruit and nut-bearing trees.

[0242] In the field of trunk injection / trunk treatment, the compounds according to the invention are particularly suitable against wood-boring insects of the above-mentioned orders Lepidoptera and Coleoptera, in particular the woodborers listed in Tables A and B below.

[0243] [Table 2]

[0244] [Table 3-1] [Table 3-2] [Table 3-3]

[0245] The present invention may be used to control any insect pest that may be present in turfgrass, including, for example, beetles, caterpillars, fire ants, ground pearls, millipedes, pill bugs, mites, mole crickets, scale insects, mealybugs, mites, boxworms, southern chinch bugs, and grubs. The present invention may also be used to control insect pests in various stages of their life cycle, including eggs, larvae, nymphs, and adults.

[0246] In particular, the present invention relates to the treatment of grubs (Cyclocephala spp. (e.g., masked chafer, C. lurida), Rhizotrogus spp. (e.g., European chafer, R. majalis), Cotinus spp. (e.g., blue swallowtail, C. nitida), Popillia spp. (e.g., Japanese beetle, P. japonica), Phyllophaga spp. (e.g., May / June beetle), Ataenius spp., and the like). spp. (e.g., Black turfgrass ataenius, A. spretulus), Maladera spp. (e.g., red-veined scarab beetle, M. castanea) and Tomarus spp.), cotton bollworms (Margarodes spp.), mole crickets (tawny, southern and brachypterous; Scapteriscus spp., Gryllotalpa africana) and leatherjackets (European crane fly, Tipula The compounds may be used to control insect pests that feed on the roots of turfgrass, including Pseudomonas spp.

[0247] The present invention may also be used to control straw-dwelling insect pests of turfgrass, including cutworms (such as Spodoptera frugiperda and the common armyworm (Pseudaletia unipuncta)), cutworms, weevils (such as Sphenophorus spp., S. venatus verstitus, and S. parvulus) and sod webworms (such as Crambus spp. and the tropical sod webworm, Herpetogramma phaeopteralis).

[0248] The present invention may also be used to control insect pests that live on the ground and feed on turfgrass leaves, including the lesser stink bug (such as the southern kinkbag, Blissus insularis), bermudagrass mite (Eriophyes cynodoniensis), rhodesgrass mealybug (Antonina graminis), two-lined spittlebug (Propsapia bicincta), leafhoppers, cutworms (Noctuidae), and greengrass aphids.

[0249] The present invention may also be used to control other pests of turfgrass, such as the red fire ant (Solenopsis invicta), which creates ant mounds in turfgrass.

[0250] In the hygiene field, the compositions according to the invention are effective against ectoparasites such as hard ticks, soft ticks, scabies mites, chiggers, flies (stable flies and licking flies), parasitic fly larvae, lice, pubic lice, biting lice and fleas.

[0251] Examples of such parasites are: Among the Anoplurida, the genera Haematopinus, Linognathus, Pediculus, Phtirus, and Solenopotes are included.

[0252] From the order Mallophagida, the genera Trimenopon, Menopon, Trinoton, Bovicola, Werneckiella, Lepikentron, Damalina, Trichodectes and Felicola.

[0253] Among the order Diptera and its suborders Nematocerina and Brachycerina, for example, the genera Aedes, Anopheles, Culex, Simulium, Eusimulium, Phlebotomus, Lutzomyia, Culicoides, Chrysops, Hybomitra, Atylotus, Tabanus, Haematopota, spp.), Philipomyia spp., Braula spp., Musca spp., Hydrotaea spp., Stomoxys spp., Haematobia spp., Morellia spp., Fannia spp., Glossina spp., Calliphora spp., Lucilia spp., Chrysomyia spp., Wohlfahrtia spp., Sarcophaga spp.), sheep flies (Oestrus spp.), cow flies (Hypoderma spp.), bot flies (Gasterophilus spp.), hood flies (Hippobosca spp.), deer flies (Lipoptena spp.) and sheep hood flies (Melophagus spp.).

[0254] Among the Siphonapterida, for example, the human flea genus (Pulex spp.), the dog flea genus (Ctenocephalides spp.), the mouse flea genus (Xenopsylla spp.), and the long flea genus (Ceratophyllus spp.).

[0255] From the order Heteropterida, for example, Cimex spp., Triatoma spp., Rhodnius spp., and Panstrongylus spp.

[0256] From the order Blattaria, for example, the Asian cockroach (Blatta orientalis), the American cockroach (Periplaneta americana), the German cockroach (Blattela germanica) and the genus Supella.

[0257] Among the subclass Acaria (Acarida) and the suborder Metastigmata and Mesostigmata, for example, the genera Argas spp., Ornithodorus spp., Otobius spp., Ixodes spp., Amblyomma spp., Boophilus spp., Dermacentor spp., Haemophysalis spp., Hyalomma spp., Rhipicephalus spp., Dermanyssus spp., Raillietia spp. spp.), Pneumonyssus spp., Sternostoma spp. and Varroa spp.

[0258] From the orders Actinedida (Prostigmata) and Acaridida (Astigmata), for example, the genera Acarapis, Cheyletiella, Ornithocheyletia, Myobia, Psorergates, Demodex, Trombicula, Listrophorus, Acarus, Tyrophagus, Caloglyphus, Hypodectes spp.), Pterolichus spp., Psoroptes spp., Chorioptes spp., Otodectes spp., Sarcoptes spp., Notoedres spp., Knemidocoptes spp., Cytodites spp. and Laminosioptes spp.

[0259] The compositions according to the invention are also suitable for protecting against insect infestation in materials such as wood, textiles, plastics, adhesives, glues, paints, paper and cardboard, leather, floor coverings and building materials.

[0260] The compositions according to the invention can be used, for example, against the following pests: European house borer (Hylotrupes bajulus), Chlorophorus pilosis, Anobium punctatum, Xestobium rufovillosum, Ptilinuspecticornis, Dendrobium pertinex, pine wood beetle (Ernobius mollis), longhorn beetle (Priobium carpini), flat-headed beetle (Lyctus brunneus), African flat-headed beetle (Lyctus africanus), American flat-headed beetle (Lyctus planicollis), oak flat-headed beetle (Lyctus linearis, Lyctus pubescens, Trogoxylon aequale, Minthesrugicollis, Xyleborus spec., Tryptodendron spec., Apate monachus, Bostrychus capucins, Heterobostrychus brunneus, Sinoxylon spec.and Dinoderus minutus, as well as hymenopteran insects such as Sirex juvencus, Urocerus gigas, Urocerus gigas taignus, and Urocerus augur, as well as Kalotermes flavicollis, Cryptotermes brevis, Heterotermes indicola, Reticulitermes flavipes, Reticulitermes santonensis, Reticulitermes lucifugus, and other insects of the genus Kalotermes. Termites such as Mastotermes darwiniensis, Zootermopsis nevadensis, and Coptotermes formosanus, as well as wood mites such as Lepisma saccharina.

[0261] Although the compounds of the present invention can be used as pesticides in their native form, they are generally formulated into compositions using formulation aids such as carriers, solvents, and surfactants in various ways. The formulations can be in various physical forms, such as dustable powders, gels, wettable powders, water-dispersible granules, water-dispersible tablets, effervescent pellets, emulsifiable concentrates, microemulsifiable concentrates, oil-in-water emulsions, oil-based flowables, aqueous dispersions, oil-based dispersions, suspoemulsions, capsule suspensions, emulsifiable granules, soluble liquids, water-soluble concentrates (containing water or a water-miscible organic solvent as a carrier), impregnated polymer films, or other forms known from, for example, the Manual on Development and Use of FAO and WHO Specifications for Pesticides, United Nations, First Edition, Second Revision (2010). Such formulations can be used directly or diluted before use. Dilution can be carried out, for example, with water, liquid fertilizers, trace elements, biological materials, oils, or solvents.

[0262] The formulations can be prepared by mixing the active ingredient with formulation aids to obtain a composition in the form of, for example, finely divided solids, granules, solutions, dispersions, or emulsions. The active ingredient can also be formulated with other adjuvants, such as finely divided solids, mineral oil, vegetable or animal oil, modified vegetable or animal oil, organic solvent, water, surfactant, or combinations thereof.

[0263] The active ingredient can also be contained in extremely fine microcapsules. Microcapsules contain the active ingredient in a porous carrier, allowing the active ingredient to be released into the environment in controlled amounts (e.g., sustained release). Microcapsules typically have diameters of 0.1 to 500 microns. They contain the active ingredient in an amount of about 25 to 95% by weight of the capsule. The active ingredient can be in the form of a bulk solid, fine particles in a solid or liquid dispersion, or a suitable solution. The encapsulating membrane can comprise, for example, natural or synthetic rubber, cellulose, styrene / butadiene copolymer, polyacrylonitrile, polyacrylate, polyester, polyamide, polyurea, polyurethane, or chemically modified polymers, and starch xanthate, or other polymers known to those skilled in the art. Alternatively, extremely fine microcapsules can be formed containing the active ingredient in the form of fine particles in a base solid matrix, but the microcapsules themselves are not encapsulated.

[0264] The formulation auxiliaries suitable for preparing the compositions according to the invention are known per se. Examples of liquid carriers include water, toluene, xylene, petroleum ether, vegetable oils, acetone, methyl ethyl ketone, cyclohexanone, acid anhydrides, acetonitrile, acetophenone, amyl acetate, 2-butanone, butylene carbonate, chlorobenzene, cyclohexane, cyclohexanol, alkyl esters of acetic acid, diacetone alcohol, 1,2-dichloropropane, diethanolamine, p-diethylbenzene, diethylene glycol, diethylene glycol abietic acid, diethylene glycol butyl ether, diethylene glycol ethyl ether, diethylene glycol methyl ether, N,N-dimethylformamide, dimethyl sulfoxide, 1,4-dioxane, dipropylene glycol, dipropylene glycol methyl ether, dipropylene glycol dibenzoate, diproxitol, alkylpyrrolidone, ethyl acetate, 2-ethylhexanol, ethylene carbonate, 1,1,1-Trichloroethane, 2-heptanone, α-pinene, d-limonene, ethyl lactate, ethylene glycol, ethylene glycol butyl ether, ethylene glycol methyl ether, γ-butyrolactone, glycerol, glycerol acetate, glycerol diacetate, glycerol triacetate, hexadecane, hexylene glycol, isoamyl acetate, isobornyl acetate, isooctane, isophorone, isopropyl benzene, isopropyl myristate, lactic acid, laurylamine, mesityl oxide, methoxypropanol, methyl isoamyl ketone, methyl isobutyl ketone, methyl laurate, methyl octanoate, methyl oleate, methylene chloride, m-xylene, n-hexane, n-octylamine, octadecanoic acid, octylamine acetate Examples of suitable solvents include ethanol, 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 high molecular weight alcohols such as amyl alcohol, tetrahydrofurfuryl alcohol, hexanol, octanol, ethylene glycol, propylene glycol, glycerol, and N-methyl-2-pyrrolidone.

[0265] Suitable solid carriers are, for example, talc, titanium dioxide, pyrophyllite clay, silica, attapulgite clay, kiesl lager, limestone, calcium carbonate, bentonite, calcium montmorillonite, cotton hulls, wheat flour, soybean flour, pumice, wood flour, ground walnut shells, lignin, and similar materials.

[0266] Many surface-active substances can be used advantageously in both solid and liquid formulations, especially in formulations that can be diluted with a carrier before use. The surface-active substances can be anionic, cationic, nonionic, or polymeric, and they can be used as emulsifying agents, wetting agents, or suspending agents, or for other purposes. Typical surface-active substances include, for example, salts of alkyl sulfates such as diethanolammonium lauryl sulfate; salts of alkylarylsulfonates such as calcium dodecylbenzenesulfonate; alkylphenol / alkylene oxide adducts such as nonylphenol ethoxylate; alcohol / alkylene oxide adducts such as tridecyl alcohol ethoxylate; soaps such as sodium stearate; salts of alkylnaphthalenesulfonates such as sodium dibutylnaphthalenesulfonate; dialkyl esters of sulfosuccinates such as sodium di(2-ethylhexyl)sulfosuccinate; sorbitol esters such as sorbitol oleate; quaternary amines such as lauryltrimethylammonium chloride, polyethylene glycol esters of fatty acids such as polyethylene glycol stearate; block copolymers of ethylene oxide and propylene oxide; and salts of mono- and di-alkyl phosphate esters; and further substances described, for example, in McCutcheon's Detergents and Emulsifiers Annual, MC Publishing Corp., Ridgewood, New Jersey (1981).

[0267] Additional adjuvants that may be used in the pest control formulations include crystallization inhibitors, viscosity modifiers, suspending agents, dyes, antioxidants, foaming agents, light absorbers, mixing aids, antifoaming agents, complexing agents, neutralizing or pH adjusting and buffering agents, corrosion inhibitors, fragrances, wetting agents, uptake enhancers, trace elements, plasticizers, glidants, lubricants, dispersants, thickeners, antifreeze agents, fungicides and liquid and solid fertilizers.

[0268] The compositions of the present invention may contain additives including vegetable or animal oils, mineral oils, alkyl esters of such oils, or mixtures of such oils and oil derivatives. The amount of oil additive in the compositions of the present invention is generally 0.01 to 10% based on the mixture to be applied. For example, the oil additive can be added to the spray tank at the desired concentration after the spray mixture has been prepared. Preferred oil additives include mineral oils or vegetable oils such as rapeseed oil, olive oil, or sunflower oil, emulsified vegetable oils, alkyl esters of vegetable oils such as methyl derivatives, or animal oils such as fish oil or beef tallow. Preferred oil additives are C8 to C 22 Alkyl esters of fatty acids, especially C 12 ~C 18 Methyl derivatives of fatty acids, including, for example, the methyl esters of lauric acid, palmitic acid, and oleic acid (methyl laurate, methyl palmitate, and methyl oleate, respectively). Many oil derivatives are listed in the Compendium of Herbicide Adjuvants, 10 th Edition, Southern Illinois University, 2010.

[0269] The compositions of the present invention generally comprise 0.1 to 99% by weight, especially 0.1 to 95% by weight, of the compounds of the present invention and 1 to 99.9% by weight of formulation aids, which preferably include 0 to 25% by weight of surfactants. Although commercial products may preferably be formulated as concentrates, end users will typically utilize diluted formulations.

[0270] The application rates vary within wide limits and depend on the nature of the soil, the method of application, the crop plant, the pests to be controlled, the prevailing weather conditions and other factors which depend on the method, time of application and the target crop. As a general guideline, the compounds may be applied in amounts of 1 to 2000 l / ha, especially 10 to 1000 l / ha.

[0271] A preferred formulation may have the following composition (by weight): Emulsifiable concentrate: Active ingredient: 1-95%, preferably 60-90% Surface active agent: 1 to 30%, preferably 5 to 20% Liquid carrier: 1 to 80%, preferably 1 to 35%

[0272] Powder: Active ingredient: 0.1 to 10%, preferably 0.1 to 5% Solid carrier: 99.9 to 90%, preferably 99.9 to 99%

[0273] Suspension concentrate: Active ingredient: 5-75%, preferably 10-50% Water: 94-24%, preferably 88-30% Surface active agent: 1 to 40%, preferably 2 to 30%

[0274] Wettable powder: Active ingredient: 0.5 to 90%, preferably 1 to 80% Surface active agent: 0.5 to 20%, preferably 1 to 15% Solid carrier: 5 to 95%, preferably 15 to 90%

[0275] Granules: Active ingredient: 0.1 to 30%, preferably 0.1 to 15% Solid carrier: 99.5 to 70%, preferably 97 to 85%

[0276] The following examples further illustrate, but do not limit, the present invention.

[0277] [Table 4]

[0278] The complex is thoroughly mixed with the adjuvant and the mixture is thoroughly ground in a suitable mill to obtain a wettable powder that can be diluted with water to obtain a suspension of the desired concentration.

[0279] [Table 5]

[0280] The complex is thoroughly mixed with the adjuvant and the mixture is thoroughly ground in a suitable mill to obtain a powder that can be used directly as a seed treatment.

[0281] [Table 6]

[0282] Emulsions of any required dilution that can be used for plant protection are available from this concentrate by dilution with water.

[0283] [Table 7]

[0284] Ready-to-use dusts are obtained by mixing the complex with a carrier and grinding the mixture in a suitable mill. Such powders can also be used as dry seed dressings.

[0285] [Table 8]

[0286] The compound is mixed and ground with the adjuvant, the mixture is moistened with water, the mixture is extruded and then dried in a stream of air.

[0287] [Table 9]

[0288] In a mixer, the finely ground composite is applied uniformly to kaolin moistened with polyethylene glycol, resulting in coated, dust-free granules.

[0289] [Table 10]

[0290] The finely ground composite is thoroughly mixed with adjuvants to give a suspension concentrate which can be diluted with water to give a suspension of any desired dilution, and such dilutions can be used to treat and protect living plants and plant propagation material against microbial infestation by spraying, pouring or dipping.

[0291] [Table 11]

[0292] The finely ground composite is thoroughly mixed with adjuvants to give a suspension concentrate which can be diluted with water to give a suspension of any desired dilution, and such dilutions can be used to treat and protect living plants and plant propagation material against microbial infestation by spraying, pouring or dipping.

[0293] slow-release capsule suspension 28 parts of the composite are mixed with 2 parts aromatic solvent and 7 parts toluene diisocyanate / polymethylene-polyphenylisocyanate (8:1) mixture. This mixture is emulsified in a mixture of 1.2 parts polyvinyl alcohol, 0.05 parts defoamer, and 51.6 parts water until the desired particle size is achieved. A mixture of 2.8 parts 1,6-diaminohexane in 5.3 parts water is added to this emulsion. The mixture is stirred until the polymerization reaction is complete. The resulting capsule suspension is stabilized by adding 0.25 parts thickener and 3 parts dispersant. The capsule suspension formulation contains 28% active ingredient. The diameter of the medium-sized capsules is 8 to 15 microns. The resulting formulation is applied to seeds as an aqueous suspension in an apparatus suitable for this purpose.

[0294] 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 (EO), emulsions, oil-in-water (EW), microemulsions (ME), oil dispersions (OD), oil-miscible flowables (OF), oil-miscible liquids (OL), soluble concentrates (SL), ultra-low volume suspensions (SU), ultra-low volume liquids (UL), technical concentrates (TK), dispersible concentrates (DC), wettable powders (WP), soluble granules (SG) or any technically preferred formulation in combination with agriculturally acceptable adjuvants. [Example]

[0295] Preparation example: "Mp" means melting point (°C). The free radical represents a methyl group. 1 H NMR measurements were recorded on a Brucker 400 MHz spectrometer and chemical shifts are given in ppm relative to a TMS standard. Spectra were run in deuterated solvents as specified. Compounds were characterized using one of the following LCMS methods. The unique LCMS values ​​obtained for each compound consist of the retention time ("Rt", reported in minutes) and the observed molecular ion (M+H). + or (MH) - It was.

[0296] LCMS and GCMS methods: Method 1: Spectra were recorded on a Waters mass spectrometer (ZQ single quadrupole mass spectrometer) equipped with an electrospray source (polarity: positive or negative ion, capillary: 3.00 kV, cone range: 30-60 V, extractor: 2.00 V, source temperature: 150 °C, desolvation temperature: 350 °C, cone gas flow: 0 L / hr, desolvation gas flow: 650 L / hr, mass range: 100-900 Da) and a Waters Acquity UPLC: binary pump, heated column compartment, and diode-array detector. Solvent degasser, binary pump, heated column compartment, and diode-array detector. Column: Waters UPLC HSS T3, 1.8 μm, 30 × 2.1 mm; Temperature: 60 °C; DAD wavelength range (nm): 210–500; Solvent gradient: A = water + 5% MeOH + 0.05% HCOOH, B = acetonitrile + 0.05% HCOOH; Gradient: 0% B for 0 min, 100% A; 1.2–1.5 min, 100% B; Flow (ml / min) 0.85.

[0297] Method 2: Spectra were recorded on a Waters mass spectrometer (SQD or ZQ single quadrupole mass spectrometer) equipped with an electrospray source (polarity: positive or negative, capillary: 3.00 kV, cone range: 30-60 V, extractor: 2.00 V, source temperature: 150 °C, desolvation temperature: 350 °C, cone gas flow: 0 L / hr, desolvation gas flow: 650 L / hr, mass range: 100-900 Da) and a Waters Acquity UPLC: binary pump, heated column compartment, and diode-array detector. Solvent degasser, binary pump, heated column compartment, and diode-array detector. Column: Waters UPLC HSS T3, 1.8 μm, 30 × 2.1 mm; Temperature: 60 °C; DAD wavelength range (nm): 210–500; Solvent gradient: A = water + 5% MeOH + 0.05% HCOOH, B = acetonitrile + 0.05% HCOOH; Gradient: 0% B for 0 min, 100% A; 100% B for 2.7–3.0 min; Flow (ml / min) 0.85.

[0298] Method 3: Spectra were recorded on an Agilent Technologies mass spectrometer (6410 Triple Quadruple Mass Spectrometer) equipped with an electrospray source (polarity: anode and cathode switched, capillary: 4.00 kV, fragmentor: 100.00 V, gas temperature: 350 °C, gas flow: 11 L / min, nebulizer gas: 45 psi, mass range: 110-1000 Da, DAD wavelength range: 210-400 nm). Column: KINETEX EVO C18, 50 mm length, 4.6 mm diameter, 2.6 μm particle size. Column oven temperature: 40 °C. Solvent gradient: A = water + 0.1% formic acid: acetonitrile (95:5 v / v). B = acetonitrile + 0.1% formic acid. Gradient = 0 min 90% A, 10% B; 0.9–1.8 min 0% A, 100% B; 2.2–2.5 min 90% A, 10% B. Flow rate 1.8 mL / min.

[0299] Method 4: Spectra were recorded on a Waters mass spectrometer (Acquity SDS mass spectrometer) equipped with the following: electrospray source (polarity: anode and cathode switched, capillary: 3.00 kV, cone voltage: 41.00 V, source temperature: 150 °C, desolvation gas flow: 1000 L / Hr, desolvation temperature: 500 °C, gas flow @ cone: 50 L / hr, mass range: 110-800 Da, PDA wavelength range: 210-400 nm. Column: Acquity UPLC HSS T3 C18, 30 mm length, 2.1 mm diameter, 1.8 μm particle size. Column oven temperature: 40 °C. Solvent gradient: A = water + 0.1% formic acid:acetonitrile (95:5 v / v). B = acetonitrile + 0.05% formic acid. Gradient = 90% A, 10% B for 0 min; 50% A, 50% B for 0.2 min; 0.7-1.3 min. A, 100% B; 1.4–1.6 min 90% A, 10% B. Flow rate 0.8 mL / min.

[0300] Method 5: Spectra were recorded on a Waters mass spectrometer (SQ Detector 2 single quadrupole mass spectrometer) equipped with an electrospray source (polarity: positive or negative ion, capillary voltage: 2.50 kV, cone voltage: 41 V, extractor voltage: 3.00 V, source temperature: 150 °C, desolvation temperature: 500 °C, cone gas flow: 50 L / hr, desolvation gas flow: 1000 L / hr, mass range: 100–600 Da) and a Waters Acquity UPLC with a quaternary pump, heated column compartment, and diode-array detector. The column used was a Waters UPLC HSS T3, 1.8 μm, 30 × 2.1 mm. Column oven temperature: 40 °C. DAD wavelength range (nm): 200–350. Solvent gradient: A = water + 5% acetonitrile + 0.05% HCOOH, B = acetonitrile + 0.05% HCOOH. Gradient: 0 min 90% A, 10% B; 0.2 min 50% A, 50% B; 0.7–1.3 min 0% A, 100% B; 1.4–1.6 min 90% A, 10% B. Flow rate: 0.6 mL / min.

[0301] Preparation of Examples of Compounds of Formula (I): Example P1: Preparation of 2-[[5-(cyclopropylmethylsulfonyl)-6-[7-methyl-3-(trifluoromethyl)imidazo[4,5-c]pyridazin-6-yl]-3-pyridyl]oxy]-2-methyl-propanenitrile (compound P1) [ka] Step 1: Preparation of 2-[[5-(cyclopropylmethylsulfanyl)-6-[7-methyl-3-(trifluoromethyl)imidazo[4,5-c]pyridazin-6-yl]-3-pyridyl]oxy]-2-methyl-propanamide (compound I8) [ka] 5-(Cyclopropylmethylsulfanyl)-6-[7-methyl-3-(trifluoromethyl)imidazo[4,5-c]pyridazin-6-yl]pyridin-3-ol (compound I7, prepared similarly to step 1 of Example P2) was treated under the same conditions as described in step 2 of Example P2 to give the desired compound. LCMS (method 5): m / z467[M+H] + ;Retention time: 1.13 minutes.

[0302] Step 2: Preparation of 2-[[5-(cyclopropylmethylsulfanyl)-6-[7-methyl-3-(trifluoromethyl)imidazo[4,5-c]pyridazin-6-yl]-3-pyridyl]oxy]-2-methyl-propanenitrile (compound I9) [ka] 2-[[5-(Cyclopropylmethylsulfanyl)-6-[7-methyl-3-(trifluoromethyl)imidazo[4,5-c]pyridazin-6-yl]-3-pyridyl]oxy]-2-methyl-propanamide (compound I8 prepared as described above) was treated under the same conditions as described in Step 3 of Example P2 to give the desired compound. LCMS (Method 5): m / z449[M+H] + ;Retention time: 1.21 minutes.

[0303] Step 3: Preparation of 2-[[5-(cyclopropylmethylsulfonyl)-6-[7-methyl-3-(trifluoromethyl)imidazo[4,5-c]pyridazin-6-yl]-3-pyridyl]oxy]-2-methyl-propanenitrile (compound P1) [ka] 2-[[5-(Cyclopropylmethylsulfanyl)-6-[7-methyl-3-(trifluoromethyl)imidazo[4,5-c]pyridazin-6-yl]-3-pyridyl]oxy]-2-methyl-propanenitrile (compound I9 prepared as described above) was treated under the same conditions as described in Step 4 of Example P2 to give the desired compound. LCMS (Method 5): m / z481[M+H] + ;Retention time: 1.17 minutes.

