Pesticidal Active Heterocyclic Derivatives Having Sulfoximine-Containing Substituents - Patent application

Abstract

Compounds of formula (I) 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 arthropods, in particular insects, or animal pests, including representatives of the order Acarina. TIFF2024520657000286.tif40158

Description

[Technical Field]

[0001] The present invention relates to pesticidally active, in particular insecticidally active, heterocyclic derivatives containing sulfoximine 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 active heterocyclic sulfoximine derivatives have already been described in the literature, for example in WO 2015 / 071180, WO 2016 / 039441, WO 2018 / 206348, WO 2019 / 219689, WO 2019 / 229089, WO 2019 / 234158, WO 2020 / 084075 and WO 2020 / 141136. Summary of the Invention [Means for solving the problem]

[0003] It has surprisingly been found that certain novel sulfoximine-containing phenyl and pyridyl derivatives bearing stereogenic sulfur and cyanoisopropoxy, cyanoisopropyl, or cyanocyclopropyl groups have favorable properties as pesticides and are stereospecifically accessible by stereoselective oxidation followed by a stereospecific iminization reaction.

[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; S * is a stereogenic sulfur atom in the R- or S-configuration; R8 is cyanoisopropoxy, cyanoisopropyl, or cyanocyclopropyl; R9 is hydrogen or C1-C4 alkyl; Q is the formula Q1 to Q5 [ka] (wherein the arrow indicates the point of attachment to the ring incorporating the A group; 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. or Agrochemically acceptable salts, stereoisomers, enantiomers, tautomers or N-oxides of compounds of formula I are provided. 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 straight-chained or branched and are, for example, methyl, ethyl, n-propyl, isopropyl, n-butyl, sec-butyl, isobutyl, tert-butyl, pentyl, hexyl, and branched isomers thereof. Haloalkylsulfanyl, haloalkylsulfinyl, haloalkylsulfonyl, and alkoxy groups are derived from the alkyl groups described above.

[0007] As used herein, the term "cyanoisopropyl" refers to an isopropyl group (as defined above), in which one hydrogen atom may be replaced by a cyano group. Cyanoisopropyl is, for example, 1-cyano-1-methylethyl or 2-cyano-1-methylethyl.

[0008] Halogen is generally fluorine, chlorine, bromine or iodine. This also applies correspondingly to halogen in combination with other meanings, such as haloalkyl.

[0009] Haloalkyl groups have 1 to n carbon atoms, preferably straight or branched saturated C1-C6 groups with a chain length of 1 to 6 carbon atoms. n It refers to alkyl groups (as defined above), in which some or all of the hydrogen atoms in these groups may be replaced by fluorine, chlorine, bromine and / or iodine. 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.

[0010] The alkoxy groups preferably have 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 tert-butoxy, and also the isomeric pentyloxy and hexyloxy groups; preferred are methoxy and ethoxy.

[0011] As used herein, the term "cyanoisopropoxy" refers to an i-propoxy group (as defined above), in which one hydrogen atom may be replaced by a cyano group. Cyanoisopropoxy is, for example, 1-cyano-1-methylethoxy or 2-cyano-1-methylethoxy.

[0012] As used herein, "C1-C n The term "haloalkoxy" refers to C1-C nA linear or branched saturated C1-C group having 1 to n carbon atoms bonded via an oxygen atom, similar to alkoxy. n Refers to a haloalkyl group (as defined above).

[0013] Alkylsulfanyl is, for example, methylsulfanyl, ethylsulfanyl, propylsulfanyl, isopropylsulfanyl, butylsulfanyl, pentylsulfanyl and hexylsulfanyl.

[0014] Alkylsulfinyl is, for example, methylsulfinyl, ethylsulfinyl, propylsulfinyl, isopropylsulfinyl, butylsulfinyl, pentylsulfinyl and hexylsulfinyl.

[0015] Alkylsulfonyl is, for example, methylsulfonyl, ethylsulfonyl, propylsulfonyl, isopropylsulfonyl, butylsulfonyl, pentylsulfonyl and hexylsulfonyl.

[0016] As used herein, "C1-C nThe term "haloalkylsulfanyl" refers to an alkylsulfanyl group as defined above that is partially or fully substituted with fluorine, chlorine, bromine and / or iodine. The haloalkylsulfanyl group preferably has a chain length of 1 to 4 carbon atoms and includes, for example, fluoromethylthio, difluoromethylthio, trifluoromethylthio, chlorodifluoromethylthio, bromodifluoromethylthio, 2-fluoroethylthio, 2-chloroethylthio, 2-bromoethylthio, 2-iodoethylthio, 2,2-difluoroethylthio, 2,2,2-trifluoroethylthio, 2,2,2-trichloroethylthio, 2-chloro-2-fluoroethylthio, 2-chloro-2,2-difluoroethylthio, 2,2-dichloro-2-fluoroethylthio, pentafluoroethylthio, 2-fluoropropylthio, 3 ... propylthio, 2-chloropropylthio, 3-chloropropylthio, 2-bromopropylthio, 3-bromopropylthio, 2,2-difluoropropylthio, 2,3-difluoropropylthio, 2,3-dichloropropylthio, 3,3,3-trifluoropropylthio, 3,3,3-trichloropropylthio, 2,2,3,3,3-pentafluoropropylthio, heptafluoropropylthio, 1-(fluoromethyl)-2-fluoroethylthio, 1-(chloromethyl)-2-chloroethylthio, 1-(bromomethyl)-2-bromoethylthio, 4-fluorobutylthio, 4-chlorobutylthio, or 4-bromobutylthio.

[0017] Similar considerations apply to C1~C n Haloalkylsulfanyl (as above) but with sulfur in different oxidation states, "C1-C n Haloalkylsulfinyl" and "C1-C n The term "haloalkylsulfonyl" applies to, for example, sulfoxide -S(O)C1-C2 n Haloalkyl or sulfone -S(O)2C1~C n haloalkyl. Thus, for example, groups such as trifluoromethylsulfinyl, trifluoromethylsulfonyl or 2,2,2-trifluoroethylsulfonyl.

[0018] Cycloalkyl groups preferably have from 3 to 6 ring carbon atoms, for example cyclopropyl, cyclobutyl, cyclopentyl and cyclohexyl.

[0019] As used herein, the term "cyanocyclopropyl" refers to cyclopropyl (as defined above), in which one hydrogen atom may be replaced by a cyano group. Cyanocyclopropyl is, for example, 1-cyanocyclopropyl or 2-cyanocyclopropyl.

[0020] The compounds of formula I according to the present invention also include hydrates which may be formed during salt formation.

[0021] The sulfur stereogenic center (S * The presence of a chiral sulfur atom S ) means that the compound can occur in optically isomeric forms, i.e., enantiomeric or diastereomeric forms. Preferably, and in the absence of additional asymmetric carbon or sulfur atoms, the present invention therefore provides a chiral sulfur atom S * The present invention refers to both enantiomers resulting from the presence of the stereogenic sulfur atom, i.e., the present invention encompasses compounds of formula (I) in the (R) or (S) configuration at the stereogenic sulfur atom, as well as mixtures thereof (pure enantiomers or mixtures of enantiomers, i.e., single enantiomers with enantiomeric excess). The present invention also refers to the individual enantiomers obtained after separation of a racemic mixture using known resolution methods or obtained by stereoselective synthesis. For example, the first and second eluting enantiomers obtained by chromatographic separation using a chiral stationary phase (such as an amylose- or cellulose-based CHIRALPAK® column); or enantiomers obtained stereospecifically by iminization of stereogenic sulfinyl derivatives produced by stereoselective oxidation of the corresponding sulfanyl compounds, are also subject of the present invention.

[0022] Certain embodiments of the present invention are provided as described below.

[0023] Embodiment 1 provides a compound of Formula I, or an agrochemically acceptable salt, stereoisomer, enantiomer, tautomer, or N-oxide thereof, as defined above.

[0024] Embodiment 2 provides a compound according to embodiment 1, or an agrochemically acceptable salt, stereoisomer, enantiomer, tautomer, or N-oxide thereof, wherein: A is CH or N; R1 is ethyl, propyl, or isopropyl; R8 is cyanoisopropoxy, cyanoisopropyl, or cyanocyclopropyl; and R9 is hydrogen, methyl or ethyl.

[0025] 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; R8 is cyanoisopropoxy, cyanoisopropyl, or cyanocyclopropyl; and R9 is hydrogen or methyl.

[0026] 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; R8 is 1-cyano-1-methyl-ethoxy, 1-cyano-1-methyl-ethyl or 1-cyanocyclopropyl; and R9 is hydrogen or methyl.

[0027] Embodiment 3c 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; R8 is 1-cyano-1-methyl-ethoxy, 1-cyano-1-methyl-ethyl or 1-cyanocyclopropyl; and R9 is hydrogen or methyl.

[0028] 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; R8 is 1-cyano-1-methyl-ethoxy, 1-cyano-1-methyl-ethyl or 1-cyanocyclopropyl; and R9 is hydrogen.

[0029] 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; R8 is 1-cyano-1-methyl-ethoxy, 1-cyano-1-methyl-ethyl or 1-cyanocyclopropyl; and R9 is hydrogen.

[0030] Embodiment 4c 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; R8 is 1-cyano-1-methyl-ethoxy, 1-cyano-1-methyl-ethyl or 1-cyanocyclopropyl; and R9 is hydrogen.

[0031] 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; R8 is 1-cyano-1-methyl-ethoxy, 1-cyano-1-methyl-ethyl or 1-cyanocyclopropyl; and R9 is methyl.

[0032] 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; R8 is 1-cyano-1-methyl-ethoxy, 1-cyano-1-methyl-ethyl or 1-cyanocyclopropyl; and R9 is methyl.

[0033] Embodiment 5c 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; R8 is 1-cyano-1-methyl-ethoxy, 1-cyano-1-methyl-ethyl or 1-cyanocyclopropyl; and R9 is methyl.

[0034] Embodiment 6a provides a compound according to embodiment 1, or an agrochemically acceptable salt, stereoisomer, enantiomer, tautomer, or N-oxide thereof, wherein: Q is a group selected from the group consisting of formulas Q1 to Q5, where the arrow indicates the point of attachment to the ring in which the A group is incorporated; 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 each independently N or CH.

[0035] Embodiment 6b provides a compound according to embodiment 1, or an agrochemically acceptable salt, stereoisomer, enantiomer, tautomer, or N-oxide thereof, wherein: Q is a group selected from the group consisting of formulas Q1 to Q5, where the arrow indicates the point of attachment to the ring in which the A group is incorporated; and, R2 is C1-C2 haloalkyl or C1-C2 haloalkylsulfanyl; X1 is NCH3; R3 is C1-C2 alkyl; R4 is C1-C2 alkyl, C1-C2 alkoxy or cyclopropyl; and G1 and G2 are each independently N or CH.

[0036] 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 incorporating the A group; and, R2 is C1-C2 fluoroalkyl, trifluoromethylsulfanyl, trifluoromethylsulfinyl, trifluoromethylsulfonyl, difluoromethylsulfanyl, difluoromethylsulfinyl, or difluoromethylsulfonyl; X1 is NCH3; R3 is methyl; R4 is methyl, ethyl, methoxy or cyclopropyl; and G1 and G2 are, independently of each other, N or CH. is a group selected from

[0037] 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 incorporating the A group; and, R2 is trifluoromethyl, pentafluoroethyl, trifluoromethylsulfanyl, trifluoromethylsulfinyl, or trifluoromethylsulfonyl; X1 is NCH3; R3 is methyl; R4 is ethyl, methoxy or cyclopropyl. is a group selected from When Q is Q1, G1 is N and G2 is CH, or G1 is CH and G2 is N, or G1 and G2 are both N; and When Q is Q2, G2 is CH or N.

[0038] 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 incorporating the A group; and, R2 is trifluoromethyl, pentafluoroethyl, or trifluoromethylsulfanyl; X1 is NCH3; R3 is methyl; R4 is ethyl, methoxy or cyclopropyl. is a group selected from When Q is Q1, G1 is N and G2 is CH, or G1 is CH and G2 is N, or G1 and G2 are both N; and When Q is Q2, G2 is CH or N.

[0039] 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 and Q5 [ka] (wherein the arrow indicates the point of attachment to the ring incorporating the A group; and, R2 is trifluoromethyl or trifluoromethylsulfanyl; X1 is NCH3; R3 is methyl; R4 is ethyl, methoxy or cyclopropyl. is a group selected from When Q is Q1, G1 is N and G2 is CH, or G1 is CH and G2 is N, or G1 and G2 are both N; and When Q is Q2, G2 is CH or N.

[0040] Embodiment 9a provides a compound according to embodiment 1, or an agrochemically acceptable salt, stereoisomer, enantiomer, tautomer, or N-oxide thereof, wherein: Q is the Q1 group [ka] (wherein the arrow indicates the point of attachment to the ring incorporating the A group; and, R2 is trifluoromethyl, pentafluoroethyl, trifluoromethylsulfanyl, trifluoromethylsulfinyl or trifluoromethylsulfonyl. and X1 is NCH3; and G1 is N and G2 is CH, or G1 is CH and G2 is N, or G1 and G2 are both N.

[0041] Embodiment 9b provides a compound according to embodiment 1, or an agrochemically acceptable salt, stereoisomer, enantiomer, tautomer, or N-oxide thereof, wherein: Q is the Q1 group [ka] (wherein the arrow indicates the point of attachment to the ring incorporating the A group; and, R2 is trifluoromethyl, pentafluoroethyl, or trifluoromethylsulfanyl; X1 is NCH3; and G1 is N and G2 is CH, or G1 is CH and G2 is N, or G1 and G2 are both N. is.

[0042] Embodiment 9c provides a compound according to embodiment 1, or an agrochemically acceptable salt, stereoisomer, enantiomer, tautomer, or N-oxide thereof, wherein: Q is the Q1 group [ka] (wherein the arrow indicates the point of attachment to the ring incorporating the A group; and, R2 is trifluoromethyl; X1 is NCH3; and G1 is N and G2 is CH, or G1 is CH and G2 is N, or G1 and G2 are both N. is.

[0043] Embodiment 10a provides a compound according to embodiment 1, or an agrochemically acceptable salt, stereoisomer, enantiomer, tautomer, or N-oxide thereof, wherein: Q is a Q2 group [ka] (wherein the arrow indicates the point of attachment to the ring incorporating the A group; and, R2 is trifluoromethyl, pentafluoroethyl, trifluoromethylsulfanyl, trifluoromethylsulfinyl, or trifluoromethylsulfonyl; and G2 is CH or N is.

[0044] Embodiment 10b provides a compound according to embodiment 1, or an agrochemically acceptable salt, stereoisomer, enantiomer, tautomer, or N-oxide thereof, wherein: Q is a Q2 group [ka] (wherein the arrow indicates the point of attachment to the ring incorporating the A group; and, R2 is trifluoromethyl, pentafluoroethyl, or trifluoromethylsulfanyl; and G2 is CH or N is.

[0045] Embodiment 10c provides a compound according to embodiment 1, or an agrochemically acceptable salt, stereoisomer, enantiomer, tautomer, or N-oxide thereof, wherein: Q is a Q2 group [ka] (wherein the arrow indicates the point of attachment to the ring incorporating the A group; and, R2 is trifluoromethyl or trifluoromethylsulfanyl; and G2 is CH or N is.

[0046] Embodiment 10d provides a compound according to embodiment 1, or an agrochemically acceptable salt, stereoisomer, enantiomer, tautomer, or N-oxide thereof, wherein: Q is a Q2 group [ka] (wherein the arrow indicates the point of attachment to the ring incorporating the A group; and, R2 is trifluoromethyl; and G2 is CH or N is.

[0047] 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 Q5 group [ka] (wherein the arrow indicates the point of attachment to the ring incorporating the A group; and, R2 is trifluoromethyl, pentafluoroethyl, trifluoromethylsulfanyl, trifluoromethylsulfinyl, or trifluoromethylsulfonyl; R3 is methyl; and R4 is ethyl, methoxy or cyclopropyl. is.

[0048] Embodiment 11b provides a compound according to embodiment 1, or an agrochemically acceptable salt, stereoisomer, enantiomer, tautomer, or N-oxide thereof, wherein: Q is the Q5 group [ka] (wherein the arrow indicates the point of attachment to the ring incorporating the A group; and, R2 is trifluoromethyl, pentafluoroethyl, or trifluoromethylsulfanyl; R3 is methyl; and R4 is ethyl, methoxy or cyclopropyl. is.

[0049] Embodiment 11c provides a compound according to embodiment 1, or an agrochemically acceptable salt, stereoisomer, enantiomer, tautomer, or N-oxide thereof, wherein: Q is the Q5 group [ka] (wherein the arrow indicates the point of attachment to the ring incorporating the A group; and, R2 is trifluoromethyl; R3 is methyl; and R4 is ethyl, methoxy or cyclopropyl. is.

[0050] 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, or isopropyl; R8 is cyanoisopropoxy, cyanoisopropyl, or cyanocyclopropyl; R9 is hydrogen, methyl or ethyl; Q is the formula Q1 to Q5 (wherein the arrow indicates the point of attachment to the ring incorporating the A group; 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 the group consisting of:

[0051] 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; R8 is cyanoisopropoxy, cyanoisopropyl, or cyanocyclopropyl; R9 is hydrogen or methyl; Q is Q1, Q2 and Q5 [ka] (wherein the arrow indicates the point of attachment to the ring incorporating the A group; and, R2 is C1-C2 fluoroalkyl, trifluoromethylsulfanyl, trifluoromethylsulfinyl, trifluoromethylsulfonyl, difluoromethylsulfanyl, difluoromethylsulfinyl, or difluoromethylsulfonyl; X1 is NCH3; R3 is methyl; R4 is methyl, ethyl, methoxy or cyclopropyl; and G1 and G2 are, independently of each other, N or CH. is a group selected from

[0052] 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 ethyl; R8 is 1-cyano-1-methyl-ethoxy, 1-cyano-1-methyl-ethyl or 1-cyanocyclopropyl; R9 is hydrogen or methyl; Q is Q1, Q2 and Q5 [ka] (wherein the arrow indicates the point of attachment to the ring incorporating the A group; and, R2 is C1-C2 fluoroalkyl, trifluoromethylsulfanyl, trifluoromethylsulfinyl, trifluoromethylsulfonyl, difluoromethylsulfanyl, difluoromethylsulfinyl, or difluoromethylsulfonyl; X1 is NCH3; R3 is methyl; R4 is methyl, ethyl, methoxy or cyclopropyl; and G1 and G2 are, independently of each other, N or CH. is a group selected from

[0053] Embodiment 15a 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; R8 is 1-cyano-1-methyl-ethoxy, 1-cyano-1-methyl-ethyl or 1-cyanocyclopropyl; R9 is hydrogen or methyl; Q is Q1, Q2 and Q5 [ka] (wherein the arrow indicates the point of attachment to the ring incorporating the A group; and, R2 is trifluoromethyl, pentafluoroethyl, trifluoromethylsulfanyl, trifluoromethylsulfinyl, or trifluoromethylsulfonyl; X1 is NCH3; R3 is methyl; R4 is ethyl, methoxy or cyclopropyl. is a group selected from When Q is Q1, G1 is N and G2 is CH, or G1 is CH and G2 is N, or G1 and G2 are both N; and When Q is Q2, G2 is CH or N.

[0054] Embodiment 15b 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; R8 is 1-cyano-1-methyl-ethoxy, 1-cyano-1-methyl-ethyl or 1-cyanocyclopropyl; R9 is hydrogen or methyl; Q is Q1, Q2 and Q5 [ka] (wherein the arrow indicates the point of attachment to the ring incorporating the A group; and, R2 is trifluoromethyl, pentafluoroethyl, trifluoromethylsulfanyl, trifluoromethylsulfinyl, or trifluoromethylsulfonyl; X1 is NCH3; R3 is methyl; R4 is ethyl, methoxy or cyclopropyl. is a group selected from When Q is Q1, G1 is N and G2 is CH, or G1 is CH and G2 is N, or G1 and G2 are both N; and When Q is Q2, G2 is CH or N.

[0055] 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; R8 is 1-cyano-1-methyl-ethoxy, 1-cyano-1-methyl-ethyl or 1-cyanocyclopropyl; R9 is hydrogen or methyl; Q is Q1, Q2 and Q5 [ka] (wherein the arrow indicates the point of attachment to the ring incorporating the A group; and, R2 is trifluoromethyl, pentafluoroethyl, or trifluoromethylsulfanyl; X1 is NCH3; R3 is methyl; R4 is ethyl, methoxy or cyclopropyl. is a group selected from When Q is Q1, G1 is N and G2 is CH, or G1 is CH and G2 is N, or G1 and G2 are both N; and When Q is Q2, G2 is CH or N.

[0056] Embodiment 16b 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; R8 is 1-cyano-1-methyl-ethoxy, 1-cyano-1-methyl-ethyl or 1-cyanocyclopropyl; R9 is hydrogen or methyl; Q is Q1, Q2 and Q5 [ka] (wherein the arrow indicates the point of attachment to the ring incorporating the A group; and, R2 is trifluoromethyl, pentafluoroethyl, or trifluoromethylsulfanyl; X1 is NCH3; R3 is methyl; R4 is ethyl, methoxy or cyclopropyl. is a group selected from When Q is Q1, G1 is N and G2 is CH, or G1 is CH and G2 is N, or G1 and G2 are both N; and When Q is Q2, G2 is CH or N.

[0057] Embodiment 17a 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; R8 is 1-cyano-1-methyl-ethoxy, 1-cyano-1-methyl-ethyl or 1-cyanocyclopropyl; R9 is hydrogen; Q is Q1, Q2 and Q5 [ka] (wherein the arrow indicates the point of attachment to the ring incorporating the A group; and, R2 is trifluoromethyl or trifluoromethylsulfanyl; X1 is NCH3; R3 is methyl; R4 is ethyl, methoxy or cyclopropyl. is a group selected from When Q is Q1, G1 is N and G2 is CH, or G1 is CH and G2 is N, or G1 and G2 are both N; and When Q is Q2, G2 is CH or N.

[0058] Embodiment 17b 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; R8 is 1-cyano-1-methyl-ethoxy, 1-cyano-1-methyl-ethyl or 1-cyanocyclopropyl; R9 is hydrogen; Q is Q1, Q2 and Q5 [ka] (wherein the arrow indicates the point of attachment to the ring incorporating the A group; and, R2 is trifluoromethyl or trifluoromethylsulfanyl; X1 is NCH3; R3 is methyl; R4 is ethyl, methoxy or cyclopropyl. is a group selected from When Q is Q1, G1 is N and G2 is CH, or G1 is CH and G2 is N, or G1 and G2 are both N; and When Q is Q2, G2 is CH or N.

[0059] Embodiment 18a 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; R8 is 1-cyano-1-methyl-ethoxy, 1-cyano-1-methyl-ethyl or 1-cyanocyclopropyl; R9 is methyl; Q is Q1, Q2 and Q5 [ka] (wherein the arrow indicates the point of attachment to the ring incorporating the A group; and, R2 is trifluoromethyl or trifluoromethylsulfanyl; X1 is NCH3; R3 is methyl; R4 is ethyl, methoxy or cyclopropyl. is a group selected from When Q is Q1, G1 is N and G2 is CH, or G1 is CH and G2 is N, or G1 and G2 are both N; and When Q is Q2, G2 is CH or N.

[0060] Embodiment 18b 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; R8 is 1-cyano-1-methyl-ethoxy, 1-cyano-1-methyl-ethyl or 1-cyanocyclopropyl; R9 is methyl; Q is Q1, Q2 and Q5 [ka] (wherein the arrow indicates the point of attachment to the ring incorporating the A group; and, R2 is trifluoromethyl or trifluoromethylsulfanyl; X1 is NCH3; R3 is methyl; R4 is ethyl, methoxy or cyclopropyl. is a group selected from When Q is Q1, G1 is N and G2 is CH, or G1 is CH and G2 is N, or G1 and G2 are both N; and When Q is Q2, G2 is CH or N.

[0061] Embodiment 19a provides a compound according to embodiment 1, or an agrochemically acceptable salt, stereoisomer, enantiomer, tautomer, or N-oxide thereof, wherein: A is N or CH; R1 is ethyl; R8 is 1-cyano-1-methyl-ethoxy, 1-cyano-1-methyl-ethyl or 1-cyanocyclopropyl; R9 is hydrogen or methyl; Q is the Q1 group [ka] (wherein the arrow indicates the point of attachment to the ring incorporating the A group; and, R2 is trifluoromethyl; X1 is NCH3; and G1 is N and G2 is CH, or G1 is CH and G2 is N, or G1 and G2 are both N. is.

[0062] Embodiment 19b provides a compound according to embodiment 1, or an agrochemically acceptable salt, stereoisomer, enantiomer, tautomer, or N-oxide thereof, wherein: A is N or CH; R1 is ethyl; R8 is 1-cyano-1-methyl-ethoxy, 1-cyano-1-methyl-ethyl or 1-cyanocyclopropyl; R9 is hydrogen or methyl; Q is the Q1 group [ka] (wherein the arrow indicates the point of attachment to the ring incorporating the A group; and, R2 is trifluoromethyl; X1 is NCH3; and G1 is N and G2 is CH, or G1 is CH and G2 is N is.

[0063] Embodiment 19c provides a compound according to embodiment 1, or an agrochemically acceptable salt, stereoisomer, enantiomer, tautomer, or N-oxide thereof, wherein: A is N or CH; R1 is ethyl; R8 is 1-cyano-1-methyl-ethoxy or 1-cyanocyclopropyl; R9 is hydrogen or methyl; Q is the Q1 group [ka] (wherein the arrow indicates the point of attachment to the ring incorporating the A group; and, R2 is trifluoromethyl; X1 is NCH3; and G1 is N and G2 is CH, or G1 is CH and G2 is N, or G1 and G2 are both N. is.

[0064] Embodiment 20a 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; R8 is 1-cyano-1-methyl-ethoxy, 1-cyano-1-methyl-ethyl or 1-cyanocyclopropyl; R9 is hydrogen; Q is the Q1 group [ka] (wherein the arrow indicates the point of attachment to the ring incorporating the A group; and, R2 is trifluoromethyl; X1 is NCH3; and G1 is N and G2 is CH, or G1 is CH and G2 is N, or G1 and G2 are both N. is.

[0065] Embodiment 20b 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; R8 is 1-cyano-1-methyl-ethoxy, 1-cyano-1-methyl-ethyl or 1-cyanocyclopropyl; R9 is hydrogen; Q is the Q1 group [ka] (wherein the arrow indicates the point of attachment to the ring incorporating the A group; and, R2 is trifluoromethyl; X1 is NCH3; and G1 is N and G2 is CH, or G1 is CH and G2 is N is.

[0066] Embodiment 20c 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; R8 is 1-cyano-1-methyl-ethoxy or 1-cyanocyclopropyl; R9 is hydrogen; Q is the Q1 group [ka] (wherein the arrow indicates the point of attachment to the ring incorporating the A group; and, R2 is trifluoromethyl; X1 is NCH3; and G1 is N and G2 is CH, or G1 is CH and G2 is N, or G1 and G2 are both N. is.

[0067] Embodiment 21a 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; R8 is 1-cyano-1-methyl-ethoxy, 1-cyano-1-methyl-ethyl or 1-cyanocyclopropyl; R9 is methyl; Q is the Q1 group [ka] (wherein the arrow indicates the point of attachment to the ring incorporating the A group; and, R2 is trifluoromethyl; X1 is NCH3; and G1 is N and G2 is CH, or G1 is CH and G2 is N, or G1 and G2 are both N. is.

[0068] Embodiment 21b 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; R8 is 1-cyano-1-methyl-ethoxy, 1-cyano-1-methyl-ethyl or 1-cyanocyclopropyl; R9 is methyl; Q is the Q1 group [ka] (wherein the arrow indicates the point of attachment to the ring incorporating the A group; and, R2 is trifluoromethyl; X1 is NCH3; and G1 is N and G2 is CH, or G1 is CH and G2 is N is.

[0069] Embodiment 21c 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; R8 is 1-cyano-1-methyl-ethoxy; R9 is methyl; Q is the Q1 group [ka] (wherein the arrow indicates the point of attachment to the ring incorporating the A group; and, R2 is trifluoromethyl; X1 is NCH3; and G1 is N and G2 is CH, or G1 is CH and G2 is N is.

[0070] Embodiment 22a 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; R8 is 1-cyano-1-methyl-ethoxy, 1-cyano-1-methyl-ethyl or 1-cyanocyclopropyl; R9 is hydrogen; Q is the Q1 group [ka] (wherein the arrow indicates the point of attachment to the ring incorporating the A group; and, R2 is trifluoromethyl; X1 is NCH3; and G1 is N and G2 is CH, or G1 is CH and G2 is N, or G1 and G2 are both N. is.

[0071] Embodiment 22b 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; R8 is 1-cyano-1-methyl-ethoxy, 1-cyano-1-methyl-ethyl or 1-cyanocyclopropyl; R9 is hydrogen; Q is the Q1 group [ka] (wherein the arrow indicates the point of attachment to the ring incorporating the A group; and, R2 is trifluoromethyl; X1 is NCH3; and G1 is N and G2 is CH, or G1 is CH and G2 is N is.

[0072] Embodiment 22c 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; R8 is 1-cyanocyclopropyl; R9 is hydrogen; Q is the Q1 group [ka] (wherein the arrow indicates the point of attachment to the ring incorporating the A group; and, R2 is trifluoromethyl; X1 is NCH3; and G1 is N and G2 is CH, or G1 is CH and G2 is N is.

[0073] Embodiment 23a 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; R8 is 1-cyano-1-methyl-ethoxy, 1-cyano-1-methyl-ethyl or 1-cyanocyclopropyl; R9 is hydrogen; Q is a Q2 group [ka] (wherein the arrow indicates the point of attachment to the ring incorporating the A group; and, R2 is trifluoromethyl, pentafluoroethyl, trifluoromethylsulfanyl, trifluoromethylsulfinyl, or trifluoromethylsulfonyl; and G2 is CH or N is.

[0074] Embodiment 23b 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; R8 is 1-cyano-1-methyl-ethoxy, 1-cyano-1-methyl-ethyl or 1-cyanocyclopropyl; R9 is hydrogen; Q is a Q2 group [ka] (wherein the arrow indicates the point of attachment to the ring incorporating the A group; and, R2 is trifluoromethyl, pentafluoroethyl, or trifluoromethylsulfanyl; and G2 is CH or N is.

