Pesticidal heterocyclic derivatives having sulfur-containing substituents

Abstract

Compounds having formula (I), wherein G1, G2, X, R1, R2, R3, and R4 are as defined in claim 1. Furthermore, the present invention relates to agricultural chemical compositions comprising compounds having formula (I), to the preparation of such compositions, and to the use of said compounds or compositions in agriculture or horticulture for combating, preventing, or controlling animal pests, including arthropods, particularly insects, mollusks, nematodes, or representatives of the orders Acari.

Description

[0001] This invention relates to heterocyclic derivatives containing sulfur substituents that have pest-killing activity (particularly insecticidal activity), methods for their preparation, compositions containing such compounds, and their use in controlling animal pests (including arthropods and particularly insects, or representatives of the order Acari).

[0002] Dihydropyrrolidone and phthalimide derivatives with sulfur-containing substituents and heterocyclic benzo[a]cyclization have been described in the literature, for example in J. Org. Chem. [Organic Chemistry Journal] 2003, 62, 8240 and Bull. ChemSoc. Chim. Belg. [Bulletin of the Belgian Chemical Society] 1997, 106, 151. However, none of these references describe any biocidal activity. Structurally different biocidal heterocyclic derivatives with sulfur-containing substituents have been described, for example, in WO 2012 / 012086848, WO 2013 / 018928, WO 2019 / 131575, WO 2018 / 130437, WO 2018 / 130443 and WO 2020 / 002082.

[0003] It has now been unexpectedly discovered that certain novel bioactive derivatives with sulfur-containing substituents possess advantageous properties as biocides.

[0004] Therefore, the present invention provides compounds having formula I,

[0005]

[0006] in

[0007] G1 and G2 are independently CH or N;

[0008] R2 is a C1-C6 haloalkyl, C1-C4 haloalkylthioalkyl, C1-C4 haloalkylsulfinyl, C1-C4 haloalkylsulfonyl, C1-C6 haloalkoxy or C1-C4 haloalkylsulfonyloxy.

[0009] X is S, SO, or SO2;

[0010] R1 is a C1-C4 alkyl or a C3-C6 cycloalkyl-C1-C4 alkyl;

[0011] R4 is a C1-C4 alkyl group;

[0012] R3 is hydrogen, halogen, C1-C4 alkyl, C1-C6 haloalkyl, C3-C6 cycloalkyl, C3-C6 cycloalkyl monosubstituted with cyano, C1-C6 cyanoalkyl, C1-C6 alkoxy, C1-C6 haloalkoxy, -CO(NR5R6), -NR5COR7, (C3-C8)cycloalkyl-(C1-C6)alkyl- or (C3-C8)cycloalkyl monosubstituted with cyano-(C1-C6)alkyl; or

[0013] R3 is a five- to six-membered saturated, partially saturated, or heteroaromatic ring system, connected by a ring carbon atom to an imidazole ring linked to substituent R4. The ring system is unsubstituted or mono- or poly-substituted by substituents selected from the group consisting of: halogen, cyano, C1-C4 alkyl, C1-C4 haloalkyl, C1-C4 alkoxy, C1-C4 haloalkoxy, C1-C4 alkylthioalkyl, C1-C4 alkylsulfinyl, C1-C4 alkylsulfonyl. The ring system may contain 1, 2 or 3 cyclic heteroatoms selected from the group consisting of nitrogen, oxygen and sulfur, wherein the ring system may not contain more than one epoxy atom and may not contain more than one cyclic sulfur atom; or

[0014] R3 is a five-membered heteroaromatic ring system with an imidazole ring linked to a nitrogen atom, wherein the imidazole ring is linked to a substituent R4, and the ring system is either unsubstituted or mono- or poly-substituted with substituents selected from the group consisting of: halogen, cyano, C1-C4 alkyl, C1-C4 haloalkyl, C1-C4 alkoxy, C1-C4 haloalkoxy, C1-C4 alkylthioalkyl, C1-C4 alkylsulfinyl, C1-C4 alkylsulfonyl, C3-C6 cycloalkyl. The ring system comprises cyano-monosubstituted C3-C6 cycloalkyl, C1-C6 cyanoalkyl, (C3-C8)cycloalkyl-(C1-C6)alkyl-, and cyano-(C1-C6)alkyl-monosubstituted (C3-C8)cycloalkyl; and the ring system contains 1, 2, or 3 cyclic heteroatoms selected from the group consisting of nitrogen, oxygen, and sulfur, wherein the ring system contains at least one cyclic nitrogen atom and may not contain more than one epoxide atom and may not contain more than one cyclic sulfur atom;

[0015] R5 and R6 are independently H, C1-C6 alkyl, C1-C6 haloalkyl, or C3-C6 cycloalkyl; and

[0016] R7 is a C1-C6 alkyl, C1-C6 haloalkyl, or C3-C6 cycloalkyl.

[0017] The present invention also provides agrochemically acceptable salts, stereoisomers, enantiomers, tautomers and N-oxides of compounds having Formula I.

[0018] Compounds of formula I having at least one basic center can form acid addition salts, for example, with: strong inorganic acids (such as mineral acids, such as perchloric acid, sulfuric acid, nitric acid, nitrous acid, phosphoric acid, or hydrohalic acid), strong organic carboxylic acids (such as unsubstituted or, for example, halogenated C1-C4 alkylcarboxylic acids, such as acetic acid, such as saturated or unsaturated dicarboxylic acids, such as oxalic acid, malonic acid, succinic acid, maleic acid, fumaric acid, or phthalic acid, such as hydroxycarboxylic acids, such as ascorbic acid, lactic acid, malic acid, tartaric acid, or citric acid, or such as benzoic acid), or organic sulfonic acids (such as unsubstituted or, for example, halogenated C1-C4 alkylsulfonic acids or arylsulfonic acids, such as methanesulfonic acid or p-toluenesulfonic acid). Compounds of Formula I having at least one acidic group can, for example, form salts with bases, such as mineral salts, like alkali metal or alkaline earth metal salts, such as sodium, potassium, or magnesium salts; or form salts with ammonia or organic amines (such as morpholine, piperidine, pyrrolidine, mono-, di-, or tri-alkylamines, such as ethylamine, diethylamine, triethylamine, or dimethylpropylamine, or mono-, di-, or tri-hydroxyalkylamines, such as monoethanolamine, diethanolamine, or triethanolamine).

[0019] In each case, the compound having formula (I) according to the invention is in a free form, in an oxidized form (such as an N-oxide) or in a salt form (e.g., in the form of an agronomically available salt).

[0020] N-oxides are the oxidized forms of tertiary amines or nitrogen-containing heteroaromatic compounds. For example, they are described by A. Albini and S. Pietra in their 1991 book, "Heterocyclic N-oxides," published by CRC Press in Boca Raton.

[0021] The compounds of formula I according to the invention also include hydrates that may form during salt formation.

[0022] When a substituent is indicated to be further substituted, this means that it contains one or more of the same or different substituents, for example, one to four substituents. Typically, no more than three such optional substituents are present simultaneously. Preferably, no more than two such substituents are present simultaneously (i.e., the group is substituted by one or both of the indicated substituents). When the additional substituent is a larger group such as a cycloalkyl or phenyl group, it is most preferred that only one such optional substituent is present. When a group is indicated to be substituted with, for example, an alkyl group, this includes those groups that are part of other groups, such as alkyl groups in alkylthio groups.

[0023] As used in this article, the term "C1-C" n "Alkyl" refers to a saturated straight-chain or branched hydrocarbon group having 1 to n carbon atoms attached via any one of the carbon atoms, such as any one of the following groups: methyl, ethyl, n-propyl, 1-methylbutyl, 2-methylbutyl, 3-methylbutyl, 2,2-dimethylpropyl, 1-ethylpropyl, n-hexyl, n-pentyl, 1,1-dimethylpropyl, 1,2-dimethylpropyl, 1-methylpentyl, 2-methylpentyl, 3-methylpentyl, 4-methylpentyl, 1,1-dimethylbutyl, 1,2-dimethylbutyl, 1,3-dimethylbutyl, 2,2-dimethylbutyl, 2,3-dimethylbutyl, 3,3-dimethylbutyl, 1-ethylbutyl, 2-ethylbutyl, 1,1,2-trimethylpropyl, 1,2,2-trimethylpropyl, 1-ethyl-1-methylpropyl, or 1-ethyl-2-methylpropyl.

[0024] As used in this article, the term "C1-C" n "Haloalkyl" refers to a straight-chain or branched saturated alkyl group (as mentioned above) having 1 to n carbon atoms attached via any one carbon atom, wherein some or all of the hydrogen atoms in these groups may be replaced by fluorine, chlorine, bromine and / or iodine, i.e., any one of the following: chloromethyl, dichloromethyl, trichloromethyl, fluoromethyl, difluoromethyl, trifluoromethyl, chlorofluoromethyl, dichlorofluoromethyl, chlorodifluoromethyl, 2-fluoroethyl, 2-chloroethyl, 2-bromoethyl, 2-iodoethyl, 2,2-difluoroethyl, 2,2,2-trifluoroethyl, 2-chloro-2-fluoroethyl, 2-chloro-2,2-difluoroethyl, 2,2-dichloro-2-fluoroethyl, 2,2,2-trichloroethyl, pentafluoroethyl, 2-fluoropropyl, 3-fluoropropyl, 2,2-difluoropropyl, 2,3-difluoropropyl The alkyl group includes 2-chloropropyl, 3-chloropropyl, 2,3-dichloropropyl, 2-bromopropyl, 3-bromopropyl, 3,3,3-trifluoropropyl, 3,3,3-trichloropropyl, 2,2,3,3,3-pentafluoropropyl, heptafluoropropyl, 1-(fluoromethyl)-2-fluoroethyl, 1-(chloromethyl)-2-chloroethyl, 1-(bromomethyl)-2-bromoethyl, 4-fluorobutyl, 4-chlorobutyl, 4-bromobutyl, or nonafluorobutyl. Accordingly, the term "C1-C2-fluoroalkyl" will refer to a C1-C2-alkyl group carrying 1, 2, 3, 4, or 5 fluorine atoms, such as any of the following: difluoromethyl, trifluoromethyl, 1-fluoroethyl, 2-fluoroethyl, 2,2-difluoroethyl, 2,2,2-trifluoroethyl, 1,1,2,2-tetrafluoroethyl, or pentafluoroethyl.

[0025] As used in this article, the term "C1-C" n"Alkoxy" refers to a straight-chain or branched saturated alkyl group (as mentioned above) with 1 to n carbon atoms attached via an oxygen atom, i.e., any one of the following: methoxy, ethoxy, n-propoxy, 1-methylethoxy, n-butoxy, 1-methylpropoxy, 2-methylpropoxy, or 1,1-dimethylethoxy.

[0026] As used in this article, the term "C1-C" n "Haloalkoxy" refers to the C1-C haloalkoxy group mentioned above. n An alkoxy group, partially or wholly replaced by fluorine, chlorine, bromine and / or iodine, i.e., any one of the following: chloromethoxy, dichloromethoxy, trichloromethoxy, fluoromethoxy, difluoromethoxy, trifluoromethoxy, chlorofluoromethoxy, dichlorofluoromethoxy, chlorodifluoromethoxy, 2-fluoroethoxy, 2-chloroethoxy, 2-bromoethoxy, 2-iodoethoxy, 2,2-difluoroethoxy, 2,2,2-trifluoroethoxy, 2-chloro-2-fluoroethoxy, 2-chloro-2,2-difluoroethoxy, 2,2-dichloro-2-fluoroethoxy, 2,2,2-trichloroethoxy Pentafluoroethoxy, 2-fluoropropoxy, 3-fluoropropoxy, 2,2-difluoropropoxy, 2,3-difluoropropoxy, 2-chloropropoxy, 3-chloropropoxy, 2,3-dichloropropoxy, 2-bromopropoxy, 3-bromopropoxy, 3,3,3-trifluoropropoxy, 3,3,3-trichloropropoxy, 2,2,3,3,3-pentafluoropropoxy, heptafluoropropoxy, 1-(fluoromethyl)-2-fluoroethoxy, 1-(chloromethyl)-2-chloroethoxy, 1-(bromomethyl)-2-bromoethoxy, 4-fluorobutoxy, 4-chlorobutoxy, or 4-bromobutoxy.

[0027] As used in this article, the term "C1-C" n "alkylthioalkyl" refers to a straight-chain or branched saturated alkyl group (as mentioned above) with 1 to n carbon atoms attached via a sulfur atom, such as any of the following: methylthio, ethylthio, n-propylthio, 1-methylethylthio, butylthio, 1-methylpropylthio, 2-methylpropylthio, or 1,1-dimethylethylthio.

[0028] As used in this article, the term "C1-C" n"alkyl sulfinyl" refers to a straight-chain or branched saturated alkyl group (as mentioned above) having 1 to n carbon atoms attached via a sulfur atom of the sulfinyl group, i.e., any one of the following: methyl sulfinyl, ethyl sulfinyl, n-propyl sulfinyl, 1-methyl ethyl sulfinyl, n-butyl sulfinyl, 1-methyl propyl sulfinyl, 2-methyl propyl sulfinyl, 1,1-dimethyl ethyl sulfinyl, n-pentyl sulfinyl, 1-methyl butyl sulfinyl, 2-methyl butyl sulfinyl, 3-methyl butyl sulfinyl, 1,1-dimethyl propyl sulfinyl, 1,2-dimethyl propyl sulfinyl, 2,2-dimethyl propyl sulfinyl, or 1-ethyl propyl sulfinyl.

[0029] As used in this article, the term "C1-C" n "alkylsulfonyl" refers to a straight-chain or branched saturated alkyl group (as mentioned above) having 1 to n carbon atoms attached via the sulfur atom of the sulfonyl group, i.e., any one of the following: methylsulfonyl, ethylsulfonyl, n-propylsulfonyl, isopropylsulfonyl, n-butylsulfonyl, 1-methylpropylsulfonyl, 2-methylpropylsulfonyl or tert-butylsulfonyl.

[0030] As used in this article, the term "C1-C" n "Halogenated alkyl thioalkyl" refers to C1-C n Alkylthioalkyl groups (as mentioned above), partially or wholly substituted with fluorine, chlorine, bromine and / or iodine, i.e., any one of the following: fluoromethylthio, difluoromethylthio, trifluoromethylthio, chlorodifluoromethylthio, bromodifluoromethylthio, 2-fluoroethylthio, 2-chloroethylthio, 2-bromoethylthio, 2-iodoethylthio, 2,2-difluoroethylthio, 2,2,2-trifluoroethylthio, 2,2,2-trichloroethylthio, 2-chloro-2-fluoroethylthio, 2-chloro-2,2-difluoroethylthio, 2,2-dichloro-2-fluoroethylthio, pentafluoroethylthio, 2-Fluoropropylthio, 3-Fluoropropylthio, 2-Chloropropylthio, 3-Chloropropylthio, 2-Bromopropylthio, 3-Bromopropylthio, 2,2-Difluoropropylthio, 2,3-Difluoropropylthio, 2,3-Dichloropropylthio, 3,3,3-Trifluoropropylthio, 3,3,3-Trichloropropylthio, 2,2,3,3,3-Pentafluoropropylthio, Heptafluoropropylthio, 1-(Fluoromethyl)-2-Fluoroethylthio, 1-(Chloromethyl)-2-Chloroethylthio, 1-(Bromomethyl)-2-Bromoethylthio, 4-Fluorobutylthio, 4-Chlorobutylthio, or 4-Bromobutylthio.

[0031] The term "C1-C" n "halogenated alkyl sulfinyl" and "C1-C" n "Halogenated alkyl sulfonyl" refers to the above groups, but in which sulfur is in oxidation state 1 or 2.

[0032] The term "C1-C" used in this article n "Halogenated alkyl sulfonyloxy group" refers to a C1-C group attached by an oxygen atom. n Halogenated alkyl sulfonyl groups (as mentioned above).

[0033] As used in this article, the term "C1-C" n "Cyanoalkyl" refers to a straight-chain or branched saturated alkyl group having 1 to n carbon atoms that is replaced by a cyano group (as mentioned above), such as cyanomethylene, cyanoethylene, 1,1-dimethylcyanomethyl, cyanomethyl, cyanoethyl, and 1-dimethylcyanomethyl.

[0034] The term "C3-C" used in this article n "Cycloalkyl" refers to a saturated or partially unsaturated monocyclic, bicyclic or tricyclic hydrocarbon having 3 to n carbon atoms, preferably 3 to 8 carbon atoms, such as cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, cycloheptyl, cyclooctyl, bicyclic [2.2.1]heptyl and bicyclic [2.2.2]octyl.

[0035] The term "C3-C" used in this article is replaced by "cyanomono" n "Cycloalkyl" refers to saturated or partially unsaturated monocyclic, bicyclic, or tricyclic hydrocarbons having 3 to n carbon atoms that are substituted with a cyano group (as mentioned above).

[0036] As used in this article, the term "C3-C" n The suffix "-C1-C" after "cycloalkyl" n "alkyl" refers to a compound formed by C3-C2. n Cycloalkyl-substituted straight-chain or branched saturated alkyl groups having 1 to n carbon atoms (as mentioned above). C3-C n cycloalkyl-C1-C n An example of an alkyl group is, for example, cyclopropylmethyl.

[0037] Halogens are typically fluorine, chlorine, bromine, or iodine. This also applies accordingly to halogens combined with other meanings, such as alkyl halogens.

[0038] In the context of this invention, the term "monosubstituted or polysubstituted" in the definition of R3 substituent typically means, depending on the chemical structure of the substituent, monosubstituted to pentasubstituted, more preferably monosubstituted, disubstituted or trisubstituted.

[0039] In the context of this invention, the phrases “R3 is a five- to six-membered saturated, partially saturated aromatic ring system or heteroaromatic ring system, wherein the ring system is connected to an imidazole ring via a ring carbon atom, and the imidazole ring is connected to a substituent R4…” and “R3 is a five-membered aromatic ring system connected to an imidazole ring via a ring nitrogen atom, and the imidazole ring is connected to a substituent R4…”, as the case may be, refer to the attachment manner of a specific embodiment of the substituent R3 in Formula I, as the case may be.

[0040] In the context of this invention, examples of "R3 is a five- to six-membered saturated or partially saturated aromatic ring system or heteroaromatic ring system, connected to an imidazole ring via a ring carbon atom, the imidazole ring being connected to a substituent R4, ...; and the ring system may contain one, two, or three cyclic heteroatoms..." are, but are not limited to, phenyl, pyrazolyl, imidazole, triazolyl, pyridinyl, isoxazolyl, dihydroisooxazolyl, oxazolyl, and pyrimidinyl.

[0041] In the context of this invention, examples of “R3 is a five-membered heteroaromatic ring system connected to an imidazole ring via a cyclic nitrogen atom, the imidazole ring being connected to a substituent R4…; and the ring system comprising one, two, or three cyclic heteroatoms…” are, but are not limited to, pyrazolyl, pyrroleyl, imidazoleyl, and triazoleyl.

[0042] The following provides certain embodiments according to the present invention.

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

[0044] Example 2 provides the compound according to Example 1 or its agrochemically acceptable salt, stereoisomer, enantiomer, tautomer, or N-oxide, wherein the preferred values ​​of G1, G2, X, R1, R2, R3, R4, R5, R6, and R7 in any combination thereof are listed below:

[0045] It is preferred that G1 and G2 are CH or N independently of each other.

[0046] It is also preferable that both G1 and G2 are N.

[0047] More preferably, G1 is N and G2 is CH, or G1 is CH and G2 is N;

[0048] The optimal choices for both G1 and G2 are CH.

[0049] Preferably, X is S or SO2.

[0050] Ideally, X is SO2.

[0051] Preferably, R1 is a C1-C4 alkyl or a cyclopropyl-C1-C4 alkyl.

[0052] More preferably, R1 is ethyl or cyclopropylmethyl.

[0053] Most preferably, R1 is an ethyl group.

[0054] Preferably, R2 is a C1-C6 haloalkyl, C1-C4 haloalkylsulfonyl, C1-C6 haloalkoxy, or C1-C4 haloalkylsulfonyloxy.

[0055] It is also preferred that R2 is a C1-C6 fluoroalkyl, C1-C4 fluoroalkylsulfonyl, C1-C6 fluoroalkoxy, or C1-C4 fluoroalkylsulfonyloxy.

[0056] More preferably, R2 is -CF3, -OCF3, -SO2CF3, or -CF2CF3.

[0057] Even more preferably, R2 is -OCF3, -CF2CF3, or -CF3.

[0058] Most preferably, R2 is -CF3 or -OCF3.

[0059] Preferably, R3 is hydrogen, halogen, C1-C4 alkyl, C1-C6 haloalkyl, C3-C6 cycloalkyl, C3-C6 cycloalkyl substituted with cyano, C1-C6 cyanoalkyl, C1-C6 alkoxy, C1-C6 haloalkoxy, -CO(NR5R6), -NR5COR7, (C3-C8)cycloalkyl-(C1-C6)alkyl- or (C3-C8)cycloalkyl substituted with cyano-(C1-C6)alkyl.

[0060] Preferably, R3 is a five- to six-membered partially saturated aromatic ring system or heteroaromatic ring system, connected by a ring carbon atom to an imidazole ring linked to substituent R4, wherein the ring system is unsubstituted or monosubstituted by substituents selected from the group consisting of: halogens, C1-C4 haloalkyl, C1-C4 alkoxy, C1-C4 haloalkoxy, C1-C4 alkylthioalkyl, C1-C4 alkylsulfinyl, C1-C4 alkylsulfonyl, C3-C6 cycloalkyl, C3-C6 cycloalkyl monosubstituted with cyano, C1-C6 cyanoalkyl, (C3-C8)cycloalkyl-(C1-C6)alkyl- and (C3-C8)cycloalkyl monosubstituted with cyano-(C1-C6)alkyl-; and the ring system may contain one or two cycloheteratomes selected from the group consisting of nitrogen and oxygen, wherein the ring system may not contain more than one epoxy atom.

[0061] More preferably, R3 is a five-membered heteroaromatic ring system connected to an imidazole ring via a cyclic nitrogen atom, wherein the imidazole ring is connected to a substituent R4, and the ring system is unsubstituted or monosubstituted by a substituent selected from the group consisting of: halogen, cyano, C1-C4 alkyl, C1-C4 haloalkyl, C1-C4 alkoxy, C1-C4 haloalkoxy, C1-C4 alkylthioalkyl, C1-C4 alkylsulfinyl, C1-C4 alkylsulfonyl, C3-C6 cycloalkyl, C3-C6 cycloalkyl monosubstituted with cyano, C1-C6 cyanoalkyl, (C3-C8)cycloalkyl-(C1-C6)alkyl- and (C3-C8)cycloalkyl monosubstituted with cyano-(C1-C6)alkyl-; and the ring system contains one or two cyclic nitrogen atoms.

[0062] More preferably, R3 is a C3-C6 cycloalkyl C1-C6 haloalkoxy group; -CO(NR5R6); or -NR5COR7.