[0304] Example P2: Preparation of 2-[[5-ethylsulfonyl-6-[7-methyl-3-(trifluoromethyl)imidazo[4,5-c]pyridazin-6-yl]-3-pyridyl]oxy]-2-methyl-propanenitrile (compound P2) [ka] Step 1: Preparation of 5-ethylsulfanyl-6-[7-methyl-3-(trifluoromethyl)imidazo[4,5-c]pyridazin-6-yl]pyridin-3-ol (compound I1) [ka] Cesium carbonate (19.5 g, 59.8 mmol, 2.50 equiv.) and (E)-benzaldehyde oxime (3.4 mL, 31.1 mmol, 1.30 equiv.) were added to a solution of 6-(5-bromo-3-ethylsulfanyl-2-pyridyl)-7-methyl-3-(trifluoromethyl)imidazo[4,5-c]pyridazine (prepared according to WO2016059145) (10.0 g, 23.9 mmol) in acetonitrile (240 mL). The resulting suspension was stirred at 50 °C for 42 h. After cooling to room temperature, the reaction mixture was concentrated under reduced pressure, and the crude residue was partitioned between ethyl acetate and water. The pH of the aqueous phase was adjusted to 1-2 by the addition of 1 N hydrochloric acid solution. The aqueous phase was extracted twice with ethyl acetate, and the combined organic phases were dried over sodium sulfate, filtered, and concentrated. Purification of the crude material by flash chromatography on silica gel (0-10% methanol in dichloromethane) gave the desired product as a yellow solid (6.90 g, 19.0 mmol). 1 H NMR (400 MHz, dimethyl sulfoxide-d6) δ ppm 1.25 (t, J = 7.34 Hz, 3H) 2.99 (q, J = 7.34 Hz, 2H) 4.13 (s, 3H) 7.38 (d, J = 2.20 Hz, 1H) 8.17 (d, J = 2.20 Hz, 1H) 8.55 (s, 1H) 10.94 (s, 1H).

[0305] Step 2: Preparation of 2-[[5-ethylsulfanyl-6-[7-methyl-3-(trifluoromethyl)imidazo[4,5-c]pyridazin-6-yl]-3-pyridyl]oxy]-2-methyl-propanamide (compound I2) [ka] Cesium carbonate (303 mg, 0.93 mmol, 1.10 equiv.) was added to a solution of 5-ethylsulfanyl-6-[7-methyl-3-(trifluoromethyl)imidazo[4,5-c]pyridazin-6-yl]pyridin-3-ol (compound I1, prepared as described above) (300 mg, 0.84 mmol) in acetonitrile (8.4 mL). The resulting suspension was stirred for 5 minutes, after which 2-bromo-2-methyl-propanamide (294 mg, 1.77 mmol, 2.10 equiv.) was added, and the reaction mixture was heated and stirred at 70° C. overnight. After cooling to room temperature, the reaction mixture was concentrated under reduced pressure, and the crude residue was partitioned between ethyl acetate and water, and the pH of the aqueous phase was adjusted to 1 by the addition of 1 N hydrochloric acid solution. The aqueous phase was extracted three times with ethyl acetate and once with dichloromethane, and the combined organic phases were dried over sodium sulfate, filtered, and concentrated. Purification of the crude material by flash chromatography on silica gel (0-10% methanol in dichloromethane) afforded the desired product as a yellow solid (156 mg, 0.56 mmol). 1 H NMR (400 MHz, dimethyl sulfoxide-d6) δ ppm 1.26 (t, J = 7.34 Hz, 3H), 1.60 (s, 6H), 2.96 (q, J = 7.34 Hz, 2H), 4.15 (s, 3H), 7.30 (s broad, 1H), 7.41 (d, J = 2.20 Hz, 1H), 7.49 (m, 1H), 8.23 ​​(d, J = 2.20 Hz, 1H), 8.69 (s, 1H).

[0306] Step 3: Preparation of 2-[[5-ethylsulfanyl-6-[7-methyl-3-(trifluoromethyl)imidazo[4,5-c]pyridazin-6-yl]-3-pyridyl]oxy]-2-methyl-propanenitrile (compound I3) [ka] Trifluoroacetic anhydride (182 μL, 1.30 mmol, 3.00 equiv.) was added to a solution of 2-[[5-ethylsulfanyl-6-[7-methyl-3-(trifluoromethyl)imidazo[4,5-c]pyridazin-6-yl]-3-pyridyl]oxy]-2-methyl-propanamide (compound I2, prepared as described above) (317 mg, 0.43 mmol) in dichloromethane (4.30 mL) and triethylamine (243 μL, 1.73 mmol, 4.00 equiv.) at 0° C. After stirring overnight at room temperature, additional trifluoroacetic anhydride (182 μL, 1.30 mmol, 3.00 equiv.) and triethylamine (243 μL, 1.73 mmol, 4.00 equiv.) were added, and the reaction mixture was further stirred at room temperature for 2 hours. The reaction mixture was carefully quenched by the addition of methanol followed by saturated sodium bicarbonate solution. The aqueous phase was extracted twice with dichloromethane, and the combined organic layers were dried over sodium sulfate, filtered, and concentrated. The crude material was purified by flash chromatography on silica gel (0-10% methanol in dichloromethane) to give the desired product as a yellow oil (156 mg, 0.37 mmol). 1 H NMR (400 MHz, chloroform-d) δ ppm 1.42 (t, J = 7.34 Hz, 3H) 1.88 (s, 6H) 3.03 (q, J = 7.34 Hz, 2H) 4.31 (s, 3H) 7.72 (d, J = 2.57 Hz, 1H) 8.26 (s, 1H) 8.39 (d, J = 2.57 Hz, 1H).

[0307] Step 4: Preparation of 2-[[5-ethylsulfonyl-6-[7-methyl-3-(trifluoromethyl)imidazo[4,5-c]pyridazin-6-yl]-3-pyridyl]oxy]-2-methyl-propanenitrile (compound P2) [ka] To a solution of 2-[[5-ethylsulfanyl-6-[7-methyl-3-(trifluoromethyl)imidazo[4,5-c]pyridazin-6-yl]-3-pyridyl]oxy]-2-methyl-propanenitrile (compound I3, prepared as described above) (156 mg, 0.37 mmol) in dichloromethane (3.12 mL) at 0 °C, 3-chloroperbenzoic acid (191.2 mg, 0.776 mmol) was added, and the mixture was stirred at 0 °C for 30 minutes and then at room temperature overnight. The reaction mixture was quenched with an aqueous solution of sodium hydroxide (1 N, 5 mL) and sodium thiosulfate (5 mL). The aqueous layer was extracted three times with dichloromethane, and the combined organic layers were washed twice with 1 N aqueous sodium hydroxide, brine, dried over sodium sulfate, filtered, and evaporated under reduced pressure. The crude material was triturated in cyclohexane, and the precipitate formed was filtered and dried to give the desired product. Alternatively, the crude material may be purified by flash chromatography on silica gel. LCMS (method 1): m / z455[M+H] + ;Retention time: 0.98 min.

[0308] Example P3: Preparation of 2-[[5-ethylsulfonyl-6-[3-methyl-6-(trifluoromethyl)imidazo[4,5-b]pyridin-2-yl]-3-pyridyl]oxy]-2-methyl-propanenitrile (compound P3) [ka] Step 1: Preparation of 5-ethylsulfanyl-6-[3-methyl-6-(trifluoromethyl)imidazo[4,5-b]pyridin-2-yl]pyridin-3-ol (compound I4) [ka] Cesium carbonate (12.9 g, 39.5 mmol, 2.20 equiv.) and (E)-benzaldehyde oxime (2.55 mL, 23.4 mmol, 1.30 equiv.) were added to a solution of 2-(5-bromo-3-ethylsulfanyl-2-pyridyl)-3-methyl-6-(trifluoromethyl)imidazo[4,5-b]pyridine (CAS 1421955-74-9) (7.50 g, 18.0 mmol) in N,N-dimethylformamide (36 mL). The resulting suspension was stirred at 80 °C overnight. After cooling to room temperature, the reaction mixture was diluted with dichloromethane (500 mL), the organic phase was washed with water (3 × 200 mL), and the pH of the aqueous phase was adjusted to 1-2 by the addition of 1 N hydrochloric acid solution. The aqueous phase was extracted with dichloromethane (5 x 300 mL), and the combined organic phases were dried over sodium sulfate, filtered, and concentrated. Purification of the crude material by flash chromatography on silica gel (ethyl acetate in cyclohexane) gave the desired product (5.80 g, 16.4 mmol). LCMS (method 1): m / z355[M+H] + ;Retention time: 0.94 min.

[0309] Step 2: Preparation of 2-[[5-ethylsulfanyl-6-[3-methyl-6-(trifluoromethyl)imidazo[4,5-b]pyridin-2-yl]-3-pyridyl]oxy]acetonitrile (compound I5) [ka] Potassium carbonate (1.21 g, 8.47 mmol, 1.50 equiv.) followed by bromoacetonitrile (608 μL, 8.47 mmol, 1.50 equiv.) was added to a solution of 5-ethylsulfanyl-6-[3-methyl-6-(trifluoromethyl)imidazo[4,5-b]pyridin-2-yl]pyridin-3-ol (compound I4, prepared as described above) (2.00 g, 5.64 mmol) in N,N-dimethylformamide (40 mL) at room temperature under an argon atmosphere. After stirring for 5 hours, the reaction mixture was poured into water (300 mL), and the aqueous phase was extracted twice with ethyl acetate (300 mL). The combined organic phases were washed with water (3 × 200 mL), dried over sodium sulfate, filtered, and concentrated. The crude material was purified by chromatography on silica gel (ethyl acetate in cyclohexane) to give the desired compound as a yellow solid (2.08 g, 5.28 mmol). LCMS (method 1): m / z394[M+H] + ;Retention time: 1.01 minutes.

[0310] Step 3: Preparation of 2-[[5-ethylsulfanyl-6-[3-methyl-6-(trifluoromethyl)imidazo[4,5-b]pyridin-2-yl]-3-pyridyl]oxy]-2-methyl-propanenitrile (compound I6) [ka] A 1 M solution of lithium hexamethyldisilazane in tetrahydrofuran (15.8 mL, 15.8 mmol, 3.00 equiv.) was added dropwise via a dropping funnel to a solution of 2-[[5-ethylsulfanyl-6-[3-methyl-6-(trifluoromethyl)imidazo[4,5-b]pyridin-2-yl]-3-pyridyl]oxy]acetonitrile (compound I5, prepared as described above) (2.07 g, 5.26 mmol) and methyl iodide (1.31 mL, 21.0 mmol, 4.00 equiv.) in tetrahydrofuran (32 mL) cooled to 0 °C. After the addition was complete, the reaction mixture was stirred in an ice bath for 1 h, then allowed to warm to room temperature and stirred overnight. The reaction mixture was quenched by pouring into saturated aqueous sodium bicarbonate at 0 °C (50 mL). The aqueous phase was extracted with ethyl acetate (2 × 50 mL). The combined organic phases were dried over sodium sulfate, filtered and evaporated. The crude material was purified by flash chromatography on silica gel (ethyl acetate in cyclohexane) to give the desired compound (700 mg, 1.66 mmol). LCMS (method 1): m / z422[M+H] + ;Retention time: 1.11 minutes.

[0311] Step 4: Preparation of 2-[[5-ethylsulfonyl-6-[3-methyl-6-(trifluoromethyl)imidazo[4,5-b]pyridin-2-yl]-3-pyridyl]oxy]-2-methyl-propanenitrile (compound P3) [ka] 2-[[5-Ethylsulfanyl-6-[3-methyl-6-(trifluoromethyl)imidazo[4,5-b]pyridin-2-yl]-3-pyridyl]oxy]-2-methyl-propanenitrile (compound I6 prepared as described above) was treated under the same conditions as described in step 4 of example P2 to give the desired compound. LCMS (method 1): m / z454[M+H] + ;Retention time: 1.05 minutes.

[0312] Example P5: Preparation of 2-[[5-ethylsulfonyl-6-[5-methoxy-3-methyl-4-oxo-6-(trifluoromethyl)imidazo[4,5-c]pyridin-2-yl]-3-pyridyl]oxy]-2-methyl-propanenitrile (compound P5) [ka] 2-[[5-Ethylsulfanyl-6-[5-methoxy-3-methyl-4-oxo-6-(trifluoromethyl)imidazo[4,5-c]pyridin-2-yl]-3-pyridyl]oxy]-2-methyl-propanenitrile (compound I10) was treated under the same conditions as described in step 4 of example P2 to give the desired compound. LCMS (method 5): m / z500[M+H] + ;Retention time: 1.02 minutes.

[0313] Example P4: Preparation of 2-[[5-ethylsulfonyl-2-methyl-6-[3-methyl-6-(trifluoromethyl)imidazo[4,5-b]pyridin-2-yl]-3-pyridyl]oxy]-2-methyl-propanenitrile (compound P4) [ka] Step 1: Preparation of 5-ethylsulfanyl-2-iodo-6-[3-methyl-6-(trifluoromethyl)imidazo[4,5-b]pyridin-2-yl]pyridin-3-ol (compound I13) [ka] Molecular iodine (8.69 g, 34.2 mmol) was added in several portions to a mixture of 5-ethylsulfanyl-6-[3-methyl-6-(trifluoromethyl)imidazo[4,5-b]pyridin-2-yl]pyridin-3-ol (compound I4, prepared as described in Step 1 of Example P3) (10.1 g, 28.5 mmol) and sodium carbonate (6.34 g, 59.8 mmol) in water (85.5 mL) and acetonitrile (85.5 mL) at room temperature under an argon atmosphere. After stirring for 3 hours, the reaction mixture was quenched with 10% w / w aqueous sodium thiosulfate solution and then extracted with ethyl acetate. The combined organic phases were washed with brine, dried over sodium sulfate, filtered, and concentrated to give the desired product. This material was used directly in the next step. LCMS (method 1): m / z481[M+H] + ;Retention time: 1.06 minutes.

[0314] Step 2: Preparation of 5-ethylsulfanyl-2-methyl-6-[3-methyl-6-(trifluoromethyl)imidazo[4,5-b]pyridin-2-yl]pyridin-3-ol (compound I14) [ka] Trimethylboroxine (10.4 mL, 73.49 mmol) was added to a mixture of 5-ethylsulfanyl-2-iodo-6-[3-methyl-6-(trifluoromethyl)imidazo[4,5-b]pyridin-2-yl]pyridin-3-ol (compound I13, prepared as described above) (14.12 g, 29.39 mmol), potassium carbonate (12.83 g, 88.18 mmol), and [1,1'-bis(diphenylphosphino)ferrocene]palladium(II) dichloride dichloromethane complex (6.05 g, 7.42 mmol) in 1,4-dioxane (147 mL) at room temperature under an argon atmosphere. The reaction mixture was heated to 100 °C and stirred for 3 h. After cooling to room temperature, the crude mixture was filtered through a pad of Celite, and the residue was washed with ethyl acetate. The filtrate was concentrated under reduced pressure to give the crude product, which was purified by flash chromatography on silica gel (ethyl acetate in cyclohexane) to give the desired product. LCMS (method 1): m / z369[M+H] + ;Retention time: 0.96 min.

[0315] Step 3: Preparation of 2-[[5-ethylsulfanyl-2-methyl-6-[3-methyl-6-(trifluoromethyl)imidazo[4,5-b]pyridin-2-yl]-3-pyridyl]oxy]acetonitrile (compound I15) [ka] 5-Ethylsulfanyl-2-methyl-6-[3-methyl-6-(trifluoromethyl)imidazo[4,5-b]pyridin-2-yl]pyridin-3-ol (compound I14 prepared as described above) was treated under the same conditions as described in Step 2 of Example P3 to give the desired compound. LCMS (method 1): m / z408[M+H] + ;Retention time: 1.05 minutes.

[0316] Step 4: Preparation of 2-[[5-ethylsulfanyl-2-methyl-6-[3-methyl-6-(trifluoromethyl)imidazo[4,5-b]pyridin-2-yl]-3-pyridyl]oxy]-2-methyl-propanenitrile (compound I16) [ka] 2-[[5-Ethylsulfanyl-2-methyl-6-[3-methyl-6-(trifluoromethyl)imidazo[4,5-b]pyridin-2-yl]-3-pyridyl]oxy]acetonitrile (compound I15 prepared as above) was treated under the same conditions as described in Step 3 of Example P3 to give the desired compound. LCMS (method 1): m / z436[M+H] + ;Retention time: 1.16 minutes.

[0317] Step 5: Preparation of 2-[[5-ethylsulfonyl-2-methyl-6-[3-methyl-6-(trifluoromethyl)imidazo[4,5-b]pyridin-2-yl]-3-pyridyl]oxy]-2-methyl-propanenitrile (compound P4) [ka] 2-[[5-Ethylsulfanyl-2-methyl-6-[3-methyl-6-(trifluoromethyl)imidazo[4,5-b]pyridin-2-yl]-3-pyridyl]oxy]-2-methyl-propanenitrile (compound I16 prepared as described above) was treated under the same conditions as described in Step 4 of Example P2 to give the desired compound. LCMS (method 1): m / z468[M+H] + ;Retention time: 1.07 minutes.

[0318] Example P7: Preparation of 2-[[6-[5-cyclopropyl-3-methyl-4-oxo-6-(trifluoromethyl)imidazo[4,5-c]pyridin-2-yl]-5-ethylsulfonyl-3-pyridyl]oxy]-2-methyl-propanenitrile (compound P7) [ka] Step 1: Preparation of 5-cyclopropyl-2-(3-ethylsulfanyl-5-hydroxy-2-pyridyl)-3-methyl-6-(trifluoromethyl)imidazo[4,5-c]pyridin-4-one (compound I17) [ka] Cesium carbonate (2.75 g, 8.43 mmol, 3.00 equiv.) and (E)-benzaldehyde oxime (614 μL, 5.62 mmol, 2.00 equiv.) were added to a solution of 2-(5-bromo-3-ethylsulfanyl-2-pyridyl)-5-cyclopropyl-3-methyl-6-(trifluoromethyl)imidazo[4,5-c]pyridin-4-one (prepared as described in WO2017089190) (1.33 g, 2.81 mmol) in N,N-dimethylformamide (12 mL). The resulting suspension was stirred at 45 °C overnight. After cooling to room temperature, the reaction mixture was diluted with water, and the pH of the aqueous phase was adjusted to 1 by the addition of 2 N hydrochloric acid solution. The aqueous phase was extracted with ethyl acetate, and the combined organic phases were dried over sodium sulfate, filtered, and concentrated. Purification of the crude material by flash chromatography on silica gel (ethyl acetate in cyclohexane) gave the desired product as a white solid (1.00 g, 2.44 mmol). LCMS (method 1): m / z355[M+H] + ;Retention time: 0.94 min. 1 H NMR(400MHz,chloroform-d)δ ppm 1.06(br s,2H)1.18-1.37(m,5H)2.75(q,J=7.38Hz,2H)3.07-3.16(m,1H)4.04(s,3H)7.06(d,J=2.45Hz,1H)7.28(m,1H)7.98(d,J=2.45Hz,1H).

[0319] Step 2: Preparation of 2-[[6-[5-cyclopropyl-3-methyl-4-oxo-6-(trifluoromethyl)imidazo[4,5-c]pyridin-2-yl]-5-ethylsulfanyl-3-pyridyl]oxy]acetonitrile (compound I18) [ka] Potassium carbonate (404 mg, 2.92 mmol, 1.50 equiv.) was added to a solution of 5-cyclopropyl-2-(3-ethylsulfanyl-5-hydroxy-2-pyridyl)-3-methyl-6-(trifluoromethyl)imidazo[4,5-c]pyridin-4-one (compound I17, prepared as above) (800 mg, 1.95 mmol) in N,N-dimethylformamide (8.0 mL) at 0 °C under an argon atmosphere, followed by bromoacetonitrile (177 μL, 2.53 mmol, 1.30 equiv.) stirred for 10 min. After stirring at room temperature for 2 h, the reaction mixture was poured into ice water, and the aqueous phase was extracted twice with ethyl acetate. The combined organic phases were washed with water, dried over sodium sulfate, filtered, and concentrated. The crude material was used directly without further purification. LCMS (method 3): m / z450[M+H] + ;Retention time: 1.48 minutes.

[0320] Step 3: Preparation of 2-[[6-[5-cyclopropyl-3-methyl-4-oxo-6-(trifluoromethyl)imidazo[4,5-c]pyridin-2-yl]-5-ethylsulfanyl-3-pyridyl]oxy]-2-methyl-propanenitrile (compound I19) [ka] A 2 M solution of lithium hexamethyldisilazide in tetrahydrofuran (2.50 mL, 5.00 mmol, 3.00 equiv.) was added dropwise to a solution of 2-[[6-[5-cyclopropyl-3-methyl-4-oxo-6-(trifluoromethyl)imidazo[4,5-c]pyridin-2-yl]-5-ethylsulfanyl-3-pyridyl]oxy]acetonitrile (compound I18, prepared as described above) (750 mg, 1.67 mmol) and methyl iodide (418 μL, 6.68 mmol, 4.00 equiv.) in tetrahydrofuran (20 mL) cooled to 0 °C. The reaction mixture was stirred in an ice bath for 2 h and then quenched by pouring into saturated aqueous sodium bicarbonate solution. The aqueous phase was extracted with ethyl acetate. The combined organic phases were washed with brine, dried over sodium sulfate, filtered, and evaporated. The crude material was purified by flash chromatography on silica gel (ethyl acetate in cyclohexane) to give the desired compound (700 mg, 1.66 mmol). LCMS (method 3): m / z478[M+H] + ;Retention time: 1.54 minutes.

[0321] Step 4: Preparation of 2-[[6-[5-cyclopropyl-3-methyl-4-oxo-6-(trifluoromethyl)imidazo[4,5-c]pyridin-2-yl]-5-ethylsulfonyl-3-pyridyl]oxy]-2-methyl-propanenitrile (compound P7) [ka] 2-[[6-[5-Cyclopropyl-3-methyl-4-oxo-6-(trifluoromethyl)imidazo[4,5-c]pyridin-2-yl]-5-ethylsulfanyl-3-pyridyl]oxy]-2-methyl-propanenitrile (compound I19 prepared as described above) was treated under the same conditions as described in Step 4 of Example P2 to give the desired compound. LCMS (method 3): m / z510[M+H] + ;Retention time: 1.46 minutes.

[0322] Example P6: Preparation of 2-[[6-[5-ethyl-3-methyl-4-oxo-6-(trifluoromethyl)imidazo[4,5-c]pyridin-2-yl]-5-ethylsulfonyl-3-pyridyl]oxy]-2-methyl-propanenitrile (compound P6) [ka] Step 1: Preparation of 5-ethyl-2-(3-ethylsulfanyl-5-hydroxy-2-pyridyl)-3-methyl-6-(trifluoromethyl)imidazo[4,5-c]pyridin-4-one (compound I20) [ka] 2-(5-Bromo-3-ethylsulfanyl-2-pyridyl)-5-ethyl-3-methyl-6-(trifluoromethyl)imidazo[4,5-c]pyridin-4-one (prepared as described in WO2017084879) was treated under the same conditions as described in Step 1 of Example P7 to give the desired compound. LCMS (method 3): m / z399[M+H] + ;Retention time: 1.38 minutes. 1 H NMR (400 MHz, chloroform-d) δ ppm 7.99 (m, 1H) 7.29 (m, 1H) 7.06 (m, 1H) 4.26 (q, J = 6.89 Hz, 2H) 4.08 (s, 3H) 2.75 (q, J = 7.46 Hz, 2H) 1.42-1.37 (m, 3H) 1.18-1.23 (m, 3H).

[0323] Step 2: Preparation of 2-[[6-[5-ethyl-3-methyl-4-oxo-6-(trifluoromethyl)imidazo[4,5-c]pyridin-2-yl]-5-ethylsulfanyl-3-pyridyl]oxy]acetonitrile (compound I21) [ka] 5-Ethyl-2-(3-ethylsulfanyl-5-hydroxy-2-pyridyl)-3-methyl-6-(trifluoromethyl)imidazo[4,5-c]pyridin-4-one (compound I20 prepared as described above) was treated under the same conditions as described in Step 2 of Example P7 to give the desired compound. LCMS (method 4): m / z438[M+H] + ;Retention time: 1.01 minutes. 1 H NMR (400 MHz, chloroform-d) δ ppm 8.25 (m, 1H) 7.33 (m, 1H) 7.31 (m, 1H) 4.93 (m, 2H) 4.28 (m, 2H) 4.20 (m, 3H) 2.95 (m, 2H) 1.41-1.34 (m, 6H).

[0324] Step 3: Preparation of 2-[[6-[5-ethyl-3-methyl-4-oxo-6-(trifluoromethyl)imidazo[4,5-c]pyridin-2-yl]-5-ethylsulfanyl-3-pyridyl]oxy]-2-methyl-propanenitrile (compound I22) [ka] 2-[[6-[5-Ethyl-3-methyl-4-oxo-6-(trifluoromethyl)imidazo[4,5-c]pyridin-2-yl]-5-ethylsulfanyl-3-pyridyl]oxy]acetonitrile (compound I21 prepared as above) was treated under the same conditions as described in Step 3 of Example P7 to give the desired compound. LCMS (method 4): m / z466[M+H] + ;Holding time: 1.10 minutes. 1 H NMR (400 MHz, chloroform-d) δ ppm 8.31 (m, 1H) 7.65 (m, 1H) 7.32 (m, 1H) 4.25 (m, 6H) 2.96 (m, 2H) 1.81-1.84 (m, 6H).

[0325] Step 4: Preparation of 2-[[6-[5-ethyl-3-methyl-4-oxo-6-(trifluoromethyl)imidazo[4,5-c]pyridin-2-yl]-5-ethylsulfonyl-3-pyridyl]oxy]-2-methyl-propanenitrile (compound P6) [ka] 2-[[6-[5-Ethyl-3-methyl-4-oxo-6-(trifluoromethyl)imidazo[4,5-c]pyridin-2-yl]-5-ethylsulfanyl-3-pyridyl]oxy]-2-methyl-propanenitrile (compound I22 prepared as described above) was treated under the same conditions as described in Step 4 of Example P2 to give the desired compound. LCMS (method 5): m / z498[M+H] + ;Retention time: 1.05 minutes.