[0075] Embodiment 23c 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; R8 is 1-cyano-1-methyl-ethoxy, 1-cyano-1-methyl-ethyl or 1-cyanocyclopropyl; R9 is hydrogen; Q is a Q2 group [ka] (wherein the arrow indicates the point of attachment to the ring incorporating the A group; and, R2 is trifluoromethyl or trifluoromethylsulfanyl; and G2 is CH or N is.

[0076] Embodiment 23d 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; R8 is 1-cyano-1-methyl-ethoxy, 1-cyano-1-methyl-ethyl or 1-cyanocyclopropyl; R9 is hydrogen; Q is a Q2 group [ka] (wherein the arrow indicates the point of attachment to the ring incorporating the A group; and, R2 is trifluoromethyl; and G2 is CH or N is.

[0077] Embodiment 23e 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; R8 is 1-cyano-1-methyl-ethoxy; R9 is hydrogen; Q is a Q2 group [ka] (wherein the arrow indicates the point of attachment to the ring incorporating the A group; and, R2 is trifluoromethyl; and G2 is CH or N is.

[0078] Embodiment 24a 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; R8 is 1-cyano-1-methyl-ethoxy, 1-cyano-1-methyl-ethyl or 1-cyanocyclopropyl; R9 is hydrogen; Q is a Q2 group [ka] (wherein the arrow indicates the point of attachment to the ring incorporating the A group; and, R2 is trifluoromethyl or trifluoromethylsulfanyl; and G2 is CH or N is.

[0079] Embodiment 24b 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; R8 is 1-cyano-1-methyl-ethoxy, 1-cyano-1-methyl-ethyl or 1-cyanocyclopropyl; R9 is hydrogen; Q is a Q2 group [ka] (wherein the arrow indicates the point of attachment to the ring incorporating the A group; and, R2 is trifluoromethyl; and G2 is CH or N is.

[0080] Embodiment 24c 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; R8 is 1-cyano-1-methyl-ethoxy; R9 is hydrogen; Q is a Q2 group [ka] (wherein the arrow indicates the point of attachment to the ring incorporating the A group; and, R2 is trifluoromethyl; and G2 is CH or N is.

[0081] Embodiment 25a 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; R8 is 1-cyano-1-methyl-ethoxy, 1-cyano-1-methyl-ethyl or 1-cyanocyclopropyl; R9 is hydrogen; Q is the Q5 group [ka] (wherein the arrow indicates the point of attachment to the ring incorporating the A group; and, R2 is trifluoromethyl; R3 is methyl; and R4 is ethyl, methoxy or cyclopropyl. is.

[0082] Embodiment 25b 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; R8 is 1-cyano-1-methyl-ethoxy or 1-cyanocyclopropyl; R9 is hydrogen; Q is the Q5 group [ka] (wherein the arrow indicates the point of attachment to the ring incorporating the A group; and, R2 is trifluoromethyl; R3 is methyl; and R4 is ethyl, methoxy or cyclopropyl. is.

[0083] Embodiment 25c 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; R8 is 1-cyano-1-methyl-ethoxy; R9 is hydrogen; Q is the Q5 group [ka] (wherein the arrow indicates the point of attachment to the ring incorporating the A group; and, R2 is trifluoromethyl; R3 is methyl; and R4 is ethyl or cyclopropyl. is.

[0084] Embodiment 25d 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; R8 is 1-cyanocyclopropyl; R9 is hydrogen; Q is the Q5 group [ka] (wherein the arrow indicates the point of attachment to the ring incorporating the A group; and, R2 is trifluoromethyl; R3 is methyl; and R4 is ethyl or methoxy. is.

[0085] Embodiment 26a 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; R8 is 1-cyano-1-methyl-ethoxy, 1-cyano-1-methyl-ethyl or 1-cyanocyclopropyl; R9 is hydrogen; Q is the Q5 group [ka] (wherein the arrow indicates the point of attachment to the ring incorporating the A group; and, R2 is trifluoromethyl; R3 is methyl; and R4 is ethyl, methoxy or cyclopropyl. is.

[0086] Embodiment 26b 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; R8 is 1-cyano-1-methyl-ethoxy or 1-cyanocyclopropyl; R9 is hydrogen; Q is the Q5 group [ka] (wherein the arrow indicates the point of attachment to the ring incorporating the A group; and, R2 is trifluoromethyl; R3 is methyl; and R4 is ethyl, methoxy or cyclopropyl. is.

[0087] Embodiment 27 provides a compound according to any one of embodiments 1 to 26b above, or an agrochemically acceptable salt, stereoisomer, enantiomer, tautomer, or N-oxide thereof, wherein S * is in the R-configuration.

[0088] Embodiment 28 provides a compound according to embodiment 27, or an agrochemically acceptable salt, stereoisomer, enantiomer, tautomer, or N-oxide thereof, wherein the S * The center is in enantiomerically pure form or is at least 40%, e.g., at least 50%, 60%, 70%, or 80%, preferably at least 90%, more preferably at least 95%, even more preferably at least 98%, and most preferably at least 99% (S * ) R- is an enantiomerically enriched form that is enantiomerically enriched in enantiomeric excess (ee).

[0089] Embodiment 29 provides a compound according to any one of embodiments 1 to 26b above, or an agrochemically acceptable salt, stereoisomer, enantiomer, tautomer, or N-oxide thereof, wherein S * is in the S-configuration.

[0090] Embodiment 30 provides a compound according to embodiment 29, or an agrochemically acceptable salt, stereoisomer, enantiomer, tautomer, or N-oxide thereof, wherein the S * The center is in enantiomerically pure form or is at least 40%, e.g., at least 50%, 60%, 70% or 80%, preferably at least 90%, more preferably at least 95%, even more preferably at least 98%, and most preferably at least 99% (S * ) S- is an enantiomerically enriched form that is enantiomerically enriched in enantiomeric excess (ee).

[0091] Embodiment 31 provides a compound according to any one of embodiments 1 to 30 above, or an agrochemically acceptable salt, stereoisomer, enantiomer, tautomer, or N-oxide thereof, comprising: (A) a sulfanyl compound of formula (II): [ka] (wherein Q, R1, R2, G1, G2, X1, R3, R4, R8, R9 and A are as defined in formula (I)). in the presence of an oxidizing agent, in the presence of a metal catalyst, in the presence of a chiral ligand, and optionally in the presence of a suitable additive, in a suitable solvent (or diluent) to give a sulfinyl compound of formula (III) [ka] (wherein Q, R1, R2, G1, G2, X1, R3, R4, R8, R9 and A are as defined in formula (I), and S * is a stereogenic sulfur atom in the R- or S-configuration, wherein the S * The center is in enantiomerically pure or enantiomerically enriched form. generating (B) A sulfinyl compound of formula (III) [ka] (wherein Q, R1, R2, G1, G2, X1, R3, R4, R8, R9 and A are as defined in formula (I), and S * is a stereogenic sulfur atom in the R- or S-configuration, wherein the S * The center is in enantiomerically pure or enantiomerically enriched form. with an iminizing reagent in the presence of a catalyst, and optionally in the presence of suitable additives, in a suitable solvent (or diluent) to stereospecifically produce a sulfoximine compound of formula (I). The preferences and preferred embodiments relating to the process for preparing a compound of formula (I), including steps (A) and (B), reaction conditions, and compounds of formulas (II) and (III), which are further described below, are also valid for this embodiment 31.

[0092] Embodiment 31a provides a compound according to any one of embodiments 1 to 26b, or an agrochemically acceptable salt, stereoisomer, enantiomer, tautomer, or N-oxide thereof, comprising a compound of Formula I that is the first eluting enantiomer in a chiral resolution of a racemate by preparative chromatography using an immobilized amylose-based (CHIRALPAK® IA, CHIRALPAK® IG) or cellulose-based (CHIRALPAK® IC) chiral phase.

[0093] Embodiment 31b provides a compound according to any one of embodiments 1 to 26b, or an agrochemically acceptable salt, stereoisomer, enantiomer, tautomer, or N-oxide thereof, comprising a compound of Formula I that is the first eluting enantiomer in a chiral resolution of a racemate by preparative SFC (supercritical fluid chromatography) using an immobilized amylose-based (CHIRALPAK® IA, CHIRALPAK® IG) or cellulosic-based (CHIRALPAK® IC) chiral phase.

[0094] Embodiment 31c provides a compound according to any one of embodiments 1 to 26b, or an agrochemically acceptable salt, stereoisomer, enantiomer, tautomer, or N-oxide thereof, comprising a compound of Formula I that is the first eluting enantiomer in a chiral resolution of a racemate by preparative SFC using an immobilized amylose-based (CHIRALPAK® IA, CHIRALPAK® IG) or cellulose-based (CHIRALPAK® IC) chiral phase with supercritical CO2 and, preferably, an alcohol co-solvent, such as methanol, ethanol, or isopropyl alcohol, as the mobile phase.

[0095] Embodiment 32 provides a compound according to any one of embodiments 31a to 31c, or an agrochemically acceptable salt, stereoisomer, enantiomer, tautomer, or N-oxide thereof, in enantiomerically pure form or having an enantiomeric excess (ee) of the first eluting enantiomer of at least 40%, e.g., at least 50%, 60%, 70%, or 80%, preferably at least 90%, more preferably at least 95%, even more preferably at least 98%, and most preferably at least 99%.

[0096] Embodiment 33a provides a compound according to any one of embodiments 1 to 26b, or an agrochemically acceptable salt, stereoisomer, enantiomer, tautomer, or N-oxide thereof, comprising a compound of Formula I that is the second eluting enantiomer in a chiral resolution of a racemate by preparative chromatography using an immobilized amylose-based (CHIRALPAK® IA, CHIRALPAK® IG) or cellulose-based (CHIRALPAK® IC) chiral phase.

[0097] Embodiment 33b provides a compound according to any one of embodiments 1 to 26b, or an agrochemically acceptable salt, stereoisomer, enantiomer, tautomer, or N-oxide thereof, comprising a compound of Formula I that is the second eluting enantiomer in the chiral resolution of a racemate by preparative SFC (supercritical fluid chromatography) using an immobilized amylose-based (CHIRALPAK® IA, CHIRALPAK® IG) or cellulosic (CHIRALPAK® IC) chiral phase.

[0098] Embodiment 33c provides a compound according to any one of embodiments 1 to 26b, or an agrochemically acceptable salt, stereoisomer, enantiomer, tautomer, or N-oxide thereof, comprising a compound of Formula I that is the second eluting enantiomer in a chiral resolution of a racemate by preparative SFC using an immobilized amylose-based (CHIRALPAK® IA, CHIRALPAK® IG) or cellulosic (CHIRALPAK® IC) chiral phase with supercritical CO2 and, preferably, an alcohol co-solvent, such as methanol, ethanol, or isopropyl alcohol, as the mobile phase.

[0099] Embodiment 34 provides a compound according to any one of embodiments 33a to 33c, or an agrochemically acceptable salt, stereoisomer, enantiomer, tautomer, or N-oxide thereof, in enantiomerically pure form or having an enantiomeric excess (ee) of the second eluting enantiomer of at least 40%, e.g., at least 50%, 60%, 70%, or 80%, preferably at least 90%, more preferably at least 95%, even more preferably at least 98%, and most preferably at least 99%.

[0100] A preferred group of compounds of formula I is the compound of formula I-1 [ka] (In the formula, R1, R2, R3, R8, R9, S *and A is as defined in Formula I above. It is expressed by:

[0101] In one preferred group of compounds of formula I-1, A is CH or N; R1 is ethyl, propyl or isopropyl; R2 is C1-C2 haloalkyl, C1-C2 haloalkylsulfanyl, C1-C2 haloalkylsulfinyl or C1-C2 haloalkylsulfonyl; R3 is C1-C2 alkyl; R9 is hydrogen, methyl or ethyl; and R8 is cyanoisopropoxy, cyanoisopropyl or cyanocyclopropyl.

[0102] 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; and R8 is cyanoisopropoxy, cyanoisopropyl or cyanocyclopropyl.

[0103] In the compounds of formula I-1 and all of the preferred embodiments of the compounds of formula I-1 described above, unless otherwise specified, R1, R2, R3, R8, R9, S * and A are as defined in formula I above; preferably, A is CH or N, more preferably, A is N; R1 is ethyl; R2 is trifluoromethyl, pentafluoroethyl or trifluoromethylsulfanyl; preferably, R2 is trifluoromethyl; R3 is methyl; R9 is hydrogen; and R8 is 1-cyano-1-methyl-ethoxy, 1-cyano-1-methyl-ethyl or 1-cyanocyclopropyl.

[0104] One group of compounds according to this embodiment are compounds of formula (I-1), or any of the preferred embodiments of compounds of formula (I-1), wherein S * is in the R-configuration.

[0105] One group of compounds according to this embodiment are compounds of formula (I-1b), which are compounds of formula (I-1) or any of the preferred embodiments of compounds of formula (I-1), wherein S * is in the S-configuration.

[0106] One group of compounds according to this embodiment are compounds of formula (I-1c), which are compounds of formula (I-1) or any of the preferred embodiments of compounds of formula (I-1), which are the first eluting enantiomers in the chiral resolution of racemates by preparative chromatography using immobilized amylose-based (CHIRALPAK® IA, CHIRALPAK® IG) or cellulose-based (CHIRALPAK® IC) chiral phases.

[0107] One group of compounds according to this embodiment are compounds of formula (I-1d), which are compounds of formula (I-1) or any of the preferred embodiments of compounds of formula (I-1), which are the first eluting enantiomers in the chiral resolution of racemates by preparative SFC (supercritical fluid chromatography) using immobilized amylose-based (CHIRALPAK® IA, CHIRALPAK® IG) or cellulose-based (CHIRALPAK® IC) chiral phases.

[0108] One group of compounds according to this embodiment are compounds of formula (I-1e), which are compounds of formula (I-1), or any of the preferred embodiments of compounds of formula (I-1), that are the first eluting enantiomers in the chiral resolution of racemates by preparative SFC using immobilized amylose-based (CHIRALPAK® IA, CHIRALPAK® IG) or cellulose-based (CHIRALPAK® IC) chiral phases with supercritical CO2 and preferably an alcohol co-solvent such as methanol, ethanol, or isopropyl alcohol as the mobile phase.

[0109] One group of compounds according to this embodiment are compounds of formula (I-1f), which are compounds of formula (I-1) or any of the preferred embodiments of compounds of formula (I-1), which are the second eluting enantiomers in the chiral resolution of racemates by preparative chromatography using immobilized amylose-based (CHIRALPAK® IA, CHIRALPAK® IG) or cellulose-based (CHIRALPAK® IC) chiral phases.

[0110] One group of compounds according to this embodiment are compounds of formula (I-1g), which are compounds of formula (I-1) or any of the preferred embodiments of compounds of formula (I-1), which are the second eluting enantiomers in the chiral resolution of racemates by preparative SFC (supercritical fluid chromatography) using immobilized amylose-based (CHIRALPAK® IA, CHIRALPAK® IG) or cellulose-based (CHIRALPAK® IC) chiral phases.

[0111] One group of compounds according to this embodiment are compounds of formula (I-1h), which are compounds of formula (I-1), or any of the preferred embodiments of compounds of formula (I-1), that are the second eluting enantiomer in the chiral resolution of racemates by preparative SFC using immobilized amylose-based (CHIRALPAK® IA, CHIRALPAK® IG) or cellulose-based (CHIRALPAK® IC) chiral phases with supercritical CO2 and preferably an alcohol co-solvent such as methanol, ethanol, or isopropyl alcohol as the mobile phase.

[0112] Another group of compounds according to this embodiment are compounds of formula (I-1i), which are compounds of formula (I-1) or any of the preferred embodiments of compounds of formula (I-1), which are readily prepared or accessible stereospecifically by iminization of the stereodiene sulfinyl derivatives produced by stereoselective oxidation of the corresponding sulfanyl compounds as further defined and described in embodiment 31.

[0113] Another preferred group of compounds of formula I is the compounds of formula I-2 [ka] (In the formula, R1, R2, R3, R8, R9, S * and A is as defined in Formula I above. It is expressed by:

[0114] In one preferred group of compounds of formula I-2, A is CH or N; R1 is ethyl, propyl or isopropyl; R2 is C1-C2 haloalkyl, C1-C2 haloalkylsulfanyl, C1-C2 haloalkylsulfinyl or C1-C2 haloalkylsulfonyl; R3 is C1-C2 alkyl; R9 is hydrogen, methyl or ethyl; and R8 is cyanoisopropoxy, cyanoisopropyl or cyanocyclopropyl.

[0115] 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; and R8 is cyanoisopropoxy, cyanoisopropyl or cyanocyclopropyl.

[0116] In the compounds of formula I-2 and all of the preferred embodiments of the compounds of formula I-2 described above, unless otherwise specified, R1, R2, R3, R8, R9, S * and A are as defined in formula I above; preferably, A is CH or N, more preferably, A is N; R1 is ethyl; R2 is trifluoromethyl, pentafluoroethyl or trifluoromethylsulfanyl; preferably, R2 is trifluoromethyl; R3 is methyl; R9 is hydrogen; and R8 is 1-cyano-1-methyl-ethoxy, 1-cyano-1-methyl-ethyl or 1-cyanocyclopropyl.

[0117] One group of compounds according to this embodiment are compounds of formula (I-2), or any of the preferred embodiments of compounds of formula (I-2), wherein S * is in the R-configuration.

[0118] One group of compounds according to this embodiment are compounds of formula (I-2), or any of the preferred embodiments of compounds of formula (I-2), wherein S * is in the S-configuration.

[0119] One group of compounds according to this embodiment are compounds of formula (I-2c), which are compounds of formula (I-2) or any of the preferred embodiments of compounds of formula (I-2), which are the first eluting enantiomers in the chiral resolution of racemates by preparative chromatography using immobilized amylose-based (CHIRALPAK® IA, CHIRALPAK® IG) or cellulose-based (CHIRALPAK® IC) chiral phases.

[0120] One group of compounds according to this embodiment are compounds of formula (I-2d), which are compounds of formula (I-2) or any of the preferred embodiments of compounds of formula (I-2), which are the first eluting enantiomers in the chiral resolution of racemates by preparative SFC (supercritical fluid chromatography) using immobilized amylose-based (CHIRALPAK® IA, CHIRALPAK® IG) or cellulose-based (CHIRALPAK® IC) chiral phases.

[0121] One group of compounds according to this embodiment are compounds of formula (I-2e), which are compounds of formula (I-2), or any of the preferred embodiments of compounds of formula (I-2), that are the first eluting enantiomers in the chiral resolution of racemates by preparative SFC using immobilized amylose-based (CHIRALPAK® IA, CHIRALPAK® IG) or cellulose-based (CHIRALPAK® IC) chiral phases with supercritical CO2 and preferably an alcohol co-solvent such as methanol, ethanol, or isopropyl alcohol as the mobile phase.

[0122] One group of compounds according to this embodiment are compounds of formula (I-2f), which are compounds of formula (I-2) or any of the preferred embodiments of compounds of formula (I-2), which are the second eluting enantiomers in the chiral resolution of racemates by preparative chromatography using immobilized amylose-based (CHIRALPAK® IA, CHIRALPAK® IG) or cellulose-based (CHIRALPAK® IC) chiral phases.

[0123] One group of compounds according to this embodiment are compounds of formula (I-2g), which are compounds of formula (I-2) or any of the preferred embodiments of compounds of formula (I-2), which are the second eluting enantiomers in the chiral resolution of racemates by preparative SFC (supercritical fluid chromatography) using immobilized amylose-based (CHIRALPAK® IA, CHIRALPAK® IG) or cellulose-based (CHIRALPAK® IC) chiral phases.

[0124] One group of compounds according to this embodiment are compounds of formula (I-2h), which are compounds of formula (I-2), or any of the preferred embodiments of compounds of formula (I-2), that are the second eluting enantiomer in the chiral resolution of racemates by preparative SFC using immobilized amylose-based (CHIRALPAK® IA, CHIRALPAK® IG) or cellulose-based (CHIRALPAK® IC) chiral phases with supercritical CO2 and preferably an alcohol co-solvent such as methanol, ethanol, or isopropyl alcohol as the mobile phase.

[0125] Another group of compounds according to this embodiment are compounds of formula (I-2i), which are compounds of formula (I-2) or any of the preferred embodiments of compounds of formula (I-2), which are readily prepared or accessible stereospecifically by iminization of the stereodiene sulfinyl derivatives produced by stereoselective oxidation of the corresponding sulfanyl compounds as further defined and described in embodiment 31.

[0126] Another preferred group of compounds of formula I is the compounds of formula I-3 [ka] (In the formula, R1, R2, R3, R8, R9, S * and A is as defined in Formula I above. It is expressed by:

[0127] In one preferred group of compounds of formula I-3, A is CH or N; R1 is ethyl, propyl or isopropyl; R2 is C1-C2 haloalkyl, C1-C2 haloalkylsulfanyl, C1-C2 haloalkylsulfinyl or C1-C2 haloalkylsulfonyl; R3 is C1-C2 alkyl; R9 is hydrogen, methyl or ethyl; and R8 is cyanoisopropoxy, cyanoisopropyl or cyanocyclopropyl.

[0128] 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; and R8 is cyanoisopropoxy, cyanoisopropyl or cyanocyclopropyl.

[0129] In the compounds of formula I-3 and all of the preferred embodiments of the compounds of formula I-3 described above, unless otherwise specified, R1, R2, R3, R8, R9, S * and A are as defined in formula I above; preferably, A is CH or N, more preferably, A is N; R1 is ethyl; R2 is trifluoromethyl, pentafluoroethyl or trifluoromethylsulfanyl; preferably, R2 is trifluoromethyl; R3 is methyl; R9 is hydrogen; and R8 is 1-cyano-1-methyl-ethoxy, 1-cyano-1-methyl-ethyl or 1-cyanocyclopropyl.

[0130] One group of compounds according to this embodiment are compounds of formula (I-3), either compounds of formula (I-3a), or preferred embodiments of compounds of formula (I-3), wherein S * is in the R-configuration.

[0131] One group of compounds according to this embodiment are compounds of formula (I-3), or any of the preferred embodiments of compounds of formula (I-3), wherein S * is in the S-configuration.

[0132] One group of compounds according to this embodiment are compounds of formula (I-3c), which are compounds of formula (I-3) or any of the preferred embodiments of compounds of formula (I-3), which are the first eluting enantiomers in the chiral resolution of racemates by preparative chromatography using immobilized amylose-based (CHIRALPAK® IA, CHIRALPAK® IG) or cellulose-based (CHIRALPAK® IC) chiral phases.

[0133] One group of compounds according to this embodiment are compounds of formula (I-3d), which are compounds of formula (I-3) or any of the preferred embodiments of compounds of formula (I-3), which are the first eluting enantiomers in the chiral resolution of racemates by preparative SFC (supercritical fluid chromatography) using immobilized amylose-based (CHIRALPAK® IA, CHIRALPAK® IG) or cellulose-based (CHIRALPAK® IC) chiral phases.

[0134] One group of compounds according to this embodiment are compounds of formula (I-3e), which are compounds of formula (I-3), or any of the preferred embodiments of compounds of formula (I-3), that are the first eluting enantiomers in the chiral resolution of racemates by preparative SFC using immobilized amylose-based (CHIRALPAK® IA, CHIRALPAK® IG) or cellulose-based (CHIRALPAK® IC) chiral phases with supercritical CO2 and preferably an alcohol co-solvent such as methanol, ethanol, or isopropyl alcohol as the mobile phase.

[0135] One group of compounds according to this embodiment are compounds of formula (I-3f), which are compounds of formula (I-3) or any of the preferred embodiments of compounds of formula (I-3), which are the second eluting enantiomers in the chiral resolution of racemates by preparative chromatography using immobilized amylose-based (CHIRALPAK® IA, CHIRALPAK® IG) or cellulose-based (CHIRALPAK® IC) chiral phases.

[0136] One group of compounds according to this embodiment are compounds of formula (I-3g), which are compounds of formula (I-3) or any of the preferred embodiments of compounds of formula (I-3), which are the second eluting enantiomers in the chiral resolution of racemates by preparative SFC (supercritical fluid chromatography) using immobilized amylose-based (CHIRALPAK® IA, CHIRALPAK® IG) or cellulose-based (CHIRALPAK® IC) chiral phases.

[0137] One group of compounds according to this embodiment are compounds of formula (I-3h), which are compounds of formula (I-3), or any of the preferred embodiments of compounds of formula (I-3), that are the second eluting enantiomer in the chiral resolution of racemates by preparative SFC using immobilized amylose-based (CHIRALPAK® IA, CHIRALPAK® IG) or cellulose-based (CHIRALPAK® IC) chiral phases with supercritical CO2 and preferably an alcohol co-solvent such as methanol, ethanol, or isopropyl alcohol as the mobile phase.

[0138] Another group of compounds according to this embodiment are compounds of formula (I-3i), which are compounds of formula (I-3) or any of the preferred embodiments of compounds of formula (I-3), which are readily prepared or accessible stereospecifically by iminization of the stereodiene sulfinyl derivatives produced by stereoselective oxidation of the corresponding sulfanyl compounds as further defined and described in embodiment 31.

[0139] Another preferred group of compounds of formula I is the compounds of formula I-4 [ka] (In the formula, R1, R2, R3, R4, R8, R9, S * and A is as defined in Formula I above. It is expressed by:

[0140] In one preferred group of compounds of formula I-4, A is CH or N; R1 is ethyl, propyl or isopropyl; 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; R9 is hydrogen, methyl or ethyl; and R8 is cyanoisopropoxy, cyanoisopropyl or cyanocyclopropyl.

[0141] 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; and R8 is cyanoisopropoxy, cyanoisopropyl or cyanocyclopropyl.

[0142] In another preferred group of compounds of formula I-4, R4 is ethyl, methoxy or cyclopropyl.

[0143] In the compounds of formula I-4 and all of the preferred embodiments of the compounds of formula I-4 described above, unless otherwise specified, R1, R2, R3, R4, R8, R9, S *and A are as defined in formula I above; preferably, A is CH or N, more preferably, A is N; R1 is ethyl; R2 is trifluoromethyl, pentafluoroethyl or trifluoromethylsulfanyl; preferably, R2 is trifluoromethyl; R3 is methyl; R4 is ethyl, methoxy or cyclopropyl; R9 is hydrogen; and R8 is 1-cyano-1-methyl-ethoxy, 1-cyano-1-methyl-ethyl or 1-cyanocyclopropyl.

[0144] One group of compounds according to this embodiment are compounds of formula (I-4), or any of the preferred embodiments of compounds of formula (I-4), wherein S * is in the R-configuration.

[0145] One group of compounds according to this embodiment are compounds of formula (I-4), or any of the preferred embodiments of compounds of formula (I-4), wherein S * is in the S-configuration.

[0146] One group of compounds according to this embodiment are compounds of formula (I-4c), which are compounds of formula (I-4) or any of the preferred embodiments of compounds of formula (I-4), which are the first eluting enantiomers in the chiral resolution of racemates by preparative chromatography using immobilized amylose-based (CHIRALPAK® IA, CHIRALPAK® IG) or cellulose-based (CHIRALPAK® IC) chiral phases.

[0147] One group of compounds according to this embodiment are compounds of formula (I-4d), which are compounds of formula (I-4) or any of the preferred embodiments of compounds of formula (I-4), which are the first eluting enantiomers in the chiral resolution of racemates by preparative SFC (supercritical fluid chromatography) using immobilized amylose-based (CHIRALPAK® IA, CHIRALPAK® IG) or cellulose-based (CHIRALPAK® IC) chiral phases.

[0148] One group of compounds according to this embodiment are compounds of formula (I-4e), which are compounds of formula (I-4) or any of the preferred embodiments of compounds of formula (I-4), that are the first eluting enantiomers in the chiral resolution of racemates by preparative SFC using immobilized amylose-based (CHIRALPAK® IA, CHIRALPAK® IG) or cellulose-based (CHIRALPAK® IC) chiral phases with supercritical CO2 and preferably an alcohol co-solvent such as methanol, ethanol, or isopropyl alcohol as the mobile phase.

[0149] One group of compounds according to this embodiment are compounds of formula (I-4f), which are compounds of formula (I-4) or any of the preferred embodiments of compounds of formula (I-4), which are the second eluting enantiomers in the chiral resolution of racemates by preparative chromatography using immobilized amylose-based (CHIRALPAK® IA, CHIRALPAK® IG) or cellulose-based (CHIRALPAK® IC) chiral phases.

[0150] One group of compounds according to this embodiment are compounds of formula (I-4g), which are compounds of formula (I-4) or any of the preferred embodiments of compounds of formula (I-4), which are the second eluting enantiomers in the chiral resolution of racemates by preparative SFC (supercritical fluid chromatography) using immobilized amylose-based (CHIRALPAK® IA, CHIRALPAK® IG) or cellulose-based (CHIRALPAK® IC) chiral phases.

[0151] One group of compounds according to this embodiment are compounds of formula (I-4h), which are compounds of formula (I-4) or any of the preferred embodiments of compounds of formula (I-4), that are the second eluting enantiomer in the chiral resolution of racemates by preparative SFC using immobilized amylose-based (CHIRALPAK® IA, CHIRALPAK® IG) or cellulose-based (CHIRALPAK® IC) chiral phases with supercritical CO2 and preferably an alcohol co-solvent such as methanol, ethanol, or isopropyl alcohol as the mobile phase.

[0152] Another group of compounds according to this embodiment are compounds of formula (I-4i), which are compounds of formula (I-4) or any of the preferred embodiments of compounds of formula (I-4), which are readily prepared or accessible stereospecifically by iminization of the stereodiene sulfinyl derivatives produced by stereoselective oxidation of the corresponding sulfanyl compounds as further defined and described in embodiment 31.

[0153] Another preferred group of compounds of formula I is the compounds of formula I-5 [ka] (In the formula, R1, R2, R8, R9, S * and A is as defined in Formula I above. It is expressed by:

[0154] In one preferred group of compounds of formula I-5, A is CH or N; R1 is ethyl, propyl or isopropyl; R2 is C1-C2 haloalkyl, C1-C2 haloalkylsulfanyl, C1-C2 haloalkylsulfinyl or C1-C2 haloalkylsulfonyl; R9 is hydrogen, methyl or ethyl; and R8 is cyanoisopropoxy, cyanoisopropyl or cyanocyclopropyl.

[0155] 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; and R8 is cyanoisopropoxy, cyanoisopropyl or cyanocyclopropyl.