[0063] More preferably, R3 is a phenyl group that can be monosubstituted by a C3-C6 cycloalkyl group, wherein the C3-C6 cycloalkyl group is monosubstituted by a cyano group; a C-linked pyrimidinyl group; a C-linked pyrazolyl group that can be monosubstituted by a C1-C4 haloalkyl group, a C3-C6 cycloalkyl group, a (C3-C8) cycloalkyl-(C1-C6)alkyl- or a cycloalkyl-(C1-C6)alkyl-; or a C-linked dihydroisoxazole group that can be monosubstituted by a C3-C6 cycloalkyl group.

[0064] More preferably, R3 is an N-linked pyrazolyl group that can be monosubstituted by a halogen, a C1-C4 haloalkyl group, or a C3-C6 cycloalkyl group.

[0065] More preferably, R3 is hydrogen, halogen, cyclopropyl, cyanocyclopropyl, trifluoroethoxy, -CONCH3(CH2CF3), or -N(CH3)COCH2CF3.

[0066] More preferably, R3 is selected from an N-linked pyrazolyl group that can be monosubstituted by chlorine, cyclopropyl or trifluoromethyl; a C-linked pyrimidinyl group; a C-linked pyrazolyl group that can be monosubstituted by cyclopropyl, -CHF2, -CH2CHF2, -CH2CF3, -(CH2)-cyclopropyl, -(CH2)-1-cyanocyclopropyl or trifluoromethyl; a C-linked dihydroisoxazole that can be monosubstituted by chlorine, trifluoromethyl or cyclopropyl; and a phenyl group that can be monosubstituted by: chlorine or fluorine, cyclopropyl, or cyclopropyl substituted by cyano.

[0067] Most preferably, R3 is selected from -OCH2CF3; -N(CH3)COCH2CF3; -CON(CH3)CH2CF3; 3-chloro-pyrazole-1-yl; 3-cyclopropyl-pyrazole-1-yl; 4-(1-cyanocyclopropyl)phenyl; 3-(1-cyanocyclopropyl)phenyl; pyrimidin-5-yl; pyrimidin-2-yl; 1-cyclopropylpyrazole-4-yl; cyclopropyl; 1-di Fluoromethylpyrazole-4-yl; 1-(2,2-difluoroethyl)pyrazole-4-yl; 1-(2,2,2-trifluoroethyl)pyrazole-4-yl, 3-cyclopropyl-4,5-dihydro-isoxazol-5-yl; 3-trifluoromethyl-pyrazole-1-yl; 4-trifluoromethyl-pyrazole-1-yl; 1-(cyclopropylmethyl)pyrazole-4-yl and 1-(1-cyanocyclopropylmethyl)pyrazole-4-yl.

[0068] Preferably, R4 is a C1-C4 alkyl group.

[0069] More preferably, R4 is methyl or ethyl; most preferably, R4 is methyl.

[0070] Preferably, R5 and R6 are independently H, C1-C6 alkyl, C1-C6 haloalkyl, or C3-C6 cycloalkyl.

[0071] More preferably, R5 and R6 are independently C1-C4 alkyl or C1-C4 haloalkyl.

[0072] Most preferably, R5 is a C1-C2 alkyl and R6 is a C1-C2 fluoroalkyl.

[0073] It is also preferred that R5 is methyl and R6 is -CF3 or -CH2CF3.

[0074] Preferably, R7 is a C1-C6 alkyl, C1-C6 haloalkyl, or C3-C6 cycloalkyl.

[0075] More preferably, R7 is a C1-C4 alkyl or a C1-C4 haloalkyl.

[0076] Most preferably, R7 is a C1-C2 fluoroalkyl group.

[0077] Preferably, R7 is -CF3 or -CH2CF3.

[0078] The following describes another embodiment of the invention.

[0079] A preferred group of compounds having formula I is represented by the following: compounds having formula I-A1

[0080]

[0081] R1, R2, R3, X, R4, R5, R6 and R7 are, as defined above under Formula I; or are agriculturally chemically acceptable salts, stereoisomers, enantiomers, tautomers or N-oxides of compounds having Formula I-A1.

[0082] In a preferred group of compounds having formula I-A1, R2 is a C1-C6 haloalkyl, C1-C4 haloalkylthioalkyl, C1-C4 haloalkylsulfinyl, C1-C4 haloalkylsulfonyl, C1-C6 haloalkoxy or C1-C4 haloalkylsulfonyloxy.

[0083] And X is S, SO or SO2; R1 is C1-C4 alkyl or C3-C6 cycloalkyl-C1-C4 alkyl;

[0084] R4 is a C1-C4 alkyl; R3 is hydrogen, halogen, C1-C4 alkyl, C1-C6 haloalkyl, C3-C6 cycloalkyl, C3-C6 cycloalkyl monosubstituted with cyano, C1-C6 cyanoalkyl, C1-C6 alkoxy, C1-C6 haloalkoxy, -CO(NR5R6), -NR5COR7, (C3-C8)cycloalkyl-(C1-C6)alkyl- or (C3-C8)cycloalkyl monosubstituted with cyano-(C1-C6)alkyl-; R5 and R6 are independently H, C1-C6 alkyl, C1-C6 haloalkyl or C3-C6 cycloalkyl; and

[0085] R7 is a C1-C6 alkyl, C1-C6 haloalkyl, or C3-C6 cycloalkyl.

[0086] In another preferred group of compounds having formula I-A1, R2 is a C1-C6 haloalkyl, C1-C4 haloalkylthioalkyl, C1-C4 haloalkylsulfinyl, C1-C4 haloalkylsulfonyl, C1-C6 haloalkoxy or C1-C4 haloalkylsulfonyloxy.

[0087] And in which; X is S, SO or SO2; R1 is C1-C4 alkyl, or C3-C6 cycloalkyl-C1-C4 alkyl;

[0088] R4 is a C1-C4 alkyl group; and R3 is a five- to six-membered saturated, partially saturated, or heteroaromatic ring system connected by a ring carbon atom to an imidazole ring linked to substituent R4, wherein the ring system is unsubstituted or mono- or poly-substituted by substituents selected from the group consisting of: halogen, cyano, C1-C4 alkyl, C1-C4 haloalkyl, C1-C4 alkoxy, C1-C4 haloalkoxy, C1-C4 alkylthioalkyl, C1-C4 alkylsulfinyl, C The ring system may contain 1-C4 alkylsulfonyl, C3-C6 cycloalkyl, C3-C6 cycloalkyl monosubstituted with cyano, C1-C6 cyanoalkyl, (C3-C8)cycloalkyl-(C1-C6)alkyl-, and (C3-C8)cycloalkyl monosubstituted with cyano-(C1-C6)alkyl-; and the ring system may contain 1, 2, or 3 cyclic heteroatoms selected from the group consisting of nitrogen, oxygen, and sulfur, wherein the ring system may not contain more than one epoxy atom and may not contain more than one cyclic sulfur atom.

[0089] In another, more preferred group of compounds having formula I-A1, R3 is a five-membered heteroaromatic ring system connected by a cyclic nitrogen atom to an imidazole ring, the imidazole ring being connected to a substituent R4, the ring system being unsubstituted or mono- or poly-substituted by substituents selected from the group consisting of: halogen, cyano, C1-C4 alkyl, C1-C4 haloalkyl, C1-C4 alkoxy, C1-C4 haloalkoxy, C1-C4 alkylthioalkyl, C1-C4 alkylsulfinyl, C1-C4 alkylsulfonyl, C3-C6 cycloalkyl, C3-C6 cycloalkyl monosubstituted with cyano, and C1-C6 cyanoalkyl; and the ring system contains one, two, or three cyclic heteroatoms selected from the group consisting of: nitrogen, oxygen, and sulfur, wherein the ring system contains at least one cyclic nitrogen atom and may not contain more than one cyclic oxygen atom and may not contain more than one cyclic sulfur atom.

[0090] In all preferred embodiments of the compounds having formula I-A1 mentioned above, unless otherwise stated, R1, R2, R3, X, R4, R5, R6, and R7 are as defined above under formula I; preferably, R1 is ethyl or cyclopropylmethyl; most preferably, R1 is ethyl; preferably, R2 is -OSO2CF3, SO2CF3, -OCF3, CF2CF3, or CF3; more preferably, R2 is -OCF3, -CF2CF3, or -CF3; most preferably, R2 is -CF3 or -OCF3; preferably, X is S or SO2; most preferably, X is SO2; preferably, R4 is methyl or ethyl; Most preferably, R4 is methyl; preferably, R3 is selected from hydrogen; halogen; cyclopropyl; cyanocyclopropyl; trifluoroethoxy; -CONCH3(CH2CF3); -N(CH3)COCH2CF3; N-linked pyrazolyl group that may be monosubstituted by chlorine, cyclopropyl or trifluoromethyl; C-linked pyrimidinyl group; C-linked pyrazolyl group that may be monosubstituted by cyclopropyl, -CHF2, -CH2CHF2, -CH2CF3, -(CH2)-cyclopropyl, -(CH2)-1-cyanocyclopropyl or trifluoromethyl; C-linked dihydroisoxazole that may be monosubstituted by chlorine, trifluoromethyl or cyclopropyl; and phenyl group that may be monosubstituted by: chlorine or fluorine, cyclopropyl, cyclopropyl substituted by cyano.

[0091] Another preferred group of compounds having formula I is represented by the following: compounds having formula I-B1

[0092]

[0093] R1, R2, R3, X, R4, R5, R6 and R7 are, as defined above under Formula I; or are agriculturally chemically acceptable salts, stereoisomers, enantiomers, tautomers or N-oxides of compounds having Formula I-B1.

[0094] In a preferred group of compounds having formula I-B1, R2 is a C1-C6 haloalkyl, C1-C4 haloalkylthioalkyl, C1-C4 haloalkylsulfinyl, C1-C4 haloalkylsulfonyl, C1-C6 haloalkoxy or C1-C4 haloalkylsulfonyloxy.

[0095] And X is S, SO or SO2; R1 is C1-C4 alkyl or C3-C6 cycloalkyl-C1-C4 alkyl;

[0096] R4 is a C1-C4 alkyl; R3 is hydrogen, halogen, C1-C4 alkyl, C1-C6 haloalkyl, C3-C6 cycloalkyl, C3-C6 cycloalkyl monosubstituted with cyano, C1-C6 cyanoalkyl, C1-C6 alkoxy, C1-C6 haloalkoxy, -CO(NR5R6), -NR5COR7, (C3-C8)cycloalkyl-(C1-C6)alkyl- or (C3-C8)cycloalkyl monosubstituted with cyano-(C1-C6)alkyl-; R5 and R6 are independently H, C1-C6 alkyl, C1-C6 haloalkyl, C3-C6 cycloalkyl; and

[0097] R7 is a C1-C6 alkyl, C1-C6 haloalkyl, or C3-C6 cycloalkyl.

[0098] In another preferred group of compounds having formula I-B1, R2 is a C1-C6 haloalkyl, C1-C4 haloalkylthioalkyl, C1-C4 haloalkylsulfinyl, C1-C4 haloalkylsulfonyl, C1-C6 haloalkoxy or C1-C4 haloalkylsulfonyloxy.

[0099] And in which; X is S, SO or SO2; R1 is C1-C4 alkyl, or C3-C6 cycloalkyl-C1-C4 alkyl;

[0100] R4 is a C1-C4 alkyl group; and R3 is a five- to six-membered saturated, partially saturated, or heteroaromatic ring system connected by a ring carbon atom to an imidazole ring linked to substituent R4, wherein the ring system is unsubstituted or mono- or poly-substituted by substituents selected from the group consisting of: halogen, cyano, C1-C4 alkyl, C1-C4 haloalkyl, C1-C4 alkoxy, C1-C4 haloalkoxy, C1-C4 alkylthioalkyl, C1-C4 alkylsulfinyl, C The ring system may contain 1-C4 alkylsulfonyl, C3-C6 cycloalkyl, C3-C6 cycloalkyl monosubstituted with cyano, C1-C6 cyanoalkyl, (C3-C8)cycloalkyl-(C1-C6)alkyl- or (C3-C8)cycloalkyl monosubstituted with cyano-(C1-C6)alkyl-; and the ring system may contain 1, 2 or 3 cyclic heteroatoms selected from the group consisting of nitrogen, oxygen and sulfur, wherein the ring system may not contain more than one epoxy atom and may not contain more than one cyclic sulfur atom.

[0101] In another preferred group of compounds having formula I-B1, R3 is a five-membered heteroaromatic ring system connected to an imidazole ring via a cyclic nitrogen atom, the imidazole ring being connected to a substituent R4, the ring system being unsubstituted or mono- or poly-substituted by substituents selected from the group consisting of: halogen, cyano, C1-C4 alkyl, C1-C4 haloalkyl, C1-C4 alkoxy, C1-C4 haloalkoxy, C1-C4 alkylthioalkyl, C1-C4 alkylsulfinyl, C1-C4 alkylsulfonyl The ring system comprises a cycloalkyl group, a C3-C6 cycloalkyl group, a C3-C6 cycloalkyl group monosubstituted with a cyano group, a C1-C6 cyanoalkyl group, a (C3-C8) cycloalkyl-(C1-C6) alkyl-, and a (C3-C8) cycloalkyl group monosubstituted with a cyano-(C1-C6) alkyl-; and the ring system contains 1, 2, or 3 cyclic heteroatoms selected from the group consisting of nitrogen, oxygen, and sulfur, wherein the ring system contains at least one cyclic nitrogen atom and may not contain more than one cyclic oxygen atom and may not contain more than one cyclic sulfur atom.

[0102] In all preferred embodiments of the compounds having formula I-B1 mentioned above, unless otherwise stated, R1, R2, R3, X, R4, R5, R6, and R7 are as defined above under formula I; preferably, R1 is ethyl or cyclopropylmethyl; most preferably, R1 is ethyl; preferably, R2 is -OSO2CF3, SO2CF3, -OCF3, CF2CF3, or CF3; more preferably, R2 is -OCF3, -CF2CF3, or -CF3; most preferably, R2 is -CF3 or -OCF3; preferably, X is S or SO2; most preferably, X is SO2; preferably, R4 is methyl or ethyl; Most preferably, R4 is methyl; preferably, R3 is selected from hydrogen; halogen; cyclopropyl; cyanocyclopropyl; trifluoroethoxy; -CONCH3(CH2CF3); -N(CH3)COCH2CF3; N-linked pyrazolyl group that may be monosubstituted by chlorine, cyclopropyl or trifluoromethyl; C-linked pyrimidinyl group; C-linked pyrazolyl group that may be monosubstituted by cyclopropyl, -CHF2, -CH2CHF2, -CH2CF3, -(CH2)-cyclopropyl, -(CH2)-1-cyanocyclopropyl or trifluoromethyl; C-linked dihydroisoxazole that may be monosubstituted by chlorine, trifluoromethyl or cyclopropyl; and phenyl group that may be monosubstituted by: chlorine or fluorine, cyclopropyl, cyclopropyl substituted by cyano.

[0103] Another preferred group of compounds having formula I is represented by the following: compounds having formula I-C1

[0104]

[0105] R1, R2, R3, X, R4, R5, R6 and R7 are, as defined above under Formula I; or are agriculturally chemically acceptable salts, stereoisomers, enantiomers, tautomers or N-oxides of compounds having Formula I-C1.

[0106] In a preferred group of compounds having formula I-C1, R2 is C1-C6 haloalkyl, C1-C4 haloalkylthioalkyl, C1-C4 haloalkylsulfinyl, C1-C4 haloalkylsulfonyl, C1-C6 haloalkoxy or C1-C4 haloalkylsulfonyloxy.

[0107] And X is S, SO or SO2; R1 is C1-C4 alkyl, or C3-C6 cycloalkyl-C1-C4 alkyl;

[0108] R4 is a C1-C4 alkyl; R3 is hydrogen, halogen, C1-C4 alkyl, C1-C6 haloalkyl, C3-C6 cycloalkyl, C3-C6 cycloalkyl monosubstituted with cyano, C1-C6 cyanoalkyl, C1-C6 alkoxy, C1-C6 haloalkoxy, -CO(NR5R6), -NR5COR7, (C3-C8)cycloalkyl-(C1-C6)alkyl- or (C3-C8)cycloalkyl monosubstituted with cyano-(C1-C6)alkyl-; R5 and R6 are independently H, C1-C6 alkyl, C1-C6 haloalkyl, C3-C6 cycloalkyl; and R7 is C1-C6 alkyl, C1-C6 haloalkyl, C3-C6 cycloalkyl.

[0109] In another preferred group of compounds having formula I-C1, R2 is a C1-C6 haloalkyl, C1-C4 haloalkylthioalkyl, C1-C4 haloalkylsulfinyl, C1-C4 haloalkylsulfonyl, C1-C6 haloalkoxy or C1-C4 haloalkylsulfonyloxy.

[0110] And in which; X is S, SO or SO2; R1 is C1-C4 alkyl or C3-C6 cycloalkyl-C1-C4 alkyl;

[0111] R4 is a C1-C4 alkyl group; R3 is a five- to six-membered saturated, partially saturated, or heteroaromatic ring system connected by a ring carbon atom to an imidazole ring linked to substituent R4, wherein the ring system is unsubstituted or mono- or poly-substituted by substituents selected from the group consisting of: halogen, cyano, C1-C4 alkyl, C1-C4 haloalkyl, C1-C4 alkoxy, C1-C4 haloalkoxy, C1-C4 alkylthioalkyl, C1-C4 alkylsulfinyl, C1 -C4 alkylsulfonyl, C3-C6 cycloalkyl, C3-C6 cycloalkyl monosubstituted with cyano, C1-C6 cyanoalkyl, (C3-C8)cycloalkyl-(C1-C6)alkyl- and (C3-C8)cycloalkyl monosubstituted with cyano-(C1-C6)alkyl-; and the ring system may contain 1, 2 or 3 cyclic heteroatoms selected from the group consisting of nitrogen, oxygen and sulfur, wherein the ring system may not contain more than one epoxy atom and may not contain more than one cyclic sulfur atom;

[0112] In another preferred group of compounds having formula I-C1, R3 is a five-membered aromatic ring system connected to an imidazole ring via a cyclic nitrogen atom, the imidazole ring being connected to a substituent R4, the ring system being unsubstituted or mono- or poly-substituted by substituents selected from the group consisting of: halogen, cyano, C1-C4 alkyl, C1-C4 haloalkyl, C1-C4 alkoxy, C1-C4 haloalkoxy, C1-C4 alkylthioalkyl, C1-C4 alkylsulfinyl, C1-C4 alkylsulfonyl. The ring system comprises C3-C6 cycloalkyl, C3-C6 cycloalkyl monosubstituted with cyano, C1-C6 cyanoalkyl, (C3-C8)cycloalkyl-(C1-C6)alkyl- or (C3-C8)cycloalkyl monosubstituted with cyano-(C1-C6)alkyl-; and the ring system contains 1, 2 or 3 cyclic heteroatoms selected from the group consisting of nitrogen, oxygen and sulfur, wherein the ring system contains at least one cyclic nitrogen atom and may not contain more than one cyclic oxygen atom and may not contain more than one cyclic sulfur atom.

[0113] In all preferred embodiments of the compounds having formula I-C1 mentioned above, unless otherwise stated, R1, R2, R3, X, R4, R5, R6, and R7 are as defined above under formula I; preferably, R1 is ethyl or cyclopropylmethyl; most preferably, R1 is ethyl; preferably, R2 is -OSO2CF3, SO2CF3, -OCF3, CF2CF3, or CF3; more preferably, R2 is -OCF3, -CF2CF3, or -CF3; most preferably, R2 is -CF3 or -OCF3; preferably, X is S or SO2; most preferably, X is SO2; preferably, R4 is methyl or ethyl; Most preferably, R4 is methyl; preferably, R3 is selected from hydrogen; halogen; cyclopropyl; cyanocyclopropyl; trifluoroethoxy; -CONCH3(CH2CF3); -N(CH3)COCH2CF3; N-linked pyrazolyl group that may be monosubstituted by chlorine, cyclopropyl or trifluoromethyl; C-linked pyrimidinyl group; C-linked pyrazolyl group that may be monosubstituted by cyclopropyl, -CHF2, -CH2CHF2, -CH2CF3, -(CH2)-cyclopropyl, -(CH2)-1-cyanocyclopropyl or trifluoromethyl; C-linked dihydroisoxazole that may be monosubstituted by chlorine, trifluoromethyl or cyclopropyl; and phenyl group that may be monosubstituted by: chlorine or fluorine, cyclopropyl, cyclopropyl substituted by cyano.

[0114] Another preferred group of compounds having formula I is represented by the following: compounds having formula I-D1

[0115]

[0116] R1, R2, R3, X, R4, R5, R6 and R7 are as defined above under Formula I; or are agrochemically acceptable salts, stereoisomers, enantiomers, tautomers or N-oxides of compounds having Formula I-D1.

[0117] In a preferred group of compounds having formula I-D1, R2 is a C1-C6 haloalkyl, C1-C4 haloalkylthioalkyl, C1-C4 haloalkylsulfinyl, C1-C4 haloalkylsulfonyl, C1-C6 haloalkoxy or C1-C4 haloalkylsulfonyloxy.

[0118] And X is S, SO or SO2; R1 is C1-C4 alkyl or C3-C6 cycloalkyl-C1-C4 alkyl;

[0119] R4 is a C1-C4 alkyl group and R3 is hydrogen, halogen, C1-C4 alkyl, C1-C6 haloalkyl, C3-C6 cycloalkyl, C3-C6 cycloalkyl monosubstituted with cyano, C1-C6 cyanoalkyl, C1-C6 alkoxy, C1-C6 haloalkoxy, -CO(NR5R6), -NR5COR7, (C3-C8)cycloalkyl-(C1-C6)alkyl- or (C3-C8)cycloalkyl monosubstituted with cyano-(C1-C6)alkyl-; R5 and R6 are independently H, C1-C6 alkyl, C1-C6 haloalkyl, C3-C6 cycloalkyl; and

[0120] R7 is a C1-C6 alkyl, C1-C6 haloalkyl, or C3-C6 cycloalkyl.

[0121] In another preferred group of compounds having formula I-D1, R2 is a C1-C6 haloalkyl, C1-C4 haloalkylthioalkyl, C1-C4 haloalkylsulfinyl, C1-C4 haloalkylsulfonyl, C1-C6 haloalkoxy or C1-C4 haloalkylsulfonyloxy.

[0122] And in which; X is S, SO or SO2; R1 is C1-C4 alkyl or C3-C6 cycloalkyl-C1-C4 alkyl;

[0123] R4 is a C1-C4 alkyl group and R3 is a five- to six-membered saturated, partially saturated, or heteroaromatic ring system, connected by a ring carbon atom to an imidazole ring linked to substituent R4. The ring system is unsubstituted or mono- or poly-substituted by substituents selected from the group consisting of: halogen, cyano, C1-C4 alkyl, C1-C4 haloalkyl, C1-C4 alkoxy, C1-C4 haloalkoxy, C1-C4 alkylthioalkyl, C1-C4 alkylsulfinyl, C1 -C4 alkylsulfonyl, C3-C6 cycloalkyl, C3-C6 cycloalkyl monosubstituted with cyano, C1-C6 cyanoalkyl, (C3-C8)cycloalkyl-(C1-C6)alkyl- and (C3-C8)cycloalkyl monosubstituted with cyano-(C1-C6)alkyl-; and the ring system may contain 1, 2 or 3 cyclic heteroatoms selected from the group consisting of nitrogen, oxygen and sulfur, wherein the ring system may not contain more than one epoxy atom and may not contain more than one cyclic sulfur atom.