[0326] Example P8: Preparation of 2-[[5-ethylsulfonyl-6-[7-(trifluoromethyl)imidazo[1,2-a]pyridin-2-yl]-3-pyridyl]oxy]-2-methyl-propanenitrile (compound P8) [ka] Step 1: Preparation of 1-(3-ethylsulfanyl-5-hydroxy-2-pyridyl)ethanone (compound I23) [ka] Cesium carbonate (6.65 g, 20.40 mmol, 2.20 equiv.) and (E)-benzaldehyde oxime (1.32 mL, 12.1 mmol, 1.30 equiv.) were added to a solution of 1-(5-chloro-3-ethylsulfanyl-2-pyridyl)ethanone (prepared as described in WO2016071214) (2.00 g, 9.27 mmol) in N,N-dimethylformamide (18 mL). The resulting suspension was stirred overnight at room temperature. The reaction mixture was diluted with water, and the pH of the aqueous phase was adjusted to 1 by adding 1 N hydrochloric acid solution. The aqueous phase was extracted with ethyl acetate, and the combined organic phases were dried over sodium sulfate, filtered, and concentrated. Purification of the crude material by flash chromatography on silica gel (ethyl acetate in cyclohexane) afforded the desired product as a white solid (1.47 g, 2.44 mmol). 1 H NMR (400 MHz, dimethyl sulfoxide-d6) δ ppm 1.28 (t, J = 7.34 Hz, 3H) 2.86 (q, J = 7.34 Hz, 2H) 3.33 (s, 3H) 7.15 (d, J = 2.20 Hz, 1H) 7.98 (d, J = 2.20 Hz, 1H) 10.94 (s br, 1H).

[0327] Step 2: Preparation of 2-[(6-acetyl-5-ethylsulfanyl-3-pyridyl)oxy]-2-methyl-propanamide (compound I24) [ka] Cesium carbonate (9.2 g, 28 mmol, 1.5 equiv.) was added to a solution of 1-(3-ethylsulfanyl-5-hydroxy-2-pyridyl)ethanone (compound I23, prepared as described above) (3.7 g, 19 mmol) in acetonitrile (94 mL). The resulting suspension was stirred for 5 minutes, after which 2-bromo-2-methyl-propanamide (5.0 g, 30 mmol, 1.6 equiv.) was added, and the reaction mixture was heated and stirred overnight at room temperature. After cooling to room temperature, the reaction mixture was poured into water, and the aqueous phase was extracted three times with ethyl acetate. The combined organic phases were dried over sodium sulfate, filtered, and concentrated. The crude material was used in the next step without further purification. 1 H NMR (400 MHz, dimethyl sulfoxide-d6) δ ppm 1.28 (t, J = 7.34 Hz, 3H) 1.56 (s, 6H) 1.85 (s, 3H) 2.83 (q, J = 7.34 Hz, 2H) 7.15 (d, J = 2.20 Hz, 1H) 7.33 (s, 1H) 7.45 (s, 1H) 8.04 (d, J = 2.20 Hz, 1H).

[0328] Step 3: Preparation of 2-[(6-acetyl-5-ethylsulfanyl-3-pyridyl)oxy]-2-methyl-propanenitrile (compound I25) [ka] Trifluoroacetic anhydride (6.27 mL, 44.6 mmol, 3.00 equiv.) was added to a solution of 2-[(6-acetyl-5-ethylsulfanyl-3-pyridyl)oxy]-2-methyl-propanamide (compound I24, prepared as described above) (6.0 g, 14.9 mmol) in dichloromethane (149 mL) and triethylamine (8.38 mL, 59.5 mmol, 4.00 equiv.) at 0 °C. After stirring at room temperature for 2 h, the reaction mixture was carefully quenched by the addition of methanol followed by saturated sodium bicarbonate solution. The aqueous phase was extracted twice with dichloromethane, and the combined organic layers were dried over sodium sulfate, filtered, and concentrated. The crude material was purified by flash chromatography on silica gel (0 to 100% ethyl acetate in cyclohexane) to give the desired product as a yellow oil (3.69 g). 1 H NMR(400MHz,chloroform-d)δ ppm 1.44(t,J=7.34Hz,3H)1.83(s,6H)2.71(s,3H)2.93(q,J=7.34Hz,2H)7.57(d,J=2.20Hz,1H)8.22(d,J=2.20Hz,1H).

[0329] Step 4: Preparation of 2-[[6-(2-bromoacetyl)-5-ethylsulfanyl-3-pyridyl]oxy]-2-methyl-propanenitrile (compound I26) [ka] Trimethyl(phenyl)ammonium tribromide (1.43 g, 3.78 mmol) was added to a solution of 2-[(6-acetyl-5-ethylsulfanyl-3-pyridyl)oxy]-2-methyl-propanenitrile (compound I25, prepared as above) (1.00 g, 3.78 mmol) in tetrahydrofuran (14.4 mL, freshly opened bottle) cooled to 0 °C. The resulting orange suspension was stirred at room temperature for 42 h, after which the reaction was quenched with water. The aqueous phase was extracted three times with ethyl acetate, and the combined organic phases were washed with brine, dried over sodium sulfate, filtered, and concentrated. The crude yellow oil was triturated in cold cyclohexane (15 mL) containing some dichloromethane (1.0 mL) to give a precipitate, which was filtered and washed with cyclohexane to give the desired compound as a yellow solid (812 mg). The filtrate was purified by flash chromatography on silica gel (ethyl acetate in cyclohexane) to give a second less pure crop of the desired compound as a yellow oil (500 mg). 1 H NMR(400MHz,chloroform-d)δ ppm 1.45(t,J=7.34Hz,3H)1.85(s,6H)2.96(q,J=7.34Hz,2H)4.82(s,2H)7.59(d,J=2.57z,1H)8.21(d,J=2.57Hz,1H).

[0330] Step 5: Preparation of 2-[[5-ethylsulfanyl-6-[7-(trifluoromethyl)imidazo[1,2-a]pyridin-2-yl]-3-pyridyl]oxy]-2-methyl-propanenitrile (compound I28) [ka] A suspension of 2-[[6-(2-bromoacetyl)-5-ethylsulfanyl-3-pyridyl]oxy]-2-methyl-propanenitrile (compound I26, prepared as described above) (100 mg, 0.20 mmol) and 4-(trifluoromethyl)pyridin-2-amine (commercially available) (35 mg, 0.21 mmol) in acetonitrile (1.5 mL) was heated at 70 °C and stirred overnight. Magnesium oxide (8 mg, 0.20 mmol) was added to the reaction mixture, and heating was continued for 3 h to drive the reaction to completion. After cooling to room temperature, the mixture was poured into water, and the aqueous phase was extracted twice with ethyl acetate. The combined organic phases were washed with brine, dried over sodium sulfate, filtered, and concentrated. The crude material was partially purified by flash chromatography on silica gel (ethyl acetate in cyclohexane) to give the desired product (60 mg) as a yellow oil. 1 H NMR(400MHz,chloroform-d)δ ppm 1.44(t,J=7.34Hz,3H)1.81(s,6H)3.04(q,J=7.34Hz,2H)7.02(dd,J1=7.34;J2=1.65Hz,1H)7.65( d,J=2.57Hz,1H)8.06(s,1H)8.29(d,J=7.34Hz,1H)8.32(d,J=2.57Hz,1H)8.37(d,J=1.65Hz,1H).

[0331] Step 6: Preparation of 2-[[5-ethylsulfonyl-6-[7-(trifluoromethyl)imidazo[1,2-a]pyridin-2-yl]-3-pyridyl]oxy]-2-methyl-propanenitrile (compound P8) [ka] 2-[[5-Ethylsulfanyl-6-[7-(trifluoromethyl)imidazo[1,2-a]pyridin-2-yl]-3-pyridyl]oxy]-2-methyl-propanenitrile (compound I28 prepared as described above) was treated under the same conditions as described in step 4 of example P2 to give the desired compound. LCMS (method 1): m / z439[M+H] + ;Retention time: 0.98 min.

[0332] Example P9: Preparation of 2-[[5-ethylsulfonyl-6-[7-(trifluoromethyl)imidazo[1,2-b]pyridazin-2-yl]-3-pyridyl]oxy]-2-methyl-propanenitrile (compound P9) [ka] Step 1: Preparation of 2-[[5-ethylsulfanyl-6-[7-(trifluoromethyl)imidazo[1,2-b]pyridazin-2-yl]-3-pyridyl]oxy]-2-methyl-propanenitrile (compound I11) [ka] 2-[[6-(2-Bromoacetyl)-5-ethylsulfanyl-3-pyridyl]oxy]-2-methyl-propanenitrile (compound I26 prepared as above) and 5-(trifluoromethyl)pyridazin-3-amine (CAS 1211591-88-6) were treated under the same conditions as described in step 5 of example P8 to give the desired compound. LCMS (method 1): m / z408[M+H] + ;Retention time: 1.09 min.

[0333] Step 2: Preparation of 2-[[5-ethylsulfonyl-6-[7-(trifluoromethyl)imidazo[1,2-b]pyridazin-2-yl]-3-pyridyl]oxy]-2-methyl-propanenitrile (compound P9) [ka] 2-[[5-Ethylsulfanyl-6-[7-(trifluoromethyl)imidazo[1,2-b]pyridazin-2-yl]-3-pyridyl]oxy]-2-methyl-propanenitrile (compound I11 prepared as described above) was treated under the same conditions as described in Step 4 of Example P2 to give the desired compound. LCMS (method 1): m / z440[M+H] + ;Retention time: 0.99 min.

[0334] Example P14: Preparation of 2-[[5-ethylsulfonyl-6-[1-methyl-5-(trifluoromethylsulfonyl)benzimidazol-2-yl]-3-pyridyl]oxy]-2-methyl-propanenitrile (compound P14) [ka] Step 1: Preparation of N-[2-amino-4-(trifluoromethylsulfanyl)phenyl]-5-(1-cyano-1-methyl-ethoxy)-3-ethylsulfanyl-N-methyl-pyridine-2-carboxamide (compound I41) [ka] To a solution of N1-methyl-4-(trifluoromethylsulfanyl)benzene-1,2-diamine (WO 2012 / 086848) (400 mg, 1.80 mmol, 1.05 equiv.) and triethylamine (3.0 equiv.) in tetrahydrofuran (15 mL) was added dropwise a solution of 5-(1-cyano-1-methyl-ethoxy)-3-ethylsulfanyl-pyridine-2-carbonyl chloride (compound I32, prepared as described below) (1.0 equiv.) in tetrahydrofuran (15 mL) at 0° C. The reaction mixture was stirred at room temperature for 3 hours and then evaporated under reduced pressure. The residue was diluted with water (50 mL) and extracted with ethyl acetate (3×50 mL). The combined organic layers were washed with brine (20 mL), dried over sodium sulfate, filtered, and concentrated under reduced pressure to give the desired crude product. This material was used directly in the next step. LCMS (method 3): m / z471[M+H] + ;Retention time: 1.64 min.

[0335] Step 2: Preparation of 2-[[5-ethylsulfanyl-6-[1-methyl-5-(trifluoromethylsulfanyl)benzimidazol-2-yl]-3-pyridyl]oxy]-2-methyl-propanenitrile (compound I40) [ka] A solution of N-[2-amino-4-(trifluoromethylsulfanyl)phenyl]-5-(1-cyano-1-methyl-ethoxy)-3-ethylsulfanyl-N-methyl-pyridine-2-carboxamide (compound I41, prepared as described above) (800 mg, 1.70 mmol) in glacial acetic acid (12 mL) was heated at 150° C. for 2 hours. The reaction mixture was concentrated under reduced pressure, and the residue was quenched with water (50 mL) and extracted with ethyl acetate (3×50 mL). The combined organic layers were washed with brine (20 mL), dried over sodium sulfate, filtered, and concentrated in vacuo. The residue was purified by column chromatography on silica gel (combiflash) (30% ethyl acetate-cyclohexane) to give the desired product as an off-white solid. LCMS (method 5): m / z453[M+H] + ;Retention time: 1.12 minutes.

[0336] Step 3: Preparation of 2-[[5-ethylsulfonyl-6-[1-methyl-5-(trifluoromethylsulfanyl)benzimidazol-2-yl]-3-pyridyl]oxy]-2-methyl-propanenitrile (compound P13) [ka] 2-[[5-Ethylsulfanyl-6-[1-methyl-5-(trifluoromethylsulfanyl)benzimidazol-2-yl]-3-pyridyl]oxy]-2-methyl-propanenitrile (compound I40 prepared as described above) was treated with 2.2 equivalents of the oxidizing agent 3-chloroperbenzoic acid under conditions similar to those described in Step 4 of Example P2, and after stirring at room temperature for 2 hours, the desired compound was obtained. The crude product obtained after extractive workup was purified by column chromatography (combiflash) on silica gel (40% ethyl acetate in cyclohexane). LCMS (method 5): m / z485[M+H] + ;Retention time: 1.12 minutes.

[0337] Step 4: Preparation of 2-[[5-ethylsulfonyl-6-[1-methyl-5-(trifluoromethylsulfonyl)benzimidazol-2-yl]-3-pyridyl]oxy]-2-methyl-propanenitrile (compound P14) [ka] 2-[[5-Ethylsulfanyl-6-[1-methyl-5-(trifluoromethylsulfanyl)benzimidazol-2-yl]-3-pyridyl]oxy]-2-methyl-propanenitrile (compound I40 prepared as described above) was treated with 4.5 equivalents of the oxidizing agent 3-chloroperbenzoic acid under conditions similar to those described in Step 4 of Example P2 to give the desired compound after stirring overnight at room temperature. The crude product obtained after extractive workup was purified by column chromatography (combiflash) on silica gel (40% ethyl acetate in cyclohexane). LCMS (method 5): m / z517[M+H] + ;Retention time: 1.02 minutes.

[0338] Example P15: Preparation of 2-[[6-(2,2-difluoro-7-methyl-[1,3]dioxolo[4,5-f]benzimidazol-6-yl)-5-ethylsulfonyl-3-pyridyl]oxy]-2-methyl-propanenitrile (compound P15) [ka] Step 1: Preparation of 5-(1-cyano-1-methyl-ethoxy)-N-[2,2-difluoro-6-(methylamino)-1,3-benzodioxol-5-yl]-3-ethylsulfanyl-pyridine-2-carboxamide (compound I42) [ka] To a solution of 5-(1-cyano-1-methyl-ethoxy)-3-ethylsulfanyl-pyridine-2-carboxylic acid (compound I36) (350 mg, 1.31 mmol) prepared as described below) in ethyl acetate (5.25 mL) was added dropwise 2,2-difluoro-N5-methyl-1,3-benzodioxole-5,6-diamine hydrochloride (408 mg, 1.71 mmol), N,N-diisopropyl-ethylamine (0.689 mL, 4.02 mmol), and a 50% solution of T3P [propanephosphonic anhydride] in methyl-tetrahydrofuran (1.61 mL, 2.63 mmol) under a nitrogen atmosphere at 0 °C. The mixture was stirred at 0 °C for 2 hours and then diluted with aqueous sodium bicarbonate. The product was extracted twice with ethyl acetate, and the combined organic layers were washed with saturated aqueous sodium bicarbonate, dried over magnesium sulfate, filtered, and concentrated under reduced pressure. The residue was purified by Combiflash (ethyl acetate gradient in cyclohexane) to give the desired product. LCMS (method 1): m / z451[M+H] + ;Retention time: 1.17 minutes.

[0339] Step 2: Preparation of 2-[[6-(2,2-difluoro-7-methyl-[1,3]dioxolo[4,5-f]benzimidazol-6-yl)-5-ethylsulfanyl-3-pyridyl]oxy]-2-methyl-propanenitrile (compound I43) [ka] A solution of 5-(1-cyano-1-methyl-ethoxy)-N-[2,2-difluoro-6-(methylamino)-1,3-benzodioxol-5-yl]-3-ethylsulfanyl-pyridine-2-carboxamide (compound I42, prepared as described above) (245 mg, 0.54 mmol) was refluxed in glacial acetic acid (2.2 mL) for 1 hour. The mixture was concentrated under reduced pressure, and the residue was diluted with ethyl acetate and aqueous sodium bicarbonate. The product was extracted twice with ethyl acetate, and the combined organic layers were washed with saturated aqueous sodium bicarbonate, dried over magnesium sulfate, filtered, and concentrated under reduced pressure. The residue was purified by Combiflash (gradient ethyl acetate in cyclohexane) to give the desired product. LCMS (method 1): m / z433[M+H] + ;Retention time: 1.11 minutes.

[0340] Step 3: Preparation of 2-[[6-(2,2-difluoro-7-methyl-[1,3]dioxolo[4,5-f]benzimidazol-6-yl)-5-ethylsulfonyl-3-pyridyl]oxy]-2-methyl-propanenitrile (compound P15) [ka] 2-[[6-(2,2-Difluoro-7-methyl-[1,3]dioxolo[4,5-f]benzimidazol-6-yl)-5-ethylsulfanyl-3-pyridyl]oxy]-2-methyl-propanenitrile (compound I43 prepared as described above) in ethyl acetate was treated with 2.3 equivalents of the oxidant 3-chloroperbenzoic acid under conditions similar to those described in Step 4 of Example P2 to give the desired compound after stirring at room temperature for 4 hours. The crude product obtained after extractive workup was purified by column chromatography (combiflash) on silica gel (10-45% ethyl acetate in cyclohexane). LCMS (method 1): m / z465[M+H] + ;Retention time: 1.05 minutes. 1H NMR (400 MHz, chloroform-d) δ ppm 1.39 (t, 3H), 1.91 (s, 6H), 3.77 (s, 3H), 3.87 (q, 2H), 7.13 (s, 1H), 7.44 (s, 1H), 8.30 (d, 1H), 8.83 (d, 1H).

[0341] Example P16: Preparation of 2-[[6-(2,2-difluoro-[1,3]dioxolo[4,5-f][1,3]benzoxazol-6-yl)-5-ethylsulfonyl-3-pyridyl]oxy]-2-methyl-propanenitrile (compound P16) [ka] Step 1: Preparation of N-(6-bromo-2,2-difluoro-1,3-benzodioxol-5-yl)-5-(1-cyano-1-methyl-ethoxy)-3-ethylsulfanyl-pyridine-2-carboxamide (compound I44) [ka] To a solution of 5-(1-cyano-1-methyl-ethoxy)-3-ethylsulfanyl-pyridine-2-carboxylic acid (compound I36) (250 mg, 0.94 mmol) prepared as described below) in ethyl acetate (3.75 mL) was added dropwise 6-bromo-2,2-difluoro-1,3-benzodioxol-5-amine (CAS 887267-84-7) (241 mg, 0.94 mmol), triethylamine (0.196 mL, 1.41 mmol), and a 50% solution of T3P [propanephosphonic anhydride] in methyl-tetrahydrofuran (0.747 mL, 1.22 mmol) under a nitrogen atmosphere at 0 °C. The mixture was stirred at room temperature for 16 hours and then diluted with aqueous sodium bicarbonate. The product was extracted twice with ethyl acetate, and the combined organic layers were washed with saturated aqueous sodium bicarbonate, dried over magnesium sulfate, filtered, and concentrated under reduced pressure. The residue was purified by Combiflash (gradient of t-butyl methyl ether in cyclohexane) to give the desired product. LCMS (method 1): m / z500 / 502[M+H] +;Retention time: 1.34 minutes.

[0342] Step 2: Preparation of 2-[[6-(2,2-difluoro-[1,3]dioxolo[4,5-f][1,3]benzoxazol-6-yl)-5-ethylsulfanyl-3-pyridyl]oxy]-2-methyl-propanenitrile (compound I45) [ka] A microwave vial was charged with N-(6-bromo-2,2-difluoro-1,3-benzodioxol-5-yl)-5-(1-cyano-1-methyl-ethoxy)-3-ethylsulfanyl-pyridine-2-carboxamide (compound I44, prepared as described above) (131 mg, 0.26 mmol), potassium carbonate (47 mg, 0.34 mmol), copper(I) iodide (10 mg, 0.052 mmol), N,N'-dimethylethylenediamine (5.7 μL, 0.052 mmol), and toluene (1.3 mL). The mixture was flushed with argon and then heated in a microwave at 150 °C for 4 h. Additional copper(I) iodide (10 mg) was added, and heating was continued at 150 °C for 3 h. The reaction mixture was filtered through Hyflo, and the residue was washed with ethyl acetate and water. The layers of the filtrate were separated, the aqueous phase was extracted twice with ethyl acetate, and the combined organic layers were washed with brine, dried over magnesium sulfate, filtered, and concentrated in vacuo. The residue was purified by Combiflash (ethyl acetate gradient in cyclohexane) to give the desired product. LCMS (method 1): m / z420[M+H] + ;Holding time: 1.20 minutes.

[0343] Step 3: Preparation of 2-[[6-(2,2-difluoro-[1,3]dioxolo[4,5-f][1,3]benzoxazol-6-yl)-5-ethylsulfonyl-3-pyridyl]oxy]-2-methyl-propanenitrile (compound P16) [ka] 2-[[6-(2,2-Difluoro-[1,3]dioxolo[4,5-f][1,3]benzoxazol-6-yl)-5-ethylsulfanyl-3-pyridyl]oxy]-2-methyl-propanenitrile (compound I45, prepared as described above) in ethyl acetate was treated with 2.2 equivalents of the oxidant 3-chloroperbenzoic acid under conditions similar to those described in Step 4 of Example P2 to give the desired compound after stirring at room temperature for 16 hours. The crude product obtained after extractive workup was purified by column chromatography (combiflash) on silica gel (0-45% ethyl acetate in cyclohexane). LCMS (method 1): m / z452[M+H] + ;Retention time: 1.09 min. 1 H NMR (400 MHz, chloroform-d) δ ppm 1.46 (t, 3H), 1.91 (s, 6H), 4.05 (q, 2H), 7.43 (s, 1H), 7.51 (s, 1H), 8.37 (d, 1H), 8.88 (d, 1H).

[0344] [Table 12-1] [Table 12-2] [Table 12-3] [Table 12-4]

[0345] [Table 13-1] [Table 13-2] [Table 13-3] [Table 13-4] [Table 13-5] [Table 13-6] [Table 13-7] [Table 13-8] [Table 13-9] [Table 13-10] [Table 13-11] [Table 13-12] [Table 13-13] [Table 13-14]

[0346] Example I32: Preparation of 5-(1-cyano-1-methyl-ethoxy)-3-ethylsulfanyl-pyridine-2-carbonyl chloride (compound I32) [ka] Step 1: Preparation of methyl 3-ethylsulfanyl-5-hydroxy-pyridine-2-carboxylate (compound I33) [ka] To a solution of methyl 5-bromo-3-ethylsulfanyl-pyridine-2-carboxylate (prepared as described in WO 2016 / 026848) (10.0 g, 36.21 mmol) in acetonitrile (72 ml) were added cesium carbonate (25.96 g, 79.67 mmol) and (E)-benzaldehyde oxime (5.7 g, 47.08 mmol), and the suspension was heated to 80 °C overnight. The solvent was evaporated under reduced pressure, and the residue was dissolved in ethyl acetate and water. The separated aqueous layer was acidified with 1 M aqueous hydrochloric acid and extracted with ethyl acetate (3x) and dichloromethane (1x). The combined organic phases were dried over sodium sulfate, filtered, and concentrated. The residue was purified by flash chromatography on silica gel (0-10% gradient of methanol in dichloromethane) to give methyl 3-ethylsulfanyl-5-hydroxy-pyridine-2-carboxylate (compound I33). LCMS (Method 1): m / z 214 [M+H] + ;Retention time: 0.68 min.

[0347] Step 2: Preparation of methyl 5-(2-amino-1,1-dimethyl-2-oxo-ethoxy)-3-ethylsulfanyl-pyridine-2-carboxylate (compound I34) [ka] To a solution of methyl 3-ethylsulfanyl-5-hydroxy-pyridine-2-carboxylate (compound I33) (2.5 g, 11.72 mmol) in acetonitrile (59 ml) was added cesium carbonate (5.7 g, 17.49 mmol) and 2-bromo-2-methyl-propanamide (3.1 g, 18.67 mmol) after 5 minutes. The reaction mixture was stirred overnight at room temperature and poured into water and ethyl acetate. The separated aqueous layer was extracted with ethyl acetate (3x), and the combined organic layers were dried over sodium sulfate, filtered, and evaporated to give crude methyl 5-(2-amino-1,1-dimethyl-2-oxo-ethoxy)-3-ethylsulfanyl-pyridine-2-carboxylate (compound I34). This material was used in the next step without further purification. LCMS (Method 1): m / z 299 [M+H] +;Retention time: 0.71 min.

[0348] Step 3: Preparation of methyl 5-(1-cyano-1-methyl-ethoxy)-3-ethylsulfanyl-pyridine-2-carboxylate (compound I35) [ka] To a mixture of crude methyl 5-(2-amino-1,1-dimethyl-2-oxo-ethoxy)-3-ethylsulfanyl-pyridine-2-carboxylate (compound I34 prepared as above) (4.18 g, 14.0 mmol) and triethylamine (5.73 g, 7.89 mL, 56.0 mmol) in dichloromethane (140 mL) was added trifluoroacetic anhydride (8.92 g, 5.90 mL, 42.0 mmol) dropwise at 0° C. The resulting suspension was stirred at room temperature for 2 hours. The reaction mixture was carefully quenched with methanol and then aqueous sodium bicarbonate solution. The aqueous layer was extracted twice with dichloromethane, and the combined organic layers were dried over sodium sulfate, filtered, and evaporated. The residue was purified by combiflash (0-45% gradient of ethyl acetate in cyclohexane) to give methyl 5-(1-cyano-1-methyl-ethoxy)-3-ethylsulfanyl-pyridine-2-carboxylate (compound I35). LCMS (Method 1): m / z 281 [M+H] + ;Retention time: 0.90 minutes. 1 H NMR(400MHz,CDCl3)δ ppm 1.43(t,J=7.40Hz,3H),1.80(s,6H),2.95(q,J=7.40Hz,2H),3.99(s,3H),7.58(d,J=2.32Hz,1H),8.22(d,J=2.32Hz,1H).