[0156] In the compounds of formula I-5 and all of the preferred embodiments of the compounds of formula I-5 described above, unless otherwise specified, R1, R2, R8, R9, S * and A are as defined in formula I above; preferably, A is CH or N, more preferably, A is N; R1 is ethyl; R2 is trifluoromethyl, pentafluoroethyl or trifluoromethylsulfanyl; preferably, R2 is trifluoromethyl; R9 is hydrogen; and R8 is 1-cyano-1-methyl-ethoxy, 1-cyano-1-methyl-ethyl or 1-cyanocyclopropyl.

[0157] One group of compounds according to this embodiment are compounds of formula (I-5), or any of the preferred embodiments of compounds of formula (I-5), wherein S * is in the R-configuration.

[0158] One group of compounds according to this embodiment are compounds of formula (I-5), or any of the preferred embodiments of compounds of formula (I-5), wherein S * is in the S-configuration.

[0159] One group of compounds according to this embodiment are compounds of formula (I-5c), which are compounds of formula (I-5) or any of the preferred embodiments of compounds of formula (I-5), which are the first eluting enantiomers in the chiral resolution of racemates by preparative chromatography using immobilized amylose-based (CHIRALPAK® IA, CHIRALPAK® IG) or cellulose-based (CHIRALPAK® IC) chiral phases.

[0160] One group of compounds according to this embodiment are compounds of formula (I-5d), which are compounds of formula (I-5) or any of the preferred embodiments of compounds of formula (I-5), which are the first eluting enantiomers in the chiral resolution of racemates by preparative SFC (supercritical fluid chromatography) using immobilized amylose-based (CHIRALPAK® IA, CHIRALPAK® IG) or cellulose-based (CHIRALPAK® IC) chiral phases.

[0161] One group of compounds according to this embodiment are compounds of formula (I-5e), which are compounds of formula (I-5) or any of the preferred embodiments of compounds of formula (I-5), that are the first eluting enantiomers in the chiral resolution of racemates by preparative SFC using immobilized amylose-based (CHIRALPAK® IA, CHIRALPAK® IG) or cellulose-based (CHIRALPAK® IC) chiral phases with supercritical CO2 and preferably an alcohol co-solvent such as methanol, ethanol, or isopropyl alcohol as the mobile phase.

[0162] One group of compounds according to this embodiment are compounds of formula (I-5f), which are compounds of formula (I-5) or any of the preferred embodiments of compounds of formula (I-5), which are the second eluting enantiomers in the chiral resolution of racemates by preparative chromatography using immobilized amylose-based (CHIRALPAK® IA, CHIRALPAK® IG) or cellulose-based (CHIRALPAK® IC) chiral phases.

[0163] One group of compounds according to this embodiment are compounds of formula (I-5g), which are compounds of formula (I-5) or any of the preferred embodiments of compounds of formula (I-5), which are the second eluting enantiomers in the chiral resolution of racemates by preparative SFC (supercritical fluid chromatography) using immobilized amylose-based (CHIRALPAK® IA, CHIRALPAK® IG) or cellulose-based (CHIRALPAK® IC) chiral phases.

[0164] One group of compounds according to this embodiment are compounds of formula (I-5h), which are compounds of formula (I-5) or any of the preferred embodiments of compounds of formula (I-5), that are the second eluting enantiomer in the chiral resolution of racemates by preparative SFC using immobilized amylose-based (CHIRALPAK® IA, CHIRALPAK® IG) or cellulose-based (CHIRALPAK® IC) chiral phases with supercritical CO2 and preferably an alcohol co-solvent such as methanol, ethanol, or isopropyl alcohol as the mobile phase.

[0165] Another group of compounds according to this embodiment are compounds of formula (I-5i), which are compounds of formula (I-5) or any of the preferred embodiments of compounds of formula (I-5), which are readily prepared or accessible stereospecifically by iminization of the stereodiene sulfinyl derivatives produced by stereoselective oxidation of the corresponding sulfanyl compounds as further defined and described in embodiment 31.

[0166] Another preferred group of compounds of formula I is the compounds of formula I-6 [ka] (In the formula, R1, R2, R8, R9, S * and A is as defined in Formula I above. It is expressed by:

[0167] In one preferred group of compounds of formula I-6, A is CH or N; R1 is ethyl, propyl or isopropyl; R2 is C1-C2 haloalkyl, C1-C2 haloalkylsulfanyl, C1-C2 haloalkylsulfinyl or C1-C2 haloalkylsulfonyl; R9 is hydrogen, methyl or ethyl; and R8 is cyanoisopropoxy, cyanoisopropyl or cyanocyclopropyl.

[0168] 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; and R8 is cyanoisopropoxy, cyanoisopropyl or cyanocyclopropyl.

[0169] In the compounds of formula I-6 and all of the preferred embodiments of the compounds of formula I-6 described above, unless otherwise specified, R1, R2, R8, R9, S * and A are as defined in formula I above; preferably, A is CH or N, more preferably, A is N; R1 is ethyl; R2 is trifluoromethyl, pentafluoroethyl or trifluoromethylsulfanyl; preferably, R2 is trifluoromethyl; R9 is hydrogen; and R8 is 1-cyano-1-methyl-ethoxy, 1-cyano-1-methyl-ethyl or 1-cyanocyclopropyl.

[0170] One group of compounds according to this embodiment are compounds of formula (I-6), either compounds of formula (I-6a), or preferred embodiments of compounds of formula (I-6), wherein S * is in the R-configuration.

[0171] One group of compounds according to this embodiment are compounds of formula (I-6), or any of the preferred embodiments of compounds of formula (I-6), wherein S * is in the S-configuration.

[0172] One group of compounds according to this embodiment are compounds of formula (I-6c), which are compounds of formula (I-6) or any of the preferred embodiments of compounds of formula (I-6), which are the first eluting enantiomers in the chiral resolution of racemates by preparative chromatography using immobilized amylose-based (CHIRALPAK® IA, CHIRALPAK® IG) or cellulose-based (CHIRALPAK® IC) chiral phases.

[0173] One group of compounds according to this embodiment are compounds of formula (I-6d), which are compounds of formula (I-6) or any of the preferred embodiments of compounds of formula (I-6), which are the first eluting enantiomers in the chiral resolution of racemates by preparative SFC (supercritical fluid chromatography) using immobilized amylose-based (CHIRALPAK® IA, CHIRALPAK® IG) or cellulose-based (CHIRALPAK® IC) chiral phases.

[0174] One group of compounds according to this embodiment are compounds of formula (I-6) or any of the preferred embodiments of compounds of formula (I-6), which are the first eluting enantiomers in the chiral resolution of racemates by preparative SFC using immobilized amylose-based (CHIRALPAK® IA, CHIRALPAK® IG) or cellulose-based (CHIRALPAK® IC) chiral phases with supercritical CO2 and preferably an alcohol co-solvent such as methanol, ethanol, or isopropyl alcohol as the mobile phase.

[0175] One group of compounds according to this embodiment are compounds of formula (I-6f), which are compounds of formula (I-6) or any of the preferred embodiments of compounds of formula (I-6), which are the second eluting enantiomers in the chiral resolution of racemates by preparative chromatography using immobilized amylose-based (CHIRALPAK® IA, CHIRALPAK® IG) or cellulose-based (CHIRALPAK® IC) chiral phases.

[0176] One group of compounds according to this embodiment is the compounds of formula (I-6) or any of the preferred embodiments of the compounds of formula (I-6) represented by formula (I-6g), which are the second eluting enantiomers in the chiral resolution of racemates by preparative SFC (supercritical fluid chromatography) using immobilized amylose-based (CHIRALPAK® IA, CHIRALPAK® IG) or cellulose-based (CHIRALPAK® IC) chiral phases.

[0177] One group of compounds according to this embodiment are compounds of formula (I-6h), which are compounds of formula (I-6), or any of the preferred embodiments of compounds of formula (I-6), that are the second eluting enantiomer in the chiral resolution of racemates by preparative SFC using immobilized amylose-based (CHIRALPAK® IA, CHIRALPAK® IG) or cellulose-based (CHIRALPAK® IC) chiral phases with supercritical CO2 and preferably an alcohol co-solvent such as methanol, ethanol, or isopropyl alcohol as the mobile phase.

[0178] Another group of compounds according to this embodiment are compounds of formula (I-6i), which are compounds of formula (I-6) or any of the preferred embodiments of compounds of formula (I-6), which are readily prepared or accessible stereospecifically by iminization of the stereodiene sulfinyl derivatives produced by stereoselective oxidation of the corresponding sulfanyl compounds as further defined and described in embodiment 31.

[0179] Another preferred group of compounds of formula I is the compounds of formula I-7 [ka] (In the formula, R1, R2, R8, R9, S * and A is as defined in Formula I above. It is expressed by:

[0180] In one preferred group of compounds of formula I-7, A is CH or N; R1 is ethyl, propyl or isopropyl; R2 is C1-C2 haloalkyl, C1-C2 haloalkylsulfanyl, C1-C2 haloalkylsulfinyl or C1-C2 haloalkylsulfonyl; R9 is hydrogen, methyl or ethyl; and R8 is cyanoisopropoxy, cyanoisopropyl or cyanocyclopropyl.

[0181] 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; and R8 is cyanoisopropoxy, cyanoisopropyl or cyanocyclopropyl.

[0182] In the compounds of formula I-7 and all of the preferred embodiments of the compounds of formula I-7 described above, unless otherwise specified, R1, R2, R8, R9, S * and A are as defined in formula I above; preferably, A is CH or N, more preferably, A is N; R1 is ethyl; R2 is trifluoromethyl, pentafluoroethyl or trifluoromethylsulfanyl; preferably, R2 is trifluoromethyl; R9 is hydrogen; and R8 is 1-cyano-1-methyl-ethoxy, 1-cyano-1-methyl-ethyl or 1-cyanocyclopropyl.

[0183] One group of compounds according to this embodiment are compounds of formula (I-7), either compounds of formula (I-7a), or preferred embodiments of compounds of formula (I-7), wherein S * is in the R-configuration.

[0184] One group of compounds according to this embodiment are compounds of formula (I-7), or any of the preferred embodiments of compounds of formula (I-7), wherein S * is in the S-configuration.

[0185] One group of compounds according to this embodiment are compounds of formula (I-7), which are compounds of formula (I-7c), or any of the preferred embodiments of compounds of formula (I-7), which are the first eluting enantiomers in the chiral resolution of racemates by preparative chromatography using immobilized amylose-based (CHIRALPAK® IA, CHIRALPAK® IG) or cellulose-based (CHIRALPAK® IC) chiral phases.

[0186] One group of compounds according to this embodiment are compounds of formula (I-7d), which are compounds of formula (I-7) or any of the preferred embodiments of compounds of formula (I-7), which are the first eluting enantiomers in the chiral resolution of racemates by preparative SFC (supercritical fluid chromatography) using immobilized amylose-based (CHIRALPAK® IA, CHIRALPAK® IG) or cellulose-based (CHIRALPAK® IC) chiral phases.

[0187] One group of compounds according to this embodiment are compounds of formula (I-7) or any of the preferred embodiments of compounds of formula (I-7), which are the first eluting enantiomers in the chiral resolution of racemates by preparative SFC using immobilized amylose-based (CHIRALPAK® IA, CHIRALPAK® IG) or cellulose-based (CHIRALPAK® IC) chiral phases with supercritical CO2 and preferably an alcohol co-solvent such as methanol, ethanol, or isopropyl alcohol as the mobile phase.

[0188] One group of compounds according to this embodiment are compounds of formula (I-7f), which are compounds of formula (I-7) or any of the preferred embodiments of compounds of formula (I-7), which are the second eluting enantiomers in the chiral resolution of racemates by preparative chromatography using immobilized amylose-based (CHIRALPAK® IA, CHIRALPAK® IG) or cellulose-based (CHIRALPAK® IC) chiral phases.

[0189] One group of compounds according to this embodiment are compounds of formula (I-7g), which are compounds of formula (I-7) or any of the preferred embodiments of compounds of formula (I-7), which are the second eluting enantiomers in the chiral resolution of racemates by preparative SFC (supercritical fluid chromatography) using immobilized amylose-based (CHIRALPAK® IA, CHIRALPAK® IG) or cellulose-based (CHIRALPAK® IC) chiral phases.

[0190] One group of compounds according to this embodiment are compounds of formula (I-7h), which are compounds of formula (I-7), or any of the preferred embodiments of compounds of formula (I-7), that are the second eluting enantiomer in the chiral resolution of racemates by preparative SFC using immobilized amylose-based (CHIRALPAK® IA, CHIRALPAK® IG) or cellulose-based (CHIRALPAK® IC) chiral phases with supercritical CO2 and preferably an alcohol co-solvent such as methanol, ethanol, or isopropyl alcohol as the mobile phase.

[0191] Another group of compounds according to this embodiment are compounds of formula (I-6i), which are compounds of formula (I-6) or any of the preferred embodiments of compounds of formula (I-6), which are readily prepared or accessible stereospecifically by iminization of the stereodiene sulfinyl derivatives produced by stereoselective oxidation of the corresponding sulfanyl compounds as further defined and described in embodiment 31.

[0192] Another preferred group of compounds of formula I is the compounds of formula I-8 [ka] (In the formula, R1, R2, R8, R9, S * and A is as defined in Formula I above. It is expressed by:

[0193] In one preferred group of compounds of formula I-8, A is CH or N; R1 is ethyl, propyl or isopropyl; R2 is C1-C2 haloalkyl, C1-C2 haloalkylsulfanyl, C1-C2 haloalkylsulfinyl or C1-C2 haloalkylsulfonyl; R9 is hydrogen, methyl or ethyl; and R8 is cyanoisopropoxy, cyanoisopropyl or cyanocyclopropyl.

[0194] 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; and R8 is cyanoisopropoxy, cyanoisopropyl or cyanocyclopropyl.

[0195] In the compounds of formula I-8 and all of the preferred embodiments of the compounds of formula I-8 described above, unless otherwise specified, R1, R2, R8, R9, S * and A are as defined in formula I above; preferably, A is CH or N, more preferably, A is N; R1 is ethyl; R2 is trifluoromethyl, pentafluoroethyl or trifluoromethylsulfanyl; preferably, R2 is trifluoromethyl; R9 is hydrogen; and R8 is 1-cyano-1-methyl-ethoxy, 1-cyano-1-methyl-ethyl or 1-cyanocyclopropyl.

[0196] One group of compounds according to this embodiment are compounds of formula (I-8), either compounds of formula (I-8a), or preferred embodiments of compounds of formula (I-8), wherein S * is in the R-configuration.

[0197] One group of compounds according to this embodiment are compounds of formula (I-8), or any of the preferred embodiments of compounds of formula (I-8), wherein S * is in the S-configuration.

[0198] One group of compounds according to this embodiment are compounds of formula (I-8c), which are compounds of formula (I-8) or any of the preferred embodiments of compounds of formula (I-8), which are the first eluting enantiomers in the chiral resolution of racemates by preparative chromatography using immobilized amylose-based (CHIRALPAK® IA, CHIRALPAK® IG) or cellulose-based (CHIRALPAK® IC) chiral phases.

[0199] One group of compounds according to this embodiment are compounds of formula (I-8) or any of the preferred embodiments of compounds of formula (I-8) of formula (I-8d), which are the first eluting enantiomers in the chiral resolution of racemates by preparative SFC (supercritical fluid chromatography) using immobilized amylose-based (CHIRALPAK® IA, CHIRALPAK® IG) or cellulose-based (CHIRALPAK® IC) chiral phases.

[0200] One group of compounds according to this embodiment are compounds of formula (I-8) or any of the preferred embodiments of compounds of formula (I-8) of formula (I-8e), which are the first eluting enantiomers in the chiral resolution of racemates by preparative SFC using immobilized amylose-based (CHIRALPAK® IA, CHIRALPAK® IG) or cellulose-based (CHIRALPAK® IC) chiral phases with supercritical CO2 and preferably an alcohol co-solvent such as methanol, ethanol, or isopropyl alcohol as the mobile phase.

[0201] One group of compounds according to this embodiment are compounds of formula (I-8f), which are compounds of formula (I-8) or any of the preferred embodiments of compounds of formula (I-8), which are the second eluting enantiomers in the chiral resolution of racemates by preparative chromatography using immobilized amylose-based (CHIRALPAK® IA, CHIRALPAK® IG) or cellulose-based (CHIRALPAK® IC) chiral phases.

[0202] One group of compounds according to this embodiment are compounds of formula (I-8) or any of the preferred embodiments of compounds of formula (I-8) of formula (I-8g), which are the second eluting enantiomers in the chiral resolution of racemates by preparative SFC (supercritical fluid chromatography) using immobilized amylose-based (CHIRALPAK® IA, CHIRALPAK® IG) or cellulose-based (CHIRALPAK® IC) chiral phases.

[0203] One group of compounds according to this embodiment are compounds of formula (I-8h), which are compounds of formula (I-8), or any of the preferred embodiments of compounds of formula (I-8), that are the second eluting enantiomer in the chiral resolution of racemates by preparative SFC using immobilized amylose-based (CHIRALPAK® IA, CHIRALPAK® IG) or cellulose-based (CHIRALPAK® IC) chiral phases with supercritical CO2 and preferably an alcohol co-solvent such as methanol, ethanol, or isopropyl alcohol as the mobile phase.

[0204] Another group of compounds according to this embodiment are compounds of formula (I-8i), which are compounds of formula (I-8) or any of the preferred embodiments of compounds of formula (I-8), which are readily prepared or accessible stereospecifically by iminization of the stereodiene sulfinyl derivatives produced by stereoselective oxidation of the corresponding sulfanyl compounds as further defined and described in embodiment 31.

[0205] Another preferred group of compounds of formula I is the compounds of formula I-9 [ka] (In the formula, R1, R2, R8, R9, S * and A is as defined in Formula I above. It is expressed by:

[0206] In one preferred group of compounds of formula I-9, A is CH or N; R1 is ethyl, propyl or isopropyl; R2 is C1-C2 haloalkyl, C1-C2 haloalkylsulfanyl, C1-C2 haloalkylsulfinyl or C1-C2 haloalkylsulfonyl; R9 is hydrogen, methyl or ethyl; and R8 is cyanoisopropoxy, cyanoisopropyl or cyanocyclopropyl.

[0207] 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; and R8 is cyanoisopropoxy, cyanoisopropyl or cyanocyclopropyl.

[0208] In the compounds of formula I-9 and all of the preferred embodiments of the compounds of formula I-9 described above, unless otherwise specified, R1, R2, R8, R9, S * and A are as defined in formula I above; preferably, A is CH or N, more preferably, A is N; R1 is ethyl; R2 is trifluoromethyl, pentafluoroethyl or trifluoromethylsulfanyl; preferably, R2 is trifluoromethyl; R9 is hydrogen; and R8 is 1-cyano-1-methyl-ethoxy, 1-cyano-1-methyl-ethyl or 1-cyanocyclopropyl.

[0209] One group of compounds according to this embodiment are compounds of formula (I-9), either compounds of formula (I-9a), or preferred embodiments of compounds of formula (I-9), wherein S * is in the R-configuration.

[0210] One group of compounds according to this embodiment are compounds of formula (I-9), or any of the preferred embodiments of compounds of formula (I-9), wherein S * is in the S-configuration.

[0211] One group of compounds according to this embodiment are compounds of formula (I-9c), which are compounds of formula (I-9) or any of the preferred embodiments of compounds of formula (I-9), which are the first eluting enantiomers in the chiral resolution of racemates by preparative chromatography using immobilized amylose-based (CHIRALPAK® IA, CHIRALPAK® IG) or cellulose-based (CHIRALPAK® IC) chiral phases.

[0212] One group of compounds according to this embodiment are compounds of formula (I-9d), which are compounds of formula (I-9) or any of the preferred embodiments of compounds of formula (I-9), which are the first eluting enantiomers in the chiral resolution of racemates by preparative SFC (supercritical fluid chromatography) using immobilized amylose-based (CHIRALPAK® IA, CHIRALPAK® IG) or cellulose-based (CHIRALPAK® IC) chiral phases.

[0213] One group of compounds according to this embodiment are compounds of formula (I-9) or any of the preferred embodiments of compounds of formula (I-9) of formula (I-9e), which are the first eluting enantiomers in the chiral resolution of racemates by preparative SFC using immobilized amylose-based (CHIRALPAK® IA, CHIRALPAK® IG) or cellulose-based (CHIRALPAK® IC) chiral phases with supercritical CO2 and preferably an alcohol co-solvent such as methanol, ethanol, or isopropyl alcohol as the mobile phase.

[0214] One group of compounds according to this embodiment are compounds of formula (I-9f), which are compounds of formula (I-9) or any of the preferred embodiments of compounds of formula (I-9), which are the second eluting enantiomers in the chiral resolution of racemates by preparative chromatography using immobilized amylose-based (CHIRALPAK® IA, CHIRALPAK® IG) or cellulose-based (CHIRALPAK® IC) chiral phases.

[0215] One group of compounds according to this embodiment are compounds of formula (I-9) or any of the preferred embodiments of compounds of formula (I-9), which are the second eluting enantiomers in the chiral resolution of racemates by preparative SFC (supercritical fluid chromatography) using immobilized amylose-based (CHIRALPAK® IA, CHIRALPAK® IG) or cellulose-based (CHIRALPAK® IC) chiral phases.

[0216] One group of compounds according to this embodiment are compounds of formula (I-9h), which are compounds of formula (I-9), or any of the preferred embodiments of compounds of formula (I-9), that are the second eluting enantiomer in the chiral resolution of racemates by preparative SFC using immobilized amylose-based (CHIRALPAK® IA, CHIRALPAK® IG) or cellulose-based (CHIRALPAK® IC) chiral phases with supercritical CO2 and preferably an alcohol co-solvent such as methanol, ethanol, or isopropyl alcohol as the mobile phase.

[0217] Another group of compounds according to this embodiment are compounds of formula (I-9i), which are compounds of formula (I-9) or any of the preferred embodiments of compounds of formula (I-9), which are readily prepared or accessible stereospecifically by iminization of the stereodiene sulfinyl derivatives produced by stereoselective oxidation of the corresponding sulfanyl compounds as further defined and described in embodiment 31.

[0218] Another preferred group of compounds of formula I is the compounds of formula I-10 [ka] (In the formula, R1, R2, R8, R9, S * and A is as defined in Formula I above. It is expressed by:

[0219] In one preferred group of compounds of formula I-10, A is CH or N; R1 is ethyl, propyl or isopropyl; R2 is C1-C2 haloalkyl, C1-C2 haloalkylsulfanyl, C1-C2 haloalkylsulfinyl or C1-C2 haloalkylsulfonyl; R9 is hydrogen, methyl or ethyl; and R8 is cyanoisopropoxy, cyanoisopropyl or cyanocyclopropyl.

[0220] In another preferred group of compounds of formula I-10, 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; and R8 is cyanoisopropoxy, cyanoisopropyl or cyanocyclopropyl.

[0221] In the compounds of formula I-10 and all of the preferred embodiments of the compounds of formula I-10 described above, unless otherwise specified, R1, R2, R8, R9, S * and A are as defined in formula I above; preferably, A is CH or N, more preferably, A is N; R1 is ethyl; R2 is trifluoromethyl, pentafluoroethyl or trifluoromethylsulfanyl; preferably, R2 is trifluoromethyl; R9 is hydrogen; and R8 is 1-cyano-1-methyl-ethoxy, 1-cyano-1-methyl-ethyl or 1-cyanocyclopropyl.

[0222] One group of compounds according to this embodiment are compounds of formula (I-10), either compounds of formula (I-10a), or preferred embodiments of compounds of formula (I-10), wherein S * is in the R-configuration.

[0223] One group of compounds according to this embodiment are compounds of formula (I-10), or any of the preferred embodiments of compounds of formula (I-10), wherein S * is in the S-configuration.

[0224] One group of compounds according to this embodiment are compounds of formula (I-10), which are compounds of formula (I-10c), or any of the preferred embodiments of compounds of formula (I-10), which are the first eluting enantiomers in the chiral resolution of racemates by preparative chromatography using immobilized amylose-based (CHIRALPAK® IA, CHIRALPAK® IG) or cellulose-based (CHIRALPAK® IC) chiral phases.

[0225] One group of compounds according to this embodiment are compounds of formula (I-10) or any of the preferred embodiments of compounds of formula (I-10), which are the first eluting enantiomers in the chiral resolution of racemates by preparative SFC (supercritical fluid chromatography) using immobilized amylose-based (CHIRALPAK® IA, CHIRALPAK® IG) or cellulose-based (CHIRALPAK® IC) chiral phases.

[0226] One group of compounds according to this embodiment are compounds of formula (I-10e), which are compounds of formula (I-10), or any of the preferred embodiments of compounds of formula (I-10), which are the first eluting enantiomers in chiral resolution of racemates by preparative SFC using immobilized amylose-based (CHIRALPAK® IA, CHIRALPAK® IG) or cellulose-based (CHIRALPAK® IC) chiral phases with supercritical CO2 and preferably an alcohol co-solvent such as methanol, ethanol, or isopropyl alcohol as the mobile phase.

[0227] One group of compounds according to this embodiment are compounds of formula (I-10f), which are compounds of formula (I-10) or any of the preferred embodiments of compounds of formula (I-10), which are the second eluting enantiomers in the chiral resolution of racemates by preparative chromatography using immobilized amylose-based (CHIRALPAK® IA, CHIRALPAK® IG) or cellulose-based (CHIRALPAK® IC) chiral phases.

[0228] One group of compounds according to this embodiment is the compounds of formula (I-10), which are compounds of formula (I-10g), or any of the preferred embodiments of compounds of formula (I-10), which are the second eluting enantiomers in the chiral resolution of racemates by preparative SFC (supercritical fluid chromatography) using immobilized amylose-based (CHIRALPAK® IA, CHIRALPAK® IG) or cellulose-based (CHIRALPAK® IC) chiral phases.

[0229] One group of compounds according to this embodiment are compounds of formula (I-10), which are compounds of formula (I-10h), or any of the preferred embodiments of compounds of formula (I-10), which are the second eluting enantiomers in the chiral resolution of racemates by preparative SFC using immobilized amylose-based (CHIRALPAK® IA, CHIRALPAK® IG) or cellulose-based (CHIRALPAK® IC) chiral phases with supercritical CO2 and preferably an alcohol co-solvent such as methanol, ethanol, or isopropyl alcohol as the mobile phase.

[0230] Another group of compounds according to this embodiment are compounds of formula (I-10i), which are compounds of formula (I-10) or any of the preferred embodiments of compounds of formula (I-10), which are readily prepared or accessible stereospecifically by iminization of the stereodiene sulfinyl derivatives produced by stereoselective oxidation of the corresponding sulfanyl compounds as further defined and described in embodiment 31.

[0231] Another preferred group of compounds of formula I are those in which Q, R3, R4 and X1 are as defined in formula I (above); A is CH or N, preferably A is N; S * is a stereogenic sulfur atom in the R- or S-configuration; R1 is ethyl, propyl or isopropyl; preferably, R1 is ethyl; R2 is trifluoromethyl, pentafluoroethyl or trifluoromethylsulfanyl; preferably, R2 is trifluoromethyl; R8 is 1-cyano-1-methyl-ethoxy, 1-cyano-1-methyl-ethyl or 1-cyanocyclopropyl; R9 is hydrogen or methyl; preferably, R9 is hydrogen; and For compounds where Q is Q1 or Q4, G1 is N and G2 is CH, or G1 is CH and G2 is N, or G1 and G2 are both N; and For compounds where Q is Q2, G2 is N or CH; or an agrochemically acceptable salt, stereoisomer, enantiomer, tautomer or N-oxide thereof.

[0232] 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 or I-10, wherein A is CH or N, preferably A is N; S * is a stereogenic sulfur atom in the R- or S-configuration; R1 is ethyl, propyl or isopropyl; preferably, R1 is ethyl; R2 is trifluoromethyl, pentafluoroethyl or trifluoromethylsulfanyl; preferably, R2 is trifluoromethyl; R8 is 1-cyano-1-methyl-ethoxy, 1-cyano-1-methyl-ethyl or 1-cyanocyclopropyl; R9 is hydrogen or methyl; preferably, R9 is hydrogen; and For compounds of formula I-1, I-2, I-3 and I-4, R3 is methyl; and for compounds of formula I-4, R4 is ethyl, methoxy or cyclopropyl.

[0233] A preferred group of compounds of formula I are those containing a stereogenic sulfur center (S * ) is represented by the (S) absolute configuration.

[0234] Another preferred group of compounds of formula I are in (S) enantiomerically pure form or have an S-enantiomeric excess (ee) of at least 40%, e.g., at least 50%, 60%, 70% or 80%, preferably at least 90%, more preferably at least 95%, even more preferably at least 98%, and most preferably at least 99%.

[0235] Another preferred group of compounds of formula I are those containing a stereogenic sulfur center (S * ) is represented by the (R) absolute configuration.

[0236] Another preferred group of compounds of formula I are in (R) enantiomerically pure form or have an R-enantiomeric excess (ee) of at least 40%, e.g., at least 50%, 60%, 70% or 80%, preferably at least 90%, more preferably at least 95%, even more preferably at least 98%, and most preferably at least 99%.

[0237] An especially preferred group of compounds of formula I are those represented by the (S)- or (R)-enantiomer compounds P1 to P19 as defined in Table Y below.

[0238] [Table 1-1] [Table 1-2] [Table 1-3] [Table 1-4] [Table 1-5] [Table 1-6] [Table 1-7]

[0239] Another preferred group of compounds of formula I are those that comprise the first eluting enantiomers in chiral resolution by preparative chromatography using immobilized amylose-based (CHIRALPAK® IA, CHIRALPAK® IG) or cellulose-based (CHIRALPAK® IC) chiral phases.

[0240] Another preferred group of compounds of formula I are those which comprise the first eluting enantiomer in the chiral resolution of racemates by preparative SFC (supercritical fluid chromatography) using immobilized amylose-based (CHIRALPAK® IA, CHIRALPAK® IG) or cellulose-based (CHIRALPAK® IC) chiral phases.

[0241] Another preferred group of compounds of Formula I comprises the first eluting enantiomer in chiral resolution of racemates by preparative SFC using immobilized amylose-based (CHIRALPAK® IA, CHIRALPAK® IG) or cellulose-based (CHIRALPAK® IC) chiral phases with supercritical CO2 and, preferably, an alcohol co-solvent such as methanol, ethanol, or isopropyl alcohol as the mobile phase.