[0124] In another preferred group of compounds having formula I-D1, R3 is a five-membered aromatic ring system connected to an imidazole ring via a cyclic nitrogen atom, the imidazole ring being connected to a substituent R4, the ring system being unsubstituted or mono- or poly-substituted by substituents selected from the group consisting of: halogen, cyano, C1-C4 alkyl, C1-C4 haloalkyl, C1-C4 alkoxy, C1-C4 haloalkoxy, C1-C4 alkylthioalkyl, C1-C4 alkylsulfinyl, C1-C4 alkylsulfonyl. The ring system comprises C3-C6 cycloalkyl, C3-C6 cycloalkyl monosubstituted with cyano, C1-C6 cyanoalkyl, (C3-C8)cycloalkyl-(C1-C6)alkyl-, and (C3-C8)cycloalkyl monosubstituted with cyano-(C1-C6)alkyl-; and the ring system contains 1, 2, or 3 cyclic heteroatoms selected from the group consisting of nitrogen, oxygen, and sulfur, wherein the ring system contains at least one cyclic nitrogen atom and may not contain more than one cyclic oxygen atom and may not contain more than one cyclic sulfur atom.

[0125] In all preferred embodiments of the compounds having formula I-D1 mentioned above, unless otherwise stated, R1, R2, R3, X, R4, R5, R6, and R7 are as defined above under formula I; preferably, R1 is ethyl or cyclopropylmethyl; most preferably, R1 is ethyl; preferably, R2 is -OSO2CF3, SO2CF3, -OCF3, CF2CF3, or CF3; more preferably, R2 is -OCF3, -CF2CF3, or -CF3; most preferably, R2 is -CF3 or -OCF3; preferably, X is S or SO2; most preferably, X is SO2; preferably, R4 is methyl or ethyl; Most preferably, R4 is methyl; preferably, R3 is selected from hydrogen; halogen; cyclopropyl; cyanocyclopropyl; trifluoroethoxy; -CONCH3(CH2CF3); -N(CH3)COCH2CF3; N-linked pyrazolyl group that may be monosubstituted by chlorine, cyclopropyl or trifluoromethyl; C-linked pyrimidinyl group; C-linked pyrazolyl group that may be monosubstituted by cyclopropyl, -CHF2, -CH2CHF2, -CH2CF3, -(CH2)-cyclopropyl, -(CH2)-1-cyanocyclopropyl or trifluoromethyl; C-linked dihydroisoxazole that may be monosubstituted by chlorine, trifluoromethyl or cyclopropyl; and phenyl group that may be monosubstituted by: chlorine or fluorine, cyclopropyl, cyclopropyl substituted by cyano.

[0126] A distinguished group of compounds according to the invention are those having the formula IE.

[0127]

[0128] in

[0129] G1 and G2 are independently CH or N;

[0130] R1 is a C1-C4 alkyl or cyclopropyl-C1-C4 alkyl; preferably, R1 is ethyl or cyclopropylmethyl; more preferably, R1 is ethyl;

[0131] R2 is a C1-C6 haloalkyl, C1-C4 haloalkylthioalkyl, C1-C4 haloalkylsulfinyl, C1-C4 haloalkylsulfonyl, or C1-C6 haloalkoxy. Preferably, R2 is CF3, CF2CF3, SCF3, SOCF3, SO2CF3, or OCF3. More preferably, R2 is -OCF3, -CF2CF3, or -CF3. Most preferably, R2 is -CF3 or -OCF3.

[0132] And among them

[0133] X is S, SO or SO2, preferably X is S or SO2, and even more preferably X is SO2;

[0134] R4 is a C1-C6 alkyl group; preferably, R4 is methyl or ethyl.

[0135] R3 is hydrogen, halogen, C1-C4 alkyl, C1-C6 haloalkyl, C3-C6 cycloalkyl, C3-C6 cycloalkyl monosubstituted with cyano, C1-C6 cyanoalkyl, C1-C6 alkoxy, C1-C6 haloalkoxy, -CO(NR5R6), -NR5COR7, (C3-C8)cycloalkyl-(C1-C6)alkyl- or (C3-C8)cycloalkyl monosubstituted with cyano-(C1-C6)alkyl-; or

[0136] R3 is a five- to six-membered saturated, partially saturated, or heteroaromatic ring system, connected by a ring carbon atom to an imidazole ring linked to substituent R4. The ring system is unsubstituted or mono- or poly-substituted by substituents selected from the group consisting of: halogen, cyano, C1-C4 alkyl, C1-C4 haloalkyl, C1-C4 alkoxy, C1-C4 haloalkoxy, C1-C4 alkylthioalkyl, C1-C4 alkylsulfinyl, C1-C4 alkylsulfonyl. The ring system may contain 1, 2 or 3 cyclic heteroatoms selected from the group consisting of nitrogen, oxygen and sulfur, wherein the ring system may not contain more than one epoxy atom and may not contain more than one cyclic sulfur atom; or

[0137] R3 is a five-membered aromatic ring system with a nitrogen atom attached to an imidazole ring. The imidazole ring is connected to a substituent R4. The ring system is either unsubstituted or mono- or poly-substituted with substituents selected from the group consisting of: halogen, cyano, C1-C4 alkyl, C1-C4 haloalkyl, C1-C4 alkoxy, C1-C4 haloalkoxy, C1-C4 alkylthioalkyl, C1-C4 alkylsulfinyl, C1-C4 alkylsulfonyl, C3-C6 cycloalkyl, etc. Cyano-monosubstituted C3-C6 cycloalkyl, C1-C6 cyanoalkyl, (C3-C8)cycloalkyl-(C1-C6)alkyl-, and (C3-C8)cycloalkyl monosubstituted with cyano-(C1-C6)alkyl-; and the ring system contains 1, 2, or 3 cyclic heteroatoms selected from the group consisting of nitrogen, oxygen, and sulfur, wherein the ring system contains at least one cyclic nitrogen atom and may not contain more than one epoxide atom and may not contain more than one cyclic sulfur atom;

[0138] R5 and R6 are independently H, C1-C6 alkyl, C1-C6 haloalkyl, or C3-C6 cycloalkyl; preferably, R5 and R6 are independently C1-C4 alkyl or C1-C4 haloalkyl; more preferably, R5 is C1-C2 alkyl and R6 is C1-C2 fluoroalkyl; and

[0139] R7 is a C1-C6 alkyl, C1-C6 haloalkyl, or C3-C6 cycloalkyl; preferably, R7 is a C1-C4 alkyl or C1-C4 haloalkyl; more preferably, R7 is a C1-C2 fluoroalkyl; or an agriculturally chemically acceptable salt, stereoisomer, enantiomer, tautomer, or N-oxide of a compound having formula IE.

[0140] A preferred set of compounds according to this embodiment is a compound having formula (IE-1), which is a compound having formula (IE), or any preferred embodiment of a compound having formula (IE), wherein preferably R3 is selected from the group consisting of: hydrogen; halogen; cyclopropyl; cyanocyclopropyl; trifluoroethoxy; -CONCH3(CH2CF3); -N(CH3)COCH2CF3; an N-linked pyrazolyl group that may be monosubstituted by chlorine, cyclopropyl or trifluoromethyl; a C-linked pyrimidinyl group; a C-linked pyrazolyl group that may be monosubstituted by cyclopropyl, -CHF2, -CH2CHF2, -CH2CF3, -(CH2)-cyclopropyl, -(CH2)-1-cyanocyclopropyl or trifluoromethyl; a C-linked dihydroisoxazole that may be monosubstituted by chlorine, trifluoromethyl or cyclopropyl; and a phenyl group that may be monosubstituted by: chlorine or fluorine, cyclopropyl, or cyano-substituted cyclopropyl.

[0141] Another preferred group of compounds according to this embodiment is a compound having formula (IE-2), which is a compound having formula (IE), or any preferred embodiment of a compound having formula (IE), wherein preferably R3 is selected from the group consisting of: halogen; cyclopropyl; 1-cyanocyclopropyl; trifluoroethoxy; -CONCH3(CH2CF3); -N(CH3)COCH2CF3; N-linked pyrazolyl group that may be monosubstituted by chlorine, cyclopropyl or trifluoromethyl; C-linked pyrimidinyl group; C-linked pyrazolyl group that may be monosubstituted by cyclopropyl, -CHF2, -CH2CHF2, -CH2CF3, -(CH2)-cyclopropyl, -(CH2)-1-cyanocyclopropyl or trifluoromethyl; C-linked dihydroisoxazole that may be monosubstituted by chlorine, trifluoromethyl or cyclopropyl; and phenyl that may be monosubstituted by: chlorine or fluorine, cyclopropyl, cyclopropyl substituted by cyano.

[0142] Another preferred group of compounds according to this embodiment is a compound having formula (IE-3), which is a compound having formula (IE), or any preferred embodiment of a compound having formula (IE), wherein R3 is selected from the group consisting of: -OCH2CF3; -N(CH3)COCH2CF3; -CON(CH3)CH2CF3; 3-chloro-pyrazole-1-yl; 3-cyclopropyl-pyrazole-1-yl; 4-(1-cyanocyclopropyl)phenyl; 3-(1-cyanocyclopropyl)phenyl; pyrimidin-5-yl; 1-cyclopropylpyrazole-4-yl; cyclopropyl; 1-difluoromethylpyrazole-4-yl; 1-(2,2-difluoroethyl)pyrazole-4-yl; 3-cyclopropyl-4,5-dihydro-isoxazole-5-yl; 3-trifluoromethyl-pyrazole-1-yl; and 1-(1-cyanocyclopropylmethyl)pyrazole-4-yl.

[0143] Another set of preferred compounds according to this embodiment is a compound having formula (IE-4), which is a compound having formula (IE), or any preferred embodiment of a compound having formula (IE), wherein preferably G1 and G2 is N.

[0144] A preferred set of compounds according to this embodiment is a compound having formula (IE-5), which is a compound having formula (IE), or any preferred embodiment of a compound having formula (IE), wherein preferably G1 is N and G2 is CH.

[0145] A preferred set of compounds according to this embodiment is a compound having formula (IE-6), which is a compound having formula (IE), or any preferred embodiment of a compound having formula (IE), wherein preferably G1 is CH and G2 is N.

[0146] Another set of preferred compounds according to this embodiment is a compound having formula (IE-7), which is a compound having formula (IE), or any preferred embodiment of a compound having formula (IE), wherein preferably G1 and G2 are both CH.

[0147] Another outstanding group of compounds according to the invention are those having the formula IF.

[0148]

[0149] in

[0150] G1 is N and G2 is CH; or both G1 and G2 are CH.

[0151] R2 is a C1-C6 haloalkyl or C1-C6 haloalkoxy; preferably, R2 is CF3, CF2CF3 or OCF3; even more preferably, R2 is CF3 or OCF3.

[0152] R4 is a C1-C6 alkyl group; preferably, R4 is methyl or ethyl; even more preferably, R4 is methyl; and

[0153] R3 is selected from the group consisting of: cyclopropyl; C1-C6 haloalkoxy, preferably trifluoroethoxy; phenyl that may be monosubstituted by cyanocyclopropyl; C-linked pyrimidinyl; N-linked pyrazolyl that may be monosubstituted by chlorine, cyclopropyl or trifluoromethyl; C-linked pyrazolyl that is N-substituted by cyclopropyl, -CHF2, -CH2CHF2, -CH2CF3, -(CH2)-cyclopropyl or -(CH2)-cyanocyclopropyl; and C-linked dihydroisoxazole that may be monosubstituted by cyclopropyl.

[0154] A preferred set of compounds according to this embodiment are compounds having formula (IF-1), which is a compound having formula (IF), or any preferred embodiment of a compound having formula (IF), wherein

[0155] R3 is selected from the group consisting of: cyclopropyl; -OCH2CF3; 4-(1-cyanocyclopropyl)phenyl; 3-(1-cyanocyclopropyl)phenyl; pyrimidin-5-yl; pyrimidin-2-yl; 3-chloro-pyrazole-1-yl; 4-chloro-pyrazole-1-yl; 3-cyclopropyl-pyrazole-1-yl; 4-cyclopropyl-pyrazole-1-yl; 3-trifluoromethyl-pyrazole-1-yl; 4-trifluoromethyl-pyrazole-1-yl; Fluoromethyl-pyrazole-1-yl; 1-cyclopropylpyrazole-4-yl; 1-difluoromethylpyrazole-4-yl; 1-(2,2-difluoroethyl)pyrazole-4-yl; 1-(2,2,2-trifluoroethyl)pyrazole-4-yl; 1-cyclopropylmethylpyrazole-4-yl; 1-(1-cyanocyclopropylmethyl)pyrazole-4-yl; and 3-cyclopropyl-4,5-dihydro-isoxazole-5-yl.

[0156] Another preferred set of compounds according to this embodiment is a compound having formula (IF-2), which is a compound having formula (IF), or any preferred embodiment of a compound having formula (IF), wherein

[0157] R3 is selected from the group consisting of: cyclopropyl; -OCH2CF3; 4-(1-cyanocyclopropyl)phenyl; pyrimidin-5-yl; pyrimidin-2-yl; 3-chloro-pyrazole-1-yl; 3-cyclopropyl-pyrazole-1-yl; 4-trifluoromethyl-pyrazole-1-yl; 1-cyclopropylpyrazole-4-yl; 1-difluoromethylpyrazole-4-yl; 1-(2,2-difluoroethyl)pyrazole-4-yl; 1-(2,2,2-trifluoroethyl)pyrazole-4-yl; 1-cyclopropylmethylpyrazole-4-yl; 1-(1-cyanocyclopropylmethyl)pyrazole-4-yl; and 3-cyclopropyl-4,5-dihydro-isoxazole-5-yl.

[0158] A preferred set of compounds according to this embodiment is a compound having formula (IF-3), which is a compound having formula (IF), or any preferred embodiment of a compound having formula (IF), wherein preferably G1 is N and G2 is CH.

[0159] Another set of preferred compounds according to this embodiment is a compound having formula (IF-4), which is a compound having formula (IF), or any preferred embodiment of a compound having formula (IF), wherein preferably G1 and G2 are both CH.

[0160] Compounds according to the invention can have any number of benefits, particularly including favorable levels of bioactivity for protecting plants against insects or superior properties for use as active ingredients in agrochemicals (e.g., higher bioactivity, favorable activity spectrum, increased safety, improved physicochemical properties, or increased biodegradability or environmental characterization). In particular, it has been unexpectedly found that certain compounds having formula (I) can exhibit favorable safety relative to non-target arthropods, especially pollinators (such as honeybees, solitary bees, and bumblebees). Most particularly, relative to the Italian bee (Apis mellifera).

[0161] In another aspect, the present invention provides a composition comprising an effective amount of an insecticidal, acaricidal, nematicidal, or molluscicidal compound as defined in any of the embodiments of compounds having formula (I), (I-B1), (I-C1), (I-D1), (IE), and (IF), or an agriculturally chemically acceptable salt, stereoisomer, enantiomer, tautomer, or N-oxide thereof, and optionally, an adjuvant or diluent.

[0162] In another aspect, the present invention provides a method for combating and controlling insects, mites, nematodes, or mollusks, the method comprising applying to the pest, the pest's site, or plants susceptible to the pest an effective amount of an insecticidal, acaricidal, nematodeicidal, or molluskic compound as defined in any of the examples (above) of the compounds having formulas (I-A1), (I-B1), (I-C1), (I-D1), (IE), and (IF), or an agrochemically acceptable salt, stereoisomer, enantiomer, tautomer, or N-oxide thereof, or a composition as defined above.

[0163] In another aspect, the present invention provides a method for protecting plant propagation material from attacks by insects, mites, nematodes or mollusks, the method comprising treating the propagation material or the site in which the propagation material is grown with a composition as defined above.

[0164] The method for preparing compounds having formula I according to the present invention is carried out by methods known to those skilled in the art. Compounds having formulas I-a3 (where X is SO2, and G1, G2, R1, R2, R3, R4, R5, R6, and R7 are as defined above under formula I) can be prepared by oxidizing compounds having formulas I-a2 (where X is SO, and G1, G2, R1, R2, R3, R4, R5, R6, and R7 are as defined above under formula I). ​​This reaction can be carried out using reagents such as peracids (e.g., peracetic acid or chloroperbenzoic acid), hydroperoxides (e.g., hydrogen peroxide or tert-butyl hydroperoxide), or inorganic oxidants (e.g., monoperoxydisulfate or potassium permanganate). Similarly, compounds having formula I-a2 (where X is SO, and G1, G2, R1, R2, R3, R4, R5, R6, and R7 are as defined above under formula I) can be prepared under similar conditions as described above by oxidizing compounds having formula I-a1 (where X is S, and G1, G2, R1, R2, R3, R4, R5, R6, and R7 are as defined above under formula I). ​​These reactions can be carried out in a variety of organic or aqueous solvents compatible with these conditions, at temperatures ranging from below 0°C to the boiling point of the solvent system. The conversion of compounds having formula I-a1 into compounds having formulas I-a2 and I-a3 is shown in Scheme 1.

[0165] Option 1:

[0166]

[0167] Compounds having formula I, wherein X, G1, G2, R1, R2, R3, R4, R5, R6 and R7 are as defined above under formula I,

[0168] Option 2:

[0169]

[0170] It can be prepared by reacting a compound having formula VII (where R2, G1, and G2 are as defined above in formula I) with a compound having formula VIII (where R1, X, R3, R4, R5, R6, and R7 are as defined above in formula I and where LG3 is a halogen (or pseudohalogen leaving group, such as trifluoromethanesulfonate)) in the presence of a base (such as sodium carbonate, potassium carbonate, or cesium carbonate, or sodium hydride), in a suitable solvent (such as tetrahydrofuran, dioxane, N,N-dimethylformamide, N,N-dimethylacetamide, or acetonitrile), at a temperature between 0°C and 150°C, optionally under microwave irradiation) (Scheme 2).

[0171] Alternatively, compounds having formula I (wherein G1, G2, R1, X, R2, R3, R4, R5, R6, and R7 as defined above in formula I) can be produced by reacting a base (such as sodium carbonate, potassium carbonate, or cesium carbonate, or potassium tert-butoxide) in the presence of a metal catalyst, or a copper catalyst (e.g., copper iodide (I)), optionally with a ligand (e.g., a diamine ligand (e.g., N,N′-dimethylethylenediamine or trans-cyclohexyldiamine) or In the presence of dibenzylacetone (dba) or 1,10-phenanthroline, at a temperature between 30°C and 180°C, optionally under microwave irradiation, or in the presence of a palladium catalyst (e.g., palladium(II) acetate, bis(dibenzylacetone)palladium(0) (Pd(dba)2) or tris(dibenzylacetone)dipalladium(0) (Pd2(dba)3, optionally in the form of a chloroform adduct) or a palladium precatalyst (e.g., palladium(II) methanesulfonate like tert-BuBrettPhos Pd G3[(2-di-tert-butylphosphino-3,6-dimethoxy-2′,4′,6′-triisopropyl-1,1′-biphenyl)-2-(2′-amino-1,1′-biphenyl)]palladium(II) methanesulfonate or BrettPhosPd G3[(2-di-cyclohexylphosphino-3,6-dimethoxy-2′,4′,6′-triisopropyl-1,1′-biphenyl)-2-(2′-amino-1,1′-biphenyl)]palladium methanesulfonate (II)], and optionally in the presence of a ligand (e.g. SPhos, t-BuBrettPhos or Xantphos), at a temperature between 60°C and 120°C, optionally under microwave irradiation, a compound having formula VII (wherein R2, G1 and G2 are as follows) The above reaction is prepared by reacting a compound having formula VIII (where R1, X, R3, R4, R5, R6, and R7 are as defined in formula I above, and where LG3 is a halogen (or a pseudohalogen leaving group, such as trifluoromethanesulfonate), preferably bromine or iodine) with a compound having formula VIII. The above reactions can be carried out in the presence of solvents such as toluene, dimethylformamide (DMF), N-methylpyrrolidine (NMP), dimethyl sulfoxide (DMSO), dioxane, or tetrahydrofuran (THF) and are described in references such as WO 2012031004, WO2009042907, and Synthetic Communications, 41:67–72, 2011.

[0172] Alternatively, a compound having formula I (wherein G1, G2, R1, X, R2, R3, R4, R5, R6, and R7 as defined above under formula I) can be prepared by reacting a compound having formula VI (wherein R2, G1, and G2 as defined above under formula I, and LG2 is a leaving group (e.g., Br, Cl, or I, preferably bromine) and R is a C1-C6 alkyl, benzyl, or phenyl) with a compound having formula IX (wherein R1, X, R3, R4, R5, R6, and R7 as defined above under formula I) in the presence of a base (e.g., sodium carbonate, potassium carbonate, or cesium carbonate, or sodium hydride, N,N-diisopropylethylamine, or KOtBu) and a solvent (e.g., ethanol, methanol, dioxane, toluene, acetonitrile, DMF, DMA, DMSO, THF) at a temperature between 0°C and 150°C, optionally under microwave irradiation) with a compound having formula IX (wherein R1, X, R3, R4, R5, R6, and R7 as defined above under formula I). Such reactions proceed via nucleophilic substitution and subsequent cyclization and have been reported in the literature, for example, as described in WO 2009042907.

[0173] Alternatively, a compound having formula I (wherein X, R2, G1, G2, R1, R3, R4, R5, R6 and R7 as defined above in formula I) can be prepared, for example, by cyclizing a compound having formula X (wherein X, R2, G1, G2, R1, R3, R4, R5, R6 and R7 as defined in formula I) at a temperature between 0°C and 180°C, preferably between 20°C and 120°C, in the presence of a base (such as triethylamine, pyridine or humin' base), or optionally in the presence of a solvent or diluent (such as toluene or xylene) (Scheme 2).

[0174] Compounds having formula I, wherein X, R2, G1, G2, R1, R3, R4, R5, R6, and R7 are as described above under formula I,

[0175] Option 3:

[0176]

[0177] Alternatively, it can be prepared by the following (Scheme 3): in the presence of a base (such as triethylamine, N,N-diisopropyl-ethylamine or pyridine), optionally in the presence of a catalyst (such as 4-dimethylaminopyridine DMAP), in an inert solvent (such as dichloromethane, tetrahydrofuran, dioxane, N,N-dimethylformamide, N,N-dimethylacetamide, acetonitrile, ethyl acetate or toluene), at a temperature between 0°C and 50°C, by cyclizing a compound having the formula Xa (wherein X, R2, G1, G2, R1, R3, R4, R5, R6 and R7 are as defined above in Formula I and where X0 is a halogen, preferably chlorine, or X0 is X 01 or X 02 Certain bases (such as pyridine and triethylamine) can be successfully used as both bases and solvents.