[0349] Step 4: Preparation of 5-(1-cyano-1-methyl-ethoxy)-3-ethylsulfanyl-pyridine-2-carboxylic acid (compound I36) [ka] To a solution of methyl 5-(1-cyano-1-methyl-ethoxy)-3-ethylsulfanyl-pyridine-2-carboxylate (compound I35) (6.0 g, 21.41 mmol) in tetrahydrofuran (60 ml) was added lithium hydroxide hydrate (1.8 g, 42.81 mmol) and water (10 ml). The reaction mixture was stirred at room temperature until completion (monitored by TLC) and then concentrated under reduced pressure. The residue was diluted with water (100 ml), acidified with 2N aqueous hydrochloric acid, and the aqueous phase was extracted with ethyl acetate (3 × 100 ml). The combined organic layers were dried over sodium sulfate, filtered, and concentrated under reduced pressure. The crude product was washed twice with n-pentane (50 ml), filtered, and evaporated to dryness to give 5-(1-cyano-1-methyl-ethoxy)-3-ethylsulfanyl-pyridine-2-carboxylic acid (compound I36) as a solid. LCMS (method 4): m / z267[M+H] + and m / z 265 [MH] - ;Retention time: 0.82 minutes. 1 H NMR(400MHz,DMSO-d6)δ ppm 1.27(t,J=7.21Hz,3H),1.78(s,6H),2.97(q,J=7.21Hz,2H),7.58(d,J=2.32Hz,1H),8.24(d,J=2.32Hz,1H).

[0350] Step 5: Preparation of 5-(1-cyano-1-methyl-ethoxy)-3-ethylsulfanyl-pyridine-2-carbonyl chloride (compound I32) [ka] To a solution of 5-(1-cyano-1-methyl-ethoxy)-3-ethylsulfanyl-pyridine-2-carboxylic acid (compound I36) (771 mg, 2.90 mmol) and N,N-dimethylformamide (1 drop) in tetrahydrofuran (19 ml) was added oxalyl chloride (0.328 ml, 3.76 mmol) at 0-5 °C, and the mixture was stirred at room temperature for 2 h. The solution was concentrated under reduced pressure, diluted twice with tetrahydrofuran, and evaporated to dryness. LCMS data for an aliquot quenched with dimethylamine indicated the formation of 5-(1-cyano-1-methyl-ethoxy)-3-ethylsulfanyl-N,N-dimethyl-pyridine-2-carboxamide (C 14 H 19 LCMS (Method 1): m / z 294 [M+H] + ;Retention time: 0.83 min.