[0242] Another preferred group of compounds of formula I are those having an enantiomeric excess (ee) of the first eluting enantiomer of at least 40%, e.g., at least 50%, 60%, 70% or 80%, preferably at least 90%, more preferably at least 95%, even more preferably at least 98%, and most preferably at least 99%.

[0243] Another preferred group of compounds of formula I are those which comprise the second eluting enantiomer in chiral resolution by preparative chromatography using immobilized amylose-based (CHIRALPAK® IA, CHIRALPAK® IG) or cellulose-based (CHIRALPAK® IC) chiral phases.

[0244] Another preferred group of compounds of formula I are those which comprise the second eluting enantiomer in the chiral resolution of racemates by preparative SFC (supercritical fluid chromatography) using immobilized amylose-based (CHIRALPAK® IA, CHIRALPAK® IG) or cellulose-based (CHIRALPAK® IC) chiral phases.

[0245] Another preferred group of compounds of Formula I comprises the second eluting enantiomer in chiral resolution of racemates by preparative SFC using immobilized amylose-based (CHIRALPAK® IA, CHIRALPAK® IG) or cellulose-based (CHIRALPAK® IC) chiral phases with supercritical CO2 and, preferably, an alcohol co-solvent such as methanol, ethanol, or isopropyl alcohol as the mobile phase.

[0246] Another preferred group of compounds of formula I are those having an enantiomeric excess (ee) of the second eluting enantiomer of at least 40%, e.g., at least 50%, 60%, 70% or 80%, preferably at least 90%, more preferably at least 95%, even more preferably at least 98%, and most preferably at least 99%.

[0247] A particularly preferred group of compounds of formula I are those represented by the first eluting (P1-A to P19-A) or second eluting (P1-B to P19-B) enantiomeric compounds P1 to P19, as defined in Table Z below.

[0248] [Table 2-1] [Table 2-2] [Table 2-3] [Table 2-4]

[0249] 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 superior properties for use as agrochemical active ingredients (e.g., high biological activity, differential biological activity of the enantiomer or enantiomerically enriched composition and the racemate, differential biological activity of the (R) enantiomer or (R) enantiomerically enriched composition and the (S) enantiomer or (S) enantiomerically enriched composition, advantageous activity spectrum, high safety profile, improved physicochemical properties, or high biodegradability or environmental profile). In particular, it has been surprisingly 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 specifically, the European honeybee (Apis mellifera).

[0250] 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 34 (above) of formula I-1, I-2, I-3, I-4, I-5, I-6, I-7, I-8, I-9 or I-10, and optionally an adjuvant or diluent.

[0251] In a further aspect, the present invention provides a method for combating and controlling insects, acaridae, nematodes or molluscs, comprising applying to the pest, the pest's habitat, or plants susceptible to attack by the pest an insecticidally, acaricidally, nematicidally or molluscicidally effective amount of a compound of formula (I), or an agrochemically acceptable salt, stereoisomer, enantiomer, tautomer or N-oxide thereof, as defined in any of embodiments 1 to 34 (above), where the compound is formula I-1, I-2, I-3, I-4, I-5, I-6, I-7, I-8, I-9 or I-10, or a composition as defined above.

[0252] 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.

[0253] The process according to the invention for preparing compounds of formula I is carried out by methods known to those skilled in the art. Individual enantiomers can be prepared, for example, by either i) enantioselective conversion, ii) resolution of a racemate or a partially enriched mixture by fractional crystallization using an enantiomerically enriched reagent, or iii) chromatographic separation of the enantiomers using an enantiomerically enriched stationary phase.

[0254] The individual enantiomers are available by chromatographic separation of the racemic mixture on a chiral stationary phase using preparative high performance liquid chromatography (HPLC, normal or reverse phase mode) or using preparative supercritical fluid chromatography (SFC).

[0255] Q, R1, R2, G1, G2, X1, R3, R4, R8, R9, S * and a compound of formula I in the form of a first or second eluting enantiomer, wherein A is as defined in formula I above. Scheme 1: [ka] For example, they can be obtained by chiral resolution of a racemic mixture of compounds of formula I (rac-I) (wherein Q, R1, R2, G1, G2, X1, R3, R4, R8, R9 and A are as defined in formula I above) by preparative SFC using immobilized amylose-based (such as CHIRALPAK® IA, CHIRALPAK® IG) or cellulosic (such as CHIRALPAK® IC) chiral phases with supercritical CO2 and preferably an alcohol co-solvent such as methanol, ethanol or isopropyl alcohol as the mobile phase (Scheme 1).

[0256] A racemic mixture of a compound of formula I (rac-I), where Q, R1, R2, G1, G2, X1, R3, R4, R8, R9 and A are as defined above for formula I, can be prepared by: Scheme 2: [ka] Sulfide compounds of formula II (wherein Q, R1, R2, G1, G2, X1, R3, R4, R8, R9 and A are as defined in formula I) can be prepared by reacting a suitable nitrogen source, such as ammonia, ammonium carbamate or ammonium acetate (preferably ammonium carbamate), in the presence of a hypervalent iodine reagent, such as diacetoxyiodobenzene, in a solvent such as toluene, acetonitrile or methanol, at a temperature between 0 and 100°C, preferably at about room temperature, as described, for example, in Chem. Commun. 53, 348-351; 2017 (and references cited therein) (Scheme 2).

[0257] Alternatively, a racemic mixture of compounds of formula I (rac-I), where Q, R1, R2, G1, G2, X1, R3, R4, R8, R9 and A are as defined above for formula I, can be prepared by: Scheme 3: [ka] The racemic sulfoxide compounds of formula rac-III (wherein Q, R, R, G, G, X, R, R, R, R, R, and A are as defined in formula I above) can be prepared by reacting them with a suitable nitrogen source, optionally in the presence of an oxidizing agent, optionally in the presence of a metal catalyst, and optionally in a solvent such as acetonitrile, dichloromethane, or methanol (Scheme 3). Typical imination conditions include O-dinitrophenylhydroxylamine / Rh(esp), NHCOONH / PhI(OAc), NaN / HSO, or O-mesitylenesulfonyl-hydroxylamine (MSH). Examples of such transformations are described in Chemistry-A European Journal 2021, 27, 17293-17321 (and references cited therein), Chemical Communications 2014, 50, 9687-9689 and Angewandte Chemie, International Edition 2016, 55, 7203-7207 (and references cited therein).

[0258] Of particular interest is a method using a hydroxylamine derivative, such as O-(4-nitrobenzoyl)-hydroxylamine triflic acid (also known as O-(4-nitrobenzoyl)-hydroxylammonium triflate or O-(4-nitrobenzoyl)-hydroxylammonium trifluoromethanesulfonate), and an iron catalyst, such as iron(II) sulfate (FeSO4) or iron(II) phthalocyanine (Fe(II) phthalocyanine, FePc), in a solvent such as acetonitrile or dichloromethane, as described in Angewandte Chemie International Edition 2018, 57 324-327.

[0259] Compounds of formula rac-III (wherein Q, R1, R2, G1, G2, X1, R3, R4, R8, R9, and A are as defined in formula I above) can be obtained by oxidation of the corresponding sulfide compounds of formula II (wherein Q, R1, R2, G1, G2, X1, R3, R4, R8, R9, and A are as defined in formula I) with reagents such as metachloroperbenzoic acid (mCPBA), hydrogen peroxide, oxone, sodium periodate, sodium hypochlorite, or tert-butyl hypochlorite, among other oxidizing agents. The oxidation reaction is generally carried out in the presence of a solvent. Examples of solvents 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. The amount of the oxidizing agent used in this reaction is preferably 1 to 1.2 moles per mole of the sulfide compound II for producing the sulfoxide compound rac-III.

[0260] Compounds of formula rac-Ia may also be useful for the preparation of compounds of formula rac-I as described in Scheme 4. Such compounds of formula rac-Ia (wherein Q, R1, R2, G1, G2, X1, R3, R4, R8, R9 and A are as defined above in Formula I, and R 10 is cyano or -C(O)R 25 where R 25 is hydrogen, C1-C6 alkyl, C1-C6 haloalkyl, C1-C6 alkoxy or C1-C6 haloalkoxy) Scheme 4: [ka] Compounds of formula rac-III (wherein Q, R1, R2, G1, G2, X1, R3, R4, R8, R9 and A are as defined in formula I above) can be reacted with reagent R as described, for example, in H. Okamura, C. Bolm, Org. Lett. 2004, 6, 1305-1307; H. Okamura, C. Bolm, Chem. Lett. 2004, 33, 482-487; D. Leca, K. Song, M. Amatore, L. Fensterbank, E. Lacote, M. Malacria, Chem. Eur. J. 2004, 10, 906-916; or M. Reggelin, C. Zur, Synthesis, 2000, 1-64. 10 -NH2 (R as defined above) 10 ) (Scheme 4). Typical iminization reagents / conditions are 10 -N3 / FeCl2, R 10 -NH2 / Fe(acac)3 / PhI=O, PhI=NR 10 / Fe(OTf)2, PhI=NR 10 / CuOTf, PhI=NR 10 / Cu(OTf)2, PhI=NR 10 / CuPF6, PhI(OAc)2 / R 10 -NH2 / MgO / Rh2(OAc)4, R 10 This may involve metal catalyzed methods such as NHOMs / FeCl2 or oxaziridines (e.g. 3-(4-cyano-phenyl)-oxaziridine-2-carboxylic acid tert-butyl ester) [see O.G. Mancheno, C. Bolm, Chem. Eur. J. 2007, 13, 6674-6681].

[0261] As described in G.Y. Cho, C. Bolm, Tetrahedron Lett. 2005, 46, 8007-8008, R 10 -NH2 and an oxidizing agent, such as PhI(OAc)2 / R 10 -NH2; or N-bromosuccinimide (NBS) / R, as described in C. Bolm et al., Synthesis 2010, No. 17, 2922-2925.10 Of particular interest are metal-free imination methods, such as those using -NH2 and bases such as sodium or potassium t-butoxide. Oxidizing agents such as N-iodosuccinimide (NIS) or iodine may alternatively be used, as described, for example, in OG Mancheno, C. Bolm, Org. Lett. 2007, 9, 3809-3811. Examples of hypochlorite salts used as oxidizing agents, such as sodium hypochlorite NaOCl or calcium hypochlorite Ca(OCl)2, are described in WO 2008 / 1060.

[0262] A compound of formula rac-Ia, wherein Q, R1, R2, G1, G2, X1, R3, R4, R8, R9 and A are as defined above in formula I, and R 10 where R is CN) can be converted to R by treatment with trifluoroacetic anhydride in a solvent such as dichloromethane, as described, for example, in O.G. Mancheno, C. Bolm, Org. Lett. 2007, 9, 3809-3811. 10 can be converted to a compound of formula rac-Ia, where is C(O)CF3.

[0263] A compound of formula rac-Ia, wherein Q, R1, R2, G1, G2, X1, R3, R4, R8, R9 and A are as defined above in formula I, and R 10 is C(O)CF3) can be converted to compounds of formula rac-I (group R 10 cleavage).

[0264] Conversely, the order of the two oxidation / imination steps disclosed in Scheme 4 for preparing compounds of formula rac-Ia may be reversed as shown in Scheme 5.

[0265] Scheme 5: [ka]

[0033] Reacting a compound of formula rac-IV (wherein Q, R1, R2, G1, G2, X1, R3, R4, R8, R9 and A are as defined above in formula I, and wherein R 10 is as defined in Scheme 4) can be achieved under the conditions already described or may use, for example, KMnO, NaMnO, mCPBA, NaIO / RuO, NaIO / RuCl, HO or oxone. In particular, the use of ruthenium salts in combination with alkali metal periodates or alkali metal permanganates is described in WO 2008 / 097235 and WO 2008 / 106006.

[0266] Compounds of formula rac-IV, wherein Q, R1, R2, G1, G2, X1, R3, R4, R8, R9 and A are as defined above in formula I, and wherein R 10 is cyano or -C(O)R 25 where R 25 is hydrogen, C1-C6 alkyl, C1-C6 haloalkyl, C1-C6 alkoxy, or C1-C6 haloalkoxy) can be prepared by subjecting a compound of Formula II (wherein Q, R1, R2, G1, G2, X1, R3, R4, R8, R9, and A are as defined in Formula I) to imination reaction conditions, as described above in Scheme 4.

[0267] A subgroup of compounds of formula II (wherein R is cyanoisopropoxy, more specifically 1-cyano-1-methyl-ethoxy, and Q, R, R, G, G, X, R, R, R, and A are as defined in formula I above) can be defined similarly to compounds of formula II-a (Scheme 6). Such compounds II-a are known or can be prepared by or analogously to the methods described, for example, in WO 2020 / 084075, JP 2019 / 081800, WO 2018 / 206348, and WO 2018 / 197315.

[0268] Scheme 6: [ka] A subgroup of compounds of formula II (wherein R is cyanoisopropyl, more specifically 1-cyano-1-methyl-ethyl, and Q, R, R, G, G, X, R, R, R, and A are as described in formula I above) may be defined as compounds of formula II-b (Scheme 6). Such compounds II-b are known or may be prepared by, or analogously to, the methods described, for example, in WO 2019 / 053182, WO 2018 / 153778, and WO 2018 / 077565.

[0269] A subgroup of compounds of formula II, where R is cyanocyclopropyl, more specifically 1-cyanocyclopropyl, and Q, R, R, G, G, X, R, R, R, and A are as described in formula I above, may be defined as compounds of formula II-c (Scheme 6). Such compounds II-c are known or may be prepared by, or analogously to, the methods described in, for example, WO 2019 / 234158, WO 2019 / 059244, WO 2018 / 108726, WO 2018 / 077565, WO 2017 / 089190, WO 2016 / 121997, and WO 2016 / 071214.

[0270] Alternatively, the individual enantiomers may be obtained by stereoselective synthesis.

[0271] The compounds of formula I in the form of individual enantiomers, wherein Q, R1, R2, G1, G2, X1, R3, R4, R8, R9 and A are as defined above in formula I, and S * is a stereogenic sulfur atom in the R- or S-configuration, wherein the S * The center (which may be in enantiomerically pure or enantiomerically enriched form) is Scheme 7: [ka] It can be prepared by adapting the conditions already described in Schemes 3 and 4 (Scheme 7).

[0272] The compounds of formula III in the form of individual enantiomers, wherein Q, R1, R2, G1, G2, X1, R3, R4, R8, R9 and A are as defined above in formula I, and S * is a stereogenic sulfur atom in the R- or S-configuration, wherein the S *The chiral sulfinyl compounds (centers in enantiomerically pure or enantiomerically enriched form) can be obtained from compounds of formula II (substituents as defined in Schemes 3 and 4) by stereoselective synthesis of chiral sulfinyl compounds, preferably in the form of catalytic enantioselective sulfoxide synthesis, by treatment with an oxidizing agent, e.g., HO or tBuOOH, in the presence of a metal salt and a chiral ligand. Examples of suitable metal salt and ligand combinations include Ti(OiPr)4 in combination with Fe(acac)3, V(O)(acac)2, or Cu(acac)2, with Schiff base or salen complexes formed from salicylaldehyde derivatives and chiral amino-alcohols, or with tartrate esters such as diisopropyl or diethyl tartrate. The reaction can be carried out in a solvent such as dichloromethane, toluene, chlorobenzene, or methanol, or a mixture of solvents, and optionally in the presence of additives such as 4-methoxybenzoic acid, benzoic acid, triethylamine, diisopropylethylamine, or water. Examples of such reactions are described in Chemical Reviews 2020, 120, 4578-4611, Chemistry-A European Journal 2005, 11, 1086-1092, Angewandte Chemie (International Edition in English) 1996, 34, 2640-2642, Journal of Organic Chemistry 2012, 3288-3296, and Synlett 1996, 404-406. Alternatively, instead of metal complexes and ligands, chiral acids such as chiral phosphoric acids derived from binol can be used as catalysts, as described in Journal of the American Chemical Society 2012, 134, 10765-10768.

[0273] Compounds of formula III in the form of individual enantiomers [ka] (In the formula, Q, R1, R2, G1, G2, X1, R3, R4, R8, R9 and A are as defined in Formula I; and S * is a stereogenic sulfur atom in the R- or S-configuration, wherein the S * The center is in enantiomerically pure or enantiomerically enriched form. are novel and have been specially developed for the preparation of compounds of formula I according to the invention and therefore represent a further object of the present invention. The preferences and preferred embodiments regarding the substituents of compounds of formula I are also valid for compounds of formula III. The sulfinyl enantiomeric compounds of formula III listed in Table P(SO) are particularly preferred.

[0274] The individual enantiomeric forms of compounds of formula I, wherein Q, R1, R2, G1, G2, X1, R3, R4, R8, R9 and A are as defined above in formula I, and S * is a stereogenic sulfur atom in the R- or S-configuration, wherein the S * The center (either in enantiomerically pure or enantiomerically enriched form) can be converted directly (conditions similar to those in Scheme 3) by an iminization step via stereospecific nitrogen migration, or to a compound of formula R 10 -NH2 reagent (R as defined above) 10 ), with a compound of formula Ia, wherein Q, R1, R2, G1, G2, X1, R3, R4, R8, R9 and A are as defined above in formula I, and S * is a stereogenic sulfur atom in the R- or S-configuration, wherein the S *

[0047] Through intermediates (conditions similar to those in Scheme 4) of the individual enantiomers of compounds of formula III (wherein Q, R1, R2, G1, G2, X1, R3, R4, R8, R9 and A are as defined in formula I above, and S * is a stereogenic sulfur atom in the R- or S-configuration, wherein the S *The centers may be obtained from (either enantiomerically pure or enantiomerically enriched).

[0275] In another aspect, the present invention provides a compound of formula (I) [ka] wherein Q, R1, R2, G1, G2, X1, R3, R4, R8, R9 and A are as defined in formula (I); and S * is a stereogenic sulfur atom in the R- or S-configuration, wherein the S * The present invention provides a process for the preparation of enantiomerically pure or enantiomerically enriched forms of benzophenone-3, which comprises: (A) A sulfanyl compound of formula (II) [ka] (wherein Q, R1, R2, G1, G2, X1, R3, R4, R8, R9 and A are as defined in formula (I)). in the presence of an oxidizing agent, in the presence of a metal catalyst, in the presence of a chiral ligand, and optionally in the presence of a suitable additive, in a suitable solvent (or diluent) to give a sulfinyl compound of formula (III) [ka] wherein Q, R1, R2, G1, G2, X1, R3, R4, R8, R9 and A are as defined in formula (I); and S * is a stereogenic sulfur atom in the R- or S-configuration, wherein the S * The center is in enantiomerically pure or enantiomerically enriched form. generating (B) A sulfinyl compound of formula (III) [ka] wherein Q, R1, R2, G1, G2, X1, R3, R4, R8, R9 and A are as defined in formula (I); and S * is a stereogenic sulfur atom in the R- or S-configuration, wherein the S * The center is in enantiomerically pure or enantiomerically enriched form. with an iminizing reagent in the presence of a catalyst and optionally in the presence of suitable additives in a suitable solvent (or diluent) to stereospecifically produce the sulfoximine compound of formula (I). Includes.

[0276] In relation to the process for preparing the compound of formula (I) comprising steps (A) and (B) above, the preferences and preferred embodiments regarding the substituents of the compound of formula (I) described above are also valid for the compounds of formula (II) and (III).

[0277] In one particularly preferred embodiment, step (A) comprises oxidation of the sulfanyl compound of formula (II) listed in step 1 of each of Preparative Examples P1 to P19.

[0278] In other particularly preferred embodiments, step (B) comprises reacting a sulfinyl enantiomeric compound of formula III listed in Table P(SO) with an iminating reagent.

[0279] With respect to the above-mentioned step (A) of the process for preparing the compound of formula (III), examples of suitable and preferred oxidizing agents, suitable and preferred metal catalysts, suitable and preferred chiral ligands, suitable and preferred additives, and suitable and preferred examples of reaction conditions (such as solvents (or diluents) and temperatures) are shown below.

[0280] In one embodiment, step (A) (A-1) The method comprises the step of oxidizing a sulfanyl compound of formula (II) in the presence of an oxidizing agent, a metal catalyst, and a chiral ligand in a suitable solvent (or diluent).

[0281] In another embodiment, step (A) (A-2) The method comprises the step of oxidizing a sulfanyl compound of formula (II) in the presence of an oxidizing agent, a metal catalyst, a chiral ligand, or a suitable additive in a suitable solvent (or diluent).

[0282] Examples of suitable and preferred oxidizing agents for steps (A-1) and (A-2) include inorganic peroxides such as hydrogen peroxide or organic peroxides such as tert-butyl hydroperoxide. Preferably, the oxidizing agent is hydrogen peroxide or tert-butyl hydroperoxide, even more preferably hydrogen peroxide. The ratio of the oxidizing agent used to the sulfanyl compound of formula (II) is within the range of 8:1 to 0.8:1, preferably 5:1 to 1:1, more preferably 3:1 to 1:1.

[0283] Examples of suitable and preferred metal catalysts for steps (A-1) and (A-2) are iron(III) acetylacetonate (Fe(acac)3) or vanadyl acetylacetonate (vanadium(IV)-oxyacetylacetonate, VO(acac)2). Preferably, the metal catalyst is iron(III) acetylacetonate. The amount of metal salt used relative to the sulfanyl compound of formula (II) is in the range of 0.01 to 10 mol%, preferably 0.1 to 8 mol%, most preferably 1 to 6 mol%.

[0284] Examples of suitable and preferred chiral ligands for steps (A-1) and (A-2) are selected from N,N'-bis(salicylidene)ethylenediamine (salen ligands) or Schiff bases formed from salicylaldehyde derivatives and chiral amino-alcohols. Preferably, the chiral ligand is a compound of formula (R)-Xa or (S)-Xa [ka] (In the formula, R 10 and R 11 are independently selected from C1-C4 alkyl and halogen, and R 12is tert-butyl, isopropyl, optionally substituted phenyl or optionally substituted benzyl). More preferably, the chiral ligand is a compound of formula (R)-Xb or (S)-Xb [ka] (In the formula, R 10 and R 11 are each independently selected from t-butyl, chloro, bromo and iodo; even more preferably selected from chloro, bromo and iodo). Chiral ligand compounds of formula (R)-Xb or (S)-Xb, where R 10 is R 11 and selected from chloro, bromo and iodo) is particularly preferred. The ratio of the chiral ligand used (preferably a compound of formula (R)-Xb or (S)-Xb) to the metal catalyst (preferably iron(III) acetylacetonate) is in the range of 10:1 to 0.5:1, preferably 3:1 to 1:1, more preferably about 2:1.

[0285] An example of a suitable and preferred additive for step (A-2) is a carbocyclic acid. Preferably, the additive is benzoic acid, optionally mono-, di-, or tri-substituted with methyl, ethyl, isopropyl, methoxy, or dimethylamino, and optionally in the form of its lithium, sodium, or potassium salt. More preferably, the additive is methoxybenzoic acid (optionally in the form of its lithium, sodium, or potassium salt), even more preferably 4-methoxybenzoic acid. The amount of the additive used relative to the sulfanyl compound of formula (II) is within the range of 0.01 to 10 mol%, preferably 0.1 to 8 mol%, and most preferably 1 to 5 mol%.

[0286] In one embodiment, for step (A) of the process according to the invention for forming a compound of formula (III), examples of suitable solvents (or diluents) are aliphatic halogenated hydrocarbons such as dichloromethane, 1,2-dichloroethane or chloroform, or aromatic, halohydrocarbon or alkoxyhydrocarbons such as toluene, xylene, chlorobenzene, methoxybenzene or benzotrifluoride, or mixtures thereof. Preferably, the solvent (or diluent) is toluene or chlorobenzene, even more preferably toluene.

[0287] In one embodiment, with respect to step (A) of the process of the present invention for forming a compound of formula (III), the reaction is advantageously carried out at a temperature range of from about −20° C. to about 50° C., preferably from about −5° C. to about 30° C. In a preferred embodiment, the reaction is carried out within the range of 0° C. to 25° C.

[0288] With respect to the above step (B) of the process for preparing the compound of formula (I), examples of suitable and preferred iminizing reagents, examples of suitable and preferred catalysts, examples of suitable and preferred additives, and examples of suitable and preferred reaction conditions (such as solvents (or diluents) and temperatures) are as follows:

[0289] In one embodiment, step (B) (B-1) Reacting the sulfinyl compound of formula (III) with an iminating agent in the presence of a catalyst in a suitable solvent (or diluent). Includes.

[0290] An example of a suitable and preferred iminating reagent for step (B-1) is O-mesitylenesulfonyl-hydroxylamine (MSH) or a hydroxylamine derivative. Preferably, the iminating reagent is a hydroxylamine derivative, more preferably a compound of formula (XX): [ka] (In the formula, R 20is phenyl mono-, di- or trisubstituted by tert-butyl or nitro, and X - is a sulfonate or hydrogen sulfate group) More preferably, the iminizing reagent is an O-acylated hydroxylamine salt represented by formula (XX) 20 is 4-nitrophenyl or 2,4-dinitrophenyl, and X - is a sulfonate group). Even more preferably, the iminating reagent compound of formula (XX) is selected from O-(4-nitrobenzoyl)-hydroxylammonium trifluoromethanesulfonate and O-(4-nitrobenzoyl)-hydroxylammonium methanesulfonic acid. As the iminating reagent compound of formula (XX), O-(4-nitrobenzoyl)-hydroxylammonium trifluoromethanesulfonic acid is particularly preferred. The ratio of the iminating reagent used to the sulfinyl compound of formula (III) is within the range of 8:1 to 0.8:1, preferably 5:1 to 1:1, more preferably 3:1 to 1:1.

[0291] Examples of suitable and preferred catalysts for step (B-1) are iron(II) sulfate (FeSO), iron(II) acetate (Fe(OAc) or iron(II) acetylacetonate (Fe(acac)), or iron(II) phthalocyanine (Fe(II) phthalocyanine, FePc), in combination with 2,2'-bipyridine or 1,10-phenanthroline, respectively. Preferably, the metal catalyst is iron(II) phthalocyanine. The amount of catalyst used relative to the sulfinyl compound of formula (III) is in the range of 0.01-10 mol%, preferably 0.1-8 mol%, most preferably 1-5 mol%.

[0292] In one embodiment, for step (B) of the process according to the present invention for forming a compound of formula (I), examples of suitable solvents (or diluents) are acetonitrile, methanol, ethanol, isopropanol, 2,2,2-trifluoroethanol (TFE), hexafluoroisopropanol (HFIP), dichloromethane (DCM), toluene, ethyl acetate, acetic acid, water, or mixtures thereof. Preferably, the solvent (or diluent) is acetonitrile, acetic acid, or dichloromethane, even more preferably dichloromethane.

[0293] In one embodiment, with respect to step (B) of the process of the present invention for forming a compound of formula (I), the reaction is advantageously carried out at a temperature range of from about −20° C. to about 50° C., preferably from about −5° C. to about 30° C. In a preferred embodiment, the reaction is carried out within the range of 10° C. to 25° C.

[0294] S * is a stereogenic sulfur atom in the R- or S-configuration, wherein said S * The products obtained by the process according to the invention, in which the center is in enantiomerically enriched form, have an enantiomeric ratio (R:S or S:R, as the case may be) of 50.5:49.5 to 99.5:0.5, preferably 75:25 to 99:1, more preferably 85:15 to 98:2.

[0295] In one embodiment, S * is a stereogenic sulfur atom in the R- or S-configuration, wherein said S * The sulfinyl compounds of formula (III) obtained by step (A) of the process according to the invention, in which the center is in enantiomerically enriched form, have an enantiomeric ratio (R:S or S:R, as the case may be) of 50.5:49.5 to 99.5:0.5, preferably 75:25 to 99:1, more preferably 85:15 to 98:2.

[0296] In other embodiments, S * is a stereogenic sulfur atom in the R- or S-configuration, wherein said S *The sulfoximine compounds of formula (I) obtained by step (B) of the process according to the invention, in which the center is in enantiomerically enriched form, have an enantiomeric ratio (R:S or S:R, as the case may be) of 50.5:49.5 to 99.5:0.5, preferably 75:25 to 99:1, more preferably 85:15 to 98:2.

[0297] In a further embodiment, the enantiomeric ratio (R:S or S:R, as the case may be) of such sulfinyl compound of Formula (III) obtained by step (A) and the enantiomeric ratio (R:S or S:R, as the case may be) of such sulfoximine compound of Formula (I) obtained by step (B) are substantially identical. In one embodiment, the enantiomeric ratio of such sulfinyl compound of Formula (III) obtained by step (A) and the enantiomeric ratio of such sulfoximine compound of Formula (I) obtained by step (B) are within ±1 percent of each other; preferably, ±0.5 percent of each other; and more preferably, ±0.1 percent of each other.

[0298] Optionally, the enantiomeric purity of such products, sulfinyl compounds of formula (III) and / or sulfoximine compounds of formula (I), can be increased by crystallization processes known to those skilled in the art, preferably via crystallization from an organic solvent or a mixture of an organic solvent and water.

[0299] Methods for determining enantiomeric excess are known to those skilled in the art and include, for example, the use of HPLC on chiral stationary phases and NMR with chiral shift reagents.

[0300] 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).

[0301] 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.

[0302] 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.

[0303] Compounds of formula I can be converted into other compounds of formula I in a manner known per se by conventional methods by replacing one or more substituents of the starting compound of formula I by other substituents according to the invention, and by subsequent modification of the compound by reactions such as oxidation, alkylation, reduction, acylation, and other methods known to those skilled in the art.

[0304] 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.

[0305] 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.

[0306] 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.

[0307] 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.

[0308] 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.

[0309] The compounds of formula I and, where appropriate, their tautomers, can exist in the form of one of the possible isomers or as mixtures thereof, in the form of pure isomers, such as 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, in each case in free form or in salt form; the invention relates to the pure isomers and also to all possible isomeric mixtures, and is to be understood in this sense above and below, respectively, even if details of the stereochemistry are not specifically stated in each case.

[0310] 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.

[0311] 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.

[0312] 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.

[0313] Several methods for determining the absolute configuration of chiral compounds are known, including many spectroscopic and diffractometric methods, such as derivatization with chiral reagents and analysis by chromatographic techniques, NMR with chiral shift reagents, optical rotatory dispersion, circular dichroism, chemical correlation, and X-ray crystallography, particularly single crystal X-ray diffraction (XRD).

[0314] 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.

[0315] 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.

[0316] 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.