[0178] Compounds having formula Xa (where X, R2, G1, G2, R1, R3, R4, R5, R6 and R7 are as defined above in formula I, and where X0 is a halogen, preferably chlorine, or X0 is X 01 or X 02 This can be prepared by activating a compound having formula X (wherein R2, G1, G2, X, R1, R3, R4, R5, R6 and R7 are as defined above in Formula I) by methods known to those skilled in the art and described, for example, in Tetrahedron, 2005, 61(46), 10827-10852. Preferably, the activated substance Xa is formed (wherein R2, G1, G2, X, R1, R3, R4, R5, R6 and R7 are as defined above in Formula I, and where X0 is a halogen, preferably chlorine). For example, in an inert solvent (e.g., dichloromethane CH2Cl2 or tetrahydrofuran THF), at a temperature between 20°C and 100°C (preferably 25°C), in the presence of a catalytic amount of N,N-dimethylformamide DMF, compound Xa (where X0 is a halogen, preferably chlorine) is formed by treating X with, for example, oxalyl chloride (COCl)2 or thionyl chloride SOCl2. Alternatively, in an inert solvent (e.g., pyridine or tetrahydrofuran THF), optionally in the presence of a base (e.g., triethylamine), at a temperature between 50°C and 180°C, a compound having formula X is treated with, for example, 1-ethyl-3-(3-dimethylaminopropyl)carbodiimide EDC or dicyclohexylcarbodiimide DCC to generate the activated substance Xa (where X0 is X...). 01 or X 02 ).

[0179] A compound having formula VII (wherein R2, G1, and G2 are as defined above in formula I) can be prepared by reacting a compound having formula VI (wherein R2, G1, and G2 are as defined above in formula I and LG2 is a leaving group (e.g., Br, Cl, or I, preferably bromine) and R is a C1-C6 alkyl, benzyl, or phenyl) with ammonia or an ammonia substitute (e.g., NH4OH) in the presence of a solvent (e.g., ethanol, methanol, dioxane, toluene, DMF, DMA, DMSO, THF) at a temperature between 0°C and 150°C, optionally under microwave irradiation) with ammonia or an ammonia substitute (e.g., NH4OH).

[0180] A compound having formula X (wherein X, R2, G1, G2, R1, R3, R4, R5, R6 and R7 are as defined above under formula I) can be prepared by the following: a nucleophilic substitution reaction of a compound having formula VI (wherein R2, G1 and G2 are as defined above under formula I, LG2 is a leaving group such as Br, Cl or I, preferably bromine and R is a C1-C6 alkyl, benzyl or phenyl group) with an amino compound having formula IX (wherein R1, X, R3, R4, R5, R6 and R7 are as defined above under formula I), followed by in-situ hydrolysis of the resulting intermediate ester having formula XVII (wherein R2, G1, G2, X, R1, R3, R4, R5, R6 and R7 are as defined above under formula I, where R is a C1-C6 alkyl, benzyl or phenyl group).

[0181]

[0182] Unhydrolyzed ester compounds of formula XVII, generated in situ, can be separated and converted via saponification in the presence of a suitable base (e.g., sodium hydroxide NaOH, lithium hydroxide LiOH, or barium hydroxide Ba(OH)2) and a solvent (e.g., ethanol, methanol, dioxane, tetrahydrofuran, or water (or mixtures thereof)) to form carboxylic acids of formula X. Alternatively, clapico-type conditions (e.g., heating substrate XVII in the presence of sodium chloride or lithium chloride in N-methylpyrrolidone or aqueous dimethyl sulfoxide DMSO, optionally under microwave irradiation) can be used to convert compounds of formula XVII to compounds of formula X. Direct conversion of compounds of formula VI to compounds of formula X can be carried out in the presence of a base (especially sodium hydride, KOtBu, butyllithium, diisopropylaminolithium) and a solvent (e.g., dioxane, DMF, DMA, DMSO, THF) at temperatures between -30°C and 150°C.

[0183] The above reaction for preparing a compound having formula X can also be carried out by reacting a compound having formula VI with a compound having formula IXa (where R1, X, R3, R4, R5, R6 and R7 are as defined above in formula I, and PG is an amino protecting group, such as tert-butoxycarbonyl (BOC)) under similar conditions as described above (for preparing a compound having formula X by reacting a compound having formula VI with a compound having formula IX), and then deprotecting the amino protecting group PG.

[0184]

[0185] Deprotection of the amino protecting group is well known to those skilled in the art, for example, by removing the BOC protecting group in the presence of an acid (such as hydrochloric acid or trifluoroacetic acid), optionally in the presence of an inert solvent (such as dichloromethane, tetrahydrofuran, dioxane, or trifluorotoluene), at a temperature between 0°C and 70°C. This method of forming compounds of formulas X (and I) from compounds having formulas VI and IXa is detailed in Scheme 2a and reflects the specific case where the group PG of IXa is a tert-butoxycarbonyl (BOC), defining compounds of formula XIX, wherein R1, X, R3, R4, R5, R6, and R7 are as defined above in formula I.

[0186] Option 2a (The previously mentioned definition of substituents remains valid):

[0187]

[0188] Compounds having formula VI and compounds having formula XIX react in the presence of a base (such as sodium carbonate, potassium carbonate or cesium carbonate, or sodium hydride, or N,N-diisopropylethylamine or potassium tert-butoxide KOtBu) and in the presence of a solvent (such as ethanol, methanol, dioxane, toluene, acetonitrile, DMF, N,N-dimethylacetamide DMA, DMSO, or THF) at a temperature between 0°C and 150°C, optionally under microwave irradiation, to form compounds having formula XVIIa.

[0189] At temperatures between 0°C and 70°C, optionally in the presence of an inert solvent (such as dichloromethane, tetrahydrofuran, dioxane, or trifluorotoluene), the removal of the tert-butoxycarbonyl (BOC) group from a compound having formula XVIIa via acid (such as hydrochloric acid or trifluoroacetic acid) yields a compound having formula XVII. In the presence of a solvent (such as ethanol, methanol, dioxane, tetrahydrofuran, or water (or mixtures thereof)), a compound having formula XVII is saponified in the presence of a suitable base (e.g., sodium hydroxide NaOH, lithium hydroxide LiOH, or barium hydroxide Ba(OH)₂) to form a carboxylic acid having formula X (alternatively, Krapcho-type conditions as described above can be used). For example, the cyclization of a compound having formula X to a compound having formula I can be achieved in the presence of phosphoryl chloride (other amide coupling agents, such as thionyl chloride SOCl2, HATU, or EDCI, may also be used), optionally in the presence of a base (such as triethylamine, pyridine, or humrind), optionally in the presence of a solvent or diluent (such as toluene or xylene), at a temperature between 0°C and 180°C, preferably between 20°C and 120°C. Alternatively, the direct cyclization of a compound having formula XVII to a compound having formula I can be achieved under the conditions mentioned in Scheme 7 below.

[0190] Compounds having formula VI (where R2, G1, and G2 are as defined above in formula I, and LG2 is a halogen leaving group (e.g., bromine Br, chlorine Cl, or iodine I (preferably bromine)), and R is C1-C6 alkyl, benzyl, or phenyl) are known (see the preparation description disclosed in WO 20 / 174094) or can be prepared by methods known to those skilled in the art.

[0191] For example, a compound having formula VI (wherein R2, G1, and G2 are as defined above in formula I, and LG2 is a leaving group (e.g., Br, Cl, or I, preferably bromine), and R is a C1-C6 alkyl, benzyl, or phenyl) can be prepared by benzyl halogenation initiated by a radical of a compound having formula V (wherein R2, G1, and G2 are as defined above in formula I, and R is a C1-C6 alkyl, benzyl, or phenyl). This reaction is well known to those skilled in the art and can be carried out in the presence of electrophilic halogenating agents (e.g., Br2, NBS, Cl2, NIS, etc.) and radical initiators (e.g., AIBN (azobisisobutyronitrile), benzoyl peroxide), or under photochemical conditions and at temperatures ranging from 20°C to the boiling point of the reaction mixture, and in the presence of a solvent (e.g., toluene, xylene, acetonitrile, hexane, dichloroethane, or carbon tetrachloride). Such reactions are known by the name Wohl–Ziegler bromination and have been reported in the literature, for example in Synthesis, 2015, 47, 1280–1290 and J. Am. Chem. Soc., 1963, 85(3), pp. 354–355.

[0192] Compounds having formula V (wherein R2, G1, and G2 are as defined above in formula I, and R is a C1-C6 alkyl, benzyl, or phenyl) can be prepared by a Suzuki reaction (Scheme 2), which involves, for example, reacting a compound having formula IV (wherein R2, G1, and G2 are as defined above in formula I, and LG1 is a halogen Br, Cl, or I (preferably Cl), and R is a C1-C6 alkyl, benzyl, or phenyl) with trimethylcycloboroxane or potassium methyltrifluoroborate and other methylboronic acid equivalents. The reaction can be catalyzed by a palladium-based catalyst (e.g., tetrakis(triphenylphosphine)palladium(0), (1,1'-bis(diphenylphosphine)ferrocene)dichloro-palladium-dichloromethane (1:1 complex) or chloro(2-dicyclohexylphosphino-2',4',6'-triisopropyl-1,1'-biphenyl)[2-(2'-amino-1,1'-biphenyl)]palladium(II) (XPhos cyclic palladium complex)) in the presence of a base (such as sodium carbonate, tripotassium phosphate, or cesium fluoride), in a solvent or solvent mixture (such as, for example, a mixture of dioxane, acetonitrile, N,N-dimethylformamide, 1,2-dimethoxyethane, and water, or a dioxane / water mixture, or a toluene / water mixture), preferably under an inert atmosphere. The reaction temperature can preferably be in the range from room temperature to the boiling point of the reaction mixture, or the reaction can be carried out under microwave irradiation. Such Suzuki reactions are well known to those skilled in the art and have been reviewed, for example, in J. Organomet. Chem. 576, 1999, 147-168.

[0193] Compounds having formula IV (wherein R2, G1, and G2 are as defined above in formula I, and LG1 is a halogen Br, Cl, I (preferably Cl) and R is a C1-C6 alkyl, benzyl, or phenyl) can be prepared by reacting a compound having formula III (wherein R2, G1, and G2 are as defined above in formula I, and LG1 is a halogen Br, Cl, I (preferably Cl)) with ROH (wherein R is a C1-C6 alkyl, benzyl, or phenyl) in the presence of an acid catalyst (e.g., sulfuric acid or a Lewis acid (e.g., Sc(OTf)3 or FeCl3)). Such reactions are well known to those skilled in the art and are known by the name Fischer esterification and have been reported in the literature, for example... As reported in J. Org. Chem., 2006, 71, 3332-3334; Chem. Commun., 1997, 351-352; and Synthesis, 2008, 3407-3410. This esterification reaction can also be carried out by reacting a compound having formula III with TMSCHN2 to form a compound having formula IV (where R2, G1, and G2 are as defined above in formula I, LG1 is a halogen Br, Cl, or I (preferably Cl), and R is a methyl group), and reported in Angew. Chem. Int. Ed., 2007, 46, 7075.

[0194] Compounds having Formula III (where R2, G1, and G2 are as defined above in Formula I, and LG1 is a halogen Br, Cl, or I (preferably Cl)) can be prepared by metallization of compounds having Formula II (where R2, G1, and G2 are as defined above in Formula I, and LG1 is a halogen Br, Cl, or I (preferably Cl)) with a suitable base, followed by reaction with carbon dioxide. This metallization reaction can be carried out using a base (especially organolithium compounds such as tetramethylpiperidine lithium, diisopropylaminolithium, or sec-BuLi) at temperatures ranging from -78°C to 40°C in the presence of a solvent (such as THF, DMPU, dioxane, or 2-Me-THF). Such reactions have been reported in the literature, for example in Tetrahedron 2004, 60(51), 11869-11874.

[0195] Alternatively, a compound having formula IV (where R2, G1, and G2 are as defined above in formula I, and LG1 is a halogen, such as Br, Cl, or I (preferably Cl), and R is a C1-C6 alkyl, benzyl, or phenyl)

[0196] Option 2b:

[0197]

[0198] The reaction can be carried out (Scheme 2b) in the presence of a hydrohalic acid H-LG1 and a copper salt Cu-LG1 (wherein LG1 is a halogen, such as Br, Cl, or I (preferably Cl)) under Sandmeyer-type reaction conditions by reacting a compound having formula IV-a (wherein R2, G1, and G2 are as defined above in formula I and R is C1-C6 alkyl, benzyl, or phenyl) with a nitrite ester (such as tert-butyl nitrite t-BuONO, isoamyl nitrite, or sodium nitrite). This conversion is preferably carried out in an inert solvent (such as acetonitrile, or a halogenated solvent such as 1,2-dichloroethane, or water) at a temperature between 0°C and 150°C, preferably in the range from room temperature to the boiling point of the reaction mixture.

[0199] Compounds having formula IV-a (wherein R2, G1, and G2 are as defined above in formula I and R is C1-C6 alkyl, benzyl, or phenyl) can be prepared from compounds having formula IV-b (wherein R2, G1, and G2 are as defined above in formula I and LG4 is a halogen, preferably Br, Cl, or I) by methods found, for example, in WO 2016 / 020286, which involve a carbonylation reaction in which a compound having formula (IV-b) is reacted with carbon monoxide (CO, typically under pressure) in the presence of a metal catalyst such as a palladium catalyst (e.g., palladium(II) acetate), in an alcohol ROH solvent (optionally in the presence of a co-solvent) (wherein R is C1-C6 alkyl, benzyl, or phenyl), and optionally in the presence of a phosphine ligand, and optionally in the presence of a base, at a temperature between 0°C and 180°C.

[0200] Compounds having formula IV-b (wherein R2, G1, and G2 are as defined above in formula I and LG4 is a halogen, preferably Br, Cl, or I) can be prepared by a halogenation reaction involving, for example, reacting a compound having formula IV-c (wherein R2, G1, and G2 are as defined above in formula I) with a halogenating agent (such as N-chlorosuccinimide (NCS), N-bromosuccinimide (NBS), or N-iodosuccinimide (NIS)), or alternatively, chlorine, bromine, or iodine. Such halogenation reactions are carried out in an inert solvent (such as chloroform, carbon tetrachloride, 1,2-dichloroethane, acetic acid, ether, acetonitrile, or N,N-dimethylformamide) at a temperature between 20°C and 200°C, preferably between room temperature and 100°C.

[0201] Alternatively, according to Scheme 4, a compound having Formula I (wherein X, R2, G1, G2, R1, R3, R4, R5, R6 and R7 as described above under Formula I) can be prepared by amidation of a compound having Formula X (wherein X, R2, G1, G2, R1, R3, R4, R5, R6 and R7 as described above under Formula I).

[0202] Option 4:

[0203]

[0204] The details of the reaction (amidation reaction) for converting a compound having formula X into a compound having formula I are described in Scheme 5, and follow the methods and conditions already described in Schemes 2 and 3 above.

[0205] Option 5:

[0206]

[0207] Compounds having formula X can be prepared by reacting a compound having formula XII (wherein G1, G2, and R2 are as defined above in formula I) with a compound having formula IX (wherein R1, X, R3, R4, R5, R6, and R7 are as defined above in formula I) under reducing amination conditions (Scheme 5). The reaction can be carried out in the presence of a reducing agent (especially, for example, sodium cyanoborohydride or sodium triacetoxyborohydride), and optionally in the presence of an acid (especially, formic acid, trifluoroacetic acid, or acetic acid), and at a temperature ranging from 0 °C to the boiling point of the reaction mixture. The reaction can be carried out in the presence of an inert solvent (such as ethanol, methanol, dioxane, or tetrahydrofuran). Such reactions involving a two-step conversion from a compound having formula XII to a compound having formula I have been described in the literature, for example in Bioorganic & Medicinal Chemistry Letters 26(2016) 5947–5950.

[0208] A compound having formula XII (wherein G1, G2 and R2 are as defined above in formula I) can be prepared by hydrolysis and subsequent cyclization reaction from a compound having formula XI (wherein G1, G2 and R2 are as defined above in formula I, and LG2 is chlorine, bromine or iodine (preferably bromine), and R is C1-C6 alkyl, benzyl or phenyl). The reaction can be carried out under alkaline conditions using a metal hydroxide, such as an aqueous solution of sodium hydroxide, in the presence of a solvent (such as dioxane, tetrahydrofuran, or water) and at a temperature ranging from 20°C to 150°C, as reported in Synlett [Synthetic Express] 1992, (6), 531-533, or under acidic aqueous conditions using acetic acid, hydrochloric acid, or sulfuric acid, in the presence of a solvent (such as water, dioxane, or a halogenated solvent (such as dichloroethane)), as reported in Tetrahedron [Tetrahedron] 62 (2006) 9589–9602.

[0209] A compound having formula XI (wherein G1, G2 and R2 are as defined above in formula I, and LG2 is chlorine, bromine or iodine (preferably bromine), and R is C1-C6 alkyl, benzyl or phenyl) can be prepared from a compound having formula V (wherein G1, G2 and R2 are as defined above in formula I, and R is C1-C6 alkyl, benzyl or phenyl) by methods and conditions similar to those described in Scheme 2 for converting a compound having formula V into a compound having formula VI.

[0210] Alternatively, compounds having formula I can be prepared, wherein X, R2, G1, G2, R1, R3, R4, R5, R6 and R7 are as described above in formula I.

[0211] Option 6:

[0212]

[0213] From compounds having formula XV (where X, R2, G1, G2, R1, R3, R4, R5, R6, and R7 are as defined above under formula I) via selective reduction of the carbonyl functional group (Scheme 6). This reaction can be carried out in the presence of a reducing agent (e.g., NaBH4, LiAlH4, palladium on carbon) in the presence of hydrogen, or in the presence of a combination of two reducing agents (e.g., NaBH4 followed by triethylsilane). Such reactions have been described, for example, in US 20100160303 A1.

[0214] Compounds having formula XV (where X, R2, G1, G2, R1, R3, R4, R5, R6 and R7 as described above under formula I) can be prepared from compounds having formula XIV (where X, R2, G1, G2, R1, R3, R4, R5, R6 and R7 as described above under formula I, and R is C1-C6 alkyl, benzyl or phenyl) by hydrolysis and subsequent cyclization, as described in Scheme 2 for converting compounds having formula X into compounds having formula I.

[0215] A compound having formula XIV (where X, R2, G1, G2, R1, R3, R4, R5, R6 and R7 are as described above under formula I, and R is C1-C6 alkyl, benzyl or phenyl) can be prepared by reacting a compound having formula XIII (where R2, G1, G2 are as described above under formula I, and R is C1-C6 alkyl, benzyl or phenyl) with a compound having formula IX (where R1, X, R3, R4, R5, R6 and R7 are as defined above under formula I) under the amidation reaction conditions described in Scheme 3.

[0216] A compound having formula XIII (wherein R2, G1, and G2 are as described above in formula I, and R is a C1-C6 alkyl, benzyl, or phenyl) can be prepared by benzyl oxidation of a compound having formula V (wherein R2, G1, and G2 are as described above in formula I, and R is a C1-C6 alkyl, benzyl, or phenyl). The reaction can be carried out in the presence of oxygen in the presence of an oxidizing agent (such as KMNO4, nBu4MnO4, K2S2O8), or under photochemical conditions in the presence of oxygen, and at a temperature ranging from 20°C to the boiling point of the reaction mixture. The reaction is carried out in the presence of an inert solvent (such as acetonitrile, ethyl acetate, DMSO, or dichloroethane). Such reactions are known in the literature, for example in Synthesis 2017, 49, 4007-4016, Synthesis 2006, 1757-1759 and IOSR Journal of Applied Chemistry 2014, 7, 16-27.

[0217] Alternatively, a compound having formula I, wherein X, R2, G1, G2, R1, R3, R4, R5, R6 and R7 as defined above in formula I, can be prepared by cyclization of a compound having formula XVII (where X, R2, G1, G2, R1, R3, R4, R5, R6 and R7 as defined above in formula I, and R is C1-C6 alkyl, benzyl or phenyl) (Scheme 7).

[0218] Option 7:

[0219]

[0220] Such reactions can be carried out in the presence of a base (especially potassium tert-butoxide, lithium diisopropylamine, or sodium hydride), at a temperature ranging from -20°C to the boiling point of the reaction mixture, and in the presence of an inert solvent (such as tetrahydrofuran, dioxane, or DMF). Such reactions have been reported, for example, in Synlett [Synthetic Letters] 2006(4):591-594.

[0221] A compound having formula XVII (wherein X, R2, G1, G2, R1, R3, R4, R5, R6 and R7 are as defined above in formula I and R is C1-C6 alkyl, benzyl or phenyl) can be prepared by reacting a compound having formula XVI (wherein R2, G1 and G2 are as defined above in formula I and R is C1-C6 alkyl, benzyl or phenyl) with a compound having formula IX (wherein R1, X, R3, R4, R5, R6 and R7 are as defined above in formula I) under photoextension conditions. Such reactions are well known to those skilled in the art and can be carried out in the presence of phosphine reagents (such as triphenylphosphine, tributylphosphine, or polymer-supported triphenylphosphine), and in the presence of azodicarbonate reagents (such as diethyl azodicarbonate or diisopropyl azodicarbonate), at temperatures ranging from 0°C to 100°C, and in the presence of inert solvents (such as acetonitrile, dichloromethane, tetrahydrofuran, or toluene). Such reactions have been reported, for example, in Synthesis, 1981(1), 1-28.

[0222] Compounds having formula XVI (wherein R2, G1, and G2 are as defined above in formula I, and R is C1-C6 alkyl, benzyl, or phenyl) can be prepared by reacting compounds having formula XIII (wherein R2, G1, and G2 are as defined above in formula I, and R is C1-C6 alkyl, benzyl, or phenyl) with a reducing agent, such as metal hydrides like lithium aluminum hydride, DIBAL-H, or boranes (especially diborane or borane tetrahydrofuran complexes), in the presence of an inert solvent (such as tetrahydrofuran or dioxane). Such reactions have been reported, for example, in Tetrahedron Letters 1982, 23, 2475-2478.

[0223] Compounds having formula XVII-a

[0224]

[0225] in

[0226] X, R2, G1, G2, R1, R3, R4, R5, R6, and R7 are as defined above in Equation I, and Ra The substituents (hydrogen, C1-C6 alkyl, benzyl, or phenyl) are novel and have been particularly developed for the preparation of compounds having formula I according to the invention, and thus represent another object of the invention. Preferred options and preferred embodiments of the substituents in compounds having formula I are also effective for compounds having formula XVII-a. Preferably, Ra is hydrogen or C1-C6 alkyl; even more preferably, Ra is hydrogen, methyl, or ethyl; most preferably, Ra is hydrogen.