[0351] The following mixtures of compounds of formula I with active ingredients are preferred (the abbreviation "TX" means "one compound selected from the group consisting of the compounds of Tables A-1 to A-22, B-1 to B-4 and Table P according to the present invention"): an adjuvant selected from the group of substances consisting of petroleum (alternative name) (628) + TX; Abamectin +TX, Acequinocyl +TX, Acetamiprid +TX, Acetoprole +TX, Acrinathrin +TX, Acinonapyr +TX, Afidopiropen +TX, Afoxolanal +TX, Alanycarb +TX, Allethrin +TX, α-Cypermethrin +TX, α-Methrin +TX, Amidoflumet +TX, Aminocarb +TX, Azocyclotine +TX, Bensultap +TX, Benzochimate +TX, Benzpyrimoxane +TX, β-Cyfluthrin +TX, β-Cypermethrin +TX, Bifenazate +TX, Bifenthrin +TX, Binapacryl + TX, Bioallethrin + TX, Bioallethrin S)-Cyclopentyl Isomer + TX, Bioresmethrin + TX, Bistrifluron + TX, Brofuranilide + TX, Broflutrinate + TX, Bromophos-ethyl + TX, Buprofezin + TX, Butocarboxim + TX, Cadusafos + TX, Carbaryl + TX, Carbosulfan + TX, Cartap + TX, CAS Number: 1632218-00-8 + TX, CAS Number: 1808115-49-2 + TX, CAS Number: 2032403-97-5 + TX, CAS Number: 2044701-44-0 + TX, CAS number: 2128706-05-6 + TX, CAS number: 2246757-58-2 (or 2249718-27-0) + TX, CAS number: 907187-07-9 + TX, chlorantraniliprole + TX, chlordane + TX, chlorfenapyr + TX, chlorprallethrin + TX, chromafenozide + TX, clenpirin + TX, cloetocarb + TX, clothianidin + TX, 2-chlorophenyl N-methylcarbamate (CPMC) + TX, cyanofenphos + TX, cyantraniliprole + TX, cyclaniliprole + TX, Cyclobutrifluram + TX, cycloprothrin + TX, cycloxapride + TX, cycloxapride + TX, cyenopyrafen + TX, cetoprafen + TX, cyflumetofen + TX, cyfluthrin + TX, cyhalodiamide + TX, cyhalothrin + TX, cypermethrin + TX, cyphenothrin + TX, cyprofuranilide + TX, cyromazine + TX, deltamethrin + TX, diafenthiuron + TX, dialifos + TX, dibrom + TX, dichloromezothiaz + TX, diflobidazin + TX, diflubenzuron + TX, dimepropyridaz + TX,Dinactin + TX, Dinocap + TX, Dinotefuran + TX, Dioxabenzophos + TX, Emamectin (or Emamectin benzoate) + TX, Empenthrin + TX, ε-Monfluorotrin + TX, ε-Metofluthrin + TX, Esfenvalerate + TX, Ethion + TX, Ethiprole + TX, Etofenprox + TX, Etoxazole + TX, Fanfur + TX, Fenazaquin + TX, Fenfluthrin + TX, Fenitrothion + TX, Fenobucarb + TX, Fenothiocarb + TX, Fenoxycarb + TX, Fenpropatri phenproximate +TX, fensulfothion +TX, fenthion +TX, fentin acetate +TX, fenvalerate +TX, fipronil +TX, flometoquin +TX, flonicamid +TX, fluacrypyrim +TX, fluazaindolizine +TX, fluazuron +TX, flubendiamide +TX, flubenzimine +TX, flucythrinate +TX, flucycloxuron +TX, flucythrinate +TX, fluensulfone +TX, flufenerim +TX, flufenprox +TX, flufiprole +TX, fluhexafon +TX, Flumethrin +TX, Fluopyram +TX, Flupentiofenox +TX, Flupyradifurone +TX, Flupirimine +TX, Fluralaner +TX, Fluvalinate +TX, Fluxamethamide +TX, Fosthiazate +TX, γ-Cyhalothrin +TX, Gossiplur® +TX, Guadipyr +TX, Halofenozide +TX, Halofenozide +TX, Halofenprox +TX, Heptafluthrin +TX, Hexythiazox +TX, Hydramethylnon +TX, Imicyaphos +TX, Imidacloprid +TX, Imiprothrin +TX, Indoki Sacarb +TX, iodomethane +TX, iprodione +TX, isocycloceram +TX, isothioate +TX, ivermectin +TX, κ-bifenthrin +TX, κ-tefluthrin +TX, lambda-cyhalothrin +TX, lepimectin +TX, lufenuron +TX, metaflumizone +TX, metaldehyde +TX, metam +TX, methomyl +TX, methoxyfenozide +TX, metofluthrin +TX, metolcarb +TX, mexacarbate +TX, milbemectin +TX, monfluorotrin +TX, niclosamide +TX, nicofurol +TX,Nitenpyram + TX, nithiazine + TX, omethoate + TX, oxamyl + TX, oxazosulfil + TX, parathion-ethyl + TX, permethrin + TX, fenothrin + TX, phosphocarb + TX, piperonyl butoxide + TX, pirimicarb + TX, pirimiphos-ethyl + TX, pirimiphos-methyl + TX, polyhedrovirus + TX, prallethrin + TX, profenofos + TX, profenofos + TX, profluthrin + TX, propargite + TX, propetamphos + TX, propoxur + TX, prothiofos + TX, protrifenbut +TX, piflubumid +TX, pymetrozine +TX, pyraclofos +TX, pyrafluprole +TX, pyridaben +TX, pyridalyl +TX, pyrifluquinazone +TX, pyrimidifen +TX, pyriminostrobin +TX, pyriprole +TX, pyriproxyfen +TX, resmethrin +TX, sarolaner +TX, selamectin +TX, silafluofen +TX, spinetoram +TX, spinosad +TX, spirodiclofen +TX, spiromesifen +TX, spiropydione +TX, spirotetramat +TX, sulfoxaflor +TX, tebufenozide do+TX, tebufenpyrad+TX, tebupirimiphos+TX, tefluthrin+TX, temephos+TX, tetrachlorantraniliprole+TX, tetradifon+TX, tetramethrin+TX, tetramethylfluthrin+TX, tetranactin+TX, tetraniliprole+TX, θ-cypermethrin+TX, thiacloprid+TX, thiamethoxam+TX, thiocyclam+TX, thiodicarb+TX, thiofanox+TX, thiometon+TX, thiosultap+TX, thioxazafen+TX, tolfenpyrad+TX, toxaphene+TX, traro Methrin + TX, Transfluthrin + TX, Triazamate + TX, Triazophos + TX, Trichlorfon + TX, Trichloronate + TX, Trichlorophon + TX, Triflumezopyrin + TX, Cyclopyrazoflor + TX, Zeta-cypermethrin + TX, Seaweed extract and fermented product from Melasse + TX, Seaweed extract and fermented product from Melasse containing urea + TX, Amino acids + TX, Potassium and molybdenum and EDTA-chelated manganese + TX, Seaweed extract and fermented plant product + TX, Seaweed extract and fermented plant product containing plant hormones + TX,Vitamins + TX, EDTA-chelated copper + TX, zinc + TX, and iron + TX, azadirachtin + TX, Bacillus aizawai + TX, Bacillus chitinosporus AQ746 (NRRL accession number B-21618) + TX, Bacillus firmus + TX, Bacillus kurstaki + TX, Bacillus mycoides AQ726 (NRRL accession number B-21664) + TX, Bacillus pumilus (NRRL accession number B-30087) + TX, Bacillus pumilus AQ717 (NRRL accession number B-21662) + TX, Bacillus sp. AQ178 (ATCC accession number 53522) + TX, Bacillus sp. AQ175 (ATCC accession number 55608) + TX, Bacillus sp. AQ177 (ATCC accession number 55609) + TX, Bacillus subtilis unspecified + TX, Bacillus subtilis AQ153 (ATCC accession number 55614) + TX, Bacillus subtilis AQ30002 (NRRL accession number B-50421) + TX, Bacillus subtilis AQ30004 (NRRL accession number B-50455) + TX, Bacillus subtilis AQ713 (NRRL accession number B-21661) + TX, Bacillus subtilis AQ743 (NRRL accession number B-21665) + TX, Bacillus thuringiensis AQ52 (NRRL accession number B-21619) + TX, Bacillus thuringiensis BD#32 (NRRL accession number B-21530) + TX, Bacillus thuringiensis subspec. kurstaki BMP 123 + TX,Beauveria bassiana + TX, D-limonene + TX, granulovirus + TX, harpin + TX, Helicoverpa armigera nucleopolyhedron virus + TX, Helicoverpa zea nucleopolyhedron virus + TX, Heliothis virescens nucleopolyhedron virus + TX, Heliothis punctigera nucleopolyhedron virus + TX, Metarhizium spp. + TX, Muscodor albus 620 (NRRL accession number 30547) + TX, Muscodor roseus A3-5 (NRRL accession number 30548) + TX, Neem tree tree product + TX, Paecilomyces fumosoroseus + TX, Paecilomyces lilacinus + TX, Pasteuria nishizawae + TX, Pasteuria penetrans + TX, Pasteuria ramosa + TX, Pasteuria thornei + TX, Pasteuria usgae + TX, P-cymene + TX, Plutella xylostella granulosis virus + TX, Plutella xylostella nucleopolyhedrovirus + TX, Polyhedrovirus + TX, Calystegia japonica + TX, QRD 420 (terpenoid blend) + TX, QRD 452 (terpenoid blend) + TX, QRD 460 (terpenoid blend) + TX, Quillaja saponaria + TX, Rhodococcus globerulus AQ719 (NRRL accession number B-21663) + TX, Spodoptera frugiperda nucleopolyhedrovirus + TX,an insect control active agent selected from Streptomyces galbus (NRRL Accession No. 30232) + TX, Streptomyces sp. (NRRL Accession No. B-30145) + TX, a terpenoid blend + TX, and Verticillium spp.; an algicide selected from the group of substances consisting of bethoxadin [CCN] + TX, copper dioctanoate (IUPAC name) (170) + TX, copper sulfate (172) + TX, sibutrin [CCN] + TX, dichloron (1052) + TX, dichlorophen (232) + TX, endothal (295) + TX, fentin (347) + TX, hydrated lime [CCN] + TX, nabam (566) + TX, quinoclamine (714) + TX, quinonamide (1379) + TX, simazine (730) + TX, triphenyltin acetate (IUPAC name) (347) and triphenyltin hydroxide (IUPAC name) (347) + TX, an anthelmintic selected from the group of substances consisting of abamectin (1) + TX, crufomate (1011) + TX, cyclobutrifluram + TX, doramectin (alternative name) [CCN] + TX, emamectin (291) + TX, emamectin benzoate (291) + TX, eprinomectin (alternative name) [CCN] + TX, ivermectin (alternative name) [CCN] + TX, milbemycin oxime (alternative name) [CCN] + TX, moxidectin (alternative name) [CCN] + TX, piperazine [CCN] + TX, selamectin (alternative name) [CCN] + TX, spinosad (737) and thiophanate (1435) + TX, an avian repellent selected from the group of substances consisting of chloralose (127) + TX, endrin (1122) + TX, fenthion (346) + TX, pyridin-4-amine (IUPAC name) (23) and strychnine (745) + TX, 1-Hydroxy-1H-pyridine-2-thione (IUPAC name) (1222) + TX, 4-(quinoxalin-2-ylamino)benzenesulfonamide (IUPAC name) (748) + TX, 8-hydroxyquinoline sulfate (446) + TX, bronopol (97) + TX, copper dioctanoate (IUPAC name) (170) + TX, copper hydroxide (IUPAC name) (169) + TX, cresol [CCN] + TX, dichlorophen (232) + TX, dipyrithione (1105) + TX, dodicine (1112) + TX, fenaminosulf (1144) + TX, formaldehyde (404) + TX, hydrargafen (alternative name) [CCN] + TX a fungicide selected from the group of substances consisting of TX, kasugamycin (483) + TX, kasugamycin hydrochloride hydrate (483) + TX, nickel bis(dimethyldithiocarbamate) (IUPAC name) (1308) + TX, nitrapyrin (580) + TX, octhilinone (590) + TX, oxolinic acid (606) + TX, oxytetracycline (611) + TX, potassium hydroxyquinoline sulfate (446) + TX, probenazole (658) + TX, streptomycin (744) + TX, streptomycin sesquisulfate (744) + TX, tecloftalam (766) + TX and thiomersal (alternative name) [CCN] + TX, Adoxophyes orana GV (alternative name) (12) + TX, Agrobacterium radiobacter (alternative name) (13) + TX, Amblyseius spp. (alternative name) (19) + TX, Anagrapha falcifera NPV (alternative name) (28) + TX, Anagrus atomus (alternative name) (29) + TX, Aphelinus abdominalis (alternative name) (33) + TX, Aphidius colemani (alternative name) (34) + TX, Aphidoletes aphidimyza (alternative name) (35) + TX, Autographa californica californica NPV (alternative name) (38) + TX, Bacillus firmus (alternative name) (48) + TX, Bacillus sphaericus Neide (scientific name) (49) + TX, Bacillus thuringiensis Berliner (scientific name) (51) + TX, Bacillus thuringiensis subsp. aizawai (scientific name) (51) + TX, Bacillus thuringiensis subsp. israelensis (scientific name) (51) + TX, Bacillus thuringiensis subsp. japonensis subsp. japonensis) (scientific name) (51) + TX, Bacillus thuringiensis subsp. kurstaki (scientific name) (51) + TX, Bacillus thuringiensis subsp. tenebrionis (Bacillus thuringiensis subsp.tenebrionis (scientific name) (51) + TX, Beauveria bassiana (alternate name) (53) + TX, Beauveria brongniartii (alternate name) (54) + TX, Chrysoperla carnea (alternate name) (151) + TX, Cryptolaemus montrouzieri (red ladybird beetle) (alternate name) (178) + TX, Cydia pomonella GV (alternate name) (191) + TX, Dacnusa sibirica (alternate name) (212) + TX, Diglyphus isaea (alternate name) (254) + TX, Encarsia formosa (scientific name) (293) + TX, Eretmocerus eremicus (alternate name) (300) + TX, Helicoverpa zea NPV (alternate name) (431) + TX, Heterorhabditis bacteriophora and H. megidis (alternate name) (433) + TX, Hippodamia convergens (alternate name) (442) + TX, Leptomastix dactylopii (alternate name) (488) + TX, Macrolophus caliginosus (alternate name) (491) + TX, Mamestra brassicae NPV (alternate name) (494) + TX, Metaphycus helvolus (alternate name) (522) + TX, Metarhizium anisopliae var. acridum (scientific name) (523) + TX, Metarhizium anisopliae var. anisopliae (scientific name) (523) + TX, Neodiprion sertifer NPV and N. leconti (N.lecontei NPV (alternate name) (575) + TX, Orius spp. (alternate name) (596) + TX, Paecilomyces fumosoroseus (alternate name) (613) + TX, Phytoseiulus persimilis (alternate name) (644) + TX, Spodoptera exigua multicapsid nuclear polyhedrosis virus (scientific name) (741) + TX, Steinernema bibionis (alternate name) (742) + TX, Steinernema carpocapsae (alternate name) (742) + TX, Steinernema felziae feltiae (alternate name) (742) + TX, Steinernema glaseri (alternate name) (742) + TX, Steinernema riobrave (alternate name) (742) + TX, Steinernema riobravis (alternate name) (742) + TX, Steinernema scapterisci (alternate name) (742) + TX, Steinernema spp. (alternate name) (742) + TX, Trichogramma spp. (alternate name) (826) + TX, Typhlodromus occidentalis a biological agent selected from the group consisting of Verticillium lecanii (alternative name) (848) + TX, a soil sterilant selected from the group of substances consisting of iodomethane (IUPAC name) (542) and methyl bromide (537) + TX; an antisterilant selected from the group of substances consisting of Afolate [CCN] + TX, Visadyl (alternative name) [CCN] + TX, Busulfan (alternative name) [CCN] + TX, Diflubenzuron (250) + TX, Zimatif (alternative name) [CCN] + TX, Hemel [CCN] + TX, Hempa [CCN] + TX, Metepa [CCN] + TX, Methiotepa [CCN] + TX, Methyl Afolate [CCN] + TX, Morzide [CCN] + TX, Penfluron (alternative name) [CCN] + TX, Tepa [CCN] + TX, Thiohempa (alternative name) [CCN] + TX, Thiotepa (alternative name) [CCN] + TX, Tretamine (alternative name) [CCN] and Uredepa (alternative name) [CCN] + TX, (E)-Deca-5-en-1-yl acetate and (E)-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-4,1 0-Dien-1-yl acetate (IUPAC name) (779) + TX, (Z)-Dodec-7-en-1-yl acetate (IUPAC name) (285) + TX, (Z)-Hexadec-11-enal (IUPAC name) (436) + TX, (Z)-Hexadec-11-en-1-yl acetate (IUPAC name) (437) + TX, (Z)-Hex Sadec-13-en-11-yn-1-yl acetate (IUPAC name) (438) + TX, (Z)-Icos-13-en-10-one (IUPAC name) (448) + TX, (Z)-tetradec-7-en-1-al (IUPAC name) (782) + TX, (Z)-tetradec-9-en-1-ol (IUPAC name) (783) + TX, ( Z)-Tetradeca-9-en-1-yl acetate (IUPAC name) (784) + TX, (7E,9Z)-dodeca-7,9-dien-1-yl acetate (IUPAC name) (283) + TX, (9Z,11E)-tetradeca-9,11-dien-1-yl acetate (IUPAC name) (780) + TX, (9Z,12E)-tetradeca-9,12-dien-1-yl acetate (IUPAC name) (781) + TX, 14-methyloctadec-1-ene (IUPAC name) (545) + TX, 4-methylnonan-5-ol and 4-methylnonan-5-one (IUPAC name) (544) + TX, α-multistriatin (alternative name) [CCN] + TX, Brevicomin (alternative name) [CCN] + TX, Codlerua (alternative name) [CCN] + TX, Codlemone (alternative name) (167) + TX, Curua ( (alternative name) (179) + TX, disparlure (277) + TX, dodec-8-en-1-yl acetate (IUPAC name) (286) + TX, dodec-9-en-1-yl acetate (IUPAC name) (287) + TX, dodec-8 + TX, 10-dien-1-yl acetate (IUPAC name) (284) + TX, dominicalure (alternative name) [CCN] + TX, ethyl 4-methyloctanoate (IUPAC name) (317) + TX, eugenol (alternative name) ) [CCN] + TX, Frontalin (alternate name) [CCN] + TX, Gossip Lua (alternate name) (420) + TX, Grand Lua (421) + TX, Grand Lua I (alternate name) (421) + TX, Grand Lua II (alternate name) (421) + TX, Grand Lua III (alternate name) (421) + TX, Grand Lua IV (alternate name) (421) + TX, Hexalua [CCN] + TX, Ipsdienol (alternate name) [CCN] + TX, Ipsenol (alternate name [ CCN] + TX, Japonirua (alternative name) (481) + TX, Lineatin (alternative name) [CCN] + TX, Litirua (alternative name) [CCN] + TX, Lupulua (alternative name) [CCN] + TX, Medurua [CCN] + TX, Megatomoic acid (alternative name) [CCN] + TX, Methyleugenol (alternative name) (540) + TX, Muscalua (563) + TX, Octadeca-2,13-dien-1-yl acetate (IUPAC name) (588) + TX, Octadeca-3,13-Dien-1-yl acetate (IUPAC name) (589) + TX, Olfrulure (alternative name) [CCN] + TX, Orictalure (alternative name) (317) + TX, Ostramon (alternative name) [CCN] + TX, Siglua [CCN] + TX, Soldigin (alternative name) (736) + TX, Sulcatol (alternative name) [CCN] + TX, Tetradec-11-en-1-yl acetate (IU an insect pheromone selected from the group of substances consisting of Trimedulla (PAC name) (785) + TX, Trimedulla (839) + TX, Trimedulla A (alternate name) (839) + TX, Trimedulla B1 (alternate name) (839) + TX, Trimedulla B2 (alternate name) (839) + TX, Trimedulla C (alternate name) (839) and Trunk-call (alternate name) [CCN] + TX, an insect repellent selected from the group of substances consisting of 2-(octylthio)ethanol (IUPAC name) (591) + TX, butopyronoxyl (933) + TX, butoxy(polypropylene glycol) (936) + TX, dibutyl adipate (IUPAC name) (1046) + TX, dibutyl phthalate (1047) + TX, dibutyl succinate (IUPAC name) (1048) + TX, diethyltoluamide [CCN] + TX, dimethylcarbate [CCN] + TX, dimethyl phthalate [CCN] + TX, ethyl hexanediol (1137) + TX, hexamide [CCN] + TX, methoquin-butyl (1276) + TX, methylneodecanamide [CCN] + TX, oxamate [CCN] and picaridin [CCN] + TX, Bis(tributyltin)oxide (IUPAC name) (913) + TX, Bromoacetamide [CCN] + TX, Calcium arsenate [CCN] + TX, Cloethocarb (999) + TX, Copper acetarsenite [CCN] + TX, Copper sulfate (172) + TX, Fentin (347) + TX, Ferric phosphate (IUPAC name) (352) + TX, Metaldehyde (518) + TX, Methiocarb (530) + TX, Niclosamide (576) + TX, Niclosamide-olamine (576) + TX, Pentachloroethylene (Phenylalanine) a molluscicide selected from the group of substances consisting of: chlorophenol (623) + TX, sodium pentachlorophenoxide (623) + TX, thazimcarb (1412) + TX, thiodicarb (799) + TX, tributyltin oxide (913) + TX, triphenmorph (1454) + TX, trimethacarb (840) + TX, triphenyltin acetate (IUPAC name) (347) and triphenyltin hydroxide (IUPAC name) (347) + TX, pyriprole [394730-71-3] + TX, AKD-3088 (compound code) + TX, 1,2-dibromo-3-chloropropane (IUPAC / Chemical Abstracts Name) (1045) + TX, 1,2-dichloropropane (IUPAC / Chemical Abstracts Name) (1062) + TX, 1,2-dichloropropane and 1,3-dichloropropene (IUPAC Name) (1063) + TX, 1,3-dichloropropene (233) + TX, 3,4-dichlorotetrahydrothiophene 1,1-dioxide (IUPAC / Chemical Abstracts Name) Abstract name) (1065) + TX, 3-(4-chlorophenyl)-5-methylrhodanine (IUPAC name) (980) + TX, 5-methyl-6-thioxo-1,3,5-thiadiazinan-3-ylacetic acid (IUPAC name) (1286) + TX, 6-isopentenylaminopurine (alternative name) (210) + TX, abamectin (1) + TX, acetoprole [CCN] + TX, alanycarb (15) + TX, aldicarb (16) + TX, aldoxicarb (863) + TX, AZ60541 (compound code) + TX, benclotiaz [CCN] + TX, benomyl (62) + TX, butylpyridaben (alternative name) + TX, cadusafos (109) + TX, carbofuran (118) + TX, carbon disulfide (945) + TX, carbosulfan (119) + TX, chloropicrin (141) + TX, chlorpyrifos (145) + TX, cloetocarb (999) + TX, cyclobutrifluram + TX, cytokinin (alternative name) (210) + T X, Dazomet (216) + TX, DBCP (1045) + TX, DCIP (218) + TX, Diamidaphos (1044) + TX, Diclofenthion (1051) + TX, Dicrifos (alternative name) + TX, Dimethoate (262) + TX, Doramectin (alternative name) [CCN] + TX, Emamectin (291) + TX, Emamectin Benzoate (291) + TX, Eprinomectin (alternative name) [CCN] + TX, Ethoprophos (312) + TX, Ethylhexyl Dibromide Styrene (316) + TX, Fenamiphos (326) + TX, Fenpyrad (alternative name) + TX, Fensulfothion (1158) + TX, Fosthiazate (408) + TX, Fostietan (1196) + TX, Furfural (alternative name) [CCN] + TX, GY-81 (development code) (423) + TX, Heterofos [CCN] + TX, Iodomethane (IUPAC name) (542) + TX, Isamidophos (1230) + TX, Isazophos (1231) + TX, Isopropylparaben Vermectin (alternative name) [CCN] + TX, Kinetin (alternative name) (210) + TX, Mecarfone (1258) + TX, Metam (519) + TX, Metam-potassium (alternative name) (519) + TX, Metam-sodium (519) + TX, Methyl bromide (537) + TX, Methyl isothiocyanate (543) + TX, Milbemycin oxime (alternative name) [CCN] + TX, Moxidectin (alternative name) [CCN] + TX, Myrotheciumverrucaria) Composition (alternative name) (565) + TX, NC-184 (compound code) + TX, Oxamyl (602) + TX, Phorate (636) + TX, Phosphamidon (639) + TX, Phosphocarb [CCN] + TX, Cebufos (alternative name) + TX, Selamectin (alternative name) [CCN] + TX, Spinosad (737) + TX, Terbam (alternative name) + TX, Terbufos (773) + TX, Tetrachlorothiophene (IU a nematicide selected from the group of substances consisting of PAC / Chemical Abstracts Name) (1422) + TX, Thiafenox (alternative name) + TX, Thionazine (1434) + TX, Triazophos (820) + TX, Triazuron (alternative name) + TX, Xylenol [CCN] + TX, YI-5302 (compound code) and Zeatin (alternative name) (210) + TX, Fluensulfone [318290-98-1] + TX, Fluopyram + TX, a nitrification inhibitor selected from the group of substances consisting of potassium ethylxanthate [CCN] and nitrapyrin (580) + TX; a plant activator selected from the group of substances consisting of acibenzolar (6) + TX, acibenzolar-S-methyl (6) + TX, probenazole (658) and Reynoutria sachalinensis extract (alternative name) (720) + TX, 2-Isovalerylindan-1,3-dione (IUPAC name) (1246) + TX, 4-(quinoxalin-2-ylamino)benzenesulfonamide (IUPAC name) (748) + TX, α-chlorohydrin [CCN] + TX, aluminum phosphide (640) + TX, antu (880) + TX, arsenic trioxide (882) + TX, barium carbonate (891) + TX, bisthiosemi (912) + TX, brodifacoium (89) + TX, bromadiolone (including alpha-bromadiolone) (mu) + TX, Bromethalin (92) + TX, Calcium cyanide (444) + TX, Chloralose (127) + TX, Chlorophacinone (140) + TX, Cholecalciferol (alternative name) (850) + TX, Coumacrol (1004) + TX, Coumafuryl (1005) + TX, Coumatetralyl (175) + TX, Crimidine (1009) + TX, Difenacoum (246) + TX, Difethialone (249) + TX, Diphacinone (273) + TX, Ergocalciferol (301) + TX, Flocoumafen (357) + TX, Fluoroacetamide (379) + TX, Flupropaline (1183) + TX, Flupropaline 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, Norbormide (1318) + TX, Fosacetim (1336) + TX, Fosacetim a rodenticide selected from the group of substances consisting of sphingosine (IUPAC name) (640) + TX, phosphorus [CCN] + TX, pindone (1341) + TX, potassium arsenite [CCN] + TX, pyrinuron (1371) + TX, sciliroside (1390) + TX, sodium arsenite [CCN] + TX, sodium cyanide (444) + TX, sodium fluoroacetate (735) + TX, strychnine (745) + TX, thallium sulfate [CCN] + TX, warfarin (851) and zinc phosphide (640) + TX, a synergist selected from the group of substances consisting of 2-(2-butoxyethoxy)ethyl piperonylate (IUPAC name) (934) + TX, 5-(1,3-benzodioxol-5-yl)-3-hexylcyclohex-2-enone (IUPAC name) (903) + TX, farnesol and nerolidol (alternative names) (324) + TX, MB-599 (development code) (498) + TX, MGK 264 (development code) (296) + TX, piperonyl butoxide (649) + TX, piperotal (1343) + TX, propyl isomer (1358) + TX, S421 (development code) (724) + TX, sesamex (1393) + TX, sesamolin (1394) and sulfoxide (1406) + TX, an animal repellent selected from the group of substances consisting of anthraquinone (32) + TX, chloralose (127) + TX, copper naphthenate [CCN] + TX, copper oxychloride (171) + TX, diazinon (227) + TX, dicyclopentadiene (chemical name) (1069) + TX, guazatine (422) + TX, guazatine acetate (422) + TX, methiocarb (530) + TX, pyridin-4-amine (IUPAC name) (23) + TX, thiram (804) + TX, trimethacarb (840) + TX, zinc naphthenate [CCN] and ziram (856) + TX, a virucidal agent selected from the group of substances consisting of Imanin (alternative name) [CCN] and Ribavirin (alternative name) [CCN] + TX, a wound protectant selected from the group of substances consisting of mercuric oxide (512) + TX, octilinone (590) and thiophanate-methyl (802) + TX, 1,1-bis(4-chlorophenyl)-2-ethoxyethanol + TX, 2,4-dichlorophenylbenzenesulfonate + TX, 2-fluoro-N-methyl-N-1-cinnamaldehyde + TX, 4-chlorophenyl phenyl sulfone + TX, acetoprole + TX, aldoxicarb + TX, amidithione + TX, amidothioate + TX, amiton + TX, amiton hydrogen oxalate + TX, amitraz + TX, alamite + TX, arsenic trioxide + TX, azobenzene + TX, azotoate + TX, benomyl + TX, benoxafos + TX, benzyl benzoate Oxalate +TX, Bixafen +TX, Brofenvalerate +TX, Bromocyclen +TX, Bromophos +TX, Bromopropylate +TX, Buprofezin +TX, Butocarboxim +TX, Butoxycarboxim +TX, Butylpyridaben +TX, Calcium polysulfate +TX, Camphechlor +TX, Carbanolate +TX, Carbophenothion +TX, Cimiazole +TX, Thiomethionate +TX, Chlorbeside +TX, Chlordimeform +TX, Chlordimeform hydrochloride +TX, Chlorphenetole +TX, Chlorfenson +TX , Chlorofensulfide +TX, Chlorobenzilate +TX, Chlormebform +TX, Chlormethiuron +TX, Chloropropylate +TX, Chlorthiophos +TX, Cinerin I +TX, Cinerin II +TX, Cinerins +TX, Closantel +TX, Coumaphos +TX, Crotamiton +TX, Crotoxyphos +TX, Kufraeb +TX, Cyanthoate +TX, DCPM +TX, DDT +TX, Demefion +TX, Demefion-O +TX, Demefion-S +TX, Demeton-methyl +TX, Demeton-O +TX, Demeton-O-methyl +TX , Demeton-S+TX, Demeton-S-methyl+TX, Demeton-S-methylsulfone+TX, Dichlofluanid+TX, Dichlorvos+TX, Dicrifos+TX, Dienochlor+TX, Dimefox+TX, Zinex+TX, Zinex-diclexin+TX, Dinocap-4+TX, Dinocap-6+TX, Dinocton+TX, Dinopenton+TX, Dinosulfone+TX, Dinotervone+TX, Dioxathion+TX, Diphenylsulfone+TX, Disulfiram+TX, DNOC+TX, Dofenapine+TX, Doramectin+TX, Endothion+TX,Epirinomectin +TX, Ethoate-methyl +TX, Etrimphos +TX, Fenazaflor +TX, Fenbutatin oxide +TX, Fenothiocarb +TX, Fenpyrad +TX, Fenpyroximate +TX, Fenpyrazamine +TX, Fenson +TX, Fentrifanil +TX, Flubenzimine +TX, Flucycloxuron +TX, Fluenethyl +TX, Fluorobenside +TX, FMC 1137 +TX, Formetanate +TX, Formetanate hydrochloride +TX, Formoparanate +TX, γ-HCH +TX, Gliodin +TX, Halfenprox +TX, Hexadecylcyclopropanecarboxylate +TX, Isocarbophos +TX, Jasmolin I +TX, Jasmolin II +TX, Jodofenphos +TX, Lindane +TX, Malonoben +TX, Mecarbam +TX, Mefosfolan +TX, Mesulfen +TX, Methacrifos +TX, methyl bromide +TX, metolcarb +TX, mexacarbate +TX, milbemycin oxime +TX, mipafox +TX, monocrotophos +TX, morphothion +TX, moxidectin +TX, naled +TX, 4-chloro-2-(2-chloro-2-methyl-propyl)-5-[(6-iodo-3-pyridyl)methoxy]pyridazin-3-one +TX, nifururidide +TX, nikkomycin +TX, nitrilacarb +TX, nitrilacarb 1:1 salt Zinc chloride complex +TX, omethoate +TX, oxydeprophos +TX, oxydisulfoton +TX, pp'-DDT +TX, parathion +TX, permethrin +TX, fenkapton +TX, phosalone +TX, phospholan +TX, phosphamidon +TX, polychloroterpene +TX, polynactin +TX, proclonol +TX, promacyl +TX, propoxur +TX, protidathion +TX, prothoate +TX, pyrethrin I +TX, pyrethrin II +TX, pyrethrins +TX, pyridaphenthion +TX, pirimitate +TX, quinalphos +TX, quinthiofos +TX, R-1492 +TX, phosglycine +TX, rotenone +TX, shladan +TX, cevufos +TX, selamectin +TX, sofamid +TX, SSI-121 +TX, sulfiram +TX, sulfuramide +TX, sulfotep +TX, sulfur +TX, diflobidazin +TX, tau-fluvalinate +TX, TEPP +TX, terbam +TX,Tetradifon + TX, Tetrasul + TX, Thiafenox + TX, Thiocarboxim + TX, Thiofanox + TX, Thiometon + TX, Thioquinox + TX, Thuringiensin + TX, Triamiphos + TX, Triatene + TX, Triazophos + TX, Triazuron + TX, Trifenofos + TX, Trinactin + TX, Vamidothion + TX, Vaniliprole + TX, Bethoxadin + TX, Copper dioctanoate + TX , Copper sulfate + TX, Sibutrin + TX, Dichlorn + TX, Dichlorophen + TX, Endothal + TX, Fentin + TX, Slaked lime + TX, Nabam + TX, Quinoclamine + TX, Quinoneamide + TX, Simazine + TX, Triphenyltin acetate + TX, Triphenyltin hydroxide + TX, Crufomate + TX, Piperazine + TX, Thiophanate + TX, Chloralose + TX, Fenthion + TX, Pyridin-4-amine + T X, strychnine + TX, 1-hydroxy-1H-pyridine-2-thione + TX, 4-(quinoxalin-2-ylamino)benzenesulfonamide + TX, 8-hydroxyquinoline sulfate + TX, bronopol + TX, copper hydroxide + TX, cresol + TX, dipyrithione + TX, doditin + TX, fenaminosulf + TX, formaldehyde + TX, hydralgafen + TX, kasugamycin + TX, kasugamycin hydrochloride hydrate + TX, nickel bis(dimethyldithiocarbamate) + TX, nitrapyrin + TX, octhilinone + TX, oxolinic acid + TX, oxytetracycline + TX, potassium hydroxyquinoline sulfate + TX, probenazole + TX, streptomycin + TX, streptomycin sesquisulfate + TX, tecloftalam + TX, thiomersal + TX, Adoxophyes orana GV+TX, Agrobacterium radiobacter+TX, Amblyseius spp.+TX, Anagrapha falcifera NPV+TX, Anagrafa atomus+TX, Aphelinus abdominalis+TX, Aphidius colemani+TX,Aphidoletes aphidimyza + TX, Autographa californica NPV + TX, Bacillus sphaericus Neide + TX, Beauveria brongniartii + TX, Chrysoperla carnea + TX, Cryptolaemus montrouzieri + TX, Codling moth (Cydia pomonella GV) + TX, Dacnusa sibirica + TX, Diglyphus isaea + TX, Encarsia formosa + TX, Eretmocerus eremicus + TX, Heterorhabditis bacteriophora and H. megidis + TX, Hippodamia convergens + TX, Leptomastix dactylopii + TX, Macrolophus caliginosus + TX, Mamestra brassicae NPV + TX, Metaphycus helvolus + TX, Metarhizium anisopliae var. acridum + TX, Metarhizium anisopliae var. anisopliae + TX, Neodiprion sertifer NPV and N. lecontei NPV + TX, Orius spp. + TX, Paecilomyces fumosoroseus + TX, Phytoseiulus persimilis + TX, Steinernema bibionis bibionis + TX, Steinernema carpocapsae + TX, Steinernema feltiae + TX, Steinernema glaseri + TX, Steinernema riobrave + TX, Steinernema riobravis + TX, Steinernema scapterisci + TX, Steinernema spp. + TX, Trichogramma spp. + TX, Typhlodromus occidentalis + TX, Verticillium lecanii) + TX, apholate + TX, Visadil + TX, busulfan + TX, dimatif + TX, hemel + TX, hempa + TX, metepa + TX, methiotepa + TX, methyl apholate + TX, molzide + TX, penfluron + TX, tepa + TX, thiohempa + TX, thiotepa + TX, tretamine + TX, uredepa + TX, (E)-dec-5-en-1-yl acetate and (E)-dec-5-en-1-ol + TX, (E)-tridec-4-en-1-yl acetate + TX,(E)-6-Methylhept-2-en-4-ol + TX, (E,Z)-tetradec-4,10-dien-1-yl acetate + TX, (Z)-dodec-7-en-1-yl acetate + TX, (Z)-hexadec-11-enal + TX, (Z)-hexadec-11-en-1-yl acetate + TX, (Z)-hexadec-13-en-11-yn-1-yl acetate + TX, (Z)-icosa-13-en-10-one + TX, (Z)-tetradec-7-en-1-al + TX, (Z)-tetradec-9-en-1-ol + TX, (Z)-tetradec-11-en-1-ol + TX Dec-9-en-1-yl acetate + TX, (7E,9Z)-dodeca-7,9-dien-1-yl acetate + TX, (9Z,11E)-tetradec-9,11-dien-1-yl acetate + TX, (9Z,12E)-tetradec-9,12-dien-1-yl acetate + TX, 14-methyloctadec-1-ene + TX, 4-methylnonan-5-ol and 4-methylnonan-5-one + TX, α-multistriatin + TX, brevicomin + TX, codrellet + TX, codlemone + TX, querle + TX, disparle + TX, dodeca-8-ene Dodec-1-enyl acetate + TX, Dodec-9-en-1-yl acetate + TX, Dodec-8 + TX, 10-dien-1-yl acetate + TX, Dominical + TX, Ethyl 4-methyloctanoate + TX, Eugenol + TX, Frontalin + TX, Grandlure + TX, Grandlure I + TX, Grandlure II + TX, Grandlure III + TX, Grandlure IV + TX, Hexalure + TX, Ipsdienol + TX, Ipsenol + TX, Japonilure + TX, Lineatin + TX, Littlea + TX, Looplure + TX, Medlure + TX, Megatomoic acid + TX, methyleugenol + TX, muscalure + TX, octadeca-2,13-dien-1-yl acetate + TX, octadeca-3,13-dien-1-yl acetate + TX, orfuralure + TX, orictalure + TX, ostramon + TX, siglua + TX, sordidin + TX, sulcatol + TX, tetradec-11-en-1-yl acetate + TX, trimedlure + TX, trimedlure A + TX, trimedlure B1 + TX, trimedlure B2 + TX, trimedlure C + TX, trunc-call + TX,2-(Octylthio)ethanol + TX, Butapyronoxyl + TX, Butoxy(Polypropylene Glycol) + TX, Dibutyl Adipate + TX, Dibutyl Phthalate + TX, Dibutyl Succinate + TX, Diethyl Toluamide + TX, Dimethyl Carbate + TX, Dimethyl Phthalate + TX, Ethyl Hexanediol + TX, Hexamide + TX, Methoxybutyl + TX, Methyl Neodecanamide + TX, Oxamate + TX, Picaridin + TX, 1-Dichloro-1-nitroethane + TX, 1,1-Dichloro-1-nitroethane + TX, 2,2-bis(4-ethylphenyl)ethane + TX, 1,2-dichloropropane and 1,3-dichloropropene + TX, 1-bromo-2-chloroethane + TX, 2,2,2-trichloro-1-(3,4-dichlorophenyl)acetate + TX, 2,2-dichlorovinyl 2-ethylsulfinylethylmethylphosphate + TX, 2-(1,3-dithiolan-2-yl)phenyldimethylcarbamate + TX, 2-(2-butoxyethoxy)ethyl thiocyanate + TX, 2-(4,5-dimethyl-1, 3-Dioxolan-2-yl)phenylmethylcarbamate + TX, 2-(4-chloro-3,5-xylyloxy)ethanol + TX, 2-chlorovinyldiethyl phosphate + TX, 2-imidazolidone + TX, 2-isovalerylindan-1,3-dione + TX, 2-methyl(prop-2-ynyl)aminophenylmethylcarbamate + TX, 2-thiocyanatoethyl laurate + TX, 3-bromo-1-chloroprop-1-ene + TX, 3-methyl-1-phenylpyrazol-5-yldimethylcarbamate Bamate + TX, 4-methyl(prop-2-ynyl)amino-3,5-xylylmethylcarbamate + TX, 5,5-dimethyl-3-oxocyclohex-1-enyldimethylcarbamate + TX, acetione + TX, acrylonitrile + TX, aldrin + TX, allosamidin + TX, alixycarb + TX, α-ecdysone + TX, aluminum phosphide + TX, aminocarb + TX, anabasine + TX, atidathion + TX, azamethiphos + TX, Bacillus thuringiensis δ-endotoxin + TX, barium hexafluorosilicate + TX, barium polysulfide + TX, bartholin + TX, Bayer 22 / 190 + TX, Bayer 22408 + TX,β-Cyfluthrin + TX, β-Cypermethrin + TX, Bioethanomethrin + TX, Biopermethrin + TX, Bis(2-chloroethyl) ether + TX, Sodium borate + TX, Bromfenvinphos + TX, Bromo-DDT + TX, Bufencarb + TX, Butacarb + TX, Butathiophos + TX, Butonate + TX, Calcium arsenate + TX, Calcium cyanide + TX, Carbon disulfide + TX, Carbon tetrachloride + TX, Cartap hydrochloride + TX, Cevadine + TX, Chlorbicyclen + TX, Chlordane + TX, Chlordecone + TX, Chloroform + TX, Chloropicrin + TX, Chlorphoxim + TX, Chlorprazophos + TX, Cis-Resmethrin + TX, Cismethrin + TX, Clocitrin + TX, Copper acetoarsenite + TX, Copper arsenate + TX, Olefin Copper phosphate +TX, chumithoate +TX, cryolite +TX, CS708 +TX, cyanofenphos +TX, cyanophos +TX, cyclethrin +TX, cythioate +TX, d-tetramethrin +TX, DAEP +TX, dazomet +TX, decarbofuran +TX, diamidaphos +TX, dikapton +TX, dichlorophenthion +TX, dicresyl +TX, dicyclanil +TX, dieldrin +TX, diethyl 5-methylpyrazol-3-yl phosphate +TX, dilol +TX, dimefluthrin +TX, dimethane +TX, dimethryn +TX, dimethylvinphos +TX, dimethyllan +TX, dinoprop +TX, dinosam +TX, dinoseb +TX, diofenolan +TX, dioxabenzophos +TX, dicyclophos +TX, DSP +TX, ecdysterone +TX, EI 1642+TX, EMPC+TX, EPBP+TX, Ethaphos+TX, Ethiofencarb+TX, Ethyl formate+TX, Ethylene dibromide+TX, Dichloroethane+TX, Ethylene oxide+TX, EXD+TX, Fenchlorphos+TX, Fenetacarb+TX, Fenitrothion+TX, Fenoxacrim+TX, Fenpyrithrin+TX, Fensulfothion+TX, Fenthion-ethyl+TX, Flucofuron+TX, Fosmetilan+TX, Fospirate+TX, Fostietan+TX, Furathiocarb+TX, Frethrin+TX, Guazatine+TX, Guazatine acetate+TX, Sodium tetrathiocarbonate+TX, Halfenprox+TX, HCH+TX, HEOD+TX,Heptachlor + TX, Heterofos + TX, HHDN + TX, Hydrogen cyanide + TX, Hikincarb + TX, IPSP + TX, Isazophos + TX, Isobenzane + TX, Isodrin + TX, Isofenphos + TX, Isolane + TX, Isoprothiolane + TX, Isoxathion + TX, Juvenile hormone I + TX, Juvenile hormone II + TX, Juvenile hormone III + TX, Kelevan + TX, Kinoprene + TX, Lead arsenate + TX, Leptophos + TX, Lilimphos + TX, Ritidathion + TX, m-Cumenylmethylcarbamate + TX, Magnesium phosphide + TX, Magidox + TX, Mecarfone + TX, Menasone + TX, Mercurous chloride + TX, Mesulfenphos + TX, Metam + TX, Metam-potassium + TX, Metam-sodium + TX, Methanesulfonyl fluoride + TX, Metocrotophos + TX, Methoprene + TX, Methotrin + TX, Methoxychlor + TX, Methyl isothiocyanate + TX, Methylchloroform + TX, Methylene chloride + TX, Methoxadiazone + TX, Mirex + TX, Naphthalophos + TX, naphthalene + TX, NC-170 + TX, nicotine + TX, nicotine sulfate + TX, nithiazine + TX, nornicotine + TX, O-5-dichloro-4-iodophenyl O-ethyl ethylphosphonothioate + TX, O,O-diethyl O-4-methyl-2-oxo-2H-chromen-7-yl phosphorothioate + TX, O,O-diethyl O-6-methyl-2-propylpyrimidin-4-yl phosphorothioate + TX, O,O,O',O'-tetrapropyl dithiopyrophosphate + TX, oleic acid + TX, para-dichlorobenzene + TX, parathion-methyl + TX, pentachlorophenol + TX, pentachlorophenyl laurate + TX, PH 60-38 + TX, Fenkapton + TX, Fosnichlor + TX, Phosphine + TX, Phoxim-methyl + TX, Pyrimetaphos + TX, Polychlorodicyclopentadiene Isomers + TX, Potassium Arsenite + TX, Potassium Thiocyanate + TX, Precocene I + TX, Precocene II + TX, Precocene III + TX, Pyrimidophos + TX, Profluthrin + TX, Promecarb + TX, Prothiofos + TX, Pyrazophos + TX, Pyreth Methrin +TX, Cassia +TX, Quinalphos-methyl +TX, Quinothione +TX, Lafoxanide +TX, Resmethrin +TX, Rotenone +TX, Cadetrin +TX, Riania +TX, Ryanodine +TX, Sabadila) +TX, Shradan +TX, Cebufos +TX, SI-0009 +TX, Tiapronil +TX, Sodium arsenite +TX, Sodium cyanide +TX, Sodium fluoride +TX, Sodium hexafluorosilicate +TX,Pentachlorophenoxide sodium salt +TX, Sodium selenate +TX, Sodium thiocyanate +TX, Sulcofuron +TX, Sulcofuron-sodium +TX, Sulfuryl fluoride +TX, Sulprofos +TX, Tar oil +TX, Thionazine +TX, TDE +TX, Tebupirimfos +TX, Temephos +TX, Telarethrin +TX, Tetrachloroethane +TX, Cyclofos +TX, Thiocyclam +TX, Thiocyclam hydrogen oxalate +TX, Thionazine +TX, Thiosultap +TX, Thiosultap-sodium +TX, Tralomethrin +TX, Transpermethrin +TX, Triazamate +TX, Trichlormethaphos-3 +TX, Trichloronat +TX, Trimethacarb +TX, Tolprocarb +TX, Triclopyricarb +TX, Triplene +TX, Veratridine +TX, Veratrine +TX, XMC +TX, Zetamethrin +TX, Zinc Phosphide +TX, Zolaprofos +TX, and meperfluthrin +TX, tetramethylfluthrin +TX, bis(tributyltin) oxide +TX, bromoacetamide +TX, ferric phosphate +TX, niclosamide-olamine +TX, tributyltin oxide +TX, pyrimorph +TX, triphenmorph +TX, 1,2-dibromo-3-chloropropane +TX, 1,3-dichloropropene +TX, 3,4-dichlorotetrahydrothiophene 1,1-dioxide +TX, 3-( 4-Chlorophenyl)-5-methylrhodanine + TX, 5-methyl-6-thioxo-1,3,5-thiadiazinan-3-ylacetic acid + TX, 6-isopentenylaminopurine + TX, 2-fluoro-N-(3-methoxyphenyl)-9H-purin-6-amine + TX, Benclotiaz + TX, cytokinin + TX, DCIP + TX, rufural + TX, isamidophos + TX, kinetin + TX, Myrothecium verrucaria (Myrothecium verrucaria) composition +TX, tetrachlorothiophene +TX, xylenol +TX, zeatin +TX, potassium ethylxanthogenate +TX, acibenzolar +TX, acibenzolar-S-methyl +TX, giant knotweed (Reynoutria sachalinensis) extract +TX, α-chlorohydrin +TX, anth +TX, barium carbonate +TX, bisthiosemi +TX, brodifacoum +TX, bromadiolone +TX,Bromethalin + TX, chlorophacinone + TX, cholecalciferol + TX, coumachlor + TX, coumafuryl + TX, coumatetralyl + TX, crimidine + TX, difenacoum + TX, difethialone + TX, diphacinone + TX, ergocalciferol + TX, flocoumafen + TX, fluoroacetamide + TX, flupropazine + TX, flupropazine hydrochloride + TX, norbormide + TX, fosacetim + TX, phosphorus + TX, pindone + TX, pyrinuron + TX, sciliroside + TX, sodium fluoroacetate + TX, thallium sulfate + TX, warfarin + TX, 2-(2-butoxyethoxy)ethyl piperonylate + TX, 5-(1,3-benzodioxol-5-yl)-3-hexylcyclohex-2-enone + TX, farnesol and nerolidol + TX, berubutin + TX, MGK 264+TX, piperonyl butoxide+TX, piprotal+TX, propyl isomers+TX, S421+TX, sesamex+TX, sesasmolin+TX, sulfoxide+TX, anthraquinone+TX, copper naphthenate+TX, copper oxychloride+TX, dicyclopentadiene+TX, thiram+TX, zinc naphthenate+TX, ziram+TX, imanin+TX, ribavirin+TX, chlorinconazide+TX, mercury(II) oxide+TX, thiophanate-methyl+TX, azaconazole+TX, bitertanol+TX, bromuconazole+TX, cyproconazole+TX, Difenoconazole +TX, diniconazole +TX, epoxiconazole +TX, fenbuconazole +TX, fluquinconazole +TX, flusilazole +TX, flutriafol +TX, furametpyr +TX, hexaconazole +TX, imazalil +TX, imibenconazole +TX, ipconazole +TX, metconazole +TX, myclobutanil +TX, paclobutrazol +TX, pefurazoate +TX, penconazole +TX, prothioconazole +TX, pyrifenox +TX, prochloraz +TX, propiconazole +TX, pyrisoxin Sasol + TX, Simeconazole + TX, Tebuconazole + TX, Tetraconazole + TX, Triadimefon + TX, Triadimenol + TX, Triflumizole + TX, Triticonazole + TX, Ancymidol + TX, Fenarimol + TX, Nuarimol + TX, Bupirimate + TX, Dimethirimol + TX, Ethirimol + TX, Dodemorph + TX, Fenpropidin + TX, Fenpropimorph + TX, Spiroxamine + TX, Tridemorph + TX, Cyprodinil + TX, Mepanipyrim + TX, Pyrimethanil + TX, Fenpiclonil + TX, Flufen Dioxonil + TX, Benalaxyl + TX, Furalaxyl + TX, Metalaxyl + TX, R-Metalaxyl + TX, Ofrace + TX, Oxadixyl + TX, Carbendazim + TX, Debacarb + TX, Fuberidazole + TX, Thiabendazole + TX, Chlozolinate + TX, Diclozolin + TX, Mycrozolin + TX, Procymidone + TX, Vinclozolin + TX, Boscalid + TX, Carboxin + TX, Fenfuram + TX, Flutolanil + TX, Mepronil + TX, Oxycarboxin + TX, Penthiopyrad + TX, Thifluzamide + TX, Dodine + TX, Iminoctadine + TX, Azoxystrobin + TX, Dimoxystrobin + TX, Enestrobulin + TX, Phenaminestrobin + TX, Flufenoxystrobin + TX, Fluoxastrobin + TX, Kresoxim-methyl + TX, Metominostrobin + TX, Trifloxystrobin + TX, Oryzastrobin + TX, Picoxystrobin + TX, Pyraclostrobin + TX, Pyrametstrobin + TX, Pyraoxystrobin + TX, Ferbam + TX, Mancozeb + TX, Maneb + ​​TX, Metiram + TX, Propineb + ​​TX,Zineb + ​​TX, Captafol + TX, Captan + TX, Fluorimide + TX, Folpet + TX, Tolylfluanid + TX, Bordeaux mixture + TX, Copper oxide + TX, Mancopper + TX, Oxine copper + TX, Nitrothal-isopropyl + TX, Edifenphos + TX, Iprobenfos + TX, Fosdifen + TX, Turcofos-methyl + TX, Anilazine + TX, Benthiavalicarb + TX, Blasticidin-S + TX, Chloroneb + ​​TX, Chlorothalonil + TX, Cyflufenamid + TX, Cymoxanil + TX, Diclocymet + TX, Diclomedine +TX, dicloran +TX, diethofencarb +TX, dimethomorph +TX, flumorph +TX, dithianon +TX, ethaboxam +TX, etridiazole +TX, famoxadone +TX, fenamidone +TX, fenoxanil +TX, ferimzone +TX, fluazinam +TX, fluopicolide +TX, flusulfamide +TX, fluxapyroxad +TX, fenhexamid +TX, fosetyl-aluminum +TX, hymexazole +TX, iprovalicarb +TX, cyazofamid +TX, methasulfocarb +TX, metrafenone +TX, pe Xancyclone + TX, Phthalide + TX, Polyoxin + TX, Propamocarb + TX, Pyribencarb + TX, Proquinazide + TX, Pyroquilon + TX, Pyriophenone + TX, Quinoxyfen + TX, Quintozene + TX, Tiadinil + TX, Triazoxide + TX, Tricyclazole + TX, Triforine + TX, Validamycin + TX, Valifenalate + TX, Zoxamide + TX, Mandipropamide + TX, Isopyrazam + TX, Sedaxane + TX, Benzovindiflupyr + TX, Pydiflumetofen + TX, 3-Difluoromethyl-1-methyl-1H- Pyrazole-4-carboxylic acid (3',4',5'-trifluoro-biphenyl-2-yl)-amide + TX, isoflucipram + TX, isotianil + TX, dipimethitrone + TX, 6-ethyl-5,7-dioxo-pyrrolo[4,5][1,4]dithiino[1,2-c]isothiazole-3-carbonitrile + TX, 2-(difluoromethyl)-N-[3-ethyl-1,1-dimethyl-indan-4-yl]pyridine-3-carboxamide + TX, 4-(2,6-difluorophenyl)-6-methyl-5-phenyl-pyridazine-3-carbonitrile + TX,(R)-3-(Difluoromethyl)-1-methyl-N-[1,1,3-trimethylindan-4-yl]pyrazole-4-carboxamide + TX, 4-(2-bromo-4-fluoro-phenyl)-N-(2-chloro-6-fluoro-phenyl)-2,5-dimethyl-pyrazol-3-amine + TX, 4-(2-bromo-4-fluorophenyl)-N-(2-chloro-6-fluorophenyl)-1,3-dimethyl-1H-pyrazol-5-amine + TX, Fluindapyr + TX, Qumethoxystrobin (Diaxiangjundi ( jiaxiangjunzhi)) + TX, rubenmixianan + TX, diclobenthiazox + TX, mandestrobin + TX, 3-(4,4-difluoro-3,4-dihydro-3,3-dimethylisoquinolin-1-yl)quinolone + TX, 2-[2-fluoro-6-[(8-fluoro-2-methyl-3-quinolyl)oxy]phenyl]propan-2-ol + TX, oxathiapiproline + TX, t-butyl N-[6-[[[(1-methyltetrazol-5-yl)-phenyl-methylene] Amino]oxymethyl]-2-pyridyl]carbamate + TX, pyraziflumide + TX, inpirfluxam + TX, turolprocarb + TX, mefentrifluconazole + TX, ipfentrifluconazole + TX, 2-(difluoromethyl)-N-[(3R)-3-ethyl-1,1-dimethyl-indan-4-yl]pyridine-3-carboxamide + TX, N'-(2,5-dimethyl-4-phenoxy-phenyl)-N-ethyl-N-methyl-formamidine + TX, N'-[4-(4,5-dichlorothiazol-2 -yl)oxy-2,5-dimethyl-phenyl]-N-ethyl-N-methyl-formamidine + TX, [2-[3-[2-[1-[2-[3,5-bis(difluoromethyl)pyrazol-1-yl]acetyl]-4-piperidyl]thiazol-4-yl]-4,5-dihydroisoxazol-5-yl]-3-chloro-phenyl]methanesulfonic acid + TX, but-3-ynyl N-[6-[[(Z)-[(1-methyltetrazol-5-yl)-phenyl-methylene]amino]oxymethyl]-2-pyridyl]carbamate + TX,Methyl N-[[5-[4-(2,4-dimethylphenyl)triazol-2-yl]-2-methyl-phenyl]methyl]carbamate + TX, 3-chloro-6-methyl-5-phenyl-4-(2,4,6-trifluorophenyl)pyridazine + TX, pyridaclomethyl + TX, 3-(difluoromethyl)-1-methyl-N-[1,1,3-trimethylindan-4-yl]pyrazole-4-carboxamide + TX, 1-[2-[[1-(4-chlorophenyl)pyrazol-3-yl]oxymethyl]-3-methyl-phenyl]-4-methyl-tetrazol-5-one + TX, 1-methyl-4-[3-methyl-2-[[2-methyl-4-(3,4,5-trimethylpyrazol-1-yl)phenoxy]methyl]phenyl]tetrazol-5-one + TX, aminopyrifen + TX, ametoctrazine + TX, amisulbrom + TX, Penflufen + TX, (Z,2E)-5-[1-(4-chlorophenyl)pyrazol-3-yl]oxy-2-methoxyimino-N,3-dimethyl-pent-3-enamide + TX, florylpicoxamide + TX, fenpicoxamide + TX, tebufloquine + TX, ipulfenoquine + TX, quinofumelin + TX, isofetamide + TX, N-[2-[2,4-dichloro-phenoxy]phenyl]-3-(difluoromethyl)-1-methyl -pyrazole-4-carboxamide + TX, N-[2-[2-chloro-4-(trifluoromethyl)phenoxy]phenyl]-3-(difluoromethyl)-1-methyl-pyrazole-4-carboxamide + TX, benzothiostrobin + TX, fenamacryl + TX, 5-amino-1,3,4-thiadiazole-2-thiol zinc salt (2:1) + TX, fluopyram + TX, flutianil + TX, fluopimomide + TX, pyrapropoin + TX, Picarbtrazox + TX, 2-(difluoromethyl)-N-(3-ethyl-1,1-dimethyl-indan-4-yl)pyridine-3-carboxamide + TX, 2-(difluoromethyl)-N-((3R)-1,1,3-trimethylindan-4-yl)pyridine-3-carboxamide + TX, 4-[[6-[2-(2,4-difluorophenyl)-1,1-difluoro-2-hydroxy-3-(1,2,4-triazol-1-yl)propyl]-3-pyridyl ]oxy]benzonitrile + TX, methyltetraprole + TX, 2-(difluoromethyl)-N-((3R)-1,1,3-trimethylindan-4-yl)pyridine-3-carboxamide + TX, α-(1,1-dimethylethyl)-α-[4'-(trifluoromethoxy)[1,1'-biphenyl]-4-yl]-5-pyrimidinemethanol + TX, fluoxapiproline + TX, enoxastrobin + TX, 4-[[6-[2-(2,4-difluorophenyl 4-[[6-[2-(2,4-difluorophenyl)-1,1-difluoro-2-hydroxy-3-(5-sulfanyl-1,2,4-triazol-1-yl)propyl]-3-pyridyl]oxy]benzonitrile + TX, 4-[[6-[2-(2,4-difluorophenyl)-1,1-difluoro-2-hydroxy-3-(5-sulfanyl-1,2,4-triazol-1-yl)propyl]-3-pyridyl]oxy]benzonitrile + TX, 4-[[6-[2-(2,4-difluorophenyl)-1,1-difluoro-2- Hydroxy-3-(5-thioxo-4H-1,2,4-triazol-1-yl)propyl]-3-pyridyl]oxy]benzonitrile + TX, trinexapac + TX, cumoxystrobin + TX, zhongshengmycin + TX, copper thiodiazole + TX, zinc thiazole + TX, amethotractin + TX, iprodione + TX, N-octyl-N'-[2-(octylamino)ethyl]ethane-1,2-diamine + TX;N'-[5-bromo-2-methyl-6-[(1S)-1-methyl-2-propoxy-ethoxy]-3-pyridyl]-N-ethyl-N-methyl-formamidine + TX, N'-[5-bromo-2-methyl-6-[(1R)-1-methyl-2-propoxy-ethoxy]-3-pyridyl]-N-ethyl-N-methyl-formamidine + TX, N'-[5-bromo-2-methyl-6-(1-methyl-2-propoxy-ethoxy)-3-pyridyl]-N-ethyl- N-methyl-formamidine + TX, N'-[5-chloro-2-methyl-6-(1-methyl-2-propoxy-ethoxy)-3-pyridyl]-N-ethyl-N-methyl-formamidine + TX, N'-[5-bromo-2-methyl-6-(1-methyl-2-propoxy-ethoxy)-3-pyridyl]-N-isopropyl-N-methyl-formamidine + TX (these compounds can be prepared by the method described in WO 2015 / 155075); N'-[5-bromo-2-methyl-6-(2-propoxypropoxy)-3-pyridyl]-N-ethyl-N-methyl-formamidine + TX (this compound can be prepared by the method described in IPCOM000249876D); N-isopropyl-N'-[5-methoxy-2-methyl-4-(2,2,2-trifluoro-1-hydroxy-1-phenyl-ethyl)phenyl]-N-methyl-formamidine + TX, N'-[4-(1-cyclopropyl-2,2,2-trifluoro-1-hydroxy-ethyl)-5-methoxy-2-methyl-phenyl]-N-isopropyl Pyr-N-methyl-formamidine + TX (these compounds can be prepared by the methods described in WO 2018 / 228896); N-ethyl-N'-[5-methoxy-2-methyl-4-[(2-trifluoromethyl)oxetan-2-yl]phenyl]-N-methyl-formamidine + TX, N-ethyl-N'-[5-methoxy-2-methyl-4-[(2-trifluoromethyl)tetrahydrofuran-2-yl]phenyl]-N-methyl-formamidine + TX (these compounds can be prepared by the methods described in WO 2019 / 110427);N-[(1R)-1-benzyl-3-chloro-1-methyl-but-3-enyl]-8-fluoro-quinoline-3-carboxamide + TX, N-[(1S)-1-benzyl-3-chloro-1-methyl-but-3-enyl]-8-fluoro-quinoline-3-carboxamide + TX, N-[(1R)-1-benzyl-3,3,3-trifluoro-1-methyl-propyl]-8-fluoro-quinoline-3-carboxamide + TX, N-[( 1S)-1-benzyl-3,3,3-trifluoro-1-methyl-propyl]-8-fluoro-quinoline-3-carboxamide + TX, N-[(1R)-1-benzyl-1,3-dimethyl-butyl]-7,8-difluoro-quinoline-3-carboxamide + TX, N-[(1S)-1-benzyl-1,3-dimethyl-butyl]-7,8-difluoro-quinoline-3-carboxamide + TX, 8-fluoro-N-[(1R)-1-[( 3-Fluorophenyl)methyl]-1,3-dimethyl-butyl]quinoline-3-carboxamide + TX, 8-Fluoro-N-[(1S)-1-[(3-fluorophenyl)methyl]-1,3-dimethyl-butyl]quinoline-3-carboxamide + TX, N-[(1R)-1-benzyl-1,3-dimethyl-butyl]-8-fluoro-quinoline-3-carboxamide + TX, N-[(1S)-1-benzyl-1,3-dimethyl-butyl]- ]-8-fluoro-quinoline-3-carboxamide + TX, N-((1R)-1-benzyl-3-chloro-1-methyl-but-3-enyl)-8-fluoro-quinoline-3-carboxamide + TX, N-((1S)-1-benzyl-3-chloro-1-methyl-but-3-enyl)-8-fluoro-quinoline-3-carboxamide + TX (these compounds can be prepared by the methods described in WO 2017 / 153380);1-(6,7-dimethylpyrazolo[1,5-a]pyridin-3-yl)-4,4,5-trifluoro-3,3-dimethyl-isoquinoline + TX, 1-(6,7-dimethylpyrazolo[1,5-a]pyridin-3-yl)-4,4,6-trifluoro-3,3-dimethyl-isoquinoline + TX, 4,4-difluoro-3,3-dimethyl-1-(6-methylpyrazolo[1,5-a]pyridin-3-yl)-4,4,6-trifluoro-3,3-dimethyl-isoquinoline + TX 4,4-difluoro-3,3-dimethyl-1-(7-methylpyrazolo[1,5-a]pyridin-3-yl)isoquinoline + TX, 4,4-difluoro-3,3-dimethyl-1-(7-methylpyrazolo[1,5-a]pyridin-3-yl)isoquinoline + TX, 1-(6-chloro-7-methyl-pyrazolo[1,5-a]pyridin-3-yl)-4,4-difluoro-3,3-dimethyl-isoquinoline + TX (these compounds were prepared by the method described in WO 2017 / 025510). 1-(4,5-dimethylbenzimidazol-1-yl)-4,4,5-trifluoro-3,3-dimethyl-isoquinoline + TX, 1-(4,5-dimethylbenzimidazol-1-yl)-4,4-difluoro-3,3-dimethyl-isoquinoline + TX, 6-chloro-4,4-difluoro-3,3-dimethyl-1-(4-methylbenzimidazol-1-yl)isoquinoline + TX, 4,4-difluoro-1-(5-fluoro-4-methyl-benzimidazol-1-yl)-3,3-dimethyl-isoquinoline + TX, 3-(4,4-difluoro-3,3-dimethyl-1-isoquinolyl)-7,8-dihydro-6H-cyclopenta[e]benzimidazole + TX (these compounds can be prepared by the methods described in WO 2016 / 156085);N-Methoxy-N-[[4-[5-(trifluoromethyl)-1,2,4-oxadiazol-3-yl]phenyl]methyl]cyclopropanecarboxamide + TX, N,2-Dimethoxy-N-[[4-[5-(trifluoromethyl)-1,2,4-oxadiazol-3-yl]phenyl]methyl]propanamide + TX, N-Ethyl-2-methyl-N-[[4-[5-(trifluoromethyl)-1,2,4-oxadiazol-3-yl]phenyl]methyl]cyclopropanecarboxamide + TX phenyl]phenyl]methyl]propanamide + TX, 1-methoxy-3-methyl-1-[[4-[5-(trifluoromethyl)-1,2,4-oxadiazol-3-yl]phenyl]methyl]urea + TX, 1,3-dimethoxy-1-[[4-[5-(trifluoromethyl)-1,2,4-oxadiazol-3-yl]phenyl]methyl]urea + TX, 3-ethyl-1-methoxy-1-[[4-[5-(trifluoromethyl)-1,2,4-oxadiazol-3-yl]phenyl]methyl]urea + TX N-[[4-[5-(trifluoromethyl)-1,2,4-oxadiazol-3-yl]phenyl]methyl]urea + TX, N-[[4-[5-(trifluoromethyl)-1,2,4-oxadiazol-3-yl]phenyl]methyl]propanamide + TX, 4,4-dimethyl-2-[[4-[5-(trifluoromethyl)-1,2,4-oxadiazol-3-yl]phenyl]methyl]isoxazolidin-3-one + TX, 5,5-dimethyl-2-[[4-[5-(trifluoromethyl)-1,2 ,4-oxadiazol-3-yl]phenyl]methyl]isoxazolidin-3-one + TX, ethyl 1-[[4-[5-(trifluoromethyl)-1,2,4-oxadiazol-3-yl]phenyl]methyl]pyrazole-4-carboxylate + TX, N,N-dimethyl-1-[[4-[5-(trifluoromethyl)-1,2,4-oxadiazol-3-yl]phenyl]methyl]-1,2,4-triazol-3-amine + TX. The compounds in this paragraph can be prepared by the methods described in WO 2017 / 055473, WO 2017 / 055469, WO 2017 / 093348 and WO 2017 / 118689;2-[6-(4-chlorophenoxy)-2-(trifluoromethyl)-3-pyridyl]-1-(1,2,4-triazol-1-yl)propan-2-ol + TX (this compound can be prepared by the method described in WO 2017 / 029179); 2-[6-(4-bromophenoxy)-2-(trifluoromethyl)-3-pyridyl]-1-(1,2,4-triazol-1-yl)propan-2-ol + TX (this compound can be prepared by the method described in WO 2017 / 029179); 3 -[2-(1-chlorocyclopropyl)-3-(2-fluorophenyl)-2-hydroxypropyl]imidazole-4-carbonitrile + TX (this compound can be prepared by the method described in WO 2016 / 156290); 3-[2-(1-chlorocyclopropyl)-3-(3-chloro-2-fluorophenyl)-2-hydroxypropyl]imidazole-4-carbonitrile + TX (this compound can be prepared by the method described in WO 2016 / 156290); (4-phenoxyphen N-methyl-4-[5-(trifluoromethyl)-1,2,4-oxadiazol-3-yl]benzene (N-methyl-4-[5-(trifluoromethyl)-1,2,4-oxadiazol-3-yl]benzene) with TX (this compound can be prepared by the method described in WO 2014 / 006945); 2,6-dimethyl-1H,5H-[1,4]dithiino[2,3-c:5,6-c']dipyrrole-1,3,5,7(2H,6H)-tetrone with TX (this compound can be prepared by the method described in WO 2011 / 138281); N-methyl-4-[5-(trifluoromethyl)-1,2,4-oxadiazol-3-yl]benzene Carbothioamide + TX; N-methyl-4-[5-(trifluoromethyl)-1,2,4-oxadiazol-3-yl]benzamide + TX; (Z,2E)-5-[1-(2,4-dichlorophenyl)pyrazol-3-yl]oxy-2-methoxyimino-N,3-dimethyl-pent-3-enamide + TX (this compound can be prepared by the method described in WO 2018 / 153707); N'-(2-chloro-5-methyl-4-phenoxy-phenyl)-N-ethyl-N-methyl-formamidine + TX;N'-[2-chloro-4-(2-fluorophenoxy)-5-methyl-phenyl]-N-ethyl-N-methyl-formamidine + TX (this compound can be prepared by the method described in WO 2016 / 202742); 2-(difluoromethyl)-N-[(3S)-3-ethyl-1,1-dimethyl-indan-4-yl]pyridine-3-carboxamide + TX (this compound can be prepared by the method described in WO 2014 / 095675); (5-methyl-2-pyridyl)-[4-[5-(trifluoromethyl (3-methylisoxazol-5-yl)-[4-[5-(trifluoromethyl)-1,2,4-oxadiazol-3-yl]phenyl]methanone + TX, (3-methylisoxazol-5-yl)-[4-[5-(trifluoromethyl)-1,2,4-oxadiazol-3-yl]phenyl]methanone + TX (these compounds can be prepared by the method described in WO 2017 / 220485); 2-oxo-N-propyl-2-[4-[5-(trifluoromethyl)-1,2,4-oxadiazol-3-yl]phenyl]acetamide + TX (this compound can be prepared by the method described in WO 2018 / 065 414); ethyl 1-[[5-[5-(trifluoromethyl)-1,2,4-oxadiazol-3-yl]-2-thienyl]methyl]pyrazole-4-carboxylate + TX (this compound can be prepared by the method described in WO 2018 / 158365); 2,2-difluoro-N-methyl-2-[4-[5-(trifluoromethyl)-1,2,4-oxadiazol-3-yl]phenyl]acetamide + TX, N-[(E)-methoxyiminomethyl]-4-[5-(trifluoromethyl)-1,2,4-oxadiazol-3-yl]phenyl]acetamide + TX a biologically active substance selected from N-[(Z)-methoxyiminomethyl]-4-[5-(trifluoromethyl)-1,2,4-oxadiazol-3-yl]benzamide + TX, N-[(Z)-methoxyiminomethyl]-4-[5-(trifluoromethyl)-1,2,4-oxadiazol-3-yl]benzamide + TX, N-[N-methoxy-C-methyl-carbonimidoyl]-4-[5-(trifluoromethyl)-1,2,4-oxadiazol-3-yl]benzamide + TX (these compounds can be prepared by the methods described in WO 2018 / 202428); Microorganisms including: Acinetobacter lwoffii + TX, Acremonium alternatum + TX + TX, Acremonium cephalosporium + TX + TX, Acremonium diospyri + TX, Acremonium obclavatum + TX, Adoxophyes orana granulovirus (AdoxGV) (Capex®) + TX, Agrobacterium radiobacter strain K84 (Galltrol-A®) + TX, Alternaria alternata + TX, Alternaria cassia + TX, cassia) + TX, Alternaria destruens (Smolder®) + TX, Ampelomyces quisqualis (AQ10®) + TX, Aspergillus flavus AF36 (AF36®) + TX, Aspergillus flavus NRRL 21882 (Aflaguard®) + TX, Aspergillus spp.) + TX, Aureobasidium pullulans + TX, Azospirillum + TX, (MicroAZ® + TX, TAZO B®) + TX, Azotobacter + TX, Azotobacter chroocuccum (Azotomeal®) + TX, Azotobacter cysts (Bionatural Blooming Blossoms®) + TX, Bacillus amyloliquefaciens + TX, Bacillus cereus + TX, Bacillus chitinosporus strain CM-1 + TX, Bacillus chitinosporus strain AQ746 + TX, Bacillus licheniformis strain HB-2 (Biostart™ Rhizoboost®) + TX, Bacillus licheniformis strain 3086 (EcoGuard® + TX, Green Releaf®) + TX, Bacillus circulans + TX, Bacillus firmus (BioSafe® + TX, BioNem-WP® + TX, VOTiVO®) + TX, Bacillus firmus strain I-1582 + TX, Bacillus macerans + TX, Bacillus marismortui + TX, Bacillus megaterium megaterium) + TX, Bacillus mycoides strain AQ726 + TX, Bacillus papillae (Milky Spore Powder®) + TX, Bacillus pumilus spp.) + TX, Bacillus pumilus strain GB34 (Yield Shield®) + TX, Bacillus pumilus strain AQ717 + TX, Bacillus pumilus strain QST 2808 (Sonata® + TX, Ballad Plus®) + TX, Bacillus spahericus (VectoLex®) + TX, Bacillus spp. + TX, Bacillus spp. strain AQ175 + TX, Bacillus spp. strain AQ177 + TX, Bacillus spp. strain AQ178 + TX, Bacillus subtilis Bacillus subtilis strain QST 713 (CEASE®+TX, Serenade®+TX, Rhapsody®)+TX, Bacillus subtilis strain QST 714 (JAZZ®)+TX, Bacillus subtilis strain AQ153+TX, Bacillus subtilis strain AQ743+TX, Bacillus subtilis strain QST3002+TX, Bacillus subtilis strain QST3004+TX, Bacillus subtilis var. amyloliquefaciens (Bacillus subtilis var.amyloliquefaciens strain FZB24 (Taegro® +TX, Rhizopro®) +TX, Bacillus thuringiensis Cry 2Ae +TX, Bacillus thuringiensis Cry1Ab +TX, Bacillus thuringiensis aizawai GC 91 (Agree®) +TX, Bacillus thuringiensis israelensis (BMP123® +TX, Aquabac® +TX, VectoBac®) +TX, Bacillus thuringiensis kurstakii kurstaki (Javelin® + TX, Deliver® + TX, CryMax® + TX, Bondide® + TX, Scutella WP® + TX, Turilav WP® + TX, Astuto® + TX, Dipel WP® + TX, Biobit® + TX, Foray®) + TX, Bacillus thuringiensis kurstaki BMP 123 (Baritone®) + TX, Bacillus thuringiensis kurstaki HD-1 (Bioprotec-CAF / 3P®) + TX, Bacillus thuringiensis strain BD#32 + TX, Bacillus thuringiensis strain BD#32 + TX, Bacillus thuringiensis strain AQ52+TX, Bacillus thuringiensis var. aizawai (XenTari®+TX, DiPel®)+TX, Bacteria spp.) (GROWMEND® +TX, GROWSWEET® +TX, Shootup®) +TX, Clavipacter michiganensis bacteriophage (AgriPhage®) +TX, Bakflor® +TX, Beauveria bassiana (Beaugenic® +TX, Brocaril WP®) +TX, Beauveria bassiana GHA (Mycotrol ES® +TX, Mycotrol O® +TX, BotaniGuard®) +TX, Beauveria brongniartii (Engerlingspilz® +TX, Schweizer Beauveria® +TX, Melocont®) +TX, Beauveria species (Beauveria spp.) + TX, Botrytis cineria + TX, Bradyrhizobium japonicum (TerraMax®) + TX, Brevibacillus brevis + TX, Bacillus thuringiensis tenebrionis (Novodor®) + TX, BtBooster + TX, Burkholderia cepacia (Deny® + TX, Intercept® + TX, Blue Circle®) + TX, Burkholderia gladii + TX, Burkholderia gladioli + TX, Burkholderia spp.) + TX, Canadian thistle fungus (CBH Canadian Bioherbicide®) + TX, Candida butyri + TX, Candida famata + TX, Candida fructus + TX, Candida glabrata + TX, Candida guilliermondii + TX, Candida melibiosica + TX, Candida oleophila strain O + TX, Candida parapsilosis + TX, Candida pelliculosa + TX, Candida pulcherrima + TX, Candida leucoffii reukaufii + TX, Candida saitoana (Bio-Coat® + TX, Biocure®) + TX, Candida sake + TX, Candida spp. + TX,. Candida tenius + TX, Cedecea dravisae + TX, Cellulomonas flavigena + TX, Chaetomium cochliodes (Nova-Cide®) + TX, Chaetomium globosum (Nova-Cide®) + TX, Chromobacterium subtsugae strain PRAA4-1T (Grandevo®) + TX, Cladosporium cladosporioides + TX, Cladosporium oxysporum + TX, Cladosporium chlorocephalum chlorocephalum + TX, Cladosporium spp. + TX, Cladosporium tenuissimum + TX, Clonostachys rosea (EndoFine®) + TX, Colletotrichum acutatum + TX, Coniothyrium minitans (Cotans WG®) + TX, Coniothyrium spp.) + TX, Cryptococcus albidus (YIELDPLUS®) + TX, Cryptococcus humicola + TX, Cryptococcus infirmo-miniatus + TX, Cryptococcus laurentii + TX, Cryptophlebia leucotreta granulovirus (Cryptex®) + TX, Cupriavidus campinensis + TX, Cydia pomonella granulovirus (CYD-X®) + TX, Cydia pomonella granulovirus granulovirus) (Madex® + TX, Madex Plus® + TX, Madex Max / Carpovirusine®) + TX, Cylindrobasidium laeve (Stumpout®) + TX, Cylindrocladium + TX, Debaryomyces hansenii + TX, Drechslera hawaiinensis + TX, Enterobacter cloacae + TX, Enterobacter iacae + TX, Entomophtora virulenta (Vektor®) + TX, Epicoccum nigrum + TX, Epicoccum purpuraense purpurascens) + TX, Epicoccum spp.) + TX, Filobasidium floriforme + TX, Fusarium acuminatum + TX, Fusarium chlamydosporum + TX, Fusarium oxysporum (Fusaclean® / Biofox C®) + TX, Fusarium proliferatum + TX, Fusarium spp. + TX, Galactomyces geotrichum + TX, Gliocladium catenulatum (Primastop® + TX, Prestop®) + TX, Gliocladium roseum roseum + TX, Gliocladium spp. (SoilGard®) + TX, Gliocladium virens (Soilgard®) + TX, Granulovirus (Granupom®) + TX, Halobacillus halophilus + TX, Halobacillus litoralis + TX, Halobacillus trueperi + TX, Halomonas spp. + TX, Halomonas subglaciescola + TX. Halovibrio variabilis + TX, Hanseniaspora uvarum + TX, Helicoverpa armigera nuclear polyhedrosis virus (Helicovex®) + TX, Helicoverpa zea nuclear polyhedrosis virus (Gemstar®) + TX, isoflavone-formononetin (Myconate®) + TX, Kloeckera apiculata + TX, Kloeckera spp.) + TX, Lagenidium giganteum (Laginex®) + TX, Greenhouse whitefly (Lecanicillium longisporum) (Vertiblast®) + TX, Lecanicillium muscarium (Vertikil®) + TX, Gypsy moth (Lymantria dispar) nuclear polyhedrosis virus (Disparvirus®) + TX, Marinococcus halophilus + TX, Meira geulakonigii + TX, Metarhizium anisopliae (Met52®) + TX, Metarhizium anisopliae (Destruxin®) + TX, WP®) + TX, Metschnikowia fruticola (Shemer®) + TX, Metschnikowia pulcherrima + TX, Microdochium dimerum (Antibot®) + TX, Micromonospora coerulea + TX, Microsphaeropsis ochracea + TX, Muscodor albus 620 (Muscudor®) + TX, Muscodor roseus strain A3-5 + TX, Mycorrhizae spp.) (AMykor® +TX, Root Maximizer®) +TX, Myrothecium verrucaria strain AARC-0255 (DiTera®) +TX, BROS PLUS® +TX, Ophiostoma piliferum strain D97 (Sylvanex®) +TX, Paecilomyces farinosus +TX, Paecilomyces fumosoroseus (PFR-97® +TX, PreFeRal®) +TX, Paecilomyces linacinus (Biostat WP®) +TX, Paecilomyces lilacinus strain 251 (MeloCon WG®) + TX, Paenibacillus polymyxa + TX, Pantoea agglomerans (BlightBan C9-1®) + TX, Pantoea spp. + TX, Pasteuria spp. (Econem®) + TX, Pasteuria nishizawae + TX, Penicillium aurantiogriseum + TX, Penicillium billai (Jumpstart® + TX, TagTeam®) + TX, Penicillium brevicompactum brevicompactum + TX, Penicillium frequentans + TX, Penicillium griseofulvum + TX, Penicillium purpurogenum + TX, Penicillium spp.) + TX, Penicillium viridicatum + TX, Phlebiopsis gigantean (Rotstop®) + TX, Phosphhomeal® + TX, Phytophthora cryptogea + TX, Phytophthora palmivora (Devine®) + TX, Pichia anomala + TX, Pichia guilermondii + TX, Pichia membranaefaciens + TX, Pichia onychis + TX, Pichia stipites + TX, Pseudomonas aeruginosa aeruginosa + TX, Pseudomonas aureofaciens (Spot-Less Biofungicide®) + TX, Pseudomonas cepacia + TX, Pseudomonas chlororaphis (AtEze®) + TX, Pseudomonas corrugate + TX, Pseudomonas fluorescens strain A506 (BlightBan A506®) + TX, Pseudomonas putida + TX, Pseudomonas reactans + TX, Pseudomonas spp.) + TX, Pseudomonas syringae (Bio-Save®) + TX, Pseudomonas viridiflava + TX, Pseudomonas fluorescens (Zequanox®) + TX, Pseudozyma flocculosa strain PF-A22 UL (Sporodex L®) + TX, Puccinia canaliculata + TX, Puccinia thlaspeos (Wood Warrior®) + TX, Pythium paroecandrum + TX, Pythium oligandrum (Polygandron® + TX, Polyversum®) + TX, Pythium periplocum + TX, Rhanella aquatilis + TX, Rhanella spp. + TX, Rhizoctonia (Dormal® + TX, Vault®) + TX, Rhizoctonia + TX, Rhodococcus globerulus strain AQ719 + TX, Rhodosporidium diobovatum + TX, Rhodosporidium toruloides + TX, Rhodotorula spp.) + TX, Rhodotorula glutinis + TX, Rhodotorula graminis + TX, Rhodotorula mucilagnosa + TX, Rhodotorula rubra + TX, Saccharomyces cerevisiae + TX, Salinococcus roseus + TX, Sclerotinia minor + TX, Sclerotinia minor (SARRITOR®) + TX, Scytalidium spp. + TX, Scytalidium uredinicola + TX, Spodoptera exigua nuclear polyhedrosis virus (Spod-X® + TX, Spexit®) + TX, Serratia marcescens + TX, Serratia plymuthica + TX, Serratia spp. + TX, Sordaria fimicola + TX, Spodoptera littoralis nuclear polyhedrosis virus (Littovir®) + TX, Sporobolomyces roseus + TX, Stenotrophomonas maltophilia + TX, Streptomyces ahygroscopicus + TX, Streptomyces albadoncus + TX, Streptomyces exfoliates + TX, Streptomyces galbus + TX, Streptomyces griseoplanus + TX, Streptomyces griseoviridis (Mycostop®) + TX, Streptomyces lydicus (Actinovate®) + TX, Streptomyces lydicus WYEC-108 (ActinoGrow®) + TX, Streptomyces violaceus + TX, Tilletiopsis minor + TX, Tilletiopsis species spp.) +TX, Trichoderma asperellum (T34 Biocontrol®) +TX, Trichoderma gamsii (Tenet®) +TX, Trichoderma atroviride (Plantmate®) +TX, Trichoderma hamatum TH 382 +TX, Trichoderma harzianum rifai (Mycostar®) +TX, Trichoderma harzianum T-22 (Trianum-P® +TX, PlantShield HC® +TX, RootShield® +TX, Trianum-G®) +TX, Trichoderma harzianum) T-39 (Trichodex®) + TX, Trichoderma inhamatum + TX, Trichoderma koningii + TX, Trichoderma spp.LC 52 (Sentinel®) + TX, Trichoderma lignorum + TX, Trichoderma longibrachiatum + TX, Trichoderma polysporum (Binab T®) + TX, Trichoderma taxi + TX, Trichoderma virens + TX, Trichoderma virens (formerly Gliocladium virens GL-21) (SoilGuard®) + TX, Trichoderma viride + TX, Trichoderma viride strain ICC 080 (Remedier®) + TX, Trichosporon pullulans pullulans) + TX, Trichosporon spp. + TX, Trichothecium spp.) + TX, Trichothecium roseum + TX, Typhula phacorrhiza strain 94670 + TX, Typhula phacorrhiza strain 94671 + TX, Ulocladium atrum + TX, Ulocladium oudemansii (Botry-Zen®) + TX, Ustilago maydis + TX, various bacteria and supplemental micronutrients (Natural II®) + TX, various fungi (Millennium Microbes®) + TX, Verticillium chlamydosporium + TX, Verticillium lecanii lecanii (Mycotal® + TX, Vertalec®) + TX, Vip3Aa20 (VIPtera®) + TX, Virgibaclillus marismortui + TX, Xanthomonas campestris pv. Poae (Camperico®) + TX, Xenorhabdus bovienii + TX, Xenorhabdus nematophilus, Plant extracts including: pine oil (Retenol®) +TX, azadirachtin (Plasma), Neem Oil® +TX, AzaGuard® +TX, MeemAzal® +TX, Molt-X® +TX, botanical insect growth regulators (Neemazad® +TX, Neemix®) +TX, rapeseed oil (Lilly Miller Vegol®) +TX, American ant's weed (Chenopodium ambrosioides near ambrosioides) (Requiem®) +TX, Chrysanthemum extract (Crisant®) +TX, neem oil extract (Trilogy®) +TX, Labiatae essential oil (Botania®) +TX, clove, rosemary, peppermint, and thyme oil extracts (Garden insect killer®) + TX, glycine betaine (Greenstim®) + TX, garlic + TX, lemongrass oil (GreenMatch®) + TX, neem oil + TX, catnip (Nepeta cataria) (catnip oil) + TX, catnip (Nepeta catarina) + TX, nicotine + TX, oregano oil (MossBuster®) + TX, sesame (Pedaliaceae) oil (Nematon®) + TX, pyrethrum + TX, soapberry (Quillaja saponaria) (NemaQ®) + TX, giant knotweed (Reynoutria sachalinensis) (Regalia® + TX, Sakalia®) + TX, rotenone (Eco Roten®) + TX, Rutaceae extract (Soleo®) + TX, soybean oil (Ortho ecosense®) +TX, tea tree oil (Timorex Gold®) +TX, thyme oil +TX, AGNIQUE® MMF +TX, BugOil® +TX, a mixture of rosemary, sesame, peppermint, thyme and cinnamon extracts (EF300®) + TX, a mixture of clove rosemary and peppermint extracts (EF 400®) + TX, a mixture of clove peppermint garlic oil and mint (Soil Shot®) + TX, kaolin (Screen®) + TX, storage glucan from brown algae (Laminarin®); Pheromones, including: blackheaded fireworm pheromone (3M Sprayable Blackheaded Fireworm Pheromone®) + TX, codling moth pheromone (Paramount dispenser-(CM) / Isomate C-Plus®) + TX, grape berry moth pheromone (3M MEC-GBM Sprayable Pheromone®) + TX, leafroller pheromone (3M MEC-LR Sprayable Pheromone®) + TX, muscamone (Snip7 Fly Bait® + TX, Starbar Premium Fly Bait®) + TX, oriental fruit moth pheromone (3M oriental fruit moth sprayable pheromone®) + TX, peachtree Borer pheromone (Isomate-P®) + TX, Tomato Pinworm pheromone (3M Sprayable pheromone®) + TX, Entostat powder (palm tree extract) (Exosex CM®) + TX, (E+TX,Z+TX,Z)-3+TX, 8+TX, 11-tetradecatrienyl acetate + TX, (Z+TX,Z+TX,E)-7+TX, 11+TX, 13-hexadecatrienal + TX, (E+TX,Z)-7+TX, 9-dodecadien-1-yl acetate + TX, 2-methyl-1-butanol + TX, calcium acetate + TX, Scenturion® + TX, Biolure® + TX, Check-Mate® + TX, lavandulyl senecioate, Macrobials including: Aphelinus abdominalis + TX, Aphidius ervi (Aphelinus-System®) + TX, Acerophagus papaya + TX, Adalia bipunctata (Adalia-System®) + TX, Adalia bipunctata (Adaline®) + TX, Adalia bipunctata (Aphidalia®) + TX, Ageniaspis citricola + TX, Ageniaspis fuscicollis + TX, Amblyseius andersonii andersoni (Anderline® + TX, Andersoni-System®) + TX, Amblyseius californicus (Amblyline® + TX, Spical®) + TX, Amblyseius cucumeris (Thripex® + TX, Bugline cucumeris®) + TX, Amblyseius fallacis (Fallacis®) + TX, Amblyseius swirskii (Bugline swirskii® + TX, Swirskii-Mite®) + TX, Amblyseius womersleyi (WomerMite®) + TX, Amitus hesperidin hesperidum + TX, Anagyrus atomus + TX, Anagyrus fusciventris + TX, Anagyrus kamali + TX, Anagyrus loecki + TX, Anagyrus pseudococcuspseudococci (Citripar®) + TX, Anicetus benefices + TX, Anisopteromalus calandrae + TX, Anthocoris nemoralis (Anthocoris-System®) + TX, Aphelinus abdominalis (Apheline® + TX, Aphiline®) + TX, Aphelinus asychis + TX, Aphidius colemani (Aphipar®) + TX, Aphidius ervi (Ervipar®) + TX, Aphidius gifuensis + TX, Aphidius matricariae matricariae (Aphipar-M®) + TX, Aphidoletes aphidimyza (Aphidend®) + TX, Aphidoletes aphidimyza (Aphidoline®) + TX, Aphytis lingnanensis + TX, Aphytis melinus + TX, Aprostocetus hagenowii + TX, Atheta coriaria (Staphyline®) + TX, Bombus spp. + TX, Bombus terrestris (Natupol Beehive® + TX, Bombus terrestris (Beeline® + TX, Tripol®) + TX, Cephalonomia stephanoderis + TX, Chilocorus nigritus + TX, Chrysoperlacarnea (Chrysoline®) + TX, Chrysoperla carnea (Chrysopa®) + TX, Chrysoperla rufilabris + TX, Cirrospilus ingenuus + TX, Cirrospilus quadristriatus + TX, Citrostichus phyllocnistoides + TX, Closterocerus chamaeleon + TX, Closterocerus spp. + TX, Coccidoxenoides perminutus (Planopar®) + TX, Coccophagus cowperi) + TX, Coccophagus lycimnia + TX, Cotesia flavipes + TX, Cotesia plutellae + TX, Cryptolaemus montrouzieri (Cryptobug® + TX, Cryptoline®) + TX, Cybocephalus nipponicus + TX, Dacnusa sibirica + TX, Dacnusa sibirica (Minusa®) + TX, Diglyphus isaea (Diminex®) + TX, Delphastus catalinae (Delphastus®) + TX, Delphastus pusillus + TX, Diachasmimorpha krausii + TX, Diachasmimorpha longicaudata + TX, Diaparsis jucunda + TX, Diaphorencyrtus aligarhensis + TX, Diglyphus isaea + TX, Diglyphus isaea (Miglyphus® + TX, Digline®) + TX, Dacnusa sibirica (DacDigline® + TX, Minex®) + TX, Diversinervus spp. + TX, Encarsia citrina + TX, Encarsia formosa (Encarsia max® + TX, Encarline® + TX, En-Strip®) + TX, Eretmocerus eremicus (Enermix®) + TX, Encarsia guadeloupae (Encarsia guadelouupae + TX, Encarsia haitiensis + TX, Episyrphus balteatus (Syrphidend®) + TX, Eretmoceris siphonini + TX, Eretmocerus californicus + TX, Eretmoceruseremicus (Ercal® + TX, Eretline e®) + TX, Eretmocerus eremicus (Bemimix®) + TX, Eretmocerus hayati + TX, Eretmocerus mundus (Bemipar® + TX, Eretline m®) + TX, Eretmocerus siphonini + TX, Exochomus quadripustulatus + TX, Feltiella acarisuga (Spidend®) + TX, Feltiella acarisuga (Feltiline®) + TX, Fopius alisanus arisanus + TX, Fopius ceratitivorus + TX, formononetin (Wirless Beehome®) + TX, Franklinothrips vespiformis (Vespop®) + TX, Galendromus occidentalis + TX, Goniozus legneri + TX, Habrobracon hebetor + TX, Harmonia axyridis (HarmoBeetle®) + TX, Heterorhabditis spp. (Lawn Patrol®) + TX, Heterorhabditis bacteriophora (NemaShield®) + TX,HB® + TX, Nemaseek® + TX, Terranem-Nam® + TX, Terranem® + TX, Larvanem® + TX, B-Green® + TX, NemAttack® + TX, Nematop® + TX, Heterorhabditis megidis (Nemasys H® + TX, BioNem H® + TX, Exhibitline hm® + TX, Larvanem-M®) + TX, Hippodamia convergens + TX, Hypoaspis aculeifer (Aculeifer-System® + TX, Entomite-A®) + TX, Hypoaspis miles (Hypoline m® + TX, Entomite-M® + TX, Lbalia leucospoides + TX, Lecanoideus floccissimus + TX, Lemophagus errabundus + TX, Leptomastidea abnormis + TX, Leptomastix dactylopii (Leptopar®) + TX, Leptomastix epona + TX, Lindorus lophanthae + TX, Lipolexis oregmae + TX, Lucilia caesar caesar) (Natufly®) + TX, Lysiphlebus testaceipes + TX, Macrolophus caliginosus (Mirical-N® + TX, Macroline c® + TX, Mirical®) + TX, Mesoseiulus longipes + TX, Metaphycus flavus + TX, Metaphycus lounsburyi + TX, Micromus angulatus (Milacewing®) + TX, Microterys flavus + TX, Muscidifurax raptorellus and Spalangia cameroni (Biopar®) + TX, Neodryinus typhlocybae + TX, Neoseiulus californicus + TX, Neoseiulus cucumeris cucumeris (THRYPEX®) + TX, Neoseiulus fallacis (Neoseiulus fallacis) + TX, Nesideocoris tenuis (NesidioBug® + TX, Nesibug®) + TX, Ophyra aenescens (Biofly®) + TX, Orius insidiosus (Thripor-I® + TX, Oriline i®) + TX, Orius laevigatus (Thripor-L® + TX, Oriline l®) + TX, Orius majusculus (Oriline m®) + TX, Orius strigicollis (Thripor-S®) + TX, Pauesia juniperorum + TX, Pediobius foveolatus + TX, Phasmarhabditishermaphrodita (Nemaslug®) + TX, Phymastichus coffea + TX, Phytoseiulus macropilus + TX, Phytoseiulus persimilis (Spidex® + TX, Phytoline p®) + TX, Podisus maculiventris (Podisus®) + TX, Pseudacteon curvatus + TX, Pseudacteon obtusus + TX, Pseudacteon tricuspis + TX, Pseudaphycus maculipennis + TX, Pseudleptomastix mexicana mexicana + TX, Psyllaephagus pilosus + TX, Psyttalia concolor (complex) + TX, Quadrastichus spp. + TX, Rhyzobius lophanthae + TX, Rodolia cardinalis + TX, Rumina decollate + TX, Semielacher petiolatus + TX, Sitobion avenae (Ervibank®) + TX, Steinernema carpocapsae (Nematac C® + TX, Millennium® + TX, BioNem C®+TX, NemAttack®+TX, Nemastar®+TX, Capsanem®+TX, Steinernema feltiae (NemaShield®+TX, Nemasys F®+TX, BioNemF® + TX, Steinernema-System® + TX, NemAttack® + TX, Nemaplus® + TX, Exhibitline sf® + TX, Scia-rid® + TX, Entonem® + TX, Steinernema kraussei (Nemasys L® + TX, BioNem L® + TX, Exhibitline srb®) + TX, Steinernema riobrave (BioVector® + TX, BioVektor®) + TX, Steinernema scapterisci (Nematac S®) + TX, Steinernema spp. + TX, Steinernema spp. spp.) (Guardian Nematodes®) + TX, Stethorus punctillum (Stethorus®) + TX, Tamarixia radiate + TX, Tetrastichus setifer + TX, Thripobius semiluteus + TX, Torymus sinensis + TX, Trichogramma brassicae (Tricholine b®) + TX, Trichogramma brassicae (Tricho-Strip®) + TX, Trichogramma evanescens + TX, Trichogramma minutum minutum) + TX, Trichogramma ostriniae + TX, Trichogramma platneri + TX, Trichogramma pretiosum + TX, Xanthopimplastemmator)、 Other biological products include: abscisic acid +TX, bioSea® +TX, Chondrostereum purpureum (Chontrol Paste®) +TX, Colletotrichum gloeosporioides (Collego®) +TX, copper octanoate (Cueva®) +TX, Delta Trap (Trapline d®) +TX, Erwinia amylovora (Harpin) (ProAct® +TX, Ni-HIBIT Gold CST®) +TX, Ferri-phosphate (Ferramol®) +TX, Funnel Trap (Trapline y®) +TX, Gallex® +TX, Grower's Secret® + TX, Homo-brassonolide + TX, Iron phosphate (Lilly Miller Worry Free Ferramol Slug & Snail Bait®) + TX, MCP hail trap (Trapline f®) + TX, Microctonus hyperodae + TX, Mycoleptodiscus terrestris (Des-X®) + TX, BioGain® + TX, Aminomite® + TX, Zenox® + TX, pheromone trap (Thripline ams®) + TX, potassium bicarbonate (MilStop®) + TX, potassium salts of fatty acids (Sanova®) + TX, potassium silicate solution (Sil-Matrix®) + TX, potassium iodide + potassium thiocyanate (Enzicur®) + TX, SuffOil-X® + TX, spider venom + TX, Nosema locustae (Semaspore Organic Grasshopper Control®) + TX, sticky traps (Trapline YF® + TX, RebellAmarillo®) + TX and trap (Takitrapline y+b®) + TX, and Safeners such as benoxacor + TX, cloquintocet (including cloquintocet-mexyl) + TX, cyprosulfamide + TX, dichlormid + TX, fenchlorazole (including fenchlorazole-ethyl) + TX, fenclorim + TX, fluxofenim + TX, furilazole + TX, isoxadifen (including isoxadifen-ethyl) + TX, mefenpyr (including mefenpyr-diethyl) + TX, metcamifen + TX and oxabetrinil + TX.