[0317] 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, for example solvents that may have been used for the crystallization of compounds present in solid form.

[0318] The compounds of formula I according to the following Tables X, A-1 to A-20 and B-1 to B-20 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.

[0319] Tables A-1 to A-20 below show specific compounds of the invention in which the stereogenic sulfur atom is in the R-configuration. [ka]

[0320] Table A-1 provides 12 compounds of formula (IR) A-1.001 to A-1.012, wherein R1 is ethyl, and A, R8 and R9 are as defined in Table X, and Q is selected from the group of formula Q1 as follows: [ka]

[0321] [Table 3]

[0322] For example, compound A-1.004 has the following structure: [ka] where (R) indicates the R-configuration at the stereogenic sulfur center.

[0323] Table A-2 provides 12 compounds of formula (IR) A-2.001 to A-2.012, wherein R1 is ethyl, and A, R8 and R9 are as defined in Table X, and Q is selected from the group of formula Q1 as follows: [ka]

[0324] Table A-3 provides 12 compounds of formula (IR) A-3.001 to A-3.012, wherein R1 is ethyl, and A, R8 and R9 are as defined in Table X, and Q is selected from the group of formula Q1 as follows: [ka]

[0325] Table A-4 provides 12 compounds of formula (IR), A-4.001 to A-4.012, wherein R1 is ethyl, and A, R8 and R9 are as defined in Table X, and Q is selected from the group of formula Q2 as follows: [ka]

[0326] Table A-5 provides 12 compounds of formula (IR), A-5.001 to A-5.012, wherein R1 is ethyl, and A, R8 and R9 are as defined in Table X, and Q is selected from the group of formula Q2 as follows: [ka]

[0327] Table A-6 provides 12 compounds of formula (IR), A-6.001 to A-6.012, wherein R1 is ethyl, and A, R8 and R9 are as defined in Table X, and Q is selected from the group of formula Q3 as follows: [ka]

[0328] Table A-7 provides 12 compounds of formula (IR), A-7.001 to A-7.012, wherein R1 is ethyl, and A, R8 and R9 are as defined in Table X, and Q is selected from the group of formula Q1 as follows: [ka]

[0329] Table A-8 provides 12 compounds of formula (IR), A-8.001 to A-8.012, wherein R1 is ethyl, and A, R8 and R9 are as defined in Table X, and Q is selected from the group of formula Q1 as follows: [ka]

[0330] Table A-9 provides 12 compounds of formula (IR), A-9.001 to A-9.012, wherein R1 is ethyl, and A, R8 and R9 are as defined in Table X, and Q is selected from the group of formula Q4 as follows: [ka]

[0331] Table A-10 provides twelve compounds of formula (IR), A-10.001 to A-10.012, wherein R1 is ethyl, and A, R8 and R9 are as defined in Table X, and Q is selected from the group of formula Q4 as follows: [ka]

[0332] Table A-11 provides 12 compounds of formula (IR) A-11.001 to A-11.012, wherein R1 is ethyl, and A, R8 and R9 are as defined in Table X, and Q is selected from the group of formula Q5 as follows: [ka]

[0333] Table A-12 provides twelve compounds of formula (IR), A-12.001 to A-12.012, wherein R1 is ethyl, and A, R8 and R9 are as defined in Table X, and Q is selected from the group of formula Q5 as follows: [ka]

[0334] Table A-13 provides twelve compounds of formula (IR), A-13.001 to A-13.012, wherein R1 is ethyl, and A, R8 and R9 are as defined in Table X, and Q is selected from the group of formula Q5 as follows: [ka]

[0335] Table A-14 provides twelve compounds of formula (IR), A-14.001 to A-14.012, wherein R1 is ethyl, and A, R8 and R9 are as defined in Table X, and Q is selected from the group of formula Q2 as follows: [ka]

[0336] Table A-15 provides twelve compounds of formula (IR), A-15.001 to A-15.012, wherein R1 is ethyl, and A, R8 and R9 are as defined in Table X, and Q is selected from the group of formula Q2 as follows: [ka]

[0337] Table A-16 provides twelve compounds of formula (IR), A-16.001 to A-16.012, wherein R1 is ethyl, and A, R8 and R9 are as defined in Table X, and Q is selected from the group of formula Q2 as follows: [ka]

[0338] Table A-17 provides twelve compounds of formula (IR), A-17.001 to A-17.012, wherein R1 is ethyl, and A, R8 and R9 are as defined in Table X, and Q is selected from the group of formula Q2 as follows: [ka]

[0339] Table A-18 provides twelve compounds of formula (IR), A-18.001 to A-18.012, wherein R1 is ethyl, and A, R8 and R9 are as defined in Table X, and Q is selected from the group of formula Q1 as follows: [ka]

[0340] Table A-19 provides twelve compounds of formula (IR), A-19.001 to A-19.012, wherein R1 is ethyl, and A, R8 and R9 are as defined in Table X, and Q is selected from the group of formula Q1 as follows: [ka]

[0341] Table A-20 provides twelve compounds of formula (IR), A-20.001 to A-20.012, wherein R1 is ethyl, and A, R8 and R9 are as defined in Table X, and Q is selected from the group of formula Q5 as follows: [ka]

[0342] Tables B-1 to B-20 below further illustrate specific compounds of the invention in which the stereogenic sulfur atom is in the S-configuration. [ka]

[0343] Table B-1 provides 12 compounds of formula (IS) B-1.001 to B-1.012, wherein R1 is ethyl, and A, R8 and R9 are as defined in Table X, and Q is selected from the group of formula Q1 as follows: [ka]

[0344] For example, compound B-17.005 has the following structure: [ka] where (S) indicates the S-configuration at the stereogenic sulfur center.

[0345] Table B-2 provides 12 compounds of formula (IS) B-2.001 to B-2.012, wherein R1 is ethyl, and A, R8 and R9 are as defined in Table X, and Q is selected from the group of formula Q1 as follows: [ka]

[0346] Table B-3 provides 12 compounds of formula (IS) B-3.001 to B-3.012, wherein R1 is ethyl, and A, R8 and R9 are as defined in Table X, and Q is selected from the group of formula Q1 as follows: [ka]

[0347] Table B-4 provides 12 compounds of formula (IS) B-4.001 to B-4.012, wherein R1 is ethyl, and A, R8 and R9 are as defined in Table X, and Q is selected from the group of formula Q2 as follows: [ka]

[0348] Table B-5 provides 12 compounds of formula (IS) B-5.001 to B-5.012, wherein R1 is ethyl, and A, R8 and R9 are as defined in Table X, and Q is selected from the group of formula Q2 as follows: [ka]

[0349] Table B-6 provides 12 compounds of formula (IS) B-6.001 to B-6.012, wherein R1 is ethyl, and A, R8 and R9 are as defined in Table X, and Q is selected from the group of formula Q3 as follows: [ka]

[0350] Table B-7 provides 12 compounds of formula (IS) B-7.001 to B-7.012, wherein R1 is ethyl, and A, R8 and R9 are as defined in Table X, and Q is selected from the group of formula Q1 as follows: [ka]

[0351] Table B-8 provides 12 compounds of formula (IS) B-8.001 to B-8.012, wherein R1 is ethyl, and A, R8 and R9 are as defined in Table X, and Q is selected from the group of formula Q1 as follows: [ka]

[0352] Table B-9 provides 12 compounds of formula (IS) B-9.001 to B-9.012, wherein R1 is ethyl, and A, R8 and R9 are as defined in Table X, and Q is selected from the group of formula Q4 as follows: [ka]

[0353] Table B-10 provides 12 compounds of formula (IS) B-10.001 to B-10.012, wherein R1 is ethyl, and A, R8 and R9 are as defined in Table X, and Q is selected from the group of formula Q4 as follows: [ka]

[0354] Table B-11 provides 12 compounds of formula (IS) B-11.001 to B-11.012, wherein R1 is ethyl, and A, R8 and R9 are as defined in Table X, and Q is selected from the group of formula Q5 as follows: [ka]

[0355] Table B-12 provides twelve compounds of formula (IS) B-12.001 to B-12.012, wherein R1 is ethyl, and A, R8 and R9 are as defined in Table X, and Q is selected from the group of formula Q5 as follows: [ka]

[0356] Table B-13 provides twelve compounds of formula (IS) B-13.001 to B-13.012, wherein R1 is ethyl, and A, R8 and R9 are as defined in Table X, and Q is selected from the group of formula Q5 as follows: [ka]

[0357] Table B-14 provides twelve compounds of formula (IS) B-14.001 to B-14.012, wherein R1 is ethyl, and A, R8 and R9 are as defined in Table X, and Q is selected from the group of formula Q2 as follows: [ka]

[0358] Table B-15 provides twelve compounds of formula (IS) B-15.001 to B-15.012, wherein R1 is ethyl, and A, R8 and R9 are as defined in Table X, and Q is selected from the group of formula Q2 as follows: [ka]

[0359] Table B-16 provides twelve compounds of formula (IS) B-16.001 to B-16.012, wherein R1 is ethyl, and A, R8 and R9 are as defined in Table X, and Q is selected from the group of formula Q2 as follows: [ka]

[0360] Table B-17 provides twelve compounds of formula (IS) B-17.001 to B-17.012, wherein R1 is ethyl, and A, R8 and R9 are as defined in Table X, and Q is selected from the group of formula Q2 as follows: [ka]

[0361] Table B-18 provides twelve compounds of formula (IS) B-18.001 to B-18.012, wherein R1 is ethyl, and A, R8 and R9 are as defined in Table X, and Q is selected from the group of formula Q1 as follows: [ka]

[0362] Table B-19 provides twelve compounds of formula (IS) B-19.001 to B-19.012, wherein R1 is ethyl, and A, R8 and R9 are as defined in Table X, and Q is selected from the group of formula Q1 as follows: [ka]

[0363] Table B-20 provides 12 compounds of formula (IS) B-20.001 to B-20.012, wherein R1 is ethyl, and A, R8 and R9 are as defined in Table X, and Q is selected from the group of formula Q5 as follows: [ka]

[0364] The compounds of formula I according to the present invention are preventively and / or therapeutically useful active ingredients in the field of pest control, even at low application rates, which have a very favorable biocidal spectrum and are well tolerated by warm-blooded animal species, fish, and plants. The active ingredients according to the present invention act not only against normally susceptible animal pests, such as representatives of insects or Acarina, nematodes, or mollusks, but also against all or individual developmental stages of resistant animal pests. The insecticidal, nematicidal, molluscicidal, or acaricidal activity of the active ingredients according to the present invention can be manifested directly (i.e., by death or destruction of the pest, which occurs immediately or only after a certain period of time, for example, during molting) or indirectly (e.g., by a reduction in egg production and / or hatchability, an antifeedant effect, and / or growth inhibition).

[0365] The compounds of formula (I) 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, differential biological activity of the enantiomer or enantiomerically enriched composition and the racemate, differential biological activity of the (R) enantiomer or (R) enantiomerically enriched composition and the (S) enantiomer or (S) enantiomerically enriched composition, advantageous activity spectrum, high safety profile, improved physicochemical properties, or high biodegradability or environmental profile). In particular, it has been unexpectedly found that certain compounds of formula (I) exhibit advantageous safety profiles against non-target organisms, such as non-target arthropods, particularly pollinators such as honeybees, solitary bees, and bumblebees. Most specifically, the European honeybee (Apis mellifera).

[0366] 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.

[0367] 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).

[0368] Putative metabolites of compounds of formula I that may be formed in the practice of the invention in connection with one or more of the methods, pests, crops and / or targets described below include amide compounds of formulas I-M1, I-M2, I-M3 and acid compounds of formulas I-M4, I-M5, I-M6, which correspond to the parent nitrile compounds of formula I, respectively: [ka] (In the formula, Q, R1, R2, R3, R4, R9, X1, G1, G2, S * 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, I-M2, or I-M3, corresponding to a parent nitrile selected from the group consisting of compounds set forth in Tables A-1 to A-20, Tables B-1 to B-20, Table Y, Table Z, and Table P(E); and (2) acid compounds of formula I-M4, I-M5, or I-M6, corresponding to a parent nitrile selected from the group consisting of compounds set forth in Tables A-1 to A-20, Tables B-1 to B-20, Table Y, Table Z, and Table P(E).

[0369] 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.

[0370] 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.

[0371] 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.

[0372] 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.

[0373] 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.

[0374] 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).

[0375] 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.

[0376] 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).

[0377] 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).

[0378] 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; 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.;

[0379] 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.

[0380] 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.

[0381] 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.

[0382] 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).

[0383] 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.

[0384] 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.

[0385] 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).

[0386] 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®.

[0387] 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.

[0388] 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.

[0389] 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.

[0390] 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.

[0391] 5. IPC 531 cotton, registration number C / ES / 96 / 02, manufactured by Monsanto Europe SA (270-272 Avenue de Tervuren, B-1150 Brussels, Belgium).

[0392] 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.

[0393] 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.

[0394] 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).

[0395] 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.

[0396] 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.

[0397] Crops also include those that have a high resistance to nematodes, such as the soybean cyst nematode.

[0398] 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.

[0399] 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).

[0400] 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.

[0401] 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.

[0402] 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.

[0403] 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.

[0404] 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.

[0405] 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.

[0406] [Table 4]

[0407] [Table 5-1] [Table 5-2] [Table 5-3] [Table 5-4]

[0408] 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.

[0409] 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.

[0410] 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).

[0411] 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.

[0412] 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.

[0413] 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.

[0414] Examples of such parasites are: Among the Anoplurida, the genera Haematopinus, Linognathus, Pediculus, Phtirus, and Solenopotes are included.

[0415] From the order Mallophagida, the genera Trimenopon, Menopon, Trinoton, Bovicola, Werneckiella, Lepikentron, Damalina, Trichodectes and Felicola.

[0416] 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.).

[0417] 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.).

[0418] From the order Heteropterida, for example, Cimex spp., Triatoma spp., Rhodnius spp., and Panstrongylus spp.

[0419] 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.

[0420] 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.

[0421] 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.

[0422] 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.

[0423] 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.

[0424] 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.

[0425] 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.

[0426] 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.

[0427] 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.

[0428] Suitable solid carriers are, for example, talc, titanium dioxide, pyrophyllite clay, silica, attapulgite clay, Kiesslager, limestone, calcium carbonate, bentonite, calcium montmorillonite, cotton hulls, wheat flour, soybean flour, pumice, wood flour, ground walnut shells, lignin, and similar materials.

[0429] 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).

[0430] 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.

[0431] 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.

[0432] 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.

[0433] 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.

[0434] 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%

[0435] Powder: Active ingredient: 0.1 to 10%, preferably 0.1 to 5% Solid carrier: 99.9 to 90%, preferably 99.9 to 99%

[0436] 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%

[0437] 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%

[0438] Granules: Active ingredient: 0.1 to 30%, preferably 0.1 to 15% Solid carrier: 99.5 to 70%, preferably 97 to 85%

[0439] The following examples further illustrate, but do not limit, the present invention.

[0440] [Table 6]

[0441] 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.

[0442] [Table 7]

[0443] 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.

[0444] [Table 8]

[0445] Emulsions of any required dilution that can be used for plant protection are available from this concentrate by dilution with water.

[0446] [Table 9]

[0447] 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.

[0448] [Table 10]

[0449] 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.

[0450] [Table 11]

[0451] In a mixer, the finely ground composite is applied uniformly to kaolin moistened with polyethylene glycol, resulting in coated, dust-free granules.

[0452] [Table 12]

[0453] 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.

[0454] [Table 13]

[0455] 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.

[0456] 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.

[0457] 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]

[0458] 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) - Specific rotation [α]: Samples were measured on an Autopol IV polarimeter manufactured by Rudolph Research Analytical.

[0459] LCMS method: Method 1: Spectra were recorded on a Waters mass spectrometer (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. 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 min 0% B, 100% A; 1.2–1.5 min 100% B; Flow rate (ml / min) 0.85.

[0460] Method 2: Spectra were recorded on a Waters mass spectrometer (SQD, SQDII single quadrupole mass spectrometer) equipped with an electrospray source (polarity: positive and negative ions, capillary: 3.00 kV, cone range: 30 V, extractor: 2.00 V, source temperature: 150 °C, desolvation temperature: 350 °C, cone gas flow: 50 l / h, desolvation gas flow: 650 l / h, mass range: 100-900 Da) and a Waters Acquity UPLC: binary pump, heated column compartment, diode-array detector, and ELSD detector. Column: Waters UPLC HSS T3, 1.8 μm, 30 × 2.1 mm; Temperature: 60 °C; DAD wavelength range (nm): 210–500; Solvent gradient: A = water + 5% MeOH + 0.05% HCOOH, B = acetonitrile + 0.05% HCOOH; Gradient: 10–100% B in 1.2 min; Flow rate (ml / min) 0.85.

[0461] Method 3: Spectra were recorded on an Agilent Technologies mass spectrometer (6410 Triple Quadrupole Mass Spectrometer) equipped with an electrospray source (polarity: positive and negative polarity 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.

[0462] Method 4: Spectra were recorded on a Waters mass spectrometer (Acquity SDS mass spectrometer) equipped with an electrospray source (polarity: positive and negative polarity switch, capillary: 3.00 kV, cone voltage: 41.00 V, source temperature: 150 °C, desolvation gas flow: 1000 L / Hr, desolvation temperature: 500 °C, gas flow @ cone: 50 L / hr, mass range: 110-800 Da, PDA wavelength range: 210-400 nm. Column: Acquity UPLC HSS T3 C18, 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: 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 0.8 mL / min.

[0463] Method 5: Spectra were recorded on a Waters mass spectrometer (Acquity SDS mass spectrometer) equipped with an electrospray source (polarity: positive and negative polarity switch, capillary: 3.00 kV, cone voltage: 41.00 V, source temperature: 150 °C, desolvation gas flow: 1000 L / Hr., desolvation temperature: 500 °C, gas flow @ cone: 50 L / hr., mass range: 110-800 Da, PDA wavelength range: 210-400 nm. Column: Acquity UPLC HSS T3 C18, 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 = 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.

[0464] Method 6: Spectra were recorded on a Waters mass spectrometer (SQD, SQDII single quadrupole mass spectrometer) equipped with an electrospray source (polarity: positive and negative ions), capillary: 3.00 kV, cone range: 30 V, extractor: 2.00 V, source temperature: 150 °C, desolvation temperature: 350 °C, cone gas flow: 50 l / h, desolvation gas flow: 650 l / h, mass range: 100-900 Da) and a Waters Acquity UPLC: binary pump, heated column compartment, diode-array detector, and ELSD detector. Column: Waters UPLC HSS T3, 1.8 μm, 30 × 2.1 mm; Temperature: 60 °C; DAD wavelength range (nm): 210–500; Solvent gradient: A = water + 5% MeOH + 0.05% HCOOH, B = acetonitrile + 0.05% HCOOH; Gradient: 10–100% B in 2.7 min; Flow rate (ml / min) 0.85.

[0465] Preparation of compounds of formula (I): Example P1: Preparation of racemic 2-[[6-[5-cyclopropyl-3-methyl-4-oxo-6-(trifluoromethyl)imidazo[4,5-c]pyridin-2-yl]-5-(ethylsulfonimidoyl)-3-pyridyl]oxy]-2-methyl-propanenitrile (compound P1) and its individual enantiomers (compounds P1-A and P1-B) [ka] Step 1: 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 [ka] This compound was prepared similarly to the method described in WO 2020 / 084075. LCMS (method 3): m / z 478[M+H] + ;Retention time: 1.54 minutes.

[0466] Step 2: Preparation of racemic 2-[[6-[5-cyclopropyl-3-methyl-4-oxo-6-(trifluoromethyl)imidazo[4,5-c]pyridin-2-yl]-5-(ethylsulfonimidoyl)-3-pyridyl]oxy]-2-methyl-propanenitrile (compound P1) [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 (prepared as described above) was treated in a similar manner to that described in WO 2020 / 084075 under conditions similar to those described in Step 2 of Example P12 to give the desired compound P1. LCMS (Method 4): m / z 509 [M+H] + ;Retention time: 0.92 min.

[0467] Step 3: Preparation of the individual enantiomeric compounds P1-A and P1-B The racemic 2-[[6-[5-cyclopropyl-3-methyl-4-oxo-6-(trifluoromethyl)imidazo[4,5-c]pyridin-2-yl]-5-(ethylsulfonimidoyl)-3-pyridyl]oxy]-2-methyl-propanenitrile (compound P1) mixture was subjected to chiral resolution by preparative SFC using the conditions described below.

[0468] Analysis SFC method: SFC:Waters Acquity UPC 2 / QDa PDA detector Waters Acquity UPC 2 Column: Daicel SFC CHIRALPAK® IA, 3 μm, 0.3 cm x 10 cm, 40°C Mobile phase: A:CO2 B:iPrOH Isocratic: 20% B in 4.8 min ABPR: 1800 psi Flow rate: 2.0ml / min Detection: 220nm Sample concentration: 1 mg / mL Injection: 1μL

[0469] Preparative SFC method: Sepiatec Prep SFC 100 Column: Daicel CHIRALPAK® IA, 5 μm, 2.0 cm x 25 cm Mobile phase: A:CO2 B:iPrOH Isocratic: 20% B in 14 min Back pressure: 150bar Flow rate: 60ml / min GLS pump: 2ml MeOH Detection: UV 220nm Sample: in MeOH / DCM

[0470] [Table 14]

[0471] Example P2: Preparation of racemic 1-[5-(ethylsulfonimidoyl)-6-[7-methyl-3-(trifluoromethyl)imidazo[4,5-c]pyridazin-6-yl]-3-pyridyl]cyclopropanecarbonitrile (compound P2) and its individual enantiomers (compounds P2-A and P2-B) [ka] Step 1: Preparation of 1-[5-ethylsulfanyl-6-[7-methyl-3-(trifluoromethyl)imidazo[4,5-c]pyridazin-6-yl]-3-pyridyl]cyclopropanecarbonitrile [ka] This compound was prepared similarly to the method described in WO 2019 / 234158. LCMS (method 6): m / z 405[M+H] + ;Retention time: 1.05 minutes.

[0472] Step 2: Preparation of racemic 1-[5-(ethylsulfonimidoyl)-6-[7-methyl-3-(trifluoromethyl)imidazo[4,5-c]pyridazin-6-yl]-3-pyridyl]cyclopropanecarbonitrile (compound P2) [ka] 1-[5-Ethylsulfanyl-6-[7-methyl-3-(trifluoromethyl)imidazo[4,5-c]pyridazin-6-yl]-3-pyridyl]cyclopropanecarbonitrile (prepared as described above) was treated similarly to the method described in WO 2019 / 234158 under similar conditions as described in Step 2 of Example P12 to give the desired compound P2. LCMS (Method 5): m / z 436 [M+H] + ;Retention time: 0.82 minutes.

[0473] Step 3: Preparation of the individual enantiomeric compounds P2-A and P2-B The racemic 1-[5-(ethylsulfonimidoyl)-6-[7-methyl-3-(trifluoromethyl)imidazo[4,5-c]pyridazin-6-yl]-3-pyridyl]cyclopropanecarbonitrile (compound P2) mixture was subjected to chiral resolution by preparative SFC using the conditions described below.

[0474] Analysis SFC method: SFC:Waters Acquity UPC 2 / QDa PDA detector Waters Acquity UPC 2 Column: Daicel SFC CHIRALPAK® IC, 3 μm, 0.46 cm x 10 cm, 40°C Mobile phase: A:CO2 B:EtOH Isocratic: 20% B in 4.8 min ABPR: 1800 psi Flow rate: 2.0ml / min Detection: 265nm Sample concentration: 1 mg / mL Injection: 1mL

[0475] Preparative SFC method: Sepiatec Prep SFC 100 Column: Daicel CHIRALPAK® IC, 5 μm, 2.0 cm x 25 cm Mobile phase: A:CO2B:EtOH isocratic composition: 25% B Back pressure: 150bar Flow rate: 75ml / min GLS pump:- Detection: UV 265nm Sample: DCM / ACN

[0476] [Table 15]

[0477] Example P3: Preparation of racemic 2-[[5-(ethylsulfonimidoyl)-6-[7-(trifluoromethyl)imidazo[1,2-a]pyridin-2-yl]-3-pyridyl]oxy]-2-methyl-propanenitrile (compound P3) and its individual enantiomers (compounds P3-A and P3-B) [ka] Step 1: Preparation of 2-[[5-ethylsulfanyl-6-[7-(trifluoromethyl)imidazo[1,2-a]pyridin-2-yl]-3-pyridyl]oxy]-2-methyl-propanenitrile [ka] This compound was prepared similarly to the method described in WO 2020 / 084075. 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).

[0478] Step 2: Preparation of racemic 2-[[5-(ethylsulfonimidoyl)-6-[7-(trifluoromethyl)imidazo[1,2-a]pyridin-2-yl]-3-pyridyl]oxy]-2-methyl-propanenitrile (compound P3) [ka] 2-[[5-Ethylsulfanyl-6-[7-(trifluoromethyl)imidazo[1,2-a]pyridin-2-yl]-3-pyridyl]oxy]-2-methyl-propanenitrile (prepared as above) was treated under similar conditions as described in Step 2 of Example P12 and similar to the method described in WO 2020 / 084075 to give the desired compound P3. LCMS (Method 1): m / z 438 [M+H] + ;Retention time: 0.88 min.

[0479] Step 3: Preparation of individual enantiomeric compounds P3-A and P3-B The racemic 2-[[5-(ethylsulfonimidoyl)-6-[7-(trifluoromethyl)imidazo[1,2-a]pyridin-2-yl]-3-pyridyl]oxy]-2-methyl-propanenitrile (compound P3) mixture was subjected to chiral resolution by preparative SFC using the conditions described below.

[0480] Analysis SFC method: SFC:Waters Acquity UPC 2 / QDa PDA detector Waters Acquity UPC 2 Column: Daicel SFC CHIRALPAK® IC, 3 μm, 0.3 cm x 10 cm, 40°C Mobile phase: A:CO2 B:MeOH Isocratic: 20% B in 4.8 min ABPR: 1800 psi Flow rate: 2.0ml / min Detection: 250nm Sample concentration: 1 mg / mL Injection: 1μL

[0481] Preparative SFC method: Sepiatec Prep SFC 100 Column: Daicel CHIRALPAK® IC, 5 μm, 2.0 cm x 25 cm Mobile phase: A:CO2 B:MeOH Isocratic: 20% B in 14 min Back pressure: 150bar Flow rate: 60ml / min GLS pump: 2ml MeOH Detection: UV 250nm Sample: in MeOH / DCM

[0482] [Table 16]

[0483] Example P4: Preparation of racemic 2-[5-(ethylsulfonimidoyl)-6-[3-methyl-6-(trifluoromethyl)imidazo[4,5-c]pyridin-2-yl]-3-pyridyl]-2-methyl-propanenitrile (compound P4) and its individual enantiomers (compounds P4-A and P4-B) [ka] Step 1: Preparation of 2-[5-ethylsulfanyl-6-[3-methyl-6-(trifluoromethyl)imidazo[4,5-c]pyridin-2-yl]-3-pyridyl]-2-methyl-propanenitrile [ka] This compound was prepared similarly to the method described in WO 2018 / 153778. LCMS (method 2): m / z 406[M+H] + ;Retention time: 1.02 minutes.

[0484] Step 2: Preparation of racemic 2-[5-(ethylsulfonimidoyl)-6-[3-methyl-6-(trifluoromethyl)imidazo[4,5-c]pyridin-2-yl]-3-pyridyl]-2-methyl-propanenitrile (compound P4) [ka] 2-[5-Ethylsulfanyl-6-[3-methyl-6-(trifluoromethyl)imidazo[4,5-c]pyridin-2-yl]-3-pyridyl]-2-methyl-propanenitrile (prepared as described above) was treated similarly to the method described in WO 2019 / 234158 under similar conditions as described in Step 2 of Example P12 to give the desired compound P4. LCMS (Method 2): m / z 437 [M+H] + ;Retention time: 0.83 minutes.

[0485] Step 3: Preparation of individual enantiomeric compounds P4-A and P4-B The racemic 2-[5-(ethylsulfonimidoyl)-6-[3-methyl-6-(trifluoromethyl)imidazo[4,5-c]pyridin-2-yl]-3-pyridyl]-2-methyl-propanenitrile (compound P4) mixture was subjected to chiral resolution by preparative SFC using the conditions described below.

[0486] Analysis SFC method: SFC:Waters Acquity UPC 2 / QDa PDA detector Waters Acquity UPC 2 Column: Daicel SFC CHIRALPAK® IG, 3 μm, 0.46 cm x 10 cm, 40°C Mobile phase: A:CO2 B:MeOH Isocratic: 30% B in 4.8 min ABPR: 1800 psi Flow rate: 2.0ml / min Detection: 265nm Sample concentration: 1 mg / mL Injection: 1μL

[0487] Preparative SFC method: Sepiatec Prep SFC 100 Column: Daicel CHIRALPAK® IG, 5 μm, 2.0 cm x 25 cm Mobile phase: A:CO2B:MeOH isocratic composition: 30% B Back pressure: 150bar Flow rate: 60ml / min GLS pump:- Detection: UV 265nm Sample: DCM / MeOH

[0488] [Table 17]

[0489] Example P5: Preparation of racemic 2-[[5-(ethylsulfonimidoyl)-2-methyl-6-[3-methyl-6-(trifluoromethyl)imidazo[4,5-b]pyridin-2-yl]-3-pyridyl]oxy]-2-methyl-propanenitrile (compound P5) and its individual enantiomers (compounds P5-A and P5-B) [ka] Step 1: 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 [ka] This compound was prepared similarly to the method described in WO 2020 / 084075. LCMS (method 1): m / z 436[M+H] + ;Retention time: 1.16 minutes.

[0490] Step 2: Preparation of racemic 2-[[5-(ethylsulfonimidoyl)-2-methyl-6-[3-methyl-6-(trifluoromethyl)imidazo[4,5-b]pyridin-2-yl]-3-pyridyl]oxy]-2-methyl-propanenitrile (compound P5) [ka] 2-[[5-Ethylsulfanyl-2-methyl-6-[3-methyl-6-(trifluoromethyl)imidazo[4,5-b]pyridin-2-yl]-3-pyridyl]oxy]-2-methyl-propanenitrile (prepared as described above) was treated similarly to the method described in WO 2020 / 084075 under similar conditions as described in Step 2 of Example P12 to give the desired compound P5. LCMS (Method 1): m / z 467 [M+H] + ;Retention time: 0.97 min.