[0227] Compounds having formula IX (where R1, X, R3, R4, R5, R6 and R7 are as defined above in formula I) can be prepared by deprotection reaction (removal of BOC groups) of compounds having formula XIX (where R1, X, R3, R4, R5, R6 and R7 are as defined above in formula I) (Scheme 8).

[0228] Option 8:

[0229]

[0230] The reaction can be carried out in the presence of an acid (especially trifluoroacetic acid, hydrochloric acid, or sulfuric acid) under the conditions described above.

[0231] Compounds having formula XIX (wherein R1, X, R3, R4, R5, R6, and R7 are as defined above in formula I) can be prepared by reacting compounds having formula XVIII (wherein R1, X, R3, R4, R5, R6, and R7 are as defined above in formula I) with an organoazide in the presence of a suitable base and tert-butanol t-BuOH, and optionally in the presence of a Lewis acid, and in the presence of an inert solvent, at a temperature between 50°C and the boiling point of the reaction mixture. The reaction can be carried out in the presence of a coupling agent (such as T3P), or by activating the carboxylic acid with SOCl2 or oxaloyl chloride, or other coupling agents as described in Scheme 3 for converting compounds having formula X to compounds having formula Xa. Examples of organoazides include TMSN3, sodium azide, or toluenesulfonyl azide, and suitable solvents can be toluene, xylene, THF, or acetonitrile. Examples of suitable Lewis acids may include, in particular, Zn(OTf)2, Sc(OTf)2 or Cu(OTf)2.

[0232] Compounds having formula XIX can also be prepared by reacting compounds having formula XVIII with diphenylphosphohydrazides in the presence of an organic base (especially triethylamine or diisopropylethylamine), in the presence of tert-butanol t-BuOH and an inert solvent (e.g., a halogenated solvent (such as dichloromethane or dichloroethane) or a cyclic ether (especially tetrahydrofuran)) at a temperature ranging from 50°C to the boiling point of the reaction mixture. Such reactions, which convert carboxylic acids into BOC-protected amines, are known by the art as the Curtius reaction and have been reported in, for example, Org. Lett., 2005, 7, 4107-4110; Journal of Medicinal Chemistry, 49(12), 3614-3627; and J. Am. Chem. Soc., 1972, 94(17), pp. 6203-6205.

[0233] Compounds having formula IX (wherein R1, X, R3, R4, R5, R6, and R7 are as defined above in formula I) can also be prepared from compounds having formula XX (wherein R1, X, R3, R4, R5, R6, and R7 are as defined above in formula I) via a Hoffmann rearrangement reaction. The reaction can be carried out in the presence of a base (e.g., an aqueous solution of a metal hydroxide, such as sodium hydroxide or potassium hydroxide, or an organic base, such as DBU (1,8-diazabicyclo(5.4.0)undec-7-ene)) and an electrophilic halogenating agent (e.g., chlorine, bromine, or N-bromosuccinimide), and at a temperature ranging from 20 °C to the boiling point of the reaction mixture. Such reactions are known by the name Hoffmann rearrangement and have been reported in the literature, for example, in Chem. Ber. [Acta Chimica Sinica] 1881, 14, 2725.

[0234] A compound having formula XX (wherein R1, X, R3, R4, R5, R6 and R7 are as defined above in Formula I) can be prepared by reacting a compound having formula XVIII (wherein R1, X, R3, R4, R5, R6 and R7 are as defined above in Formula I) with ammonia, such as NH4OH, NH3 or other ammonia substitutes, in the presence of a carboxylic acid activator as described in Scheme 3 above.

[0235] Compounds having formula XIX

[0236]

[0237] in

[0238] R1, X, R3, R4, R5, R6, and R7, as defined above in Formula I, are novel and have been particularly developed for preparing compounds having Formula I according to the invention, and thus represent another object of the invention. Preferred options and preferred embodiments of the substituents in compounds having Formula I are also effective for compounds having Formula XIX. Most preferably, X is SO2, R1 is ethyl, and R3 / R4 are as described in Table I. In one embodiment, compounds having Formula (XIX) are as described above, provided that the compounds tert-butyl N-(2-cyclopropyl-5-ethylthioalkyl-1-methyl-imidazol-4-yl)carbamate and tert-butyl N-[5-ethylthioalkyl-1-methyl-2-[4-(trifluoromethyl)phenyl]imidazol-4-yl]carbamate are excluded.

[0239] Small amounts of compounds having the formula XVIII, where X is S (sulfide),

[0240]

[0241] Known in the literature (CAS 2234901-66-5, CAS 2236074-76-1), and described in WO 2018130443 and WO2018130437.

[0242] Alternatively, compounds having Formula I (where R2, G1, G2, R1, X, R3, R4, R5, R6 and R7 as defined above in Formula I) may also be prepared according to Scheme 9.

[0243] Option 9:

[0244]

[0245] (a) Suzuki reaction: Pd catalyst (e.g., Pd(PPh3)4 or Pd(dppf)Cl2), base (e.g., Na2CO3), solvent (e.g., 1,2-dimethoxyethane / water), 25-180°C.

[0246] (b) Steer reaction: Pd catalyst (e.g., Pd(PPh3)4 or Pd(PPh3)Cl2), solvent (e.g., toluene), 25-180 °C.

[0247] (c) CN bond formation: optional base (e.g., K2CO3 or Cs2CO3), optional copper or palladium catalyst, optional additive (e.g., N,N′-dimethylethylenediamine), optional ligand (e.g., Xantphos), solvent (e.g., dioxane, pyridine or N,N-dimethylformamide DMF), 25-180 °C.

[0248] In a specific case of Scheme 9, when R3 is an optionally substituted pyrazole group (the pyrazole group is mono- or poly-substituted by a substituent selected from the group consisting of: halogen, cyano, C1-C4 alkyl, C1-C4 haloalkyl, C1-C4 alkoxy, C1-C4 haloalkoxy, C1-C4 alkylthioalkyl, C1-C4 alkylsulfinyl and C1-C4 alkylsulfonyl; C3-C6 cycloalkyl, C3-C6 cycloalkyl monosubstituted with cyano, C1- When a compound of formula I (where X is SO or SO2) is formed by linking a nitrogen atom to an imidazole ring connected to a substituent R4, it can be reacted in a solvent (e.g., an alcohol (e.g., methanol, ethanol, isopropanol or a straight-chain or branched alcohol of higher boiling point), pyridine or acetic acid), optionally in the presence of an additional base (e.g., potassium carbonate K2CO3 or cesium carbonate Cs2CO3), optionally in the presence of a copper catalyst (e.g., copper iodide (I)), at a temperature of 30-180 °C. At a temperature of ℃, optionally under microwave irradiation, a compound having the formula XXI (wherein R2, G1, G2, R1, and R4 are as defined above in Formula I and where X is SO or SO2, and where Xb is a leaving group, such as chlorine, bromine, or iodine (preferably chlorine or bromine), or an aryl- or (halo)alkyl sulfonate such as trifluoromethanesulfonate) is reacted with an optionally substituted pyrazole R3-H (which contains a suitable NH functional group) (XXIIaa) (wherein R3 is optionally substituted). The pyrazole group (which is mono- or poly-substituted by a substituent selected from the group consisting of: halogen, cyano, C1-C4 alkyl, C1-C4 haloalkyl, C1-C4 alkoxy, C1-C4 haloalkoxy, C1-C4 alkylthioalkyl, C1-C4 alkylsulfinyl and C1-C4 alkylsulfonyl; C3-C6 cycloalkyl, C3-C6 cycloalkyl monosubstituted with cyano, C1-C6 cyanoalkyl) is prepared by reaction (CN bond formation).

[0249] In the specific case of Scheme 9, when R3 is -N(R5)COR7 (where R5 and R7 are as defined in Formula I), the compound having Formula I (where X is SO or SO2) can be prepared by reacting a compound having Formula XXI (where R2, G1, G2, R1 and R4 are as defined in Formula I and where X is SO or SO2, and where Xb is a leaving group, such as chlorine, bromine or iodine (preferably chlorine or bromine), or aryl sulfonate or (halo)alkyl sulfonate (such as trifluoromethanesulfonate)) with a reagent R3-H(XXIIaa) equivalent to HN(R5)COR7 (where R5 and R7 are as defined in Formula I) (CN bond formation). This reaction is carried out in the presence of a base (such as potassium carbonate, cesium carbonate, sodium hydroxide), in an inert solvent (such as toluene, dimethylformamide DMF, N-methylpyrrolidone NMP, dimethyl sulfoxide DMSO, dioxane, tetrahydrofuran THF, etc.), optionally in the presence of a catalyst (such as palladium(II) acetate, bis(dibenzylacetone)palladium(0) (Pd(dba)2) or tris(dibenzylacetone)dipalladium(0) (Pd2(dba)3), optionally in the form of a chloroform adduct) or a palladium precatalyst (such as tert-BuBrettPhos Pd G3 [(2-di-tert-butylphosphino-3,6-dimethoxy-2',4',6'-triisopropyl-1,1'-biphenyl)-2-(2'-amino-1,1'-biphenyl)]palladium(II) methanesulfonate or BrettPhos Pd The procedure was performed in the presence of G3[(2-di-cyclohexylphosphino-3,6-dimethoxy-2',4',6'-triisopropyl-1,1'-biphenyl)-2-(2'-amino-1,1'-biphenyl)]palladium methanesulfonate(II)], and optionally in the presence of a ligand (e.g., SPhos, t-BuBrettPhos, or Xantphos), at a temperature between 60°C and 120°C, and optionally under microwave irradiation.

[0250] The reagent HN(R5)COR7 (where R5 and R7 are as defined in Formula I) or a substituted pyrazole group (which is mono- or poly-substituted by a substituent selected from the group consisting of: halogen, cyano, C1-C4 alkyl, C1-C4 haloalkyl, C1-C4 alkoxy, C1-C4 haloalkoxy, C1-C4 alkylthioalkyl, C1-C4 alkylsulfinyl and C1-C4 alkylsulfonyl; C3-C6 cycloalkyl, C3-C6 cycloalkyl monosubstituted with cyano, C1-C6 cyanoalkyl) is known, commercially available or can be prepared by methods known to those skilled in the art.

[0251] Alternatively, compounds having formula I (where X is SO or SO2) can be prepared by the Suzuki reaction, which involves, for example, making a compound having formula XXI (where R1, R2, G1, G2 and R4 are as defined in formula I, and where X is SO or SO2, and where Xb is a leaving group, such as chlorine, bromine or iodine (preferably chlorine or bromine), or aryl sulfonate or (halo)alkyl sulfonate (such as trifluoromethanesulfonate)) with a compound having formula (XXII) (where R3 is as defined above, and where Y... b1 It can be a boron-derived functional group, such as B(OH)2 or B(OR). b1 )2, where R b1 It can be a C1-C4 alkyl group, or two groups OR b1 It can form a five-membered ring with boron atoms, such as in the reaction of pinacol boronic acid ester. The reaction can be catalyzed by palladium-based catalysts (e.g., tetrakis(triphenylphosphine)palladium(O), (1,1'-bis(diphenylphosphine)ferrocene)dichloro-palladium-dichloromethane (1:1 complex), or chloro(2-dicyclohexylphosphino-2',4',6'-triisopropyl-1,1'-biphenyl)[2-(2'-amino-1,1'-biphenyl)]palladium(II) (XPhos cyclic palladium complex)) in the presence of a base (such as sodium carbonate, tripotassium phosphate, or cesium fluoride) in a solvent or solvent mixture (such as, for example, a mixture of dioxane, acetonitrile, N,N-dimethylformamide, 1,2-dimethoxyethane, and water, or a dioxane / water mixture, or a toluene / water mixture), preferably under an inert atmosphere. The reaction temperature can preferably be in the range from room temperature to the boiling point of the reaction mixture, or the reaction can be carried out under microwave irradiation. Such Suzuki reactions are well known to those skilled in the art and have been reviewed, for example, in J. Organomet. Chem. 576, 1999, 147-168.

[0252] Alternatively, a compound having formula I (where X is SO or SO2) can be produced by a compound having formula (XXIIa) (where R3 is as defined above, and where Y...). b2It is prepared by a Stieler reaction between a trialkyltin derivative, preferably tri-n-butyltin or trimethyltin, and a compound having the formula XXI (where R1, R2, G1, G2, and R4 are as defined in Formula I, and X is SO or SO2, and Xb is a leaving group, such as chlorine, bromine, or iodine (preferably chlorine or bromine), or an aryl sulfonate or (halo)alkyl sulfonate (such as trifluoromethanesulfonate)). Such Stieler reactions are typically carried out in the presence of a palladium catalyst (e.g., tetra(triphenylphosphine)palladium(O) or bis(triphenylphosphine)palladium(II) chloride), in an inert solvent (e.g., N,N-dimethylformamide, acetonitrile, toluene, or dioxane), optionally in the presence of an additive (e.g., cesium fluoride or lithium chloride), and optionally in the presence of another catalyst (e.g., copper iodide(I)). Such Stieler couplings are well known to those skilled in the art and have been described, for example, in J. Org. Chem., 2005, 70, 8601-8604, J. Org. Chem., 2009, 74, 5599-5602, and Angew. Chem. Int. Ed., 2004, 43, 1132-1136.

[0253] When R3 is a five-membered aromatic ring system in which the nitrogen atom is attached to an imidazole ring connected to the substituent R4, a compound having Formula I (where X is SO or SO2) can be formed by reacting a compound having Formula XXI (where R1, R2, G1, G2, and R4 are as defined in Formula I, and where X is SO or SO2, and where Xb is a leaving group, such as chlorine, bromine, or iodine (preferably chlorine or bromine), or an aryl sulfonate or (halo)alkyl sulfonate (such as trifluoromethanesulfonate)) with a heterocyclic R3-H (which contains a suitable NH functional group) (XX IIaa (where R3 is as defined above) is prepared by reacting in an inert solvent (such as N-methylpyrrolidone (NMP) or N,N-dimethylformamide DMF) at a temperature between 30°C and 150°C in the presence of a base (such as potassium carbonate K2CO3 or cesium carbonate Cs2CO3), optionally in the presence of a copper catalyst (e.g., copper iodide (I)), with or without additives such as L-proline, N,N'-dimethylcyclohexane-1,2-diamine or N,N'-dimethyl-ethylenediamine), optionally under microwave irradiation.

[0254] The oxidation of a compound having the formula XXI (where R1, R2, G1, G2, and R4 are as defined in Formula I, and where X is S, and where Xb is a leaving group, such as chlorine, bromine, or iodine (preferably chlorine or bromine), or aryl sulfonate or (halo)alkyl sulfonate (such as trifluoromethanesulfonate)) with a suitable oxidizing agent to a compound having the formula XXI (where X is SO or SO2) can be achieved under the conditions described above.

[0255] Numerous compounds having the formulas (XXII), (XXIIa), and (XXIIaa) are commercially available or can be prepared by those skilled in the art.

[0256] Alternatively, a compound having formula I (where X is SO or SO2) can be prepared from a compound having formula XXI (where X is S (sulfide)) by the same chemical process as described above, but by changing the order of the steps (i.e., by running XXI (X is S) to I (X is S) via Suzuki, Stieler or CN bonds, followed by an oxidation step to form I (X is SO or SO2)) (Scheme 9).

[0257] Alternatively, compounds having formula XVIII, wherein X is SO2, and wherein R1, R3, R4, R5, R6, and R7 are as defined above in formula I,

[0258] Option 10:

[0259]

[0260] The preparation (Scheme 10) can be achieved by the saponification reaction of a compound of formula XXIII (where R1, R3, R4, R5, R6 and R7 are as defined above in Formula I, and Rx is C1-C6 alkyl, benzyl or phenyl) in the presence of a suitable base (e.g., sodium hydroxide NaOH, lithium hydroxide LiOH or barium hydroxide Ba(OH)2) and a solvent (e.g., ethanol, methanol, dioxane, tetrahydrofuran or water (or mixtures thereof)) under the conditions already described above (see the discussion in Scheme 2 regarding the conversion of (VI) to (X) and in Scheme 2a regarding the conversion of (XVII) to (X); alternatively, Krapcho-type conditions as described above can also be used).

[0261] A compound having formula XXIII, wherein R1, R3, R4, R5, R6, and R7 are as defined above in formula I, and Rx is a C1-C6 alkyl, benzyl, or phenyl group, can be formed from a compound having formula XXIV (where R1 and R4 are as defined above in formula I, and Rx is a C1-C6 alkyl, benzyl, or phenyl group, and Xb is a leaving group, such as chlorine, bromine, or iodine (preferably chlorine or bromine), or an aryl sulfonate or (halogenated) alkyl sulfonate, such as trifluoromethanesulfonate) via a Suzuki, Stil, or CN bond (involving a reagent having formula XXII, XXIIa, or XXIIaa, wherein R3, R5, R6, and R7 are as defined above in formula I, and Y ..., and Rx is a leaving group, such as chlorine, bromine, or iodine, and Rx is a leaving group, such as chlorine, bromine, or iodine, and Rx is a leaving group, such as chlorine, bromine, or iodine, and Rx is a leaving group, such as chlorine, bromine, or iodine, and Rx is a leaving group, such as chlorine, bromine, or iodine, and Rx is a leaving group, such as chlorine, b1 and Y b2 Prepared under the conditions described above (see the discussion of converting (XXI) to (I) in Scheme 9, as defined in Scheme 9).

[0262] Compounds having formula XXIV (where R1 and R4 are as defined above in formula I, and Rx is C1-C6 alkyl, benzyl, or phenyl, and Xb is a leaving group, such as chlorine, bromine, or iodine (preferably chlorine or bromine), or aryl sulfonate or (halo)alkyl sulfonate such as trifluoromethanesulfonate) can be prepared by oxidation (involving a suitable oxidizing agent and under the conditions described above) of compounds having formula XXV (where R1 and R4 are as defined above in formula I, and Rx is C1-C6 alkyl, benzyl, or phenyl, and Xb is a leaving group, such as chlorine, bromine, or iodine (preferably chlorine or bromine), or aryl sulfonate or (halo)alkyl sulfonate such as trifluoromethanesulfonate).

[0263] Compounds having the formula XXV (where R1 and R4 are as defined above in Formula I, and Rx is a C1-C6 alkyl, benzyl, or phenyl group, and Xb is a leaving group, such as chlorine, bromine, or iodine (preferably chlorine or bromine), or an aryl sulfonate or (halo)alkyl sulfonate such as trifluoromethanesulfonate) are known or can be prepared according to procedures described in the literature. For example, compounds having the formula XXV (where R1 is ethyl, R4 is methyl, Xb is bromine, and Rx is ethyl (CAS 2407490-49-5)) are described in WO 2018130443, WO2018130437, and WO 2020002082.

[0264] The reactants can react in the presence of a base. Examples of suitable bases are alkali metal or alkaline earth metal hydroxides, alkali metal or alkaline earth metal hydrides, alkali metal or alkaline earth metal amides, alkali metal or alkaline earth metal alkoxides, alkali metal or alkaline earth metal acetates, alkali metal or alkaline earth metal carbonates, alkali metal or alkaline earth metal dialkylamides or alkali metal or alkaline earth metal alkylsilylamides, alkylamines, alkylene diamines, free or N-alkylated saturated or unsaturated cycloalkylamines, basic heterocycles, ammonium hydroxides, and carbocyclic amines. Examples that may be mentioned are sodium hydroxide, sodium hydride, sodium amino, sodium methoxide, sodium acetate, sodium carbonate, potassium tert-butoxide, potassium hydroxide, potassium carbonate, potassium hydride, lithium diisopropylamino, potassium bis(trimethylsilyl)amino, calcium hydride, triethylamine, diisopropylethylamine, triethylenediamine, cyclohexylamine, N-cyclohexyl-N,N-dimethylamine, N,N-diethylaniline, pyridine, 4-(N,N-dimethylamino)pyridine, quinine ring, N-methylmorpholine, benzyltrimethylammonium hydroxide, and 1,8-diazabicyclo[5.4.0]undec-7-ene (DBU).

[0265] These reactants can react with each other as is, i.e., without the addition of solvents or diluents. However, in most cases, it is advantageous to add an inert solvent or diluent, or a mixture thereof. If the reaction is carried out in the presence of a base, then these excess bases (such as triethylamine, pyridine, N-methylmorpholine, or N,N-diethylaniline) can also act as solvents or diluents.

[0266] These reactions are advantageously carried out in a temperature range from about -80°C to about +140°C, preferably from about -30°C to about +100°C, and in many cases in the range between ambient temperature and about +80°C.

[0267] A compound having Formula I can be converted into another compound having Formula I in a manner known per se by replacing one or more substituents of a starting compound having Formula I with another substituent according to the invention in a conventional manner, and by post-modifying the compound with reactions known to those skilled in the art (such as oxidation, alkylation, reduction, acylation and other methods).

[0268] Depending on the chosen reaction conditions and starting materials appropriate to the specific circumstances, it may be possible, for example, to replace only one substituent with another substituent according to the invention in a single reaction step, or to replace multiple substituents with other substituents according to the invention in the same reaction step.

[0269] Salts of compounds having formula I can be prepared in ways known per se. Thus, for example, acid addition salts of compounds having formula I are obtained by treatment with a suitable acid or a suitable ion exchanger, and salts with a base are obtained by treatment with a suitable base or a suitable ion exchanger.

[0270] Salts of compounds having formula I can be converted in a conventional manner into free compound I, acid addition salts (e.g., by treatment with a suitable basic compound or a suitable ion exchanger reagent), and salts with bases (e.g., by treatment with a suitable acid or a suitable ion exchanger reagent).

[0271] Salts of compounds having formula I can be converted in a manner known per se into other salts of compounds having formula I, acid addition salts, for example, into other acid addition salts, such as by treating salts of inorganic acids (e.g., hydrochlorides) in a suitable solvent with a suitable metal salt of the acid (e.g., a salt of sodium, barium, or silver, e.g., silver acetate), in which the inorganic salt (e.g., silver chloride) formed is insoluble and thus precipitates out of the reaction mixture.

[0272] Depending on the procedure or reaction conditions, these compounds of formula I with salt-forming properties can be obtained in free form or as salts.

[0273] Depending on the number of asymmetric carbon atoms present in the molecule, the absolute and relative configurations, and / or depending on the configuration of the non-aromatic double bonds present in the molecule, compounds having Formula I and, where appropriate, their tautomers (in each case, in free or salt form) may exist as one of the possible isomers or as mixtures of these, for example, as pure isomers, such as enantiomers and / or diastereomers, or as mixtures of isomers, such as mixtures of enantiomers, such as racemic mixtures, diastereomer mixtures, or mixtures of racemic mixtures; the present invention relates to pure isomers as well as all possible mixtures of isomers, and should be understood so in each case above and below, even if stereochemical details are not explicitly mentioned in each case.

[0274] A mixture of diastereomers or racemic mixtures of compounds of Formula I, in free or salt form (their acquisition may depend on the selected starting materials and procedures), can be isolated into pure diastereomers or racemic mixtures in a known manner, based on the physicochemical differences of these components, for example by stepwise crystallization, distillation and / or chromatography.