[0352] The reference numbers in square brackets after the active ingredient, such as [3878-19-1], refer to the Chemical Abstracts Registration Number. The above-mentioned compounds are known. When the active ingredients are included in "The Pesticide Manual" [The Pesticide Manual - A World Compendium; Thirteenth Edition; Editor: CDS Tomlin; The British Crop Protection Council], they are listed therein under the section number shown in parentheses above for the specific compound; for example, the compound "abamectin" is listed under section number (1). When "[CCN]" is added to a specific compound above, the corresponding compound is included in the "Compendium of Pesticide Common Names," which is accessible on the Internet [A. Wood; Compendium of Pesticide Common Names, (Copyright) 1995-2004]; for example, the compound "acetoprole" is listed at the Internet address: http: / / www.alanwood.net / pesticides / acetoprole.html.

[0353] Most of the active ingredients mentioned above are referred to above by so-called "common names", and the relevant "ISO common names" or another "common name" is used in individual cases. If the designation is not a "common name", the nature of the designation used instead is indicated in parentheses for the particular compound; in that case, the IUPAC name, IUPAC / Chemical Abstracts name, "chemical name", "trivial name", "compound name" or "development code" is used, or if neither one of these designations nor a "common name" is used, an "alternative name" is used. "CAS Registry Number" means the Chemical Abstracts Registry Number.