[0491] Step 3: Preparation of individual enantiomeric compounds P5-A and P5-B The racemic 2-[[5-(ethylsulfonimidoyl)-2-methyl-6-[3-methyl-6-(trifluoromethyl)imidazo[4,5-b]pyridin-2-yl]-3-pyridyl]oxy]-2-methyl-propanenitrile (compound P5) mixture was subjected to chiral resolution by preparative SFC using the conditions described below.

[0492] Analysis SFC method: SFC:Waters Acquity UPC 2 / QDa PDA detector Waters Acquity UPC 2 Column: Daicel SFC CHIRALPAK® IG, 3 μm, 0.3 cm x 10 cm, 40°C Mobile phase: A:CO2 B:MeOH Isocratic: 15% B in 4.8 min ABPR: 1800 psi Flow rate: 2.0ml / min Detection: 280nm Sample concentration: 1 mg / mL Injection: 1μL

[0493] Preparative SFC method: Sepiatec Prep SFC 100 Column: Daicel CHIRALPAK® IG, 5 μm, 2.0 cm x 25 cm Mobile phase: A:CO2 B:MeOH Isocratic: 15% B in 14 min Back pressure: 150bar Flow rate: 60ml / min GLS pump: 5ml Detection: UV 280nm Sample: in MeOH / DCM

[0494] [Table 18]

[0495] Example P6: Preparation of racemic 1-[3-(ethylsulfonimidoyl)-4-[3-methyl-6-(trifluoromethyl)imidazo[4,5-b]pyridin-2-yl]phenyl]cyclopropanecarbonitrile (compound P6) and its individual enantiomers (compounds P6-A and P6-B) [ka] Step 1: Preparation of 1-[3-ethylsulfanyl-4-[3-methyl-6-(trifluoromethyl)imidazo[4,5-b]pyridin-2-yl]phenyl]cyclopropanecarbonitrile [ka] This compound was prepared similarly to the method described in WO 2019 / 234158. LCMS (Method 6): m / z 403[M+H] + ;Retention time: 1.18 minutes.

[0496] Step 2: Preparation of racemic 1-[3-(ethylsulfonimidoyl)-4-[3-methyl-6-(trifluoromethyl)imidazo[4,5-b]pyridin-2-yl]phenyl]cyclopropanecarbonitrile (compound P6) [ka] 1-[3-Ethylsulfanyl-4-[3-methyl-6-(trifluoromethyl)imidazo[4,5-b]pyridin-2-yl]phenyl]cyclopropanecarbonitrile (prepared as above) was treated similarly to the method described in WO 2019 / 234158 under similar conditions as described in Step 2 of Example P12 to give the desired compound P6. LCMS (Method 2): m / z 434 [M+H] + ;Retention time: 0.88 min.

[0497] Step 3: Preparation of individual enantiomeric compounds P6-A and P6-B The racemic 1-[3-(ethylsulfonimidoyl)-4-[3-methyl-6-(trifluoromethyl)imidazo[4,5-b]pyridin-2-yl]phenyl]cyclopropanecarbonitrile (compound P6) mixture was subjected to chiral resolution by preparative SFC using the conditions described below.

[0498] Analysis SFC method: SFC:Waters Acquity UPC 2 / QDa PDA detector Waters Acquity UPC 2 Column: Daicel SFC CHIRALPAK® IG, 3 μm, 0.46 cm x 10 cm, 40°C Mobile phase: A:CO2 B:iPrOH Isocratic: 35% B in 4.8 min ABPR: 1800 psi Flow rate: 2.0ml / min Detection: 290nm Sample concentration: 1 mg / mL Injection: 1mL

[0499] Preparative SFC method: Sepiatec Prep SFC 100 Column: Daicel CHIRALPAK® IG, 5 μm, 2.0 cm x 25 cm Mobile phase: A: CO2B: iPrOH isocratic composition: 35% B Back pressure: 150bar Flow rate: 60ml / min GLS pump:- Detection: UV 290nm Sample: DCM / ACN

[0500] [Table 19]

[0501] Example P7: Preparation of racemic 2-[[5-(ethylsulfonimidoyl)-6-[7-(trifluoromethylsulfanyl)imidazo[1,2-c]pyrimidin-2-yl]-3-pyridyl]oxy]-2-methyl-propanenitrile (compound P7) and its individual enantiomers (compounds P7-A and P7-B) [ka] Step 1: Preparation of 2-[[5-ethylsulfanyl-6-[7-(trifluoromethylsulfanyl)imidazo[1,2-c]pyrimidin-2-yl]-3-pyridyl]oxy]-2-methyl-propanenitrile [ka] This compound was prepared similarly to the method described in WO 2020 / 084075. 1 H NMR(400MHz,chloroform-d)δ ppm 1.44(m,3H)1.82(s,6H)3.05(m,2H)7.66(d,J=2.20Hz,1H)8.02(s,1H)8.34(d,J=2.20Hz,1H)8.39(s,1H)9.10(s,1H).

[0502] Step 2: Preparation of racemic 2-[[5-(ethylsulfonimidoyl)-6-[7-(trifluoromethylsulfanyl)imidazo[1,2-c]pyrimidin-2-yl]-3-pyridyl]oxy]-2-methyl-propanenitrile (compound P7) [ka] 2-[[5-Ethylsulfanyl-6-[7-(trifluoromethylsulfanyl)imidazo[1,2-c]pyrimidin-2-yl]-3-pyridyl]oxy]-2-methyl-propanenitrile (prepared as above) was treated similarly to the method described in WO 2020 / 084075 under similar conditions as described in Step 2 of Example P12 to give the desired compound P7. LCMS (Method 1): m / z 471 [M+H] + ;Retention time: 0.89 min.

[0503] Step 3: Preparation of individual enantiomeric compounds P7-A and P7-B The racemic 2-[[5-(ethylsulfonimidoyl)-6-[7-(trifluoromethylsulfanyl)imidazo[1,2-c]pyrimidin-2-yl]-3-pyridyl]oxy]-2-methyl-propanenitrile (compound P7) mixture was subjected to chiral resolution by preparative SFC using the conditions described below.

[0504] Analysis SFC method: SFC:Waters Acquity UPC 2 / QDa PDA detector Waters Acquity UPC 2 Column: Daicel SFC CHIRALPAK® IC, 3 μm, 0.3 cm x 10 cm, 40°C Mobile phase: A:CO2 B:MeOH Isocratic: 30% B in 4.8 min ABPR: 1800 psi Flow rate: 2.0ml / min Detection: 250nm Sample concentration: 1 mg / mL Injection: 1μL

[0505] Preparative SFC method: Sepiatec Prep SFC 100 Column: Daicel CHIRALPAK® IC, 5 μm, 2.0 cm x 25 cm Mobile phase: A:CO2 B:MeOH Isocratic: 30% B in 14 min Back pressure: 150bar Flow rate: 60ml / min GLS pump: 2ml MeOH Detection: UV 250nm Sample: in MeOH / DCM

[0506] [Table 20]

[0507] Example P8: Preparation of racemic 1-[5-(ethylsulfonimidoyl)-6-[5-methoxy-3-methyl-4-oxo-6-(trifluoromethyl)imidazo[4,5-c]pyridin-2-yl]-3-pyridyl]cyclopropanecarbonitrile (compound P8) and its individual enantiomers (compounds P8-A and P8-B) [ka] Step 1: Preparation of 1-[5-ethylsulfanyl-6-[5-methoxy-3-methyl-4-oxo-6-(trifluoromethyl)imidazo[4,5-c]pyridin-2-yl]-3-pyridyl]cyclopropanecarbonitrile [ka] This compound was prepared similarly to the method described in WO 2019 / 234158. LCMS (method 5): m / z 450[M+H] + ;Retention time: 1.03 minutes.

[0508] Step 2: Preparation of racemic 1-[5-(ethylsulfonimidoyl)-6-[5-methoxy-3-methyl-4-oxo-6-(trifluoromethyl)imidazo[4,5-c]pyridin-2-yl]-3-pyridyl]cyclopropanecarbonitrile (compound P8) [ka] 1-[5-Ethylsulfanyl-6-[5-methoxy-3-methyl-4-oxo-6-(trifluoromethyl)imidazo[4,5-c]pyridin-2-yl]-3-pyridyl]cyclopropanecarbonitrile (prepared as above) was treated similarly to the method described in WO 2019 / 234158 under similar conditions as described in Step 2 of Example P12 to give the desired compound P8. LCMS (Method 5): m / z 481 [M+H] + ;Retention time: 0.85 minutes.

[0509] Step 3: Preparation of individual enantiomeric compounds P8-A and P8-B The racemic 1-[5-(ethylsulfonimidoyl)-6-[5-methoxy-3-methyl-4-oxo-6-(trifluoromethyl)imidazo[4,5-c]pyridin-2-yl]-3-pyridyl]cyclopropanecarbonitrile (compound P8) mixture was subjected to chiral resolution by preparative SFC using the conditions described below.

[0510] Analysis SFC method: SFC:Waters Acquity UPC 2 / QDa PDA detector Waters Acquity UPC 2 Column: Daicel SFC CHIRALPAK® IA, 3 μm, 0.46 cm x 10 cm, 40°C Mobile phase: A:CO2 B:iPrOH Isocratic: 25% B in 4.8 min ABPR: 1800 psi Flow rate: 2.0ml / min Detection: 220nm Sample concentration: 1 mg / mL Injection: 1mL

[0511] Preparative SFC method: Sepiatec Prep SFC 100 Column: Daicel CHIRALPAK® IA, 5 μm, 2.0 cm x 25 cm Mobile phase: A: CO2B: iPrOH isocratic composition: 25% B Back pressure: 150bar Flow rate: 60ml / min GLS pump:- Detection: UV 220nm Sample: DCM / ACN

[0512] [Table 21]

[0513] Example P9: Preparation of racemic 2-[[5-(ethylsulfonimidoyl)-6-[3-methyl-6-(trifluoromethyl)imidazo[4,5-b]pyridin-2-yl]-3-pyridyl]oxy]-2-methyl-propanenitrile (compound P9) and its individual enantiomers (compounds P9-A and P9-B) [ka] Step 1: Preparation of 2-[[5-ethylsulfanyl-6-[3-methyl-6-(trifluoromethyl)imidazo[4,5-b]pyridin-2-yl]-3-pyridyl]oxy]-2-methyl-propanenitrile [ka] This compound was prepared similarly to the method described in WO 2020 / 084075. LCMS (method 1): m / z 422[M+H] + ;Retention time: 1.11 minutes.

[0514] Step 2: Preparation of racemic 2-[[5-(ethylsulfonimidoyl)-6-[3-methyl-6-(trifluoromethyl)imidazo[4,5-b]pyridin-2-yl]-3-pyridyl]oxy]-2-methyl-propanenitrile (compound P9) [ka] 2-[[5-Ethylsulfanyl-6-[3-methyl-6-(trifluoromethyl)imidazo[4,5-b]pyridin-2-yl]-3-pyridyl]oxy]-2-methyl-propanenitrile (prepared as above) was treated similarly to the method described in WO 2020 / 084075 under similar conditions as described in Step 2 of Example P12 to give the desired compound P9. LCMS (Method 1): m / z 453 [M+H] + ;Retention time: 0.93 min.

[0515] Step 3: Preparation of the individual enantiomeric compounds P9-A and P9-B The racemic 2-[[5-(ethylsulfonimidoyl)-6-[3-methyl-6-(trifluoromethyl)imidazo[4,5-b]pyridin-2-yl]-3-pyridyl]oxy]-2-methyl-propanenitrile (compound P9) mixture was subjected to chiral resolution by preparative SFC using the conditions described below.

[0516] Analysis SFC method: SFC:Waters Acquity UPC 2 / QDa PDA detector Waters Acquity UPC 2 Column: Daicel SFC CHIRALPAK® IA, 3 μm, 0.3 cm x 10 cm, 40°C Mobile phase: A:CO2 B:EtOH Isocratic: 10% B in 4.8 min ABPR: 1800 psi Flow rate: 2.0ml / min Detection: 290nm Sample concentration: 1 mg / mL Injection: 1μL

[0517] Preparative SFC method: Sepiatec Prep SFC 100 Column: Daicel CHIRALPAK® IG, 5 μm, 2.0 cm x 25 cm Mobile phase: A:CO2 B:EtOH Isocratic: 25% B in 14 min Back pressure: 150bar Flow rate: 60ml / min GLS pump: 3ml Detection: UV 290nm Sample: in MeOH / ACN

[0518] [Table 22]

[0519] A sample of the second-eluting enantiomer, Compound P9-B (crystals from ethanol obtained according to Example P9, Step 3, with 99% chemical purity (λ = 290 nm) and >99% enantiomeric excess) was subjected to analysis by single-crystal X-ray diffraction. Single-crystal intensity data were collected on a Rigaku Oxford Diffraction Supernova X-ray generator using Cu-Kα radiation at a wavelength of 1.54184 Å at 100 K to a resolution of 0.81 Å.

[0520] The data set was refined and reduced using the data collection and processing software CrysAlisPro, and structure analysis was completed using SIR92 (Altomare A, Cascarano G, Giacovazzo C, Guagliardi A, Burla MC, Polidori G, and Camalli M, J. Appl. Cryst. 27:435 (1994)), and structure refinement was completed using the CRYSTALS software package (Betteridge PW, Carruthers JR, Cooper RI, Prout K, and Watkin DJ, J. Appl. Cryst. 36:1487 (2003)).

[0521] The individual enantiomers, compounds P9-B, crystallized in the monoclinic space group C2. The unit cell parameters from the single crystal analysis are shown in Table 1.

[0522] [Table 23]

[0523] The X-ray crystal structure of compound P9-B is shown in Figure 1. The stereochemistry is clearly determined, with the stereogenic sulfur atom (designated S1 in Figure 1) being in the S-configuration (designated by the annotation (S) in Figure 1). For technical reasons, the numbering scheme used in the structure in Figure 1 does not correspond to the systematic nomenclature.

[0524] Thus, the second eluting enantiomer P9-B was proven by X-ray crystallography to be (S)-2-[[5-(ethylsulfonimidoyl)-6-[3-methyl-6-(trifluoromethyl)imidazo[4,5-b]pyridin-2-yl]-3-pyridyl]oxy]-2-methyl-propanenitrile, corresponding to compound (S)-P9 (Table Y) obtained via enantioselective synthesis (Example E2 below). [a] D 20 = +13.7° (MeOH, C = 0.88).

[0525] Similarly, the first eluting enantiomer P9-A was proven by X-ray crystallography to be (R)-2-[[5-(ethylsulfonimidoyl)-6-[3-methyl-6-(trifluoromethyl)imidazo[4,5-b]pyridin-2-yl]-3-pyridyl]oxy]-2-methyl-propanenitrile, corresponding to compound (R)-P9 (Table Y) (Example E1 below) obtained via enantioselective synthesis. [a] D 20 =-13.2° (MeOH, C=0.87).

[0526] Example P10: Preparation of racemic 1-[5-(ethylsulfonimidoyl)-6-[3-methyl-6-(trifluoromethyl)imidazo[4,5-c]pyridin-2-yl]-3-pyridyl]cyclopropanecarbonitrile (compound P10) and its individual enantiomers (compounds P10-A and P10-B) [ka] Step 1: Preparation of 1-[5-ethylsulfanyl-6-[3-methyl-6-(trifluoromethyl)imidazo[4,5-c]pyridin-2-yl]-3-pyridyl]cyclopropanecarbonitrile [ka] This compound was prepared similarly to the method described in WO 2019 / 234158. LCMS (method 1): m / z 404[M+H] + ;Retention time: 0.98 min.

[0527] Step 2: Preparation of racemic 1-[5-(ethylsulfonimidoyl)-6-[3-methyl-6-(trifluoromethyl)imidazo[4,5-c]pyridin-2-yl]-3-pyridyl]cyclopropanecarbonitrile (compound P10) [ka] 1-[5-Ethylsulfanyl-6-[3-methyl-6-(trifluoromethyl)imidazo[4,5-c]pyridin-2-yl]-3-pyridyl]cyclopropanecarbonitrile (prepared as described above) was treated similarly to the method described in WO 2019 / 234158 under similar conditions as described in Step 2 of Example P12 to give the desired compound P10. LCMS (Method 1): m / z 435 [M+H] + ;Retention time: 0.82 minutes.

[0528] Step 3: Preparation of individual enantiomeric compounds P10-A and P10-B The racemic 1-[5-(ethylsulfonimidoyl)-6-[3-methyl-6-(trifluoromethyl)imidazo[4,5-c]pyridin-2-yl]-3-pyridyl]cyclopropanecarbonitrile (compound P10) mixture was subjected to chiral resolution by preparative SFC using the conditions described below.

[0529] Analysis SFC method: SFC:Waters Acquity UPC 2 / QDa PDA detector Waters Acquity UPC 2 Column: Daicel SFC CHIRALPAK® IG, 3 μm, 0.46 cm x 10 cm, 40°C Mobile phase: A:CO2 B:MeOH Isocratic: 40% B in 4.8 min ABPR: 1800 psi Flow rate: 2.0ml / min Detection: 250nm Sample concentration: 1 mg / mL Injection: 1μL

[0530] Preparative SFC method: Sepiatec Prep SFC 100 Column: Daicel CHIRALPAK® IG, 5 μm, 2.0 cm x 25 cm Mobile phase: A:CO2B:MeOH isocratic composition: 40% B Back pressure: 150bar Flow rate: 60ml / min GLS pump:- Detection: UV 270nm Sample: MeOH / DCM / ACN

[0531] [Table 24]

[0532] Example P11: Preparation of racemic 2-[[5-(ethylsulfonimidoyl)-6-[7-(trifluoromethyl)imidazo[1,2-c]pyrimidin-2-yl]-3-pyridyl]oxy]-2-methyl-propanenitrile (compound P11) and its individual enantiomers (compounds P11-A and P11-B) [ka] Step 1: Preparation of 2-[[5-ethylsulfanyl-6-[7-(trifluoromethyl)imidazo[1,2-c]pyrimidin-2-yl]-3-pyridyl]oxy]-2-methyl-propanenitrile [ka] This compound was prepared similarly to the method described in WO 2020 / 084075. 1 H NMR (400 MHz, chloroform-d) δ ppm 1.44 (t, J = 7.34 Hz, 3H) 1.81 (s, 6H) 3.04 (q, J = 7.34 Hz, 2H) 7.67 (s, 1H) 8.05 (s, 1H) 8.34 (s, 1H) 8.45 (s, 1H) 9.18 (s, 1H).

[0533] Step 2: Preparation of racemic 2-[[5-(ethylsulfonimidoyl)-6-[7-(trifluoromethyl)imidazo[1,2-c]pyrimidin-2-yl]-3-pyridyl]oxy]-2-methyl-propanenitrile (compound P11) [ka] 2-[[5-Ethylsulfanyl-6-[7-(trifluoromethyl)imidazo[1,2-c]pyrimidin-2-yl]-3-pyridyl]oxy]-2-methyl-propanenitrile (prepared as described above) was treated similarly to the method described in WO 2020 / 084075 under similar conditions as described in Step 2 of Example P12 to give the desired compound P11. LCMS (Method 1): m / z 439 [M+H] + ;Retention time: 0.84 min.

[0534] Step 3: Preparation of individual enantiomeric compounds P11-A and P11-B The racemic 2-[[5-(ethylsulfonimidoyl)-6-[7-(trifluoromethyl)imidazo[1,2-c]pyrimidin-2-yl]-3-pyridyl]oxy]-2-methyl-propanenitrile (compound P11) mixture was subjected to chiral resolution by preparative SFC using the conditions described below.

[0535] Analysis SFC method: SFC:Waters Acquity UPC 2 / QDa PDA detector Waters Acquity UPC 2 Column: Daicel SFC CHIRALPAK® IC, 3 μm, 0.3 cm x 10 cm, 40°C Mobile phase: A:CO2 B:MeOH Isocratic: 30% B in 4.8 min ABPR: 1800 psi Flow rate: 2.0ml / min Detection: 240nm Sample concentration: 1 mg / mL Injection: 1μL

[0536] Preparative SFC method: Sepiatec Prep SFC 100 Column: Daicel CHIRALPAK® IC, 5 μm, 2.0 cm x 25 cm Mobile phase: A:CO2 B:MeOH Isocratic: 30% B in 14 min Back pressure: 150bar Flow rate: 60ml / min GLS pump: 2ml MeOH Detection: UV 250nm Sample: in MeOH / DCM

[0537] [Table 25]

[0538] Example P12: Preparation of racemic 2-[5-(ethylsulfonimidoyl)-6-[3-methyl-6-(trifluoromethyl)imidazo[4,5-b]pyridin-2-yl]-3-pyridyl]-2-methyl-propanenitrile (compound P12) and its individual enantiomers (compounds P12-A and P12-B) [ka] Step 1: Preparation of 2-[5-ethylsulfanyl-6-[3-methyl-6-(trifluoromethyl)imidazo[4,5-b]pyridin-2-yl]-3-pyridyl]-2-methyl-propanenitrile [ka] This compound was prepared similarly to the method described in WO 2018 / 153778. LCMS (method 2): m / z 406[M+H] + ;Retention time: 1.09 min.

[0539] Step 2: Preparation of racemic 2-[5-(ethylsulfonimidoyl)-6-[3-methyl-6-(trifluoromethyl)imidazo[4,5-b]pyridin-2-yl]-3-pyridyl]-2-methyl-propanenitrile (compound P12) [ka] A solution of 2-[5-ethylsulfanyl-6-[3-methyl-6-(trifluoromethyl)imidazo[4,5-b]pyridin-2-yl]-3-pyridyl]-2-methyl-propanenitrile (prepared as described above) (300 mg, 0.74 mmol) in methanol (5 mL) was added to a solution of diacetoxyiodobenzene (596 mg, 1.85 mmol) and ammonium carbamate (116 mg, 1.48 mmol) in methanol (4 mL) at room temperature. After stirring at room temperature for 90 minutes, the reaction mixture was evaporated and the residue was diluted with dichloromethane. The organic phase was washed twice with water, dried over anhydrous sodium sulfate, filtered, and concentrated under reduced pressure. The crude product was purified by flash chromatography on silica gel (ethyl acetate in cyclohexane) to give the desired compound P12. LCMS (method 2): m / z 437[M+H] + ;Retention time: 0.91 min.

[0540] Step 3: Preparation of individual enantiomeric compounds P12-A and P12-B The racemic 2-[5-(ethylsulfonimidoyl)-6-[3-methyl-6-(trifluoromethyl)imidazo[4,5-b]pyridin-2-yl]-3-pyridyl]-2-methyl-propanenitrile (compound P12) mixture was subjected to chiral resolution by preparative SFC using the conditions described below.

[0541] Analysis SFC method: SFC:Waters Acquity UPC 2 / QDa PDA detector Waters Acquity UPC 2 Column: Daicel SFC CHIRALPAK® IG, 3 μm, 0.46 cm x 10 cm, 40°C Mobile phase: A:CO2 B:EtOH Isocratic: 20% B in 4.8 min ABPR: 1800 psi Flow rate: 2.0ml / min Detection: 220nm Sample concentration: 1 mg / mL Injection: 1mL

[0542] Preparative SFC method: Sepiatec Prep SFC 100 Column: Daicel CHIRALPAK® IG, 5 μm, 2.0 cm x 25 cm Mobile phase: A:CO2B:EtOH isocratic composition: 20% B Back pressure: 150bar Flow rate: 60ml / min GLS pump:- Detection: UV 220nm Sample: DCM / ACN

[0543] [Table 26]

[0544] Example P13: Preparation of racemic 2-[[5-(ethylsulfonimidoyl)-6-[3-methyl-6-(trifluoromethyl)imidazo[4,5-c]pyridin-2-yl]-3-pyridyl]oxy]-2-methyl-propanenitrile (compound P13) and its individual enantiomers (compounds P13-A and P13-B) [ka] Step 1: Preparation of 2-[[5-ethylsulfanyl-6-[3-methyl-6-(trifluoromethyl)imidazo[4,5-c]pyridin-2-yl]-3-pyridyl]oxy]-2-methyl-propanenitrile [ka] This compound was prepared similarly to the method described in WO 2020 / 084075. LCMS (method 1): m / z 422[M+H] + ;Retention time: 1.02 minutes.

[0545] Step 2: Preparation of racemic 2-[[5-(ethylsulfonimidoyl)-6-[3-methyl-6-(trifluoromethyl)imidazo[4,5-c]pyridin-2-yl]-3-pyridyl]oxy]-2-methyl-propanenitrile (compound P13) [ka] 2-[[5-Ethylsulfanyl-6-[3-methyl-6-(trifluoromethyl)imidazo[4,5-c]pyridin-2-yl]-3-pyridyl]oxy]-2-methyl-propanenitrile (prepared as described above) was treated under similar conditions as described in Step 2 of Example P12 and similar to the method described in WO 2020 / 084075 to give the desired compound P13. LCMS (Method 1): m / z 453 [M+H] + ;Retention time: 0.86 min.

[0546] Step 3: Preparation of the individual enantiomeric compounds P13-A and P13-B The racemic 2-[[5-(ethylsulfonimidoyl)-6-[3-methyl-6-(trifluoromethyl)imidazo[4,5-c]pyridin-2-yl]-3-pyridyl]oxy]-2-methyl-propanenitrile (compound P13) mixture was subjected to chiral resolution by preparative SFC using the conditions described below.

[0547] Analysis SFC method: SFC:Waters Acquity UPC 2 / QDa PDA detector Waters Acquity UPC 2 Column: Daicel SFC CHIRALPAK® IG, 3 μm, 0.3 cm x 10 cm, 40°C Mobile phase: A:CO2 B:MeOH Isocratic: 30% B in 4.8 min ABPR: 1800 psi Flow rate: 2.0ml / min Detection: 270nm Sample concentration: 1 mg / mL Injection: 1μL

[0548] Preparative SFC method: Sepiatec Prep SFC 100 Column: Daicel CHIRALPAK® IG, 5 μm, 2.0 cm x 25 cm Mobile phase: A:CO2 B:MeOH Isocratic: 30% B in 14 min Back pressure: 150bar Flow rate: 60ml / min GLS pump: 3ml Detection: UV 270nm Sample: in EtOH

[0549] [Table 27]

[0550] Example P14: Preparation of racemic 1-[6-[5-ethyl-3-methyl-4-oxo-6-(trifluoromethyl)imidazo[4,5-c]pyridin-2-yl]-5-(ethylsulfonimidoyl)-3-pyridyl]cyclopropanecarbonitrile (compound P14) and its individual enantiomers (compounds P14-A and P14-B) [ka] Step 1: Preparation of 1-[6-[5-ethyl-3-methyl-4-oxo-6-(trifluoromethyl)imidazo[4,5-c]pyridin-2-yl]-5-ethylsulfanyl-3-pyridyl]cyclopropanecarbonitrile [ka] This compound was prepared similarly to the method described in WO 2019 / 234158. LCMS (method 5): m / z 448[M+H] + ;Retention time: 1.13 minutes.

[0551] Step 2: Preparation of racemic 1-[6-[5-ethyl-3-methyl-4-oxo-6-(trifluoromethyl)imidazo[4,5-c]pyridin-2-yl]-5-(ethylsulfonimidoyl)-3-pyridyl]cyclopropanecarbonitrile (compound P14) [ka] 1-[6-[5-Ethyl-3-methyl-4-oxo-6-(trifluoromethyl)imidazo[4,5-c]pyridin-2-yl]-5-ethylsulfanyl-3-pyridyl]cyclopropanecarbonitrile (prepared as described above) was treated similarly to the method described in WO 2019 / 234158 under similar conditions as described in Step 2 of Example P12 to give the desired compound P14. LCMS (Method 5): m / z 479 [M+H] + ;Retention time: 0.92 min.

[0552] Step 3: Preparation of individual enantiomeric compounds P14-A and P14-B The racemic 1-[6-[5-ethyl-3-methyl-4-oxo-6-(trifluoromethyl)imidazo[4,5-c]pyridin-2-yl]-5-(ethylsulfonimidoyl)-3-pyridyl]cyclopropanecarbonitrile (compound P14) mixture was subjected to chiral resolution by preparative SFC using the conditions described below.

[0553] Analysis SFC method: SFC:Waters Acquity UPC 2 / QDa PDA detector Waters Acquity UPC 2 Column: Daicel SFC CHIRALPAK® IG, 3 μm, 0.46 cm x 10 cm, 40°C Mobile phase: A:CO2 B:iPrOH Isocratic: 35% B in 4.8 min ABPR: 1800 psi Flow rate: 2.0ml / min Detection: 220nm Sample concentration: 1 mg / mL Injection: 1mL

[0554] Preparative SFC method: Sepiatec Prep SFC 100 Column: Daicel CHIRALPAK® IG, 5 μm, 2.0 cm x 25 cm Mobile phase: A: CO2B: iPrOH isocratic composition: 35% B Back pressure: 150bar Flow rate: 60ml / min GLS pump:- Detection: UV 220nm Sample: DCM / ACN

[0555] [Table 28]

[0556] Example P15: Preparation of racemic 2-[[5-(ethylsulfonimidoyl)-6-[7-methyl-3-(trifluoromethyl)imidazo[4,5-c]pyridazin-6-yl]-3-pyridyl]oxy]-2-methyl-propanenitrile (compound P15) and its individual enantiomers (compounds P15-A and P15-B) [ka] Step 1: Preparation of 2-[[5-ethylsulfanyl-6-[7-methyl-3-(trifluoromethyl)imidazo[4,5-c]pyridazin-6-yl]-3-pyridyl]oxy]-2-methyl-propanenitrile [ka] This compound was prepared similarly to the method described in WO 2020 / 084075. 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).

[0557] Step 2: Preparation of racemic 2-[[5-(ethylsulfonimidoyl)-6-[7-methyl-3-(trifluoromethyl)imidazo[4,5-c]pyridazin-6-yl]-3-pyridyl]oxy]-2-methyl-propanenitrile (compound P15) [ka] 2-[[5-Ethylsulfanyl-6-[7-methyl-3-(trifluoromethyl)imidazo[4,5-c]pyridazin-6-yl]-3-pyridyl]oxy]-2-methyl-propanenitrile (prepared as described above) was treated similarly to the method described in WO 2020 / 084075 under similar conditions as described in Step 2 of Example P12 to give the desired compound P15. LCMS (Method 1): m / z 454 [M+H] +;Retention time: 0.89 min.