[0275] An enantiomer mixture (e.g., a racemic mixture) that can be obtained in a similar manner can be resolved into optical enantiomers by known methods, such as by recrystallization from an optically active solvent; by chromatography on a chiral adsorbent, such as high-performance liquid chromatography (HPLC) on acetylcellulose; by cleavage with a specific immobilized enzyme using suitable microorganisms; by forming a containing compound, such as using a chiral crown ether, in which only one enantiomer is complexed; or by conversion into salts of diastereomers, such as by reacting the basic final product racemic mixture with an optically active acid (e.g., a carboxylic acid, such as camphoric acid, tartaric acid, or malic acid, or a sulfonic acid, such as camphorsulfonic acid), and the diastereomer mixture that can be obtained in this manner can be separated, for example by stepwise crystallization based on its different solubilities, from which the desired enantiomer can be freed by the action of a suitable reagent (e.g., a basic reagent).

[0276] Pure diastereomers or enantiomers can be obtained according to the invention, not only by separating a suitable mixture of isomers, but also by methods of commonly known diastereoselective or enantiomeric synthesis, for example by using starting materials with suitable stereochemistry according to the invention.

[0277] N-oxides can be prepared by reacting a compound having formula I with a suitable oxidant (e.g., H₂O₂ / urea adduct) in the presence of an acid anhydride (e.g., trifluoroacetic anhydride). Such oxidations are known from the literature, for example from J. Med. Chem., 32(12), 2561-73, 1989 or WO 2000 / 15615.

[0278] If individual components have different biological activities, it is advantageous to isolate or synthesize biologically more effective isomers in each case, such as enantiomers or diastereomers, or mixtures of isomers, such as mixtures of enantiomers or diastereomers.

[0279] If appropriate, compounds having Formula I and, where appropriate, their tautomers (in free or salt form in each case) can also be obtained as hydrates and / or include other solvents, such as those that can be used to crystallize compounds that exist in solid form.

[0280] Compounds having Formula I according to Tables A-1 to A-48, C-1 to C-24, D-1 to D-12, and E-1 to E-12 can be prepared according to the method described above. The following examples are intended to illustrate the invention and to show preferred compounds having Formula I in the form of compounds having Formulas I-1 to I-4.

[0281] The following tables illustrate specific compounds of the present invention. In these tables, CH2cPr refers to CH2-cyclopropyl.

[0282] Table A-1 provides 19 compounds having formula I-1, from A-1.001 to A-1.019, wherein G1 is N, G2 is N, X is S, R1 is CH2CH3, R4 is methyl and R3 is as defined in Table B.

[0283]

[0284] For example, A-1.010 is

[0285]

[0286] Table B Definition of substituents for R3

[0287]

[0288]

[0289]

[0290] Table A-2 provides 19 compounds having formula I-1, A-2.001 to A-2.019, wherein G1 is N, G2 is N, X is S, R1 is CH2CH3, R4 is ethyl and R3 is as defined in Table B.

[0291] Table A-3 provides 19 compounds having formula I-1, A-3.001 to A-3.019, wherein G1 is N, G2 is N, X is S, R1 is CH2cPr, R4 is methyl and R3 is as defined in Table B.

[0292] Table A-4 provides 19 compounds having formula I-1, A-4.001 to A-4.019, wherein G1 is N, G2 is N, X is S, R1 is CH2cPr, R4 is ethyl and R3 is as defined in Table B.

[0293] Table A-5 provides 19 compounds having formula I-1, A-5.001 to A-5.019, wherein G1 is N, G2 is N, X is SO, R1 is CH2CH3, R4 is methyl and R3 is as defined in Table B.

[0294] Table A-6 provides 19 compounds having formula I-1, A-6.001 to A-6.019, wherein G1 is N, G2 is N, X is SO, R1 is CH2CH3, R4 is ethyl and R3 is as defined in Table B.

[0295] Table A-7 provides 19 compounds having formula I-1, A-7.001 to A-7.019, wherein G1 is N, G2 is N, X is SO, R1 is CH2cPr, R4 is methyl and R3 is as defined in Table B.

[0296] Table A-8 provides 19 compounds having formula I-1, A-8.001 to A-8.019, wherein G1 is N, G2 is N, X is SO, R1 is CH2cPr, R4 is ethyl and R3 is as defined in Table B.

[0297] Table A-9 provides 19 compounds having formula I-1, A-9.001 to A-9.019, wherein G1 is N, G2 is N, X is SO2, R1 is CH2CH3, R4 is methyl and R3 is as defined in Table B.

[0298] Table A-10 provides 19 compounds having formula I-1 from A-10.001 to A-10.019, wherein G1 is N, G2 is N, X is SO2, R1 is CH2CH3, R4 is ethyl and R3 is as defined in Table B.

[0299] Table A-11 provides 19 compounds having formula I-1 from A-11.001 to A-11.019, wherein G1 is N, G2 is N, X is SO2, R1 is CH2cPr, R4 is methyl and R3 is as defined in Table B.

[0300] Table A-12 provides 19 compounds having formula I-1, from A-12.001 to A-12.019, wherein G1 is N, G2 is N, X is SO2, R1 is CH2cPr, R4 is ethyl and R3 is as defined in Table B.

[0301] Table A-13 provides 19 compounds having formula I-1 from A-13.001 to A-13.019, wherein G1 is N, G2 is CH, X is S, R1 is CH2CH3, R4 is methyl and R3 is as defined in Table B.

[0302] Table A-14 provides 19 compounds having formula I-1, from A-14.001 to A-14.019, wherein G1 is N, G2 is CH, X is S, R1 is CH2CH3, R4 is ethyl and R3 is as defined in Table B.

[0303] Table A-15 provides 19 compounds having formula I-1 from A-15.001 to A-15.019, wherein G1 is N, G2 is CH, X is S, R1 is CH2cPr, R4 is methyl and R3 is as defined in Table B.

[0304] Table A-16 provides 19 compounds having formula I-1, A-16.001 to A-16.019, wherein G1 is N, G2 is CH, X is S, R1 is CH2cPr, R4 is ethyl and R3 is as defined in Table B.

[0305] Table A-17 provides 19 compounds having formula I-1 from A-17.001 to A-17.019, wherein G1 is N, G2 is CH, X is SO, R1 is CH2CH3, R4 is methyl and R3 is as defined in Table B.

[0306] Table A-18 provides 19 compounds having formula I-1, from A-18.001 to A-18.019, wherein G1 is N, G2 is CH, X is SO, R1 is CH2CH3, R4 is ethyl and R3 is as defined in Table B.

[0307] Table A-19 provides 19 compounds having formula I-1 from A-19.001 to A-19.019, wherein G1 is N, G2 is CH, X is SO, R1 is CH2cPr, R4 is methyl and R3 is as defined in Table B.

[0308] Table A-20 provides 19 compounds having formula I-1, from A-20.001 to A-20.019, wherein G1 is N, G2 is CH, X is SO, R1 is CH2cPr, R4 is ethyl and R3 is as defined in Table B.

[0309] Table A-21 provides 19 compounds having formula I-1, from A-21.001 to A-21.019, wherein G1 is N, G2 is CH, X is SO2, R1 is CH2CH3, R4 is methyl and R3 is as defined in Table B.

[0310] Table A-22 provides 19 compounds having formula I-1, from A-22.001 to A-22.019, wherein G1 is N, G2 is CH, X is SO2, R1 is CH2CH3, R4 is ethyl and R3 is as defined in Table B.

[0311] Table A-23 provides 19 compounds having formula I-1, from A-23.001 to A-23.019, wherein G1 is N, G2 is CH, X is SO2, R1 is CH2cPr, R4 is methyl and R3 is as defined in Table B.

[0312] Table A-24 provides 19 compounds having formula I-1, A-24.001 to A-24.019, wherein G1 is N, G2 is CH, X is SO2, R1 is CH2cPr, R4 is ethyl and R3 is as defined in Table B.

[0313] Table A-25 provides 19 compounds having formula I-1, from A-25.001 to A-25.019, wherein G1 is CH, G2 is N, X is S, R1 is CH2CH3, R4 is methyl and R3 is as defined in Table B.

[0314] Table A-26 provides 19 compounds having formula I-1, A-26.001 to A-26.019, wherein G1 is CH, G2 is N, X is S, R1 is CH2CH3, R4 is ethyl and R3 is as defined in Table B.

[0315] Table A-27 provides 19 compounds having formula I-1, from A-27.001 to A-27.019, wherein G1 is CH, G2 is N, X is S, R1 is CH2cPr, R4 is methyl and R3 is as defined in Table B.

[0316] Table A-28 provides 19 compounds having formula I-1, A-28.001 to A-28.019, wherein G1 is CH, G2 is N, X is S, R1 is CH2cPr, R4 is ethyl and R3 is as defined in Table B.

[0317] Table A-29 provides 19 compounds having formula I-1, from A-29.001 to A-29.019, wherein G1 is CH, G2 is N, X is SO, R1 is CH2CH3, R4 is methyl and R3 is as defined in Table B.

[0318] Table A-30 provides 19 compounds having formula I-1, from A-30.001 to A-30.019, wherein G1 is CH, G2 is N, X is SO, R1 is CH2CH3, R4 is ethyl and R3 is as defined in Table B.

[0319] Table A-31 provides 19 compounds having formula I-1, from A-31.001 to A-31.019, wherein G1 is CH, G2 is N, X is SO, R1 is CH2cPr, R4 is methyl and R3 is as defined in Table B.

[0320] Table A-32 provides 19 compounds having formula I-1, A-32.001 to A-32.019, wherein G1 is CH, G2 is N, X is SO, R1 is CH2cPr, R4 is ethyl and R3 is as defined in Table B.

[0321] Table A-33 provides 19 compounds having formula I-1, from A-33.001 to A-33.019, wherein G1 is CH, G2 is N, X is SO2, R1 is CH2CH3, R4 is methyl and R3 is as defined in Table B.

[0322] Table A-34 provides 19 compounds having formula I-1, from A-34.001 to A-34.019, wherein G1 is CH, G2 is N, X is SO2, R1 is CH2CH3, R4 is ethyl and R3 is as defined in Table B.

[0323] Table A-35 provides 19 compounds having formula I-1, from A-35.001 to A-35.019, wherein G1 is CH, G2 is N, X is SO2, R1 is CH2cPr, R4 is methyl and R3 is as defined in Table B.

[0324] Table A-36 provides 19 compounds having formula I-1, A-36.001 to A-36.019, wherein G1 is CH, G2 is N, X is SO2, R1 is CH2cPr, R4 is ethyl and R3 is as defined in Table B.

[0325] Table A-37 provides 19 compounds having formula I-1, from A-37.001 to A-37.019, wherein G1 is CH, G2 is CH, X is S, R1 is CH2CH3, R4 is methyl and R3 is as defined in Table B.

[0326] Table A-38 provides 19 compounds having formula I-1, A-38.001 to A-38.019, wherein G1 is CH, G2 is CH, X is S, R1 is CH2CH3, R4 is ethyl and R3 is as defined in Table B.

[0327] Table A-39 provides 19 compounds having formula I-1, from A-39.001 to A-39.019, wherein G1 is CH, G2 is CH, X is S, R1 is CH2cPr, R4 is methyl and R3 is as defined in Table B.

[0328] Table A-40 provides 19 compounds having formula I-1, from A-40.001 to A-40.019, wherein G1 is CH, G2 is CH, X is S, R1 is CH2cPr, R4 is ethyl and R3 is as defined in Table B.

[0329] Table A-41 provides 19 compounds having formula I-1, from A-41.001 to A-41.019, wherein G1 is CH, G2 is CH, X is SO, R1 is CH2CH3, R4 is methyl and R3 is as defined in Table B.

[0330] Table A-42 provides 19 compounds having formula I-1, from A-42.001 to A-42.019, wherein G1 is CH, G2 is CH, X is SO, R1 is CH2CH3, R4 is ethyl and R3 is as defined in Table B.

[0331] Table A-43 provides 19 compounds having formula I-1, from A-43.001 to A-43.019, wherein G1 is CH, G2 is CH, X is SO, R1 is CH2cPr, R4 is methyl and R3 is as defined in Table B.

[0332] Table A-44 provides 19 compounds having formula I-1, from A-44.001 to A-44.019, wherein G1 is CH, G2 is CH, X is SO, R1 is CH2cPr, R4 is ethyl and R3 is as defined in Table B.

[0333] Table A-45 provides 19 compounds having formula I-1, from A-45.001 to A-45.019, wherein G1 is CH, G2 is CH, X is SO2, R1 is CH2CH3, R4 is methyl and R3 is as defined in Table B.

[0334] Table A-46 provides 19 compounds having formula I-1, A-46.001 to A-46.019, wherein G1 is CH, G2 is CH, X is SO2, R1 is CH2CH3, R4 is ethyl and R3 is as defined in Table B.

[0335] Table A-47 provides 19 compounds having formula I-1, from A-47.001 to A-47.019, wherein G1 is CH, G2 is CH, X is SO2, R1 is CH2cPr, R4 is methyl and R3 is as defined in Table B.

[0336] Table A-48 provides 19 compounds having formula I-1, A-48.001 to A-48.019, wherein G1 is CH, G2 is CH, X is SO2, R1 is CH2cPr, R4 is ethyl and R3 is as defined in Table B.

[0337] The following tables further illustrate the specific compounds of the present invention.

[0338]

[0339] Table C-1 provides 19 compounds having formula I-2, C-1.001 to C-1.019, wherein R2 is OSO2CF3, X is S, R1 is CH2CH3, R4 is methyl and R3 is as defined in Table B.

[0340] Table C-2 provides 19 compounds having formula I-2, C-2.001 to C-2.019, wherein R2 is OSO2CF3, X is S, R1 is CH2cPr, R4 is methyl and R3 is as defined in Table B.

[0341] Table C-3 provides 19 compounds having formula I-2, C-3.001 to C-3.019, wherein R2 is OSO2CF3, X is SO, R1 is CH2CH3, R4 is methyl and R3 is as defined in Table B.

[0342] Table C-4 provides 19 compounds having formula I-2, C-4.001 to C-4.019, wherein R2 is OSO2CF3, X is SO, R1 is CH2cPr, R4 is methyl and R3 is as defined in Table B.

[0343] Table C-5 provides 19 compounds having formula I-2, C-5.001 to C-5.019, wherein R2 is OSO2CF3, X is SO2, R1 is CH2CH3, R4 is methyl and R3 is as defined in Table B.

[0344] Table C-6 provides 19 compounds having formula I-2, C-6.001 to C-6.019, wherein R2 is OSO2CF3, X is SO2, R1 is CH2cPr, R4 is methyl and R3 is as defined in Table B.

[0345] Table C-7 provides 19 compounds having formula I-2, C-7.001 to C-7.019, wherein R2 is SO2CF3, X is S, R1 is CH2CH3, R4 is methyl and R3 is as defined in Table B.

[0346] Table C-8 provides 19 compounds having formula I-2, C-8.001 to C-8.019, wherein R2 is SO2CF3, X is S, R1 is CH2cPr, R4 is methyl and R3 is as defined in Table B.

[0347] Table C-9 provides 19 compounds having formula I-2, C-9.001 to C-9.019, wherein R2 is SO2CF3, X is SO, R1 is CH2CH3, R4 is methyl and R3 is as defined in Table B.

[0348] Table C-10 provides 19 compounds having formula I-2, C-10.001 to C-10.019, wherein R2 is SO2CF3, X is SO, R1 is CH2cPr, R4 is methyl and R3 is as defined in Table B.

[0349] Table C-11 provides 19 compounds having formula I-2, C-11.001 to C-11.019, wherein R2 is SO2CF3, X is SO2, R1 is CH2CH3, R4 is methyl and R3 is as defined in Table B.

[0350] Table C-12 provides 19 compounds having formula I-2, C-12.001 to C-12.019, wherein R2 is SO2CF3, X is SO2, R1 is CH2cPr, R4 is methyl and R3 is as defined in Table B.

[0351] Table C-13 provides 19 compounds having formula I-2, C-13.001 to C-13.019, wherein R2 is OCF3, X is S, R1 is CH2CH3, R4 is methyl and R3 is as defined in Table B.

[0352] Table C-14 provides 19 compounds having formula I-2, C-14.001 to C-14.019, wherein R2 is OCF3, X is S, R1 is CH2cPr, R4 is methyl and R3 is as defined in Table B.

[0353] Table C-15 provides 19 compounds having formula I-2, C-15.001 to C-15.019, wherein R2 is OCF3, X is SO, R1 is CH2CH3, R4 is methyl and R3 is as defined in Table B.

[0354] Table C-16 provides 19 compounds having formula I-2, C-16.001 to C-16.019, wherein R2 is OCF3, X is SO, R1 is CH2cPr, R4 is methyl and R3 is as defined in Table B.

[0355] Table C-17 provides 19 compounds having formula I-2, C-17.001 to C-17.019, wherein R2 is OCF3, X is SO2, R1 is CH2CH3, R4 is methyl and R3 is as defined in Table B.

[0356] Table C-18 provides 19 compounds having formula I-2, C-18.001 to C-18.019, wherein R2 is OCF3, X is SO2, R1 is CH2cPr, R4 is methyl and R3 is as defined in Table B.

[0357] Table C-19 provides 19 compounds having formula I-2, C-19.001 to C-19.019, wherein R2 is SCF3, X is S, R1 is CH2CH3, R4 is methyl and R3 is as defined in Table B.

[0358] Table C-20 provides 19 compounds having formula I-2, C-20.001 to C-20.019, wherein R2 is SCF3, X is S, R1 is CH2cPr, R4 is methyl and R3 is as defined in Table B.

[0359] Table C-21 provides 19 compounds having formula I-2, C-21.001 to C-21.019, wherein R2 is SCF3, X is SO, R1 is CH2CH3, R4 is methyl and R3 is as defined in Table B.

[0360] Table C-22 provides 19 compounds having formula I-2, C-22.001 to C-22.019, wherein R2 is SCF3, X is SO, R1 is CH2cPr, R4 is methyl and R3 is as defined in Table B.

[0361] Table C-23 provides 19 compounds having formula I-2, C-23.001 to C-23.019, wherein R2 is SCF3, X is SO2, R1 is CH2CH3, R4 is methyl and R3 is as defined in Table B.

[0362] Table C-24 provides 19 compounds having formula I-2, C-24.001 to C-24.019, wherein R2 is SCF3, X is SO2, R1 is CH2cPr, R4 is methyl and R3 is as defined in Table B.

[0363] The following tables further illustrate the specific compounds of the present invention.

[0364]

[0365] Table D-1 provides 19 compounds having formula I-3, from D-1.001 to D-1.019, where X is S, R1 is CH2CH3, R4 is methyl and R3 is as defined in Table B.

[0366] Table D-2 provides 19 compounds having formula I-3, from D-2.001 to D-2.019, where X is S, R1 is CH2CH3, R4 is an ethyl group, and R3 is as defined in Table B.

[0367] Table D-3 provides 19 compounds having formula I-3, from D-3.001 to D-3.019, where X is S, R1 is CH2cPr, R4 is methyl and R3 is as defined in Table B.

[0368] Table D-4 provides 19 compounds having formula I-3, from D-4.001 to D-4.019, where X is S, R1 is CH2cPr, R4 is ethyl and R3 is as defined in Table B.

[0369] Table D-5 provides 19 compounds having formula I-3, from D-5.001 to D-5.019, where X is SO, R1 is CH2CH3, R4 is methyl and R3 is as defined in Table B.

[0370] Table D-6 provides 19 compounds having formula I-3, from D-6.001 to D-6.019, where X is SO, R1 is CH2CH3, R4 is ethyl, and R3 is as defined in Table B.

[0371] Table D-7 provides 19 compounds having formula I-3, from D-7.001 to D-7.019, where X is SO, R1 is CH2cPr, R4 is methyl and R3 is as defined in Table B.

[0372] Table D-8 provides 19 compounds having formula I-3, from D-8.001 to D-8.019, where X is SO, R1 is CH2cPr, R4 is ethyl and R3 is as defined in Table B.

[0373] Table D-9 provides 19 compounds having formula I-3, from D-9.001 to D-9.019, where X is SO2, R1 is CH2CH3, R4 is methyl and R3 is as defined in Table B.

[0374] Table D-10 provides 19 compounds having formula I-3, from D-10.001 to D-10.019, where X is SO2, R1 is CH2CH3, R4 is an ethyl group, and R3 is as defined in Table B.

[0375] Table D-11 provides 19 compounds having formula I-3, from D-11.001 to D-11.019, where X is SO2, R1 is CH2cPr, R4 is methyl and R3 is as defined in Table B.

[0376] Table D-12 provides 19 compounds having formula I-3, from D-12.001 to D-12.019, where X is SO2, R1 is CH2cPr, R4 is ethyl and R3 is as defined in Table B.

[0377] The following tables further illustrate the specific compounds of the present invention.

[0378]

[0379] Table E-1 provides 19 compounds having formula I-4, from E-1.001 to E-1.019, where X is S, R1 is CH2CH3, R4 is methyl and R3 is as defined in Table B.

[0380] Table E-2 provides 19 compounds having formula I-4, from E-2.001 to E-2.019, where X is S, R1 is CH2CH3, R4 is an ethyl group, and R3 is as defined in Table B.

[0381] Table E-3 provides 19 compounds having formula I-4, E-3.001 to E-3.019, where X is S, R1 is CH2cPr, R4 is methyl and R3 is as defined in Table B.

[0382] Table E-4 provides 19 compounds having formula I-4, from E-4.001 to E-4.019, where X is S, R1 is CH2cPr, R4 is ethyl and R3 is as defined in Table B.

[0383] Table E-5 provides 19 compounds having formula I-4, E-5.001 to E-5.019, where X is SO, R1 is CH2CH3, R4 is methyl and R3 is as defined in Table B.

[0384] Table E-6 provides 19 compounds having formula I-4, E-6.001 to E-6.019, where X is SO, R1 is CH2CH3, R4 is ethyl and R3 is as defined in Table B.

[0385] Table E-7 provides 19 compounds having formula I-4, E-7.001 to E-7.019, where X is SO, R1 is CH2cPr, R4 is methyl and R3 is as defined in Table B.

[0386] Table E-8 provides 19 compounds having formula I-4, E-8.001 to E-8.019, where X is SO, R1 is CH2cPr, R4 is ethyl and R3 is as defined in Table B.

[0387] Table E-9 provides 19 compounds having formula I-4, E-9.001 to E-9.019, where X is SO2, R1 is CH2CH3, R4 is methyl and R3 is as defined in Table B.

[0388] Table E-10 provides 19 compounds having formula I-4, from E-10.001 to E-10.019, where X is SO2, R1 is CH2CH3, R4 is an ethyl group, and R3 is as defined in Table B.

[0389] Table E-11 provides 19 compounds having formula I-4, from E-11.001 to E-11.019, where X is SO2, R1 is CH2cPr, R4 is methyl and R3 is as defined in Table B.