[0354] The active ingredient mixture of a compound of formula I selected from Tables A-1 to A-22, B-1 to B-4 and Table P with the above-mentioned active ingredient is preferably a mixture of a compound selected from Tables A-1 to A-22, B-1 to B-4 and Table P with the above-mentioned active ingredient in a ratio of 100:1 to 1:6000, in particular 50:1 to 1:50, in particular 20:1 to 1:20, in particular 10:1 to 1:10, in particular 5:1 to 1:5, particularly preferably 2:1 to 1:2, and also preferably 4:1 to 2:1, in particular 1:1 or 5:1. or 5:2 or 5:3 or 5:4 or 4:1 or 4:2 or 4:3 or 3:1 or 3:2 or 2:1 or 1:5 or 2:5 or 3:5 or 4:5 or 1:4 or 2:4 or 3:4 or 1:3 or 2:3 or 1:2 or 1:600 ​​or 1:300 or 1:150 or 1:35 or 2:35 or 4:35 or 1:75 or 2:75 or 4:75 or 1:6000 or 1:3000 or 1:1500 or 1:350 or 2:350 or 4:350 or 1:750 or 2:750 or 4:750. These mixing ratios are by weight.

[0355] The mixture may be used in a method for controlling pests, the method comprising the step of applying a composition comprising the mixture to the pest or its environment, excluding methods of treatment of the human or animal body by surgery or therapy and diagnostic methods performed on the human or animal body.

[0356] Mixtures comprising a compound of formula I selected from Tables A-1 to A-22, B-1 to B-4, and Table P and one or more of the active ingredients described above can be applied, for example, in a single ready-mix form, as a combined spray mixture made up of separate formulations of a single active ingredient, such as a "tank mix," and in combination with a single active ingredient when applied sequentially, i.e., one after the other within a fairly short period of time, such as a few hours or days. The order of application of the compound of formula I selected from Tables A-1 to A-22, B-1 to B-4, and Table P and the active ingredients described above is not critical to the practice of the invention.

[0357] The compositions according to the invention may also comprise further solid or liquid auxiliaries, such as stabilizers, for example non-epoxidized or epoxidized vegetable oils (for example epoxidized palm oil, rapeseed oil or soybean oil), antifoaming agents, for example silicone oils, preservatives, viscosity regulators, binders and / or tackifiers, fertilizers or other active ingredients for achieving specific effects, for example bactericides, fungicides, nematicides, plant activators, molluscicides or herbicides.

[0358] The compositions according to the invention are prepared in a manner known per se in the absence of auxiliaries, for example by grinding, sieving and / or compressing the solid active ingredient, and in the presence of at least one auxiliary, for example by intimately mixing the active ingredient with one or more auxiliaries and / or grinding it. These methods for preparing the compositions and the use of compound I for preparing these compositions are also the subject of the present invention.

[0359] The application methods for the compositions, i.e., spraying, atomizing, dusting, brushing, dusting, spreading, or pouring (which should be selected according to the intended purpose in the prevailing situation), are other subjects of the present invention. Typical concentration rates are 0.1 to 1000 ppm, preferably 0.1 to 500 ppm, of active ingredient. The application rate per hectare is generally 1 to 2000 g of active ingredient per hectare, in particular 10 to 1000 g / ha, preferably 10 to 600 g / ha.

[0360] The preferred method of application in the field of crop protection is application to the foliage of plants (foliar application), and the frequency and rate of application can be selected according to the risk of infestation by the relevant pest. Alternatively, the active ingredient can reach the plant via the root system (systemic action) by irrigating the plant habitat with a liquid composition or by introducing the active ingredient in solid form into the plant habitat, for example, the soil, for example in the form of granules (soil application). In the case of paddy rice plants, such granules can be metered into the paddy field.

[0361] The compounds of the present invention and compositions thereof are also suitable for protecting plant propagation material, such as seeds or seedlings of fruits, tubers, or grains, from the above-mentioned types of pests. The propagation material can be treated with the compounds before planting, for example, seeds can be treated before sowing. Alternatively, the compounds can be applied to the seed kernels by immersing them in a liquid composition or by applying a layer of a solid composition (coating). When the propagation material is planted at the application site, the compositions can also be applied between the furrows, for example, during drilling. These treatment methods for plant propagation material and the plant propagation material thus treated are further subjects of the present invention. Typical treatment rates depend on the plant and the pests / fungi to be controlled and are generally 1 to 200 grams per 100 kg of seeds, preferably 5 to 150 grams per 100 kg of seeds (e.g., 10 to 100 grams per 100 kg of seeds).

[0362] The term seed encompasses all types of seeds and plant propagules, including but not limited to true seeds, seed pieces, suckers, kernels, bulbs, fruits, tubers, grains, rhizomes, cuttings, cuttings, etc., and in preferred embodiments refers to true seeds.

[0363] The present invention also includes seeds coated with, treated with, or containing a compound of formula I. The term "coated with, treated with, and / or containing" generally refers to the active ingredient being present on most of the surface of the seed upon application, although depending on the application method, the active ingredient may penetrate the seed material to some extent. When the seed product is (re)planted, the active ingredient may be absorbed. In one embodiment, the present invention provides plant propagation material having attached thereto a compound of formula I, including those selected from Tables A-1 to A-22, B-1 to B-4, and P. Additionally, compositions are provided comprising plant propagation material treated with a compound of formula I, including those selected from Tables A-1 to A-22, B-1 to B-4, and P.

[0364] Seed treatment includes all suitable seed treatment techniques known in the art, such as seed dressing, seed coating, seed dusting, seed soaking, and seed pelleting. Seed treatment application of the compounds of formula I (including those selected from Tables A-1 to A-22, B-1 to B-4, and P) can be carried out by any known method, such as spraying or dusting the seeds before sowing or during sowing / planting of the seeds.

[0365] Biological Examples: The following examples illustrate the invention. Certain compounds of the invention can be distinguished from known compounds by their high efficacy at low application rates, which can be verified by those skilled in the art using the experimental procedures outlined in the examples, using lower application rates, such as 50 ppm, 12.5 ppm, 6 ppm, 3 ppm, 1.5 ppm, 0.8 ppm or 0.2 ppm, if necessary.

[0366] Example B1: Activity against Bemisia tabaci (cotton whitefly) Cotton leaf discs were placed on agar in 24-well microtiter plates and sprayed with test solutions prepared from a 10,000 ppm DMSO stock solution. After drying, the discs were infested with adult whiteflies. Samples were checked for mortality after 6 days of incubation.

[0367] The following compounds caused at least 80% mortality at an application rate of 200 ppm: P1, P2, P3, P4, P5, P6, P9, P10, P11, P12, P13, P14, P15.

[0368] Example B2: Activity against Diabrotica balteata (corn rootworm) Corn sprouts placed on agar layers in 24-well microtiter plates were treated by spraying with test solutions prepared from a 10,000 ppm DMSO stock solution. After drying, the plates were infested with L2 larvae (6-10 per well). Four days after infestation, samples were evaluated for mortality and growth inhibition compared with untreated samples.

[0369] The following compounds produced at least 80% efficacy in at least one of the two categories (mortality or growth inhibition) at an application rate of 200 ppm: P1, P2, P3, P4, P5, P6, P7, P8, P9, P10, P11, P12, P13, P14, P15, P16.

[0370] Example B3: Activity against Euschistus heros (Neotropical Brown Stink Bug) Soybean leaves on agar in 24-well microtiter plates were sprayed with test solutions prepared from a 10,000 ppm DMSO stock solution. After drying, the leaves were infested with N-2 nymphs. Samples were evaluated for mortality and growth inhibition compared to untreated samples 5 days after infestation.

[0371] The following compounds produced at least 80% efficacy in at least one of the two categories (mortality or growth inhibition) at an application rate of 200 ppm: P1, P2, P3, P4, P5, P6, P7, P8, P10, P11, P12, P13, P14, P15, P16.

[0372] Example B4: Activity against Frankliniella occidentalis (Occidental flower thrips) Sunflower leaf discs were placed on agar in 24-well microtiter plates and sprayed with test solutions prepared from a 10,000 DMSO stock solution. After drying, the discs were infested with populations of Frankliniella occidentalis at various ages. Samples were assessed for mortality 7 days after infestation.

[0373] The following compounds caused at least 80% mortality at an application rate of 200 ppm: P3, P6, P7, P8, P9, P10, P12, P13, P14.

[0374] Example B5: Activity against Plutella xylostella (Diamond back moth) Twenty-four well microtiter plates containing artificial diet were treated by pipette with test solutions prepared from a 10,000 ppm DMSO stock solution. After drying, diamondback moth eggs were pipetted onto gel blotting paper through a plastic stencil, which sealed the plate. Samples were assessed for mortality and growth inhibition compared to untreated samples 8 days after infestation.

[0375] The following compounds were at least 80% effective in at least one of the two categories (mortality or growth inhibition) at an application rate of 200 ppm: P1, P3, P13, P14, P15, P16.

[0376] Example B6: Activity against Myzus persicae (green peach aphid) Sunflower leaf discs were placed on agar in 24-well microtiter plates and sprayed with test solutions prepared from a 10,000 ppm DMSO stock solution. After drying, the discs were infested with aphid populations of various ages. Six days after infestation, samples were assessed for mortality.

[0377] The following compounds caused at least 80% mortality at an application rate of 200 ppm: P1, P2, P3, P4, P5, P6, P7, P8, P9, P10, P11, P12, P13, P14, P15, P16.

[0378] Example B7: Efficacy against Myzus persicae (green peach aphid) Roots of pea seedlings infested with aphid populations of various ages were placed directly into aqueous test solutions prepared from a 10,000 DMSO stock solution. Samples were assessed for mortality 6 days after the seedlings were placed in the test solution.

[0379] The following compounds caused at least 80% mortality at a test dose of 24 ppm: P2, P5, P11.

[0380] Example B8: Efficacy against Plutella xylostella (diamond moth) Twenty-four-well microtiter plates containing artificial diet were treated by pipette with test solutions prepared from a 10,000 ppm DMSO stock solution. After drying, the plates were infested with L2 larvae (10–15 per well). Five days after infestation, samples were assessed for mortality and growth inhibition compared with untreated samples.

[0381] The following compounds produced at least 80% efficacy in at least one of two categories (mortality or growth inhibition) at an application rate of 200 ppm: P2, P4, P5, P6, P7, P8, P9, P10, P11, P12.

[0382] Example B9: Activity against Spodoptera littoralis (Egyptian cotton leaf worm) Cotton leaf discs were placed on agar in 24-well microtiter plates and sprayed with aqueous test solutions prepared from a 10,000 ppm DMSO stock solution. After drying, the leaf discs were infested with five L1 larvae. Samples were evaluated for mortality, antifeedant effect, and growth inhibition three days after infestation compared to untreated samples. Control of Spodoptera littoralis by the test sample was indicated if at least one of the categories (mortality, antifeedant effect, and growth inhibition) was higher than that of untreated samples.

[0383] The following compounds provided at least 80% control at an application rate of 200 ppm: P1, P2, P3, P4, P5, P6, P7, P8, P9, P10, P11, P12, P13, P14, P15, P16.

[0384] Example B10: Activity against Tetranychus urticae (two-spotted spider mite) Phaseolus vulgaris leaf discs on agar in 24-well microtiter plates were sprayed with test solutions prepared from a 10,000 ppm DMSO stock solution. After drying, the discs were infested with mite populations of various ages. Eight days after infestation, samples were assessed for mortality in the mixed population (active stage).

[0385] The following compounds caused at least 80% mortality at an application rate of 200 ppm: P1, P4, P5, P8, P10.

[0386] Example B11: Efficacy against Nilaparvata lugens (brown planthopper), larvicide, feeding / contact Rice plants were treated with the diluted test solutions in a spray chamber. After drying, the plants were infested with approximately 20 N3 nymphs. Seven days after treatment, samples were evaluated for mortality and growth inhibition.

[0387] The following compounds caused at least 80% mortality at an application rate of 50 ppm: P1, P2, P9, P10, P11.

[0388] Example B12: Efficacy against Nilaparvata lugens (brown planthopper), larvicidal agent, systemic in water Rice plants grown in nutrient solution were treated with the diluted test solution in the nutrient culture system. One day after application, the plants were infested with approximately 20 N3 nymphs. Seven days after infestation, samples were evaluated for mortality and growth inhibition.

[0389] The following compounds caused at least 80% mortality at an application rate of 12.5 ppm: P1, P2, P4, P5, P9, P10, P11.

[0390] Example B13: Efficacy against sugar beet cyst nematode (Heterodera schachtii), larval mobility, in vitro profiling in 96-well plates Test solutions were prepared using the TECAN robot from a 10,000 ppm DMSO stock solution to obtain 20 μL of 500, 100, 50, 25, 12.5, and 6.25 ppm. Three replicates were generated for each concentration. To each well, 80 μL of nematode solution containing 100–150 freshly collected second-stage larvae of the sugar beet cyst nematode (Heterodera schachtii) was added. The plates were covered, kept in the dark at room temperature, and incubated for 48 hours. The mobility of exposed larvae in the treated wells was measured using an imaging tool and compared to the average of 12 untreated replicates.

[0391] The following compounds achieved at least 60% control at 100 ppm after 48 hours: P1, P4, P6, P8, P9, P10.

[0392] Example B14: Efficacy against Melodoigyne incognita, larval mobility, in vitro profiling in 96-well plates Test solutions are prepared using the TECAN robot from a 10,000 ppm DMSO stock solution to obtain 20 μL of 1000, 200, 100, 50, 25, and 12.5 ppm. Three replicates are generated for each concentration. 80 μL of nematode solution containing 100-150 freshly collected second-stage larvae of Melodoigyne incognita is added to each well. The plate is covered, kept in the dark at room temperature, and incubated for 48 hours. The mobility of exposed larvae in the treated wells is measured using an imaging tool and compared to the average of 12 untreated replicates. The following compounds achieved at least 60% control after 48 hours at 200 ppm: P4, P8.

[0393] Example B15: Efficacy against Carpocapsa (Cydia) pomonella (codling moth), larvicidal, feeding / contact Paraffin-coated food cubes were sprayed with diluted test solutions in application chambers. After drying, treated cubes (10 replicates) were infested with a single L1 larva. Samples were incubated at 26-27°C and checked for mortality and growth inhibition 14 days after infestation.

[0394] The following compounds produced at least 80% efficacy in at least one of the two categories (mortality or growth inhibition) at an application rate of 12.5 ppm: P4, P5, P11, P15, P16. Another aspect of the present invention may be as follows. [1] Compound of formula (I) [ka] (In the formula, A is CH or N; R 1 is C 1 ~C 4 Alkyl or C 3 ~C 6 Cycloalkyl-C 1 ~C 4 is alkyl; R 9 is hydrogen or C 1 ~C 4 is alkyl; Q is the formula Q 1 ~Q 7

change

change

change

change

change

change

change

[10] Compound of formula I-7

change

[11] Compound of formula I-8

change

[12] Compound of formula I-9

change

[12] , wherein is trifluoromethyl, trifluoromethylsulfonyl, or trifluoromethylsulfanyl.

[14] Compound of formula I-10

change

[15] Compound of formula I-11

change

[15] , wherein is ethyl. The compound according to any one of the above [1] to

[15] . 〔17〕R 9 is hydrogen, methyl or ethyl; preferably, R 9 The compound according to any one of the above [1] to

[16] , wherein is hydrogen.

[18] 2-[[5-(cyclopropylmethylsulfonyl)-6-[7-methyl-3-(trifluoromethyl)imidazo[4,5-c]pyridazin-6-yl]-3-pyridyl]oxy]-2-methyl-propanenitrile (compound P1); 2-[[5-ethylsulfonyl-6-[7-methyl-3-(trifluoromethyl)imidazo[4,5-c]pyridazin-6-yl]-3-pyridyl]oxy]-2-methyl-propanenitrile (compound P2); 2-[[5-ethylsulfonyl-6-[3-methyl-6-(trifluoromethyl)imidazo[4,5-b]pyridin-2-yl]-3-pyridyl]oxy]-2-methyl-propanenitrile (compound P3); 2-[[5-ethylsulfonyl-2-methyl-6-[3-methyl-6-(trifluoromethyl)imidazo[4,5-b]pyridin-2-yl]-3-pyridyl]oxy]-2-methyl-propanenitrile (compound P4); 2-[[5-ethylsulfonyl-6-[5-methoxy-3-methyl-4-oxo-6-(trifluoromethyl)imidazo[4,5-c]pyridin-2-yl]-3-pyridyl]oxy]-2-methyl-propanenitrile (compound P5); 2-[[6-[5-ethyl-3-methyl-4-oxo-6-(trifluoromethyl)imidazo[4,5-c]pyridin-2-yl]-5-ethylsulfonyl-3-pyridyl]oxy]-2-methyl-propanenitrile (compound P6); 2-[[6-[5-cyclopropyl-3-methyl-4-oxo-6-(trifluoromethyl)imidazo[4,5-c]pyridin-2-yl]-5-ethylsulfonyl-3-pyridyl]oxy]-2-methyl-propanenitrile (compound P7); 2-[[5-ethylsulfonyl-6-[7-(trifluoromethyl)imidazo[1,2-a]pyridin-2-yl]-3-pyridyl]oxy]-2-methyl-propanenitrile (compound P8); 2-[[5-ethylsulfonyl-6-[7-(trifluoromethyl)imidazo[1,2-b]pyridazin-2-yl]-3-pyridyl]oxy]-2-methyl-propanenitrile (compound P9); 2-[3-ethylsulfonyl-4-[6-(trifluoromethyl)pyrazolo[4,3-c]pyridin-2-yl]phenoxy]-2-methyl-propanenitrile (compound P10); 2-[[5-ethylsulfonyl-2-methyl-6-[7-methyl-3-(trifluoromethyl)imidazo[4,5-c]pyridazin-6-yl]-3-pyridyl]oxy]-2-methyl-propanenitrile (compound P11); 2-[3-ethylsulfonyl-4-[7-methyl-3-(trifluoromethyl)imidazo[4,5-c]pyridazin-6-yl]phenoxy]-2-methyl-propanenitrile (compound P12); 2-[[5-ethylsulfonyl-6-[1-methyl-5-(trifluoromethylsulfanyl)benzimidazol-2-yl]-3-pyridyl]oxy]-2-methyl-propanenitrile (compound P13); 2-[[5-ethylsulfonyl-6-[1-methyl-5-(trifluoromethylsulfonyl)benzimidazol-2-yl]-3-pyridyl]oxy]-2-methyl-propanenitrile (compound P14); 2-[[6-(2,2-difluoro-7-methyl-[1,3]dioxolo[4,5-f]benzimidazol-6-yl)-5-ethylsulfonyl-3-pyridyl]oxy]-2-methyl-propanenitrile (compound P15); and 2-[[6-(2,2-difluoro-[1,3]dioxolo[4,5-f][1,3]benzoxazol-6-yl)-5-ethylsulfonyl-3-pyridyl]oxy]-2-methyl-propanenitrile (compound P16) The compound of formula I described in [1] above, selected from the group consisting of:

[19] A pesticidal composition comprising, as an active ingredient, at least one compound of formula I as described in any one of [1] to

[18] above, or, if appropriate, a tautomer thereof, in each case in free form or in the form of an agrochemically usable salt, and at least one auxiliary agent.

[20] A method for controlling pests, comprising the step of applying a pesticidal amount of a compound of formula I described in any one of [1] to

[18] or a composition described in

[19] to a pest, a habitat of the pest, or a plant susceptible to attack by the pest.

[21] A method for protecting plant propagation material from attack by pests, comprising treating the propagation material or a site where the propagation material is planted with the composition described in

[19] .

Claims

1. Compounds of formula (I) 【Chemical 1】 (In the formula, A is CH or N; R 1 is C 1 ~C 4 Alkyl or C 3 ~C 6 Cycloalkyl-C 1 ~C 4 is alkyl; R 9 is hydrogen or C 1 ~C 4 is alkyl; Q is a formula Q2 to Q 7 【Chemistry 2】 wherein the arrow indicates the point of attachment to the ring containing group A; and, For Q 4 , G 1 is CH and G 2 is N, or G 1 is N and G 2 is CH; For Q 6 , X 1 is NR 3 ; For Q 7 , X 1 is NR 3 or O; R 3 is C 1 ~C 4 is alkyl; R 2 is a halogen, C 1 ~C 6 Haloalkyl, C 1 ~C 4 Haloalkylsulfanyl, C 1 ~C 4 Haloalkylsulfinyl, C 1 ~C 4 Haloalkylsulfonyl or C 1 ~C 6 haloalkoxy; R 4 is C 1 ~C 4 Alkyl, C 1 ~C 4 Haloalkyl, C 3 ~C 6 Cycloalkyl or C 1 ~C 4 alkoxy) is a group selected from the group consisting of or an agrochemically acceptable salt, stereoisomer, enantiomer, tautomer or N-oxide of a compound of formula I.

2. R 4 is ethyl, methoxy or cyclopropyl.

3. R 3 The compound according to claim 1 or 2, wherein is methyl.

4. R 2 The compound according to any one of claims 1 to 3, wherein is trifluoromethyl, pentafluoroethyl, trifluoromethylsulfanyl, trifluoromethylsulfinyl or trifluoromethylsulfonyl.

5. The compound according to claim 1, wherein R 2 is trifluoromethyl, trifluoromethylsulfonyl, or trifluoromethylsulfanyl.

6. R 1 is ethyl or -CH 2 The compound of any one of claims 1 to 5, which is cyclopropyl.

7. The compound according to claim 1, wherein R 1 is ethyl.

8. R 9 The compound according to any one of claims 1 to 7, wherein is hydrogen, methyl or ethyl.

9. The compound according to claim 1, wherein R 9 is hydrogen.

10. 2-[[5-(cyclopropylmethylsulfonyl)-6-[7-methyl-3-(trifluoromethyl)imidazo[4,5-c]pyridazin-6-yl]-3-pyridyl]oxy]-2-methyl-propanenitrile (compound P1); 2-[[5-ethylsulfonyl-6-[7-methyl-3-(trifluoromethyl)imidazo[4,5-c]pyridazin-6-yl]-3-pyridyl]oxy]-2-methyl-propanenitrile (compound P2); 2-[[5-ethylsulfonyl-6-[3-methyl-6-(trifluoromethyl)imidazo[4,5-b]pyridin-2-yl]-3-pyridyl]oxy]-2-methyl-propanenitrile (compound P3); 2-[[5-ethylsulfonyl-2-methyl-6-[3-methyl-6-(trifluoromethyl)imidazo[4,5-b]pyridin-2-yl]-3-pyridyl]oxy]-2-methyl-propanenitrile (compound P4); 2-[[5-ethylsulfonyl-6-[5-methoxy-3-methyl-4-oxo-6-(trifluoromethyl)imidazo[4,5-c]pyridin-2-yl]-3-pyridyl]oxy]-2-methyl-propanenitrile (compound P5); 2-[[6-[5-ethyl-3-methyl-4-oxo-6-(trifluoromethyl)imidazo[4,5-c]pyridin-2-yl]-5-ethylsulfonyl-3-pyridyl]oxy]-2-methyl-propanenitrile (compound P6); 2-[[6-[5-cyclopropyl-3-methyl-4-oxo-6-(trifluoromethyl)imidazo[4,5-c]pyridin-2-yl]-5-ethylsulfonyl-3-pyridyl]oxy]-2-methyl-propanenitrile (compound P7); 2-[[5-ethylsulfonyl-6-[7-(trifluoromethyl)imidazo[1,2-a]pyridin-2-yl]-3-pyridyl]oxy]-2-methyl-propanenitrile (compound P8); 2-[[5-ethylsulfonyl-6-[7-(trifluoromethyl)imidazo[1,2-b]pyridazin-2-yl]-3-pyridyl]oxy]-2-methyl-propanenitrile (compound P9); 2-[3-ethylsulfonyl-4-[6-(trifluoromethyl)pyrazolo[4,3-c]pyridin-2-yl]phenoxy]-2-methyl-propanenitrile (compound P10); 2-[[5-ethylsulfonyl-2-methyl-6-[7-methyl-3-(trifluoromethyl)imidazo[4,5-c]pyridazin-6-yl]-3-pyridyl]oxy]-2-methyl-propanenitrile (compound P11); 2-[3-ethylsulfonyl-4-[7-methyl-3-(trifluoromethyl)imidazo[4,5-c]pyridazin-6-yl]phenoxy]-2-methyl-propanenitrile (compound P12); 2-[[5-ethylsulfonyl-6-[1-methyl-5-(trifluoromethylsulfanyl)benzimidazol-2-yl]-3-pyridyl]oxy]-2-methyl-propanenitrile (compound P13); 2-[[5-ethylsulfonyl-6-[1-methyl-5-(trifluoromethylsulfonyl)benzimidazol-2-yl]-3-pyridyl]oxy]-2-methyl-propanenitrile (compound P14); 2-[[6-(2,2-difluoro-7-methyl-[1,3]dioxolo[4,5-f]benzimidazol-6-yl)-5-ethylsulfonyl-3-pyridyl]oxy]-2-methyl-propanenitrile (compound P15); and 2-[[6-(2,2-difluoro-[1,3]dioxolo[4,5-f][1,3]benzoxazol-6-yl)-5-ethylsulfonyl-3-pyridyl]oxy]-2-methyl-propanenitrile (compound P16) 2. The compound of formula I according to claim 1, selected from the group consisting of:

11. 11. A pesticidal composition comprising as active ingredient at least one compound of formula I as defined in any one of claims 1 to 10, or, where appropriate, a tautomer thereof, in each case in free form or in agrochemically available salt form, and at least one adjuvant.

12. 12. A method for controlling pests, excluding medical treatment for humans, comprising the step of applying to the pest, the pest's habitat, or to plants susceptible to attack by the pest, a pesticidally effective amount of a compound of formula I as defined in any one of claims 1 to 10 or a composition as defined in claim 11.

13. 12. A method of protecting plant propagation material from attack by pests, comprising treating the propagation material or the locus where the propagation material is to be planted with the composition of claim 11.

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