[0558] Step 3: Preparation of the individual enantiomeric compounds P15-A and P15-B The racemic 2-[[5-(ethylsulfonimidoyl)-6-[7-methyl-3-(trifluoromethyl)imidazo[4,5-c]pyridazin-6-yl]-3-pyridyl]oxy]-2-methyl-propanenitrile (compound P15) mixture was subjected to chiral resolution by preparative SFC using the conditions described below.

[0559] Analysis SFC method: SFC:Waters Acquity UPC 2 / QDa PDA detector Waters Acquity UPC 2 Column: Daicel SFC CHIRALPAK® IC, 3 μm, 0.3 cm x 10 cm, 40°C Mobile phase: A:CO2 B:EtOH Isocratic: 15% B in 4.8 min ABPR: 1800 psi Flow rate: 2.0ml / min Detection: 270nm Sample concentration: 1 mg / mL Injection: 1μL Preparative SFC method: Sepiatec Prep SFC 100 Column: Daicel CHIRALPAK® IC, 5 μm, 2.0 cm x 25 cm Mobile phase: A:CO2 B:EtOH Isocratic: 15% B in 14 min Back pressure: 150bar Flow rate: 60ml / min GLS pump: 3ml MeOH Detection: UV 250nm Sample: in MeOH / DCM

[0560] [Table 29]

[0561] Example P16: Preparation of racemic 1-[5-(ethylsulfonimidoyl)-6-[3-methyl-6-(trifluoromethyl)imidazo[4,5-b]pyridin-2-yl]-3-pyridyl]cyclopropanecarbonitrile (compound P16) and its individual enantiomers (compounds P16-A and P16-B) [ka] Step 1: Preparation of 1-[5-ethylsulfanyl-6-[3-methyl-6-(trifluoromethyl)imidazo[4,5-b]pyridin-2-yl]-3-pyridyl]cyclopropanecarbonitrile [ka] This compound was prepared similarly to the method described in WO 2019 / 234158. LCMS (method 2): m / z 404[M+H] + ;Retention time: 1.07 min.

[0562] Step 2: Preparation of racemic 1-[5-(ethylsulfonimidoyl)-6-[3-methyl-6-(trifluoromethyl)imidazo[4,5-b]pyridin-2-yl]-3-pyridyl]cyclopropanecarbonitrile (compound P16) [ka] 1-[5-Ethylsulfanyl-6-[3-methyl-6-(trifluoromethyl)imidazo[4,5-b]pyridin-2-yl]-3-pyridyl]cyclopropanecarbonitrile (prepared as above) was treated similarly to the method described in WO 2019 / 234158 under similar conditions as described in Step 2 of Example P12 to give the desired compound P16. LCMS (Method 2): m / z 435 [M+H] + ;Retention time: 0.87 min.

[0563] Step 3: Preparation of individual enantiomeric compounds P16-A and P16-B The racemic 1-[5-(ethylsulfonimidoyl)-6-[3-methyl-6-(trifluoromethyl)imidazo[4,5-b]pyridin-2-yl]-3-pyridyl]cyclopropanecarbonitrile (compound P16) mixture was subjected to chiral resolution by preparative SFC using the conditions described below.

[0564] Analysis SFC method: SFC:Waters Acquity UPC 2 / QDa PDA detector Waters Acquity UPC 2 Column: Daicel SFC CHIRALPAK® IG, 3 μm, 0.46 cm x 10 cm, 40°C Mobile phase: A:CO2 B:MeOH Isocratic: 25% B in 4.8 min ABPR: 1800 psi Flow rate: 2.0ml / min Detection: 290nm Sample concentration: 1 mg / mL Injection: 1μL

[0565] Preparative SFC method: Sepiatec Prep SFC 100 Column: Daicel CHIRALPAK® IG, 5 μm, 2.0 cm x 25 cm Mobile phase: A:CO2B:MeOH isocratic composition: 17% B Back pressure: 150bar Flow rate: 60ml / min GLS pump:- Detection: UV 290nm Sample: in MeOH / DCM

[0566] [Table 30]

[0567] Example P17: Preparation of racemic 2-[[5-(ethylsulfonimidoyl)-2-methyl-6-[3-methyl-6-(trifluoromethyl)imidazo[4,5-c]pyridin-2-yl]-3-pyridyl]oxy]-2-methyl-propanenitrile (compound P17) and its individual enantiomers (compounds P17-A and P17-B) [ka] Step 1: Preparation of 2-[[5-ethylsulfanyl-2-methyl-6-[3-methyl-6-(trifluoromethyl)imidazo[4,5-c]pyridin-2-yl]-3-pyridyl]oxy]-2-methyl-propanenitrile [ka] This compound was prepared similarly to the method described in WO 2020 / 084075. LCMS (method 1): m / z 436[M+H] + ;Retention time: 1.06 minutes.

[0568] Step 2: Preparation of racemic 2-[[5-(ethylsulfonimidoyl)-2-methyl-6-[3-methyl-6-(trifluoromethyl)imidazo[4,5-c]pyridin-2-yl]-3-pyridyl]oxy]-2-methyl-propanenitrile (compound P17) [ka] 2-[[5-Ethylsulfanyl-2-methyl-6-[3-methyl-6-(trifluoromethyl)imidazo[4,5-c]pyridin-2-yl]-3-pyridyl]oxy]-2-methyl-propanenitrile (prepared as described above) was treated similarly to the method described in WO 2020 / 084075 under similar conditions as described in Step 2 of Example P12 to give the desired compound P17. LCMS (Method 1): m / z 467 [M+H] + ;Retention time: 0.91 min.

[0569] Step 3: Preparation of the individual enantiomeric compounds P17-A and P17-B The racemic 2-[[5-(ethylsulfonimidoyl)-2-methyl-6-[3-methyl-6-(trifluoromethyl)imidazo[4,5-c]pyridin-2-yl]-3-pyridyl]oxy]-2-methyl-propanenitrile (compound P17) mixture was subjected to chiral resolution by preparative SFC using the conditions described below.

[0570] Analysis SFC method: SFC:Waters Acquity UPC 2 / QDa PDA detector Waters Acquity UPC 2 Column: Daicel SFC CHIRALPAK® IG, 3 μm, 0.3 cm x 10 cm, 40°C Mobile phase: A:CO2 B:MeOH Isocratic: 30% B in 4.8 min ABPR: 1800 psi Flow rate: 2.0ml / min Detection: 270nm Sample concentration: 1 mg / mL Injection: 1μL

[0571] Preparative SFC method: Sepiatec Prep SFC 100 Column: Daicel CHIRALPAK® IG, 5 μm, 2.0 cm x 25 cm Mobile phase: A:CO2 B:MeOH Isocratic: 30% B in 14 min Back pressure: 150bar Flow rate: 60ml / min GLS pump: 3ml Detection: UV 270nm Sample: in MeOH / DCM

[0572] [Table 31]

[0573] Example P18: Preparation of racemic 1-[3-(ethylsulfonimidoyl)-4-[3-methyl-6-(trifluoromethyl)imidazo[4,5-c]pyridin-2-yl]phenyl]cyclopropanecarbonitrile (compound P18) and its individual enantiomers (compounds P18-A and P18-B) [ka] Step 1: Preparation of 1-[3-ethylsulfanyl-4-[3-methyl-6-(trifluoromethyl)imidazo[4,5-c]pyridin-2-yl]phenyl]cyclopropanecarbonitrile [ka] This compound was prepared similarly to the method described in WO 2019 / 234158. LCMS (method 2): m / z 403[M+H] + ;Holding time: 1.00 min.

[0574] Step 2: Preparation of racemic 1-[3-(ethylsulfonimidoyl)-4-[3-methyl-6-(trifluoromethyl)imidazo[4,5-c]pyridin-2-yl]phenyl]cyclopropanecarbonitrile (compound P18) [ka] 1-[3-Ethylsulfanyl-4-[3-methyl-6-(trifluoromethyl)imidazo[4,5-c]pyridin-2-yl]phenyl]cyclopropanecarbonitrile (prepared as above) was treated similarly to the method described in WO 2019 / 234158 under similar conditions as described in Step 2 of Example P12 to give the desired compound P18. LCMS (Method 2): m / z 434 [M+H] + ;Retention time: 0.83 minutes.

[0575] Step 3: Preparation of individual enantiomeric compounds P18-A and P18-B The racemic 1-[3-(ethylsulfonimidoyl)-4-[3-methyl-6-(trifluoromethyl)imidazo[4,5-c]pyridin-2-yl]phenyl]cyclopropanecarbonitrile (compound P18) mixture was subjected to chiral resolution by preparative SFC using the conditions described below.

[0576] Analysis SFC method: SFC:Waters Acquity UPC 2 / QDa PDA detector Waters Acquity UPC 2 Column: Daicel SFC CHIRALPAK® IC, 3 μm, 0.3 cm x 10 cm, 40°C Mobile phase: A:CO2 B:EtOH Isocratic: 15% B in 4.8 min ABPR: 1800 psi Flow rate: 2.0ml / min Detection: 230nm Sample concentration: 1 mg / mL Injection: 1μL

[0577] Preparative SFC method: Sepiatec Prep SFC 100 Column: Daicel CHIRALPAK® IC, 5 μm, 2.0 cm x 25 cm Mobile phase: A:CO2 B:EtOH Isocratic: 15% B in 15 min Back pressure: 150bar Flow rate: 60ml / min GLS pump: 5ml EtOH Detection: UV 230nm Sample: in MeOH

[0578] [Table 32]

[0579] Example P19: Preparation of racemic 2-[[6-[5-ethyl-3-methyl-4-oxo-6-(trifluoromethyl)imidazo[4,5-c]pyridin-2-yl]-5-(ethylsulfonimidoyl)-3-pyridyl]oxy]-2-methyl-propanenitrile (compound P19) and its individual enantiomers (compounds P19-A and P19-B) [ka] Step 1: 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 [ka] This compound was prepared similarly to the method described in WO 2020 / 084075. LCMS (method 4): m / z 466[M+H] + ;Holding time: 1.10 minutes.

[0580] Step 2: Preparation of racemic 2-[[6-[5-ethyl-3-methyl-4-oxo-6-(trifluoromethyl)imidazo[4,5-c]pyridin-2-yl]-5-(ethylsulfonimidoyl)-3-pyridyl]oxy]-2-methyl-propanenitrile (compound P19) [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 (prepared as described above) was treated similarly to the method described in WO 2020 / 084075 under similar conditions as described in Step 2 of Example P12 to give the desired compound P19. LCMS (Method 4): m / z 497 [M+H] + ;Retention time: 0.93 min.

[0581] Step 3: Preparation of individual enantiomeric compounds P19-A and P19-B The racemic 2-[[6-[5-ethyl-3-methyl-4-oxo-6-(trifluoromethyl)imidazo[4,5-c]pyridin-2-yl]-5-(ethylsulfonimidoyl)-3-pyridyl]oxy]-2-methyl-propanenitrile (compound P19) mixture was subjected to chiral resolution by preparative SFC using the conditions described below.

[0582] Analysis SFC method: SFC:Waters Acquity UPC 2 / QDa PDA detector Waters Acquity UPC 2 Column: Daicel SFC CHIRALPAK® IA, 3 μm, 0.3 cm x 10 cm, 40°C Mobile phase: A:CO2 B:iPrOH Isocratic: 20% B in 4.8 min ABPR: 1800 psi Flow rate: 2.0ml / min Detection: 220nm Sample concentration: 1 mg / mL Injection: 1μL

[0583] Preparative SFC method: Sepiatec Prep SFC 100 Column: Daicel CHIRALPAK® IA, 5 μm, 2.0 cm x 25 cm Mobile phase: A:CO2 B:iPrOH Isocratic: 20% B in 14 min Back pressure: 150bar Flow rate: 60ml / min GLS pump: 2ml MeOH Detection: UV 220nm Sample: in MeOH / DCM

[0584] [Table 33]

[0585] [Table 34-1] [Table 34-2] [Table 34-3] [Table 34-4]

[0586] [Table 35-1] [Table 35-2] [Table 35-3] [Table 35-4] [Table 35-5] [Table 35-6] [Table 35-7]

[0587] Characteristic molecular ions (M+H) in Table P(E) + Measurements were recorded on a Waters mass spectrometer (QDa) (polarity: positive and negative ions), detector gain 1, temperature probe: 500 °C, cone voltage: 10 V, ESI capillary positive voltage 0.8 - negative voltage 0.8, sampling frequency 5 Hz, mass range: 100 - 850 Da.

[0588] Example E1: Preparation of (R)-2-[[5-(ethylsulfonimidoyl)-6-[3-methyl-6-(trifluoromethyl)imidazo[4,5-b]pyridin-2-yl]-3-pyridyl]oxy]-2-methyl-propanenitrile (compound (R)-P9) [ka] (Compound (R)-P9) The enantiomerically enriched form of compound (R)-P9 (the major (R)-stereoisomer with the absolute configuration shown in the drawing) was prepared in two steps from 2-[[5-ethylsulfanyl-6-[3-methyl-6-(trifluoromethyl)imidazo[4,5-b]pyridin-2-yl]-3-pyridyl]oxy]-2-methyl-propanenitrile by stereoselective oxidation followed by a stereospecific iminization reaction.

[0589] Step 1: Preparation of enantiomerically enriched 2-[[5-[(R)-ethylsulfinyl]-6-[3-methyl-6-(trifluoromethyl)imidazo[4,5-b]pyridin-2-yl]-3-pyridyl]oxy]-2-methyl-propanenitrile (compound (R)-SO9) [ka] (Compound (R)-SO9) 2-[[5-Ethylsulfanyl-6-[3-methyl-6-(trifluoromethyl)imidazo[4,5-b]pyridin-2-yl]-3-pyridyl]oxy]-2-methyl-propanenitrile (prepared as described above in Example P9, Step 1) (300 mg, 0.680 mmol), iron(III) acetylacetonate (12.2 mg, 0.035 mmol), 2-[(E)-[(1R)-1-(hydroxymethyl)-2,2-dimethyl-propyl]iminomethyl]-4,6-diiodo-phenol (prepared according to Chem Eur J 2005,11,1086-1092) (37.1 mg, 0.068 mmol) and 4-methoxybenzoic acid (2.6 mg, 0.017 mmol) were dissolved in toluene (2.7 mL). The solution was cooled to 0°C and hydrogen peroxide (30% aqueous solution, 0.139 mL, 1.36 mmol) was added. The reaction was stirred at 0°C for 30 minutes, then warmed to 10°C and stirred overnight, after which it was warmed to room temperature and stirred for an additional 6 hours. The reaction mixture was then poured into a mixture of ethyl acetate and aqueous sodium thiosulfate, the layers were separated, and the aqueous phase was extracted with ethyl acetate. The combined organic phases were washed with water and 0.5 M aqueous hydrochloric acid, dried over sodium sulfate, and concentrated in vacuo. The residue was purified by flash column chromatography (silica, ethyl acetate in cyclohexane) to provide the title compound. LCMS (method 6): m / z 438[M+H] + ;Retention time: 1.86 minutes.

[0590] The enantiomeric excess was determined according to the following method: Analysis SFC method: SFC:Waters Acquity UPC 2 / QDa PDA detector Waters Acquity UPC 2 Column: Daicel SFC CHIRALPAK® IG, 3 μm, 0.46 cm x 10 cm, 40°C Mobile phase: A:CO2 B:EtOH Isocratic: 20% B in 4.8 min ABPR: 1800 psi Flow rate: 2.0ml / min Detection: 310nm Sample concentration: 1 mg / mL in MeOH / ACN 50 / 50 Injection: 1μL

[0591] [Table 36]

[0592] All chiral sulfinyl compounds (R)-SO1 to (R)-SO19 having the (R)-enantiomeric configuration at sulfur of Table P(SO), in enantiomerically enriched or pure form, can be prepared similarly by applying Preparation Example E1, Step 1 (or adaptations thereof known to those skilled in the art) to the respective sulfanyl base.

[0593] Step 2: Preparation of enantiomerically enriched (R)-2-[[5-(ethylsulfonimidoyl)-6-[3-methyl-6-(trifluoromethyl)imidazo[4,5-b]pyridin-2-yl]-3-pyridyl]oxy]-2-methyl-propanenitrile (compound (R)-P9) [ka] (Compound (R)-P9) Enantiomerically enriched 2-[[5-[(R)-ethylsulfinyl]-6-[3-methyl-6-(trifluoromethyl)imidazo[4,5-b]pyridin-2-yl]-3-pyridyl]oxy]-2-methyl-propanenitrile (compound (R)-SO9) prepared as described above) (219 mg, 0.482 mmol) and iron(II) phthalocyanine (6.39 mg, 0.011 mmol) were dissolved in dichloromethane (2 mL). O-(4-Nitrobenzoyl)-hydroxylamine triflic acid (prepared according to Chem Eur J 2017, 23, 563-567) (326 mg, 0.981 mmol) was added, and the mixture was stirred at room temperature for 1 hour. Ethyl acetate and 2 M aqueous hydrochloric acid were added, and the reaction mixture was filtered through a pad of Celite. The filtrate was diluted with water and extracted with ethyl acetate. The organic phase was washed with sodium bicarbonate solution and brine, dried with sodium sulfate and concentrated in vacuo to give the title compound. LCMS (Method 6) m / z 453[M+H] + ;Retention time: 1.39 min.

[0594] The enantiomeric excess was determined according to the following method: Analysis SFC: SFC:Waters Acquity UPC 2 / QDa PDA detector Waters Acquity UPC 2 Column: Daicel SFC CHIRALPAK® IA, 3 μm, 0.3 cm x 10 cm, 40°C Mobile phase: A:CO2 B:EtOH Isocratic: 10% B in 4.8 min ABPR: 1800 psi Flow rate: 2.0ml / min Detection: 290nm Sample concentration: 1 mg / mL in ACN Injection: 1μL

[0595] [Table 37]

[0596] The first eluting major enantiomer (R)-P9 corresponds to compound P9-A (Table P(E)) obtained via chiral resolution (Example P9 above).

[0597] All chiral sulfoximine compounds (R)-P1 to (R)-P19 of Table Y having the (R)-enantiomeric configuration at sulfur, in enantiomerically enriched or pure form, can be prepared similarly by applying Preparation E1, Step 2 (or adaptations thereof known to those skilled in the art) to the respective sulfinyl groups (R)-SO1 to (R)-SO19 of Table P(SO).

[0598] [Table 38-1] [Table 38-2] [Table 38-3] [Table 38-4] [Table 38-5] [Table 38-6] [Table 38-7]

[0599] Example E2: Preparation of (S)-2-[[5-(ethylsulfonimidoyl)-6-[3-methyl-6-(trifluoromethyl)imidazo[4,5-b]pyridin-2-yl]-3-pyridyl]oxy]-2-methyl-propanenitrile (compound (S)-P9) [ka] (Compound (S)-P9) The enantiomerically enriched form of compound (S)-P9 (the major (S)-stereoisomer with the absolute configuration shown in the drawing) was prepared by a similar method using the opposite enantiomer of the chiral ligand in the sulfoxide formation (Example E1, Step 1).

[0600] Step 1: Preparation of enantiomerically enriched 2-[[5-[(S)-ethylsulfinyl]-6-[3-methyl-6-(trifluoromethyl)imidazo[4,5-b]pyridin-2-yl]-3-pyridyl]oxy]-2-methyl-propanenitrile (compound (S)-SO9) [ka] (Compound (S)-SO9) Compound (S)-SO9 was prepared from 2-[[5-ethylsulfanyl-6-[3-methyl-6-(trifluoromethyl)imidazo[4,5-b]pyridin-2-yl]-3-pyridyl]oxy]-2-methyl-propanenitrile by a procedure similar to Example E1, step 1, replacing 2-[(E)-[(1R)-1-(hydroxymethyl)-2,2-dimethylpropyl]iminomethyl]-4,6-diiodo-phenol with 2-[(E)-[(1S)-1-(hydroxymethyl)-2,2-dimethylpropyl]iminomethyl]-4,6-diiodo-phenol. LCMS (method 6): m / z 438[M+H] + ;Retention time: 1.87 min.

[0601] The enantiomeric excess was determined according to the following method: Analytical SFC method SFC:Waters Acquity UPC 2 / QDa PDA detector Waters Acquity UPC 2 Column: Daicel SFC CHIRALPAK® IG, 3 μm, 0.46 cm x 10 cm, 40°C Mobile phase: A:CO2 B:EtOH Isocratic: 20% B in 4.8 min ABPR: 1800 psi Flow rate: 2.0ml / min Detection: 310nm Sample concentration: 1 mg / mL in MeOH / ACN 50 / 50 Injection: 1μL

[0602] [Table 39]

[0603] All chiral sulfinyl compounds (S)-SO1 to (S)-SO19 having the (S)-enantiomeric configuration at sulfur of Table P(SO) in enantiomerically enriched or pure form can be prepared analogously by applying Preparation Example E2, Step 1 (or adaptations thereof known to those skilled in the art) to the respective sulfanyl base.

[0604] Step 2: Preparation of enantiomerically enriched (S)-2-[[5-(ethylsulfonimidoyl)-6-[3-methyl-6-(trifluoromethyl)imidazo[4,5-b]pyridin-2-yl]-3-pyridyl]oxy]-2-methyl-propanenitrile (compound (S)-P9) [ka] (Compound (S)-P9) Compound (S)-P9 was prepared from enantiomerically enriched 2-[[5-[(S)-ethylsulfinyl]-6-[3-methyl-6-(trifluoromethyl)imidazo[4,5-b]pyridin-2-yl]-3-pyridyl]oxy]-2-methyl-propanenitrile (compound (S)-SO9, prepared as described above) by a procedure similar to Example E1, Step 2. LCMS (Method 6): m / z 453[M+H] + ;Retention time: 1.39 min.

[0605] The enantiomeric excess was determined according to the following method: Analysis SFC SFC:Waters Acquity UPC 2 / QDa PDA detector Waters Acquity UPC 2 Column: Daicel SFC CHIRALPAK® IA, 3 μm, 0.3 cm x 10 cm, 40°C Mobile phase: A:CO2 B:EtOH Isocratic: 10% B in 4.8 min ABPR: 1800 psi Flow rate: 2.0ml / min Detection: 290nm Sample concentration: 1 mg / mL in ACN Injection: 1μL

[0606] [Table 40]

[0607] The second eluting major enantiomer (S)-P9 corresponds to compound P9-B (Table P(E)) obtained via chiral resolution (Example P9 above).

[0608] All chiral sulfoximine compounds (S)-P1 to (S)-P19 of Table Y having the (S)-enantiomeric configuration at sulfur, in enantiomerically enriched or pure form, can be similarly prepared by applying Preparation E2, Step 2 (or adaptations thereof known to those skilled in the art) to the respective sulfinyl groups (S)-SO1 to (S)-SO19 of Table P(SO).