[0390] Table E-12 provides 19 compounds having formula I-4, from E-12.001 to E-12.019, where X is SO2, R1 is CH2cPr, R4 is an ethyl group, and R3 is as defined in Table B.

[0391] The compounds of Formula I according to the invention are active ingredients with preventative and / or therapeutic value in the field of pest control. Even at low application rates, they exhibit a very favorable biocidal spectrum and are well tolerated by warm-blooded species, fish, and plants. These active ingredients according to the invention act on all or individual developmental stages of normally susceptible and resistant animal pests (such as insects or representatives of mites). The insecticidal or acaricidal activity of the active ingredients according to the invention can be directly manifested, i.e., immediate or only after some time (e.g., during molting), resulting in pest destruction; or indirectly manifested, for example, by reducing oviposition and / or hatching rates, corresponding to a good destruction rate (mortality rate) of at least 50% to 60%.

[0392] Examples of animal pests mentioned above are:

[0393] From the order Acari, for example,

[0394] Species of the genera *Acalitus*, *Aculus*, *Acaricalus*, *Aceria*, *Acarus siro*, *Amblyomma*, *Argas*, *Boophilus*, *Brevipalpus*, *Bryobia*, *Calipitrimerus*, *Chorioptes*, *Dermanyssusgallinae*, *Dermatophagoides*, *Eotetranychus*, and *Eriophyes*. Species of the genera *Hemitarsonemus*, *Hyalomma*, *Ixodes*, *Olygonychus*, *Ornithodoros*, *Polyphagotarsone latus*, *Panonychus*, *Phyllocoptruta oleivora*, *Phytonemus*, *Polyphagotarsonemus*, *Psoroptes*, *Rhipicephalus*, *Rhizoglyphus*, and *Sarcoptes*. spp.), species of the genera *Steneotarsonemus*, *Tarsonemus*, and *Tetranychus*;

[0395] From lice, for example,

[0396] Species of the genera *Haematopinus* spp., *Linognathus* spp., *Pediculus* spp., *Pemphigus* spp., and *Phylloxera* spp.;

[0397] From Coleoptera, for example,

[0398] Species of the genera *Agriotes* spp., *Amphimallon majale*, *Anomala orientalis*, *Anthonomus* spp., *Aphodius* spp., *Astylus atromaculatus*, *Ataenius* spp., *Atomaria linearis*, *Chaetocnema tibialis*, *Cerotomas* spp., *Conoderus* spp., *Cosmopolites* spp., *Cotinis nitida*, *Curculio* spp., *Cyclocephalas* spp., *Dermestes* spp., and *Diabrotica*. spp.), Argentine rhinoceros beetle (Diloboderus abderus), phytophagous ladybug species (Epilachna spp.), Eremnus species, black cane beetle (Heteronychus arator), coffee berry beetle (Hypothenemus hampei), Lagria vilosa, potato beetle (Leptinotarsa ​​decemlineata), rice weevil species (Lissorhoptrus spp.), Liogenys species, Maecolaspis species, chestnut velvet beetle (Maladera castanea), American leaf beetle species (Megascelis spp.), rapeseed flower beetle (Melighetes aeneus), dwarf beetle species (Melolontha spp.), Myochrousarmatus, sawmill beetle species (Orycaephilus spp.), ear-beaked weevil species (Otiorhynchus spp.), dwarf horned beetle species (Phyllophaga spp.), species of the genus *Phlyctinus*, species of the genus *Popillia*, species of the genus *Psylliodes*, species of the genus *Rhyssomatus aubtilis*, species of the genus *Rhizopertha*, family Scarabidae, species of the genus *Sitophilus*, and species of the genus *Sitotroga*.), species of the genera *Somaticus*, *Sternechus subsignatus*, *Tenebrio*, *Tribolium*, and *Trogoderma*.

[0399] From the order Diptera, for example,

[0400] Species of the genera *Aedes*, *Anopheles*, *Antherigonasoccata*, *Bactrocea oleae*, *Bibio hortulanus*, *Bradysia*, *Calliphora erythrocephala*, *Ceratitis*, *Chrysomyia*, *Culex*, *Cuterebra*, *Dacus*, *Delia*, *Drosophila melanogaster*, *Fannia*, *Gastrophilus*, *Geomyza tripunctata*, and *Glossina*. Species of the genera *Hypodermas*, *Hyppobosca*, *Liriomyza*, *Lucilia*, *Melanagromyza*, *Musca*, *Oestrus*, *Orseolia*, *Oscinella frit*, *Pegomyia hyoscyami*, *Phorbia*, *Rhagoletis*, *Rivelia quadrifasciata*, *Scatella*, *Sciara*, and *Stomoxys*. spp.), species of the genus Tabanus spp., species of the genus Tannia spp., and species of the genus Tipula spp.;

[0401] From Hemiptera, for example,

[0402] *Acanthocoris scabrator*, *Acanthocoris*, *Amblypeltanitida*, *Bathycoelia thalassina*, *Clavigralla*, *Clavigralla tomentosicollis*, *Creontiades*, *Dichelops furcatus*, *Edessa*, *Euschistus*, *Eurydema pulchrum*, *Horcias nobilellus*, *Acanthocoris*, *Nesidiocoris*, *Neomegalotomus*, *Nesidiocoris* (tenguis), Green Bug, Nysiussimulans, Oebalus insularis, Skin Bug, Wall Bug, Red Hunter Bug, Cocoa Mischief Bug, Scaptocoriscastanea, Black Bug (Scotinophara spp.), Thyanta, Trident Bug, Vatigailludens;

[0403] Pea webless long-tubed aphid (Acyrthosium pisum), species of the genus *Adalges*, *Agalliana ensigera*, *Talguiron vein psyllid*, species of the genus *Aleurodicus*, species of the genus *Aleurocanthus*, sugarcane hole whitefly, soft-haired whitefly (*Aleurothrixus floccosus*), cabbage whitefly (*Aleyrodes brassicae*), cotton leafhopper (*Amarasca biguttula*), lemon long-spotted leafhopper, species of the genus *Nephrodisiac*, aphids, species of the genus *Aspidiotus*, *Aphididae*, *Aphid*, species of the genus *Aspidiotus*, *Aphidia gracilis*, potato / tomato psyllid (*Bactericera cockerelli*), species of the genus *Aphidia*, species of the genus *Brachycaudus*, cabbage aphid, species of the genus *Cavariella*, etc. *Aegopodii Scop.*, *C.* species, *C.* species, *C.* species, *C.* species, *C.* species, *C.* species, *C.* species, *C.* species, *C.* species, *C.* soft scale, *C.* yellow-winged corn leafhopper, *C.* species, *C.* citrus psyllid, *C.* species, *C.* species, *C.* small green leafhopper, *C.* woolly apple aphid, *C.* species ... erysimi), Lyogenys maidis, species of the genus *Lyogenys*, species of the genus *Lyogenys*, species of the genus *Metcalfa pruinosa*, *Metcalfa pruinosa*, *Metcalfa pruinosa*, *Metcalfa pruinosa*, *Metcalfa pruinosa*, species of the genus *Metcalfa pruinosa*, species of the genus *Neotoxoptera*, species of the genus *Neotoxoptera*, species of the genus *Nilaparvata*, and species of the genus *Nilaparvata*.), Pear Green Aphid, Odonaspis ruthae, Sugarcane Cotton Aphid, Myrica Marginata Whitefly, Coxsackia, Species of the genus *Pseudatomoscelis*, Species of the genus *Gallus*, Corn Lanternfly, Species of the genus *Phylloxera*, Species of the genus *Phylloxera*, Species of the genus *Pseudatomoscelis*, Species of the genus *Pulvinaria*, Species of the genus *Pulvinaria*, Species of the genus *Pulvinaria*, Species of the genus *Quesada gigas*, Species of the genus *Recilia dorsalis*, Species of the genus *Pseudocybe ... (Festinus), striped planthopper (Tarophagus Proserpina), species of the genus *Heterophora*, species of the genus *Aphis*, species of the genus *Tridiscus sporoboli*, species of the genus *Trionymus*, African psyllid, arrowhead scale, flame leafhopper, and *Zyginidia scutellaris*.

[0404] From Hymenoptera, for example,

[0405] Species from the genera *Acromyrmex*, *Arge* spp., *Attaspp.*, *Cephus* spp., *Diprion* spp., *Diprionidae*, *Gilpinia polytoma*, *Hoplocampa* spp., *Lasius* spp., *Monomorium pharaonis*, *Neodiprions* pp., *Pogonomyrmex* spp., *Solenopsis* spp., and *Vespa* spp.;

[0406] From the order Isoptera, for example,

[0407] Species of the genera *Coptotermes* spp., *Corniternes cumulans*, *Incisitermes* spp., *Macrotermes* spp., *Mastotermes* spp., *Microtermes* spp., and *Reticulitermes* spp.; tropical fire ant (*Solenopsis geminate*).

[0408] From the order Lepidoptera, for example,

[0409] Species of the genera *Longwinged Roller*, *Brown-banded Roller*, *Clearwing Moth*, *Noctuid Moth*, cotton leafhopper, *Amylois*, *Lysimachia*, *Yellow Roller*, *Argyresthia spp.*, *Betweenleaf Roller*, *Striped Roller*, cotton leafminer, corn leafminer, powdery leafminer, peach fruit borer, *Grass moth*, *Colored Roller*, *Chrysoteuchia topiaria*, grape fruit borer, *Leaf Roller*, *Cloud Roller*, *Striped Roller*, *Sheath Moth*, *Colias lesbia*, *Cosmophila* (flava), species of the genera *Pterocarya*, *Catharanthus*, *Ophiopogon*, *Epinotus*, *Estigmene*, *Etiella*, *Etiella*, *Epinotus ... *Bifidalis*, species of *Bombyx moth*, species of *Minter*, species of *Malacosomaspp.*, *Cabbage noctuid moth*, *Tobacco hawk moth*, species of *Mythimna spp.*, species of *Noctuid moth*, species of *Geometrid moth*, *Orniodes indica*, European corn borer, species of *Small leafroller*, species of *Brown leafroller*, *Small-eyed noctuid moth*, *Stem borer*, *Red bollworm*, *Coffee leafminer*, *Armorworm*, *Potato leafminer*, cabbage white butterfly, species of *Butterfly*, diamondback moth, species of *Small white nest moth*, species of *Geometrid moth*, *Rachiplusia nu*, *Richia albicosta*, species of *Scirpophaga* spp.), species of the genera *Steel borer*, *Long-haired leafroller*, *Grey-winged leafroller*, *Cotton leafroller*, *Clearwinged moth*, *Heterodactylus*, *Roller moth*, *Powdered leafroller*, *Tomato leafminer*, and *Ophiopogon*.

[0410] From the order Mallophaga, for example,

[0411] Species of the genera *Damalinea* and *Trichodectes*;

[0412] From the order Orthoptera, for example,

[0413] Species of the genera *Blatta*, *Blattella*, *Gryllotalpa*, *Leucophaea maderae*, *Locusta*, *Neocurtilla hexadactyla*, *Periplaneta*, *Scapteriscus*, and *Schistocerca*;

[0414] From the order Psocoptera, for example,

[0415] Species of the genus *Liposcelis*;

[0416] From the order Siphonaptera, for example,

[0417] Species of the genera *Ceratophyllus* spp., *Ctenocephalides* spp., and *Xenopsylla cheopis*;

[0418] From the order Thysanoptera, for example,

[0419] Calliothrips phaseoli, Frankliniella spp., Heliothrips spp., Hercinothrips spp., Parthenothrips spp., Scirtothrips aurantii, Sericothrips variabilis, Taeniothrips spp., and Thripsspp.

[0420] From the order Thysanura, for example, silverfish (Lepisma saccharina).

[0421] The active ingredients according to the invention can be used to control (i.e., suppress or destroy) pests of the types described above, which are particularly found on plants, especially useful and ornamental plants in agriculture, horticulture and forestry, or on the organs of these plants, such as fruits, flowers, leaves, stems, tubers or roots, and in some cases, even plant organs formed at a later point in time remain protected against these pests.

[0422] In particular, suitable target crops are: cereals such as wheat, barley, rye, oats, rice, corn, or sorghum; sugar beets such as sugar beets or forage beets; fruits such as pome, stone fruits, or seedless small fruits such as apples, pears, plums, peaches, apricots, cherries, or berries such as strawberries, raspberries, or blackberries; legumes such as beans, lentils, peas, or soybeans; and oilseed crops such as rapeseed, mustard, poppies, olives, sunflowers, coconuts, castor beans, and cocoa beans. Or peanuts; cucurbit crops, such as pumpkins, cucumbers, or melons; fiber plants, such as cotton, flax, hemp, or jute; citrus fruits, such as oranges, lemons, grapefruits, or tangerines; vegetables, such as spinach, lettuce, asparagus, cabbage, carrots, onions, tomatoes, potatoes, or bell peppers; Lauraceae, such as avocados, cinnamon, or camphor; and also tobacco, nuts, coffee, eggplant, sugarcane, tea, pepper, grapevines, hops, plantains, and latex plants.

[0423] The compositions and / or methods of the present invention can also be used on any ornamental plants and / or vegetable crops (including flowers, shrubs, broad-leaved trees and evergreens).

[0424] For example, this invention can be used for any of the following ornamental plant species: Ageratum species, Alonsoa spp. species, Anemone species, Anisodontea capsenisis, Chrysanthemum species, Snapdragon species, Aster species, Begonia species (e.g., Rieger begonia, Begonia semperflorens, B. tubéreux), Bougainvillea species, Brachycome spp. species, Brassica species (ornamental plants), Calceolaria species, Chili pepper, Vinca minor, Canna species, Cornflower species, Chrysanthemum species, Cineraria species (C. maritime), Coreopsis species, Crassula coccinea, Cupeaignea, Dahlia species, Delphinium species, Bleeding heart, Dorotheantus species spp.), lisianthus, forsythia species, fuchsia species, geranium gnaphalium, semperflorens species, globe amaranth, heliotrope species, sunflower species, hibiscus species, hydrangea species, hydrangea species, crape myrtle species, impatiens species (African impatiens), Iresines spp., kalanchoe species, lantana, Marchflower, lion's ear flower species, lily species, pine needle chrysanthemum species, ground cherry species, peppermint species, dragon's face chrysanthemum species, marigold species, carnation species, canna species, oxalis species, daisy species, geranium species (shield geranium, horseshoe geranium), violet species (pansy), petunia species, oleander species, peperomia species spp.), species of the genera *Poinsettia*, *Parthenocissus* (including five-leaved *Parthenocissus* and *Parthenocissus tricuspidata*), species of the genera *Primula*, *Rhododendron*, species of the genera *Rosa*, species of the genera *Datura*, species of the genera *Viola*, species of the genera *Salvia*, *Scaevola aemola*, *Schizanthus wisetonensis*, species of the genera *Sedum*, species of the genera *Solanum*, species of the genera *Surfinia*, species of the genera *Marigold*, species of the genera *Nicotiana*, species of the genera *Verbena*, species of the genera *Zinnia*, and other flower bed plants.

[0425] For example, this invention can be used for any of the following vegetable species: Allium (garlic, onion, shallot (A. oschaninii), leek, scallion, green onion), parsley, celery, asparagus, beet, Brassica (cabbage, Chinese cabbage, turnip), chili, chickpea, endive, chicory (chicory, endive), watermelon, cucumber (cucumber, melon), squash (zucchini, squash), artichoke (artichoke, spiny artichoke), carrot, fennel, St. John's wort, lettuce, tomato (tomato, cherry tomato), mint, basil, parsley, common bean (bean, green bean), pea, radish, edible rhubarb, rosemary, sage, black ginseng, eggplant, spinach, neovalerian (lettuce valerian, V. eriocarpa), and broad bean.

[0426] Preferred ornamental plant species include African violet, Begonia, Dahlia, Sedum, Hydrangea, Verbena, Rosa, Kalanchoe, Poinsettia, Aster, Cornflower, Coreopsis, Delphinium, Mentha, Oleander, Yellow Daisy, Sedum, Petunia, Viola, Impatiens, Geranium, Chrysanthemum, Ranunculus, Fuchsia, Sage, Hydrangea, Rosemary, Sage, St. John's wort, Mint, Sweet pepper, Tomato, and Cucumber.

[0427] The active ingredients according to the invention are particularly suitable for controlling bean aphids, cucumber leaf beetles, tobacco shoot moths, peach aphids, diamondback moths, and sea takin moths on cotton, vegetables, corn, rice, and soybean crops. These active ingredients according to the invention are also particularly suitable for controlling cabbage leafminer (preferably on vegetables), codling moths (preferably on apples), small green leafhoppers (preferably in vegetables and vineyards), potato leaf beetles (preferably on potatoes), and rice stem borers (preferably on rice).

[0428] The active ingredients according to the invention are particularly suitable for controlling bean aphids, cucumber leaf beetles, tobacco shoot moths, peach aphids, diamondback moths, and sea takin moths on cotton, vegetables, corn, rice, and soybean crops. These active ingredients according to the invention are also particularly suitable for controlling cabbage leafminer (preferably on vegetables), codling moths (preferably on apples), small green leafhoppers (preferably in vegetables and vineyards), potato leaf beetles (preferably on potatoes), and rice stem borers (preferably on rice).

[0429] In another aspect, the present invention may also relate to a method for controlling damage to plants and their parts caused by plant parasitic nematodes (endoparasitic, semi-endoparasitic, and ectoparasitic nematodes), particularly the following plant parasitic nematodes: root knot nematodes, northern root knot nematode (Meloidogyne hapla), southern root knot nematode (Meloidogyne incognita), Javan root knot nematode (Meloidogyne javanica), peanut root knot nematode (Meloidogyne arenaria), and other root knot nematode species; cyst-forming nematodes, potato golden nematode (Globodera rostochiensis), and other Globodera species; cereal cyst nematode (Heterodera avenae), soybean cyst nematode (Heteroderaglycines), and beet cyst nematode (Heterodera... *Heterodera trifolii* and other species of the genus *Heterodera*; *Seed gall nematodes* and *Anguina* species; *Stem and foliar nematodes* and *Aphelenchoides* species; *Sting nematodes*, *Belonolaimus longicaudatus* and other species of the genus *Belonolaimus*; *Pine nematodes*, *Bursaphelenchus xylophilus* and other species of the genus *Bursaphelenchus*; *Ring nematodes*. Species of the genera *Criconema*, *Criconemella*, *Criconemoides*, and *Mesocriconema*; *Stemand bulb nematodes*, *Ditylenchus destructor*, *Ditylenchus dipsaci*, and other *Ditylenchus* species; *Awl nematodes* and *Dolichodorus* species;Spiral nematodes, Heliocotylenchus multicinctus and other species of the genus *Helicotylenchus*; Sheath and sheathoid nematodes, species of the genus *Hemicycliophora* and *Hemicriconemoides*; species of the genus *Hirshmanniella*; species of the genus *Lancenematodes* and *Hoploaimus*; species of the genus *false rootknot nematodes* and *Nacobbus*; Needle nematodes, Longidoruselongatus and other species of the genus *Longidorus*; Pin nematodes and species of the genus *Pratylenchus*; Lesion nematodes. * *Pratylenchus neglectus*, *Pratylenchus penetrans*, *Pratylenchus curvitatus*, *Pratylenchus goodeyi*, and other species of the genus *Pratylenchus*; *Burrowing nematodes*, *Radipholus similis*, and other species of the genus *Radipholus*; *Reniform nematodes*, *Rotylenchus robustus*, *Rotylenchus reniformis*, and other species of the genus *Rotylenchus*; species of the genus *Scutellonema*; *Stubby root nematodes*, *Trichodorus*, and other species of the genus *Trichodorus*. primitivus) and other species of the genus *Trichodorus*, species of the genus *Paratrichodorus*; Stunt nematodes, Tylenchorhynchus claytoni, Tylenchorhynchus dubius and other species of the genus *Tylenchorhynchus*;Citrus nematode species (Citrus nematodes, Tylenchulus); Dagger nematodes and Xiphinema species; and other plant-parasitic nematode species, such as Subanguina spp., Hypsoperine spp., Macroposthonia spp., Melinius spp., Punctodera spp., and Quinisulcius spp.

[0430] The compounds of this invention may also possess activity against mollusks. Examples include, for instance, the family Pomacea canaliculata; the family Arionidae (including the black slug *A. ater*, the ringed slug *A. circumscriptus*, the brown slug *A. hortensis*, and the red slug *A. rufus*); and the family Bradybaenidae (including the shrubby slug *Bradybaena*). fruticum); Cepaea (C. hortensis, C. Nemoralis); ochlodina; Deroceras (D. agrestis, D. empiricorum, D. laeve, D. reticulatum); Discus (D. rotundatus); Euophalia; Galba (G. trunculata); Heliclia (H. itala, H. obvia); Helicigona (Helicidae) arbustorum); Helicodiscus; Helix (H. aperta); Limax (L. cinereoniger, L. flavus, L. marginatus, L. maximus, L. tenellus); The genera *Lymnaea*; the family Milax (including *M. gates*, *M. marginatus*, and *M. sowerbyi*); the genus *Opeas*; the genus *Pomacea* (including *P. canaticulata*); and the genera *Vallonia* and *Zanitoides*.

[0431] The term "crop" should be understood to also include crop plants that have been transformed using recombinant DNA technology to enable them to synthesize one or more selectively acting toxins, such as those known to come from toxin-producing bacteria, particularly those of the genus Bacillus.

[0432] Toxins that can be expressed by such transgenic plants include, for example, insecticidal proteins, such as those from Bacillus cereus or Bacillus thuringiensis; or insecticidal proteins from Bacillus thuringiensis, such as δ-endotoxins, such as Cry1Ab, Cry1Ac, Cry1F, Cry1Fa2, Cry2Ab, Cry3A, Cry3Bb1, or Cry9C, or vegetative insecticidal proteins (Vip), such as Vip1, Vip2, Vip3, or Vip3A; or insecticidal proteins from bacterial colonizing nematodes, such as species of the genus *Photorhabdus* or species of the genus *Xenorhabdus*, such as *Photorhabdus luminescens* and *Xenorhabdus*. nematophilus; animal-derived toxins such as scorpion venom, spider venom, bee venom, and other insect-specific neurotoxins; fungal toxins such as streptotoxins; lectins such as pea lectin, barley lectin, or snowdrop lectin; agglutinin; protease inhibitors such as trypsin inhibitors, serine inhibitors, potato glycoproteins, cystatin, and papain inhibitors; ribosome-inactivating proteins (RIPs) such as ricin, maize-RIP, absinthecin, loofah seed toxin, saponin toxin, or cassia root toxin; steroid metabolic enzymes such as 3-hydroxysteroid oxidase, decidual steroid-UDP-glycosyltransferase, cholesterol oxidase, decidualin inhibitors, HMG-COA-reductase, ion channel blockers such as sodium or calcium channel blockers, juvenile hormone esterase, diuretic hormone receptor, stilbene synthase, bibenzyl synthase, chitinase, and glucanase.