[0609] 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-20, B-1 to B-20, Table Y, Table Z and Table P(E) 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, Afoxolaner +TX, Alanycarb +TX, Allethrin +TX, α-Cypermethrin +TX, Alphamethrin +TX, Amidoflumet +TX, Aminocarb +TX, Azocyclotine +TX, Bensultap +TX, Benzoximate +TX, Benzpyrimoxane + TX, beta-cyfluthrin + TX, beta-cypermethrin + TX, bifenazate + TX, bifenthrin + TX, binapacryl + TX, bioallethrin + TX, S bioallethrin + TX, bioresmethrin + TX, bistrifluron + TX, brofuranilide + TX, brofluthrinate + TX, bromophos-ethyl + TX, buprofezin + TX, butocarboxim + TX, cadusafos + TX, carbaryl + TX, carbosulfan + TX, Kartap+TX, CAS number: 1632218-00-8+TX, CAS number: 1808115-49-2+TX, CAS number: 2032403-97-5+ TX, CAS number:2044701-44-0+TX, CAS number:2128706-05-6+TX, CAS number:2095470-94-1+TX, CAS number:2 377084-09-6+TX, CAS number: 1445683-71-5+TX, CAS number: 2408220-94-8+TX, CAS number: 2408220-91- 5+TX, CAS number: 1365070-72-9+TX, CAS number: 2171099-09-3+TX, CAS number: 2396747-83-2+TX, CAS number :2133042-31-4+TX, CAS number:2133042-44-9+TX, CAS number:1445684-82-1+TX, CAS number:1445684- 82-1+TX, CAS number:1922957-45-6+TX, CAS number:1922957-46-7+TX, CAS number:1922957-47-8+TX, CA S number: 1922957-48-9+TX, CAS number: 2415706-16-8+TX, CAS number: 1594624-87-9+TX, CAS number: 159463 7-65-6+TX, CAS number: 1594626-19-3+TX, CAS number: 1990457-52-7+TX, CAS number: 1990457-55-0+TX,CAS No.: 1990457-57-2+TX, CAS No.: 1990457-77-6+TX, CAS No.: 1990457-66-3+TX, CAS No.: 1990457-85-6+TX, CAS No.: 2220132-55-6+TX, CAS No.: 1255091-74-7+TX, CAS No.: RNA (Colorado potato beetle (Leptinotarsa decemLineata)-specific recombinant double-stranded interference (GS2) + TX, CAS No.: 2719848-60-7 + TX, CAS No.: 1956329-03-5 + 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, cyenopyrafen +TX, cetopyrafen (or ethopyrafen) +TX, cyflumetofen +TX, cyfluthrin +TX, cyhalodiamide +TX, cyhalothrin +TX, cypermethrin +TX, cyphenothrin +TX, cyprofanilide +TX, cyromazine +TX, deltamethrin +TX, diafenthin Uron + TX, Dialifos + TX, Dibrom + TX, Dichloromezothiaz + TX, Diflobidazin + TX, Diflubenzuron + TX, Dinpropylidaz + TX, Dinactin + TX, Dinocap + TX, Dinotefuran + TX, Dioxabenzophos + TX, Emamectin (or Emamectin benzoate) + TX, Empenthrin + TX, Epsilon-Monfluorothrin + TX, Epsilon-Metofluthrin + TX, Esfenvalerate + TX, Ethion + TX, Ethion Tiprole +TX, Etofenprox +TX, Etoxazole +TX, Famflur +TX, Fenazaquin +TX, Fenfluthrin +TX, Fenmezodithiaz +TX, Fenitrothion +TX, Fenobucarb +TX, Fenothiocarb +TX, Fenoxycarb +TX, Fenpropathrin +TX, Fenpyroximate +TX, Fensulfothion +TX, Fenthion +TX, Fentin acetate +TX, Fenvalerate +TX, Fipronil +TX,flometoquine +TX, flonicamid +TX, fluacrypyrim +TX, fluazaindolizine +TX, fluazuron +TX, flubendiamide +TX, flubenzoimine +TX, fluchlordiniliprole +TX, flucythrinate +TX, flucycloxuron +TX, flucythrinate +TX, fluensulfone +TX, flufenerim +TX, flufenprox +TX, flufiprole +TX, fluhexafon +TX, flumethrin +TX, fluopyram +TX, flupentiofenox +TX, flupyradifuron +TX, flupirimine +TX, fluralaner +TX, fluvalinate +TX, fluxamethamide +T X, fosthiazate + TX, gamma-cyhalothrin + TX, guadipyr + TX, halofenozide + TX, halfenprox + TX, heptafluthrin + TX, hexythiazox + TX, hydramethylnon + TX, imicyafos + TX, imidacloprid + TX, imiprothrin + TX, indazapiroxameth + TX, indoxacarb + TX, iodomethane + TX, iprodione + TX, isocycloceram + TX, isothioate + TX, ivermectin + TX, kappa-bifenthrin + TX, kappa-tefluthrin + TX, lambda-cyhalothrin + TX, lepimectin + TX, lotilaner + TX, lufenuron + TX, Metaflumizone +TX, metaldehyde +TX, metam +TX, methomyl +TX, methoxyfenozide +TX, metofluthrin +TX, metolcarb +TX, mexacarbate +TX, milbemectin +TX, momfluorotrin +TX, niclosamide +TX, nicofluprole +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, pirimi Phosphol-ethyl + TX, Pirimiphos-methyl + TX, Polyhedrovirus + TX, Prallethrin + 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, Pyrifluquinazon + TX, Pyrimidifen + TX, Pyriminostrobin + TX, Pyriprole + TX, Pyriproxyfen + TX, Resmethrin + TX, sarolaner + TX, selamectin + TX, silafluofen + TX, spinetoram + TX, spinosad + TX, spirobudifen + TX, spirodiclofen + TX, spiromesifen + TX, spiropydione + TX, spirotetramat + TX, spidoxamat + TX, sulfoxaflor + TX, tebufenozide + TX, tebufenpyrad + TX, tebupirimifos + TX, tefluthrin + TX, temephos + TX, tetrachlorantraniliprole + TX, tetradifon + TX, tetramethrin + TX, tetramethylfluthrin + TX, tetra Nactin + TX, tetraniliprole + TX, theta-cypermethrin + TX, thiacloprid + TX, thiamethoxam + TX, thiocyclam + TX, thiodicarb + TX, thiofanox + TX, thiometon + TX, thiosultap + TX, tigoraner + TX, thioantraniliprole + TX, thioxazaphen + TX, tolfenpyrad + TX, toxaphene + TX, tralomethrin + TX, transfluthrin + TX, triazamate + TX, triazophos + TX, trichlorfon + TX, trichloronate + TX, trichlorfon + TX,Trifluenfronate +TX, Triflumezopyrim +TX, Cyclopyrazoflor +TX, Zeta-cypermethrin +TX, Seaweed extract and fermentation product from Melasse +TX, Seaweed extract and fermentation 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 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 thuringiensis BD#32 (NRRL accession number B-21530) + TX, Bacillus thuringiensis subspec. kurstaki BMP123 + TX, Beauveria bassiana + TX, D-limonene + TX, granulovirus + TX, harpin + TX, Helicoverpa armigera nucleopolyhedrovirus + TX, Helicoverpa zea nucleopolyhedrovirus + TX, Heliothis virescens nucleopolyhedrovirus + TX, Heliothis punctigera nucleopolyhedrovirus + TX, Metarhizium spp.) + TX, Muscodor albus 620 (NRRL accession number 30547) + TX, Muscodor roseus A3-5 (NRRL accession number 30548) + TX, Neem tree-based products + TX, Paecilomyces fumosoroseus + TX, Paecilomyces lilacinus + TX, Pasteuria nishizawae + TX, Pasteuria penetrans + TX, Pasteuria ramosa + TX, Pasteuria thornei + TX, Pasteuria usugae usgae + TX, P-cymene + TX, Plutella xylostella granulosis virus + TX, Plutella xylostella nucleopolyhedrovirus + TX, polyhedrovirus + TX, pyrethrum + TX, QRD420 (terpenoid blend) + TX, QRD452 (terpenoid blend) + TX, QRD460 (terpenoid blend) + TX, Quillaja saponaria + TX, Rhodococcus globerulus AQ719 (NRRL accession number B-21663) + TX, Spodoptera frugiperda nucleopolyhedrovirus + TX, Streptomyces gallus galbus (NRRL accession number 30232) + TX, Streptomyces sp. (NRRL accession number B-30145) + TX, terpenoid blend + TX, and Verticillium spp. + TX; an algicide selected from the group of substances consisting of bethoxadin [CCN] + TX, copper dioctanoate (IUPAC name) (170) + TX, copper sulfate (172) + TX, sibutrin [CCN] + TX, dichloron (1052) + TX, dichlorophen (232) + TX, endothal (295) + TX, fentin (347) + TX, hydrated lime [CCN] + TX, nabam (566) + TX, quinoclamine (714) + TX, quinonamide (1379) + TX, simazine (730) + TX, triphenyltin acetate (IUPAC name) (347) and triphenyltin hydroxide (IUPAC name) (347) + TX; an anthelmintic selected from the group of substances consisting of abamectin (1) + TX, crufomate (1011) + TX, 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, dodisin (1112) + TX, fenaminosulf (1144) + TX, formaldehyde (404) + TX, hydrargafen (alternative name) [CCN] + T a fungicide selected from the group of substances consisting of X, 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 (alternate name) (12) + TX, Agrobacterium radiobacter (alternate name) (13) + TX, Amblyseius spp. (alternate name) (19) + TX, Anagrapha falcifera NPV (alternate name) (28) + TX, Anagrus atomus (alternate name) (29) + TX, Aphelinus abdominalis (alternate name) (33) + TX, Aphidius colemani (alternate name) (34) + TX, Aphidoletes aphidimyza (alternate 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 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 nucleopolyhedrovirus (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 of substances consisting of Verticillium lecanii (alternative name) (848) + TX; a soil sterilant selected from the group of substances consisting of iodomethane (IUPAC name) (542) and methyl bromide (537) + TX; chemical disinfectants selected from the group of substances consisting of Apholate [CCN] + TX, Visadyl (alternative name) [CCN] + TX, Busulfan (alternative name) [CCN] + TX, Diflubenzuron (250) + TX, Dimatif (alternative name) [CCN] + TX, Hemel [CCN] + TX, Hempa [CCN] + TX, Metepa [CCN] + TX, Methiotepa [CCN] + TX, Methyl Apholate [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, alpha-multistriatin (alternative name) [CCN] + TX, Brevicomin (alternative name) [CCN] + TX, Codrelure (alternative name) [CCN] + TX, Codlemone (alternative name) (167) + TX, Cure (alternative name) (179) + TX , Disparlure (277) + TX, Dodec-8-en-1-yl acetate (IUPAC name) (286) + TX, Dodec-9-en-1-yl acetate (IUPAC name) (287) + TX, Dodec-8 + TX, 10-dien-1-yl acetate (IUPAC name) (284) + TX, Dominicalure (alternative name) [CCN] + TX, Ethyl 4-methyloctanoate (IUPAC name) (317) + TX, Eugenol (alternative name) [CCN] + TX, Frontalin (alternative name) [CCN] + T X, a 1:1 mixture of the (Z,E) and (Z,Z) isomers of Gossyplure® (alternative name: hexadeca-7,11-dien-1-yl-acetate) (420) + TX, Grandolure (421) + TX, Grandolure I (alternative name) (421) + TX, Grandolure II (alternative name) (421) + TX, Grandolure III (alternative name) (421) + TX, Grandolure IV (alternative name) (421) + TX, Hexalure [CCN] + TX, Ipsdienol (alternative name) [CCN] + TX, Ipsenol (alternative 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) (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) + TX, Dazomet (216) + TX, DBCP (1045) + TX, DCIP (218) + TX, Diamidafos (1044) + TX, Diclofenthion (1051) + TX, Dicrifos (alternative name) + TX, Dimethoate (262) + T X, doramectin (alternative name) [CCN] + TX, emamectin (291) + TX, emamectin benzoate (291) + TX, eprinomectin (alternative name) [CCN] + TX, ethoprophos (312) + TX, ethylene dibromide (316) + TX, fenamiphos (326) + TX, fenpyrad (alternative name) + TX, fensulfothion (1158) + TX, fosthiazate (408) + TX, fostietan (1196) + TX, furfural (alternative name) [CCN] + TX, GY-81 (development code) (423) + TX, heterophos [CCN] + TX,Iodomethane (IUPAC name) (542) + TX, Isamidophos (1230) + TX, Isazophos (1231) + TX, Ivermectin (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, Myrothecium verrucaria) 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 (IUP a nematicide selected from the group of substances consisting of AC / 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, alpha-chlorohydrin [CCN] + TX, aluminum phosphide (640) + TX, anthracene (880) + TX, arsenic trioxide (882) + TX, barium carbonate (891) + TX, bisthiosemi (912) + TX, brodifacoium (89) + TX, bromadiolone (including alpha-bromadiolone) +TX, Bromethalin (92) +TX, Calcium cyanide (444) +TX, Chloralose (127) +TX, Chlorophacinone (140) +TX, Cholecalciferol (alternative name) (850) +TX, Coumacrol (1004) +TX, Coumafuryl (1005) +TX, Coumatetralyl (175) +TX, Crimidine (1009) +TX, Difenacoum (246) +TX, Difethialone (249) +TX, Diphacinone (273) +TX, Ergocalciferol (301) +TX, Flo Coumaphene (357) + TX, Fluoroacetamide (379) + TX, Flupropaline (1183) + TX, Flupropaline Hydrochloride (1183) + TX, gamma-HCH (430) + TX, HCH (430) + TX, Hydrogen Cyanide (444) + TX, Iodomethane (IUPAC name) (542) + TX, Lindane (430) + TX, Magnesium Phosphide (IUPAC name) (640) + TX, Methyl Bromide (537) + TX, Norbormide (1318) + TX, 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, MGK264 (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-naphthylacetamide + TX, 4-chlorophenylphenylsulfone + TX, acetoprole + TX, aldoxicarb + TX, amidithione + TX, amidothioate + TX, amiton + TX, amiton hydrogen oxalate + TX, amitraz + TX, alamite + TX, arsenic oxide + TX, azobenzene + TX, azotoate + TX, benomyl + TX, benoxaphos + TX, ben Dibenzoate + TX, Bixafen + TX, Brofenvalerate + TX, Bromocyclen + TX, Bromophos + TX, Bromopropylate + TX, Buprofezin + TX, Butocarboxim + TX, Butoxycarboxim + TX, Butylpyridaben + TX, Calcium polysulfide + TX, Camphechlor + TX, Carbanolate + TX, Carbophenothion + TX, Cimiazol + TX, Thiomethionate + TX, Chlorbeside + TX, Chlordimeform + TX, Chlordimeform hydrochloride + TX, Chlorphenetole + TX, Chlor Fenson +TX, Chlorphenesulfide +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-methyl sulfone + 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, Dinotervon + 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, Fen-pyroximate + TX, Fenpyrazamine + TX, Fenson + TX, Fentrifanil + TX, Flubenzimine + TX, Flucycloxuron + TX, Fluenethyl + TX, Fluorobenside + TX, FMC 1137+TX, formetanate+TX, formetanate hydrochloride+TX, formparanate+TX, gamma-HCH+TX, gliodin+TX, halfenprox+TX, hexadecylcyclopropanecarboxylate+TX, isocarbophos+TX, jasmolin I+TX, jasmolin II+TX, jodofenphos+TX, lindane+TX, malonoven+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 zinc chloride complex + TX, omethoate + TX, oxydeprophos + TX, oxydisulfoton + TX, pp'-DDT + TX, parathion + TX, permethrin + TX, fencapton + TX, phosalone + TX, phospholan + TX, phosphamidon + TX, polychloroterpenes + TX, polynactin + TX, proclonol + TX, promacyl + TX, propoxur + TX, protidathion + TX, prothoate + TX, pyrethrin I + TX, pyrethrin II + TX, pyrethrin + TX, pyridaphenthion + TX, pyrimitate + TX, quinalphos + TX, quinthiofos + TX, R-1492 + TX, phosglycine + TX, rotenone + TX, Schladan + TX, Cebufos + TX, Selamectin + TX, Sofamid + TX, SSI-121 + TX, Sulfiram + TX, Sulfuramide + TX, Sulfotep + TX, Sulfur + TX, Diflavidazine + TX, Tau-fluvalinate + TX, TEPP + TX, Terbam + TX, Tetradifon + TX, Tetrasul + TX, Thiafenox + TX, Thiocarboxim + TX, Thiofanox + TX, Thiometon + TX, Thioquinox + TX, Thuringiencin + TX, Triamiphos + TX, Trialate + TX, Triazophos + TX, Triazuron + TX, Trifenofos + TX, Trinactin + TX, Vamidothion + TX, Vaniliprole + TX, Bethoxazin + TX, Copper dioctanoate + TX, Copper sulfate + TX, Sibutrin + TX, Dichloren + TX, Dichlorophen + TX, Endothal + TX, Fentin + TX, Slaked lime + TX, Nabam + TX, Quinoclamine + TX, Quinonamide + TX, Simazine + TX, Triphenyltin acetate + TX, Triphenyltin hydroxide + TX, Chlorphen Sulfonate + TX, piperazine + TX, thiophanate + TX, chloralose + TX, fenthion + TX, pyridin-4-amine + TX, 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, hydra Lugafen + TX, kasugamycin + TX, kasugamycin hydrochloride hydrate + TX, nickel bis(dimethyldithiocarbamate) + TX, nitrapyrin + TX, octhilinone + TX, oxolinic acid + TX, oxytetracycline + TX, hydroxyquinoline potassium sulfate + TX, probenazole + TX, streptomycin + TX, streptomycin sesquisulfate + TX, tecloftalam + TX, thiomersal + TX, Adoxophyes orana GV + TX, Agrobacterium radiobacter + TX, Amblyseius spp.) + TX, Anagrapha falcifera NPV + TX, Anagrus atomus + TX, Aphelinus abdominalis + TX, Aphidius colemani + TX, Aphidoletes aphidimyza + TX, Autographa californica NPV + TX, Bacillus sphaericus Neide + TX, Beauveria brongniartii + TX, Chrysoperla carnea + TX, Cryptolaemus montrouzieri + TX, 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 herbolis helvolus) + TX, Metarhizium anisopliae var. acridum + TX, Metarhizium anisopliae var. anisopliae + TX, pine sawfly (Neodiprion sertifer) NPV and N. leconti (N.lecontei NPV + TX, Orius spp. + TX, Paecilomyces fumosoroseus + TX, Phytoseiulus persimilis + TX, Steinernema bibionis + TX, Steinernema carpocapsae + TX, Steinernema feltiae + TX, Steinernema glaseri + TX, Steinernema riobrave + TX, Steinernema riobravis + TX, Steinernema skapterischii + TX, scapterisci) + TX, Steinernema spp.) + TX, Trichogramma spp.) + TX, Typhlodromus occidentalis + TX, Verticillium lecanii 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 ate + 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)-icos-13-en-10-one + TX, (Z)-tetradec-7-en-1-al + TX, (Z)-tetradec-9-en-1-ol + TX, (Z)-tetradec-9-en-1-yl acetate + TX, (7E,9Z)-dodeca-7,9-dien-1-yl acetate + TX, (9Z,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, alpha-multistriatin + TX, Brevicomin + TX, Codrelle + TX, Codlemone + TX, Querle + TX, Disparlure + TX, Dodec-8-en-1-yl acetate + TX, Dodec-9-en-1-yl acetate + TX, Dodec-8 + TX, 10-dien-1-yl acetate + TX, Dominicalure + TX, Ethyl 4-methyloctanoate + TX, Eugenol + TX, Frontalin + TX, Grandlure + TX, Gruen Landrua I + TX, Grandrua II + TX, Grandrua III + TX, Grandrua IV + TX, Hexalua + TX, Ipsdienol + TX, Ipsenol + TX, Japonilua + TX, Lineatin + TX, Litrua + TX, Lupulua + TX, Medulua + TX, Megatomoic acid + TX, Methyleugenol + TX, Muscalua + TX, Octadeca-2,13-dien-1-yl acetate + TX, Octadeca-3,13-dien-1-yl acetate + TX, Olfrulua + TX, Orictalua + TX, Ostramon + TX, Siglua + TX, Solgi Din + 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, Dimethylcarbate + TX, Dimethyl phthalate + T X, ethyl hexanediol + TX, hexamide + TX, methoquin-butyl + TX, methyl neodecaneamide + TX, oxamate + TX, picaridin + TX, 1-dichloro-1-nitroethane + TX, 1,1-dichloro-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-ethylsulfinylethyl methylphosphate + TX, 2-(1,3-Dithiolan-2-yl)phenyl dimethyl carbamate + TX, 2-(2-butoxyethoxy)ethyl thiocyanate + TX, 2-(4,5-dimethyl-1,3-dioxolan-2-yl)phenyl methyl carbamate + TX, 2-(4-chloro-3,5-xylyloxy)ethanol + TX, 2-chlorovinyl diethyl phosphate + TX, 2-imidazolidone + TX, 2-isovalerylindan-1,3-dione + TX, 2-methyl(prop-2-ynyl)aminophenyl methyl carbamate + TX, 2-thiocyanatoethyl laurate + TX, 3-bromo-1-chloroprop -1-ene + TX, 3-methyl-1-phenylpyrazol-5-yldimethylcarbamate + 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 (Bacillus thuringiensis) Delta-Endotoxin +TX, Barium Hexafluorosilicate +TX, Barium Polysulfide +TX, Bartholin +TX, Bayer 22 / 190 +TX, Bayer 22408 +TX, Beta-Cyfluthrin +TX, Beta-Cypermethrin +TX, Bioethanometrin +TX, Biopermethrin +TX, Bis(2-chloroethyl) ether + TX, Borax + 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, Cevadin + 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, Copper oleate + TX, Chumithoate + TX, Cryolite + TX, CS7 08+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, etaphos+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, fretolin+TX, guazatine+TX, guazatine acetate+TX, sodium tetrathiocarbonate+TX, halfenprox+TX, HCH+TX, HEOD+TX, heptachlor+TX, heterophos+TX, HHDN+TX, hydrogen cyanide+TX, hikincarb+TX, IPSP+TX,Isazophos + TX, Isobenzan + TX, Isodrin + TX, Isofenphos + TX, Isolane + TX, Isoprothiolane + TX, Isoxathion + TX, Juvenile Hormone I + TX, Juvenile Hormone II + TX, Juvenile Hormone III + TX, Kerevan + 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, Methyl chloroform +TX, Methylene chloride +TX, Methoxadiazone...

Claims

1. A compound of formula (I) 【Chemical 1】 (wherein A is CH or N; R 1 is C 1 to C 4 alkyl; S * is a stereogenic sulfur atom having an R- or S-configuration; R 8 is cyanoisopropoxy, cyanoisopropyl or cyanocyclopropyl; R 9 is hydrogen or C 1 ~C 4 alkyl; Q is the formula Q 1 ~Q 5 [Chemical Formula 2] (wherein the arrow indicates the point of attachment to the ring in which the A group is incorporated; and X 1 is O, S or NR 3 ; R 3 is C 1 to C 4 alkyl; R 2 is halogen, C 1 to C 6 haloalkyl, C 1 to C 4 haloalkylsulfanyl, C 1 to C 4 haloalkylsulfinyl, C 1 to C 4 haloalkylsulfonyl or C 1 to C 6 haloalkoxy; G 1 and G 2 are, independently of each other, N or CH; R 4 is C 1 to C 4 alkyl, C 1 to C 4 haloalkyl, C 3 to C 6 cycloalkyl or C 1 to C 4 alkoxy). is a group selected from the group consisting of) or an agrochemically acceptable salt, stereoisomer, enantiomer, tautomer or N-oxide of the compound of formula I.

2. A compound of formula I-1 【Chemical Formula 3】 (wherein R 1 , R 2 , R 3 , R 8 , R 9 , S * and A are as defined in formula I in claim 1) The compound of formula I according to claim 1, represented by

3. A compound of formula I-2 【Chemical 4】 (wherein R 1 , R 2 , R 3 , R 8 , R 9 , S * and A are as defined in Formula I in Claim 1) The compound of formula I according to claim 1, represented by

4. A compound of formula I-3 【Chemical Formula 5】 (wherein R 1 , R 2 , R 3 , R 8 , R 9 , S * and A are as defined in Formula I in Claim 1) The compound of formula I according to claim 1, represented by

5. A compound of formula I-4 【Chemical Formula 6】 (wherein R 1 , R 2 , R 3 , R 4 , R 8 , R 9 , S * and A are as defined in Formula I in Claim 1). The compound of formula I according to claim 1, represented by

6. A compound of formula I-5 【Chemical Formula 7】 (wherein R 1 , R 2 , R 8 , R 9 , S * and A are as defined in formula I in claim 1) The compound of formula I according to claim 1, represented by

7. A compound of formula I-6 [Chemical Formula 8] (wherein R 1 , R 2 , R 8 , R 9 , S * and A are as defined in formula I in claim 1) The compound of formula I according to claim 1, represented by

8. A compound of formula I-7 【Chemical Formula 9】 (wherein R 1 , R 2 , R 8 , R 9 , S * and A are as defined in Formula I in Claim 1) The compound of formula I according to claim 1, represented by

9. A compound of formula I-8 【Chemical 10】 (wherein R 1 , R 2 , R 8 , R 9 , S * and A are as defined in formula I in claim 1) The compound of formula I according to claim 1, represented by

10. A compound of formula I-9 【Chemical 11】 (wherein R 1 , R 2 , R 8 , R 9 , S * and A are as defined in formula I in claim 1) The compound of formula I according to claim 1, represented by

11. A compound of formula I-10 【Chemical Formula 12】 (wherein R 1 , R 2 , R 8 , R 9 , S * and A are as defined in formula I in claim 1) The compound of formula I according to claim 1, represented by

12. A is CH or N, preferably A is N; S * is a stereogenic sulfur atom having an R- or S-configuration; R 1 is ethyl, propyl or isopropyl; preferably, R 1 is ethyl; R 2 is trifluoromethyl, pentafluoroethyl or trifluoromethylsulfanyl; preferably, R 2 is trifluoromethyl; R 8 is 1-cyano-1-methylethoxy, 1-cyano-1-methylethyl or 1-cyanocyclopropyl; R 9 is hydrogen or methyl; preferably, R 9 is hydrogen; and Q is Q 1 or Q 4 in the case of a compound of formula I where G 1 is N and G 2 is CH, or G 1 is CH and G 2 is N, or G 1 and G 2 are both N; and, in the case of a compound where Q is Q 2 G 2 is N or CH; and For compounds of formulas I-1, I-2, I-3 and I-4, R 3 is methyl; and for compounds of formula I-4, R 4 is ethyl, methoxy or cyclopropyl, The compound of formula I according to claim 1.

13. S * is a compound of formula I according to any one of claims 1 to 12, which is in the R-configuration in enantiomerically pure form or in enantiomerically enriched form.

14. S * The compound of formula I according to any one of claims 1 to 12, which is in the S-configuration in enantiomerically pure form or in enantiomerically enriched form.

15. (S)-2-[[6-[5-cyclopropyl-3-methyl-4-oxo-6-(trifluoromethyl)imidazo[4,5-c]pyridin-2-yl]-5-(ethylsulfonimidoyl)-3-pyridyl]oxy]-2-methyl-propanenitrile; (R)-2-[[6-[5-cyclopropyl-3-methyl-4-oxo-6-(trifluoromethyl)imidazo[4,5-c]pyridin-2-yl]-5-(ethylsulfonimidoyl)-3-pyridyl]oxy]-2-methyl-propanenitrile; (S)-1-[5-(ethylsulfonimidoyl)-6-[7-methyl-3-(trifluoromethyl)imidazo[4,5-c]pyridazin-6-yl]-3-pyridyl]cyclopropanecarbonitrile; (R)-1-[5-(ethylsulfonimidoyl)-6-[7-methyl-3-(trifluoromethyl)imidazo[4,5-c]pyridazin-6-yl]-3-pyridyl]cyclopropanecarbonitrile; (S)-2-[[5-(ethylsulfonimidoyl)-6-[7-(trifluoromethyl)imidazo[1,2-a]pyridin-2-yl]-3-pyridyl]oxy]-2-methyl-propanenitrile; (R)-2-[[5-(ethylsulfonimidoyl)-6-[7-(trifluoromethyl)imidazo[1,2-a]pyridin-2-yl]-3-pyridyl]oxy]-2-methyl-propanenitrile; (S)-2-[5-(ethylsulfonimidoyl)-6-[3-methyl-6-(trifluoromethyl)imidazo[4,5-c]pyridin-2-yl]-3-pyridyl]-2-methyl-propanenitrile; (R)-2-[5-(ethylsulfonimidoyl)-6-[3-methyl-6-(trifluoromethyl)imidazo[4,5-c]pyridin-2-yl]-3-pyridyl]-2-methyl-propanenitrile; (S)-2-[[5-(ethylsulfonimidoyl)-2-methyl-6-[3-methyl-6-(trifluoromethyl)imidazo[4,5-b]pyridin-2-yl]-3-pyridyl]oxy]-2-methyl-propanenitrile; (R)-2-[[5-(ethylsulfonimidoyl)-2-methyl-6-[3-methyl-6-(trifluoromethyl)imidazo[4,5-b]pyridin-2-yl]-3-pyridyl]oxy]-2-methyl-propanenitrile; (S)-1-[3-(ethylsulfonimidoyl)-4-[3-methyl-6-(trifluoromethyl)imidazo[4,5-b]pyridin-2-yl]phenyl]cyclopropanecarbonitrile; (R)-1-[3-(ethylsulfonimidoyl)-4-[3-methyl-6-(trifluoromethyl)imidazo[4,5-b]pyridin-2-yl]phenyl]cyclopropanecarbonitrile; (S)-2-[[5-(ethylsulfonimidoyl)-6-[7-(trifluoromethylsulfanyl)imidazo[1,2-c]pyrimidin-2-yl]-3-pyridyl]oxy]-2-methyl-propanenitrile; (R)-2-[[5-(ethylsulfonimidoyl)-6-[7-(trifluoromethylsulfanyl)imidazo[1,2-c]pyrimidin-2-yl]-3-pyridyl]oxy]-2-methyl-propanenitrile; (S)-1-[5-(ethylsulfonimidoyl)-6-[5-methoxy-3-methyl-4-oxo-6-(trifluoromethyl)imidazo[4,5-c]pyridin-2-yl]-3-pyridyl]cyclopropanecarbonitrile; (R)-1-[5-(ethylsulfonimidoyl)-6-[5-methoxy-3-methyl-4-oxo-6-(trifluoromethyl)imidazo[4,5-c]pyridin-2-yl]-3-pyridyl]cyclopropanecarbonitrile; (S)-2-[[5-(ethylsulfonimidoyl)-6-[3-methyl-6-(trifluoromethyl)imidazo[4,5-b]pyridin-2-yl]-3-pyridyl]oxy]-2-methyl-propanenitrile; (R)-2-[[5-(ethylsulfonimidoyl)-6-[3-methyl-6-(trifluoromethyl)imidazo[4,5-b]pyridin-2-yl]-3-pyridyl]oxy]-2-methyl-propanenitrile; (S)-1-[5-(ethylsulfonimidoyl)-6-[3-methyl-6-(trifluoromethyl)imidazo[4,5-c]pyridin-2-yl]-3-pyridyl]cyclopropanecarbonitrile; (R)-1-[5-(ethylsulfonimidoyl)-6-[3-methyl-6-(trifluoromethyl)imidazo[4,5-c]pyridin-2-yl]-3-pyridyl]cyclopropanecarbonitrile; (S)-2-[[5-(ethylsulfonimidoyl)-6-[7-(trifluoromethyl)imidazo[1,2-c]pyrimidin-2-yl]-3-pyridyl]oxy]-2-methyl-propanenitrile; (R)-2-[[5-(ethylsulfonimidoyl)-6-[7-(trifluoromethyl)imidazo[1,2-c]pyrimidin-2-yl]-3-pyridyl]oxy]-2-methyl-propanenitrile; (S)-2-[5-(ethylsulfonimidoyl)-6-[3-methyl-6-(trifluoromethyl)imidazo[4,5-b]pyridin-2-yl]-3-pyridyl]-2-methyl-propanenitrile; (R)-2-[5-(ethylsulfonimidoyl)-6-[3-methyl-6-(trifluoromethyl)imidazo[4,5-b]pyridin-2-yl]-3-pyridyl]-2-methyl-propanenitrile; (S)-2-[[5-(ethylsulfonimidoyl)-6-[3-methyl-6-(trifluoromethyl)imidazo[4,5-c]pyridin-2-yl]-3-pyridyl]oxy]-2-methyl-propanenitrile; (R)-2-[[5-(ethylsulfonimidoyl)-6-[3-methyl-6-(trifluoromethyl)imidazo[4,5-c]pyridin-2-yl]-3-pyridyl]oxy]-2-methyl-propanenitrile; (S)-1-[6-[5-ethyl-3-methyl-4-oxo-6-(trifluoromethyl)imidazo[4,5-c]pyridin-2-yl]-5-(ethylsulfonimidoyl)-3-pyridyl]cyclopropanecarbonitrile; (R)-1-[6-[5-ethyl-3-methyl-4-oxo-6-(trifluoromethyl)imidazo[4,5-c]pyridin-2-yl]-5-(ethylsulfonimidoyl)-3-pyridyl]cyclopropanecarbonitrile; (S)-2-[[5-(ethylsulfonimidoyl)-6-[7-methyl-3-(trifluoromethyl)imidazo[4,5-c]pyridazin-6-yl]-3-pyridyl]oxy]-2-methyl-propanenitrile; (R)-2-[[5-(ethylsulfonimidoyl)-6-[7-methyl-3-(trifluoromethyl)imidazo[4,5-c]pyridazin-6-yl]-3-pyridyl]oxy]-2-methyl-propanenitrile; (S)-1-[5-(ethylsulfonimidoyl)-6-[3-methyl-6-(trifluoromethyl)imidazo[4,5-b]pyridin-2-yl]-3-pyridyl]cyclopropanecarbonitrile; (R)-1-[5-(ethylsulfonimidoyl)-6-[3-methyl-6-(trifluoromethyl)imidazo[4,5-b]pyridin-2-yl]-3-pyridyl]cyclopropanecarbonitrile; (S)-2-[[5-(ethylsulfonimidoyl)-2-methyl-6-[3-methyl-6-(trifluoromethyl)imidazo[4,5-c]pyridin-2-yl]-3-pyridyl]oxy]-2-methyl-propanenitrile; (R)-2-[[5-(ethylsulfonimidoyl)-2-methyl-6-[3-methyl-6-(trifluoromethyl)imidazo[4,5-c]pyridin-2-yl]-3-pyridyl]oxy]-2-methyl-propanenitrile; (S)-1-[3-(ethylsulfonimidoyl)-4-[3-methyl-6-(trifluoromethyl)imidazo[4,5-c]pyridin-2-yl]phenyl]cyclopropanecarbonitrile; (R)-1-[3-(ethylsulfonimidoyl)-4-[3-methyl-6-(trifluoromethyl)imidazo[4,5-c]pyridin-2-yl]phenyl]cyclopropanecarbonitrile; (S)-2-[[6-[5-ethyl-3-methyl-4-oxo-6-(trifluoromethyl)imidazo[4,5-c]pyridin-2-yl]-5-(ethylsulfonimidoyl)-3-pyridyl]oxy]-2-methyl-propanenitrile; and (R)-2-[[6-[5-ethyl-3-methyl-4-oxo-6-(trifluoromethyl)imidazo[4,5-c]pyridin-2-yl]-5-(ethylsulfonimidoyl)-3-pyridyl]oxy]-2-methyl-propanenitrile The compound of formula I according to claim 1, selected from the group consisting of.

16. At least one of the compounds of formula I according to claim 1 or, where appropriate, its tautomer, in each case in free form or in an agrichemically usable salt form, as active ingredient, and comprising at least one auxiliary, a pesticidal composition.

17. A method for controlling pests, which comprises applying to the pests, to their habitat, or to plants susceptible to attack by the pests, the compound of formula I according to claim 1 or the composition according to claim 16 in a pesticidally effective amount.

18. A method for protecting plant propagation material from attack by pests, which comprises treating the propagation material or the location where the propagation material is planted with the composition according to claim 16.

19. A process for the preparation of a compound of formula (I) 【Chemical Formula 13】 (wherein Q, R 1 , R 2 , G 1 , G 2 , X 1 , R 3 , R 4 , R 8 , R 9 and A are as defined in formula (I) in claim 1, and S * is a stereogenic sulfur atom of the R- or S-configuration, where said S * center is in enantiomerically pure form or enantiomerically enriched form) comprising: (A) stereoselectively oxidizing a sulfanyl compound of formula (II) 【Chemical Formula 14】 (wherein Q, R 1 , R 2 , G 1 , G 2 , X 1 , R 3 , R 4 , R 8 , R 9 and A are as defined in formula (I)) in a suitable solvent (or diluent) in the presence of an oxidizing agent, in the presence of a metal catalyst, in the presence of a chiral ligand, and optionally in the presence of a suitable additive to produce a sulfinyl compound of formula (III) 【Chemical Formula 15】 (wherein Q, R 1 , R 2 , G 1 , G 2 , X 1 , R 3 , R 4 , R 8 , R 9 and A are as defined in formula (I), and S * is a stereogenic sulfur atom of R- or S-configuration, where said S * center is in enantiomerically pure form or enantiomerically enriched form) ; and (B) reacting a sulfinyl compound of formula (III) 【Chemical Formula 16】 (wherein Q, R 1 , R 2 , G 1 , G 2 , X 1 , R 3 , R 4 , R 8 , R 9 and A are as defined in formula (I), and S * is a stereogenic sulfur atom of R- or S-configuration, where said S * center is in enantiomerically pure form or enantiomerically enriched form) with an imination reagent in a suitable solvent (or diluent) in the presence of a catalyst and optionally in the presence of a suitable additive to stereospecifically produce the sulfoximine compound of formula (I) A preparation process.

20. A compound according to any one of claims 1, which can be prepared at any time by the process according to claim 19 or is available.

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