[0433] In the context of this invention, δ-endotoxins (e.g., Cry1Ab, Cry1Ac, Cry1F, Cry1Fa2, Cry2Ab, Cry3A, Cry3Bb1, or Cry9C) or vegetative insecticidal proteins (Vip) (e.g., Vip1, Vip2, Vip3, or Vip3A) should be understood to obviously also include mixed toxins, truncated toxins, and modified toxins. Mixed toxins are generated through novel recombination of different combinations of the different domains of those 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 naturally occurring toxin are substituted. In such amino acid substitutions, it is preferable to insert a non-naturally occurring protease recognition sequence into the toxin, for example, as in the case of Cry3A055, a cathepsin-G-recognition sequence is inserted into the Cry3A toxin (see WO 03 / 018810).

[0434] Examples of such toxins or genetically modified plants capable of synthesizing such toxins are disclosed, for example, in EP-A-0 374 753, WO 93 / 07278, WO 95 / 34656, EP-A-0 427 529, EP-A-451 878 and WO 03 / 052073.

[0435] Methods for preparing such transgenic plants are generally known to those skilled in the art and are described in, for example, the disclosures mentioned above. CryI type deoxyribonucleic acid and its preparation are known, for example, from WO 95 / 34656, EP-A-0 367474, EP-A-0 401 979 and WO 90 / 13651.

[0436] The toxins contained in genetically modified plants make them resistant to harmful insects. Such insects can exist in any insect taxonomy, but are particularly common in beetles (Coleoptera), dipterans (Diptera), and moths (Lepidoptera).

[0437] Transgenic plants containing one or more genes encoding resistance to insecticides and expressing one or more toxins are known, and some of these are commercially available. Examples of such plants are: (Corn variety expressing Cry1Ab toxin); YieldGard (A maize variety expressing the Cry3Bb1 toxin); YieldGard (A maize variety that expresses Cry1Ab and Cry3Bb1 toxins); (A maize variety that expresses the Cry9C toxin); Herculex (A maize variety that expresses the Cry1Fa2 toxin and the enzyme that induces tolerance to the herbicide glufosinate-ammonium, phosphatidylcholine N-acetyltransferase (PAT)); NuCOTN (Cotton variety expressing Cry1Ac toxin); Bollgard (Cotton variety expressing Cry1Ac toxin); Bollgard (Cotton variety expressing Cry1Ac and Cry2Ab toxins); (Cotton variety expressing Vip3A and Cry1Ab toxins); (Potato variety that expresses Cry3A toxin); GT Advantage (GA21 glyphosate resistance) CB Advantage (Bt11 corn borer (CB) traits) and

[0438] Other examples of such genetically modified crops are:

[0439] 1. Bt11 maize, from Syngenta Seeds SAS, Chemin del 'Hobit 27, F-31 790 St. Sauveur, France, registration number C / FR / 96 / 05 / 10. A genetically modified maize variety that expresses a truncated Cry1Ab toxin to resist the European corn borer (corn borer and mealybug). Bt11 maize is also genetically modified to express the PAT enzyme to gain tolerance to the herbicide glufosinate.

[0440] 2. Bt176 maize, from Syngenta Seed Company, 27 Hobbit Road, F-31 790 Saint-Soville, France, Registry No. C / FR / 96 / 05 / 10. A genetically modified maize variety that expresses the Cry1Ab toxin transgenic to resist the European corn borer (corn borer and mealybug). Bt176 maize is also transgenic to express the enzyme PAT for tolerance to the herbicide glufosinate.

[0441] 3. MIR604 maize, from Syngenta Seed Company, 27 Hobbit Road, F-31 790 Saint-Soville, France, Registry No. C / FR / 96 / 05 / 10. This is a transgenic maize plant resistant to insects by expressing a modified Cry3A toxin. This toxin is modified by inserting a cathepsin-G-protease recognition sequence, Cry3A055. The preparation of this type of transgenic maize plant is described in WO 03 / 018810.

[0442] 4. MON 863 maize, from Monsanto Europe SA, 270-272 Avenue de Tervuren, B-1150 Brussels, Belgium, registration number C / DE / 02 / 9. MON 863 expresses Cry3Bb1 toxin and is resistant to certain Coleoptera insects.

[0443] 5. IPC 531 cotton, from Monsanto Europe, 270-272 Teflon Boulevard, B-1150 Brussels, Belgium, registration number C / ES / 96 / 02.

[0444] 6.1507 Maize, from Pioneer Overseas Corporation, Avenue Tedesco, 7B-1160 Brussels, Belgium, Registry No. C / NL / 00 / 10. Genetically modified maize expressing the protein Cry1F to acquire resistance to certain lepidopteran insects and expressing the PAT protein to acquire tolerance to the herbicide glufosinate.

[0445] 7. NK603 × MON 810 maize, from Monsanto Europe, 270-272 Teflon Boulevard, B-1150 Brussels, Belgium, registration number C / GB / 02 / M3 / 03. It was created by crossing the genetically modified variety NK603 with MON 810, resulting in a conventionally bred hybrid maize variety. NK603 × MON 810 maize transgenically expresses the protein CP4 EPSPS obtained from the Agrobacterium strain CP4, thus enabling herbicide tolerance. (Contains glyphosate), and also expresses the Cry1Ab toxin obtained from Bacillus thuringiensis Kurstak subspecies, making it resistant to certain lepidopteran insects, including the European corn borer.

[0446] Transgenic crops of insect-resistant plants were also described in BATS (Zentrum für Biosicherheit und Nachhaltigkeit, BATS Center, Clarastrasse 13, Basel 4058, Switzerland) report 2003. http: / / bats.ch )middle.

[0447] The term "crop" should be understood to also include crop plants that have been transformed using recombinant DNA technology to enable them to synthesize selectively active resistance substances, such as so-called "pathogenesis-associated proteins" (PRPs, see, for example, EP-A-0 392 225). Examples of such resistance substances and transgenic plants capable of synthesizing such resistance 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 disclosures mentioned above.

[0448] Crops can also be modified to increase their resistance to pathogens such as fungi (e.g., Fusarium, Anthracnose, or Phytophthora), bacteria (e.g., Pseudomonas), or viruses (e.g., Potato Leaf Roll Virus, Tomato Spotted Wilt Virus, Cucumber Mosaic Virus).

[0449] Crops also include those that have increased resistance to nematodes such as soybean heterodera.

[0450] Crops that are tolerant to abiotic stresses include those that have increased tolerance to drought, high salinity, high temperature, cold, frost or light radiation, for example, through the expression of NF-YB or other proteins known in the art.

[0451] Antipathogenic substances that can be expressed by such transgenic plants include, for example, ion channel blockers, such as sodium and calcium channel blockers, such as viral KP1, KP4, or KP6 toxins; stilbene synthase; bibenzyl synthase; chitinase; glucanase; so-called "pathogenesis-associated proteins" (PRPs; see, for example, EP-A-0 392 225); antipathogenic substances produced by microorganisms, such as peptide antibiotics or heterocyclic antibiotics (see, for example, WO 95 / 33818); or proteins or polypeptide factors involved in plant pathogen defense (so-called "plant disease resistance genes," as described in WO 03 / 000906).

[0452] Other applications of the compositions according to the invention include the protection of stored articles and storage rooms, as well as the protection of raw materials such as timber, textiles, flooring, or buildings, and also in the field of hygiene, particularly the protection of humans, livestock, and productive animals from the types of pests mentioned.

[0453] 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 includes applying the composition of the invention to the target pests, their site, surface, or substrate by brushing, rolling, spraying, coating, or impregnation. By way of example, the method of the invention is contemplated for IRS (Indoor Residual Spray) application to surfaces (such as wall, ceiling, or floor surfaces). In another embodiment, the application of such compositions to substrates, such as nonwoven or woven materials, in the form of mesh fabrics, quilts, blankets, curtains, and tents (or which can be used in the manufacture of these articles) is contemplated.

[0454] In one embodiment, a method for controlling such pests includes applying a biocidally effective amount of the composition of the invention to the target pests, their site, or a surface or substrate to provide effective residual biocidal activity on the surface or substrate. Such application can be carried out by brushing, rolling, spraying, coating, or impregnating the biocidal composition of the invention. By way of example, the method of the invention is considered for IRS application to surfaces (such as wall, ceiling, or floor surfaces) to provide effective residual biocidal activity on the surface. In another embodiment, the application of such a composition for residual control of pests on a substrate, such as a fabric material in the form of (or that may be used in the manufacture of) netting, coverings, bedding, curtains, and tents, is considered.

[0455] The substrate to be treated (including nonwovens, fabrics, or meshes) can be made of natural fibers (such as cotton, raffia leaf fibers, jute, flax, sisal, burlap, or wool) or synthetic fibers (such as polyamide, polyester, polypropylene, polyacrylonitrile, etc.). Polyester is particularly suitable. Methods for treating textiles are known, for example, WO 2008 / 151984, WO 2003 / 034823, US 5631072, WO 2005 / 64072, WO 2006 / 128870, EP 1724392, WO 2005113886, or WO2007 / 090739.

[0456] Another application of the compositions according to the invention is in the field of tree injection / trunk treatment for all ornamental trees, as well as all kinds of fruit and nut trees.

[0457] In the field of tree injection / trunk treatment, the compounds according to the invention are particularly suitable for combating wood-boring insects from the Lepidoptera and Coleoptera mentioned above, especially those listed in Tables A and B below:

[0458] Table A. Examples of economically important invasive wood-boring insects.

[0459]

[0460] Table B. Examples of local wood-boring insects of economic importance.

[0461]

[0462]

[0463]

[0464]

[0465]

[0466] This invention can also be used to control any insect pests that may be present in lawn grasses, including, for example, beetles, caterpillars, fire ants, ground pearls, millipedes, sowbugs, mites, mole crickets, scale insects, mealybugs, ticks, froghoppers, southern wheat bugs, and grubs. This invention can be used to control insect pests at all stages of their life cycle, including eggs, larvae, nymphs, and adults.

[0467] Specifically, this invention can be used to control insect pests fed on the roots of lawn grasses, including grubs (such as Cyclocephala spp.) (e.g., the marked scarab beetle, C. lurida), Rhizotrogus (e.g., the European scarab beetle, R. majalis), Cotinus (e.g., the green June beetle, C. nitida), Popillia spp. (e.g., the Japanese beetle, the ladybug (P. japonica)), Phyllophaga spp. (e.g., the May / June beetle), Ataenius (e.g., the black turfgrass beetle, A. spretulus), and Malladera spp. (e.g., the Asiatic garden beetle). (beetle), M. castanea and Tomarus), ground pearl (Margarodes spp.)), mole cricket (brownish-yellow, southern and short-winged; Scapteriscus spp., Gryllotalpa africana) and leafjackets (European crane fly, Tipula spp.)).

[0468] This invention can also be used to control insect pests in lawn grasses of thatched houses, including armyworms (such as the fall armyworm Spodoptera frugiperda and the common armyworm Pseudaletia unipuncta), root cutters, weevils (species of the genus Sphenophorus, such as S. venatus verstitus and S. parvulus), and grass moths (such as species of the genus Crambus and the tropical grass moth Herpetogramma phaeopteralis).

[0469] This invention can also be used to control insect pests in turfgrass that live on the ground and feed on the leaves of turfgrass. These insect pests include wheat bugs (such as southern wheat bugs and southern stem bugs (Blissus insularis)), bermudagrass mite (Eriophyes cynodoniensis), grass mealybug (Antonina graminis)), two-lined grasshopper (Propsapia bicincta), leafhoppers, root-cutting moths (Noctuidae), and wheat aphids.

[0470] This invention can also be used to control other harmful organisms in lawn grasses, such as introduced red imported fire ants (Solenopsis invicta) that create nests in lawns.

[0471] In the field of hygiene, the compositions according to the invention are effective against antiparasitic parasites such as hard ticks, soft ticks, scabies mites, fall mites, flies (biting and licking), parasitic fly larvae, lice, hair lice, bird lice, and fleas.

[0472] Examples of this type of parasite are:

[0473] Lice: Species of the genera *Linognathus*, *Phtirus*, *Phtirus*, and *Phtirus*.

[0474] Trichophagia: Species of the genera *Hymenopteris*, *Hymenopteris*, *Hymenopteris*, *Hymenopteris*, *Hymenopteris*, *Hymenopteris*, *Hymenopteris*, *Hymenopteris*, *Hymenopteris*, *Hymenopteris*, and *Hymenopteris*.

[0475] Diptera and the suborders Nematocerina and Brachycerina, such as species of the genera *Aedes*, *Anopheles*, *Culex*, *Simulium*, *Eusimulium*, *Phlebotomus*, *Lutzomyia*, *Culicoides*, *Chrysops*, *Hybomitra*, *Atylotus*, *Tabanus*, *Haematopota*, and *Philipomyia*. spp.), species of the genera *Braulaspp.*, *Musca spp.*, *Hydrotaea spp.*, *Hippobosca spp.*, *Haematobia spp.*, *Morellia spp.*, *Fannia spp.*, *Glossina spp.*, *Calliphora spp.*, *Lucilia spp.*, *Chrysomyia spp.*, *Wohlfahrtia spp.*, *Sarcophagas spp.*, *Oestrus spp.*, *Hypoderma spp.*, *Gasterophilus spp.*, *Hippobosca spp.*, and *Lipoptena*. spp.) and species of the genus Melophagos (Melophagus spp.).

[0476] Siphonapterida, including species of the genera *Pulex*, *Xenopsylla*, and *Xenopsylla*.

[0477] Heteropterida, including species of the genera *Pycnodon*, *Triatomine*, *Aspergillus*, and *Panstrongylus* spp.

[0478] Blattodea, including species such as the Oriental cockroach (Blatta orientalis), the American cockroach (Periplaneta americana), the German cockroach (Blattelagermanica), and species of the genus Supella (Supella spp.).

[0479] Acaria (subclass Acaria, family Acarida), and Metastigmata and Mesostigmata, including species of the genera *Argas*, *Ornithodorus*, *Otobius*, *Ixodes*, *Amblyommas*, *Boophilus*, *Dermacentor*, *Haemophysalis*, *Hyalomma*, *Rhipicephalus*, *Dermanyssus*, *Raillietia*, and *Pneumonyssus*. spp.), species of the genus *Sternostoma* spp., and species of the genus *Varroaspp.*.

[0480] Actinedida (prostigmata) and Acaridida (Astigmata), including species of the genera *Acarapis*, *Cheyletiella*, *Ornithocheyletia*, *Myobia*, *Psorergates*, *Demodex*, *Trombicula*, *Listrophorus*, *Acarus*, *Tyrophagus*, *Caloglyphus*, *Hypodectes*, and *Pterolichus*. Species of the genera *Psoroptes*, *Chorioptes*, *Otodectes*, *Sarcoptes*, *Notoedress*, *Knemidocoptes*, *Cytodites*, and *Laminosioptes*.

[0481] The compositions according to the invention are also suitable for protecting materials such as wood, textiles, plastics, adhesives, glues, paints, paper and cards, leather, flooring and buildings from insect infestation.

[0482] The compositions according to the invention can be used, for example, to combat the following pests: beetles such as the North American house longhorn beetle (Hylotrupes bajulus), the long-haired longhorn beetle (Chlorophorus pilosis), the furniture thief (Anobium punctatum), the red-haired thief (Xestobium rufovillosum), the comb-horned thief (Ptilinuspecticornis), the dendrobium pertinex, the pine bud thief (Ernobius mollis), the primed carpini, the brown powder beetle (Lyctus brunneus), the African powder beetle (Lyctus africanus), the southern powder beetle (Lyctus planicollis), the oak powder beetle (Lyctus linearis), the pubescens powder beetle (Lyctus pubescens), and the breast powder beetle (Trogoxylon). The species include *Aequale*, *Minthesrugicollis*, species of *Xyleborus* spec., species of *Tryptodendron* spec., *Apate monachus*, *Bostrychus capucins*, *Heterobostrychus brunneus*, species of *Sinoxylon* spec., and *Dinoderus minutus*, as well as hymenopterans such as *Sirex juvencus*, *Urocerus gigas*, *Urocerus gigas taignus*, and *Urocerus augu*, and termites such as *Kalotermes flavicollis*, *Cryptotermes brevis*, and *Heterotermes*. The termites include *Indicola*, *Reticulitermes flavipes*, *Reticulitermes santonensis*, *Reticulitermes lucifugus*, *Mastotermes darwiniensis*, *Zootermopsis nevadensis*, and *Coptotermes formosanus*, as well as wood-boring insects such as silverfish (*Lepisma saccharina*).

[0483] The compounds according to the invention can be used as pest control agents in their unmodified form, but they are generally formulated into compositions in a variety of ways using formulation aids (such as carriers, solvents, and surfactants). These formulations can be in various physical forms, for example, as powders, gels, wettable powders, water-dispersible granules, water-dispersible tablets, effervescent compressed tablets, emulsifiable concentrates, microemulsifiable concentrates, oil-in-water emulsions, flowable oils, aqueous dispersions, oily dispersions, suspensions, capsule suspensions, emulsifiable granules, soluble liquids, water-soluble concentrates (with water or a water-miscible organic solvent as a carrier), impregnated polymer films, or in other known forms, such as those described in the Manual on Development and Use of FAO and WHO Specifications for Pesticides, United Nations, 1st Edition, Second Revision (2010). Such formulations can be used directly or diluted before use. It can be diluted with, for example, water, liquid fertilizer, micronutrients, biological organisms, oil or solvents.

[0484] These formulations can be prepared, for example, by mixing the active ingredients with formulation aids to obtain compositions in the form of finely dispersed solids, particles, solutions, dispersions, or emulsions. These active ingredients can also be formulated with other aids, such as finely dispersed solids, mineral oils, oils of plant or animal origin, modified oils of plant or animal origin, organic solvents, water, surfactants, or combinations thereof.

[0485] These active ingredients can also be contained in very fine microcapsules. Microcapsules contain the active ingredient within a porous carrier. This allows the active ingredient to be released into the environment in a controlled amount (e.g., slow release). Microcapsules typically have a diameter from 0.1 to 500 micrometers. The amount of active ingredient they contain is approximately 25% to 95% by weight of the capsule. These active ingredients can be in the form of a monolithic solid, fine particles in a solid or liquid dispersion, or in a solution-suitable form. The encapsulating membrane can contain, for example, natural or synthetic rubber, cellulose, styrene / butadiene copolymers, polyacrylonitrile, polyacrylates, polyesters, polyamides, polyureas, polyurethanes, or chemically modified polymers, as well as starch xanthates, or other polymers known to those skilled in the art. Alternatively, very fine microcapsules can be formed in which the active ingredient is contained in the form of finely dispersed particles within a solid matrix of a base substance, but these microcapsules themselves are not encapsulated.

[0486] Suitable formulation aids for preparing compositions according to the invention are known in themselves. As liquid carriers, the following can be used: water, toluene, xylene, petroleum ether, vegetable oil, acetone, methyl ethyl ketone, cyclohexanone, acid anhydride, acetonitrile, acetophenone, amyl acetate, 2-butanone, butenyl carbonate, chlorobenzene, cyclohexane, cyclohexanol, alkyl acetate, diacetone alcohol, 1,2-dichloropropane, diethanolamine, p-diethylbenzene, diethylene glycol, diethylene glycol, diethylene glycol butyl ether, diethylene glycol ethyl ether, diethylene glycol methyl ether, N,N-dimethyl... Formamide, dimethyl sulfoxide, 1,4-dioxane, dipropylene glycol, dipropylene glycol methyl ether, dipropylene glycol dibenzoate, dipropylene glycol, 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, glyceryl acetate, glyceryl diacetate, glyceryl triacetate, deca-acetate, etc. Hexadecane, hexanediol, isopentyl acetate, isobornyl acetate, isooctane, isophorone, cumene, isopropyl myristate, lactic acid, laurylamine, isopropyl acetone, methoxypropanol, methyl isopentyl ketone, methyl isobutyl ketone, methyl lauryl ketone, methyl octanoate, methyl oleate, dichloromethane, m-xylene, n-hexane, n-octylamine, octadecanoic acid, octylamine acetate, oleic acid, oleyleneamine, o-xylene, phenol, polyethylene glycol, propionic acid, propyl lactate Propylene carbonate, propylene glycol, propylene glycol methyl ether, p-xylene, toluene, triethyl phosphate, triethylene glycol, xylenesulfonic acid, paraffin, mineral oil, trichloroethylene, perchloroethylene, ethyl acetate, amyl acetate, butyl acetate, propylene glycol methyl ether, diethylene glycol methyl ether, methanol, ethanol, isopropanol, and alcohols with higher molecular weights, such as pentanol, tetrahydrofuranol, hexanol, octanol, ethylene glycol, propylene glycol, glycerol, N-methyl-2-pyrrolidone, etc.

[0487] Suitable solid carriers include, for example, talc, titanium dioxide, pyrophyllite clay, silica, attapulgite clay, diatomaceous earth, limestone, calcium carbonate, bentonite, calcium montmorillonite, cottonseed hulls, wheat flour, soybean flour, pumice, wood flour, ground walnut shells, lignin, and similar substances.

[0488] Many surfactants can be advantageously used in both solid and liquid formulations, especially those that can be diluted with a carrier before use. Surfactants can be anionic, cationic, nonionic, or polymeric, and they can be used as emulsifiers, wetting agents, suspending agents, or for other purposes. Typical surfactants include, for example, salts of alkyl sulfates, such as diethanolammonium dodecyl sulfate; salts of alkyl aryl sulfonates, such as calcium dodecylbenzenesulfonate; alkylphenol / olefin oxide addition products, such as ethoxylated nonylphenol; alcohol / olefin oxide addition products, such as ethoxylated tridecyl alcohol; soaps, such as sodium stearate; salts of alkyl naphthalene sulfonates, such as sodium dibutylnaphthalene sulfonate; salts of dialkyl sulfosuccinates, such as sodium di(2-ethylhexyl)sulfosuccinate; sorbitol esters, such as sorbitol oleate; quaternary ammonium compounds, such as dodecyltrimethylammonium chloride; polyethylene glycol esters of fatty acids, such as polyethylene glycol stearate; block copolymers of ethylene oxide and propylene oxide; and salts of monoalkyl and dialkyl phosphate esters; and other substances, such as those described in McCutcheon's Detergents and Emulsifiers Annual, MC Publishing. Corp.), Ridgewood, New Jersey (1981).

[0489] Other adjuvants that can be used in formulations for killing pests include crystallization inhibitors, viscosity modifiers, suspending agents, dyes, antioxidants, foaming agents, light absorbers, mixing aids, defoamers, complexing agents, substances that neutralize or change pH and buffer solutions, corrosion inhibitors, fragrances, wetting agents, absorption enhancers, micronutrients, plasticizers, flow aids, lubricants, dispersants, thickeners, antifreeze agents, microbial agents, and liquid and solid fertilizers.

[0490] The compositions according to the invention may include additives comprising oils of plant or animal origin, mineral oils, alkyl esters of such oils, or mixtures of such oils with oil derivatives. The amount of oil additive in the compositions according to the invention is typically from 0.01% to 10% of the mixture to be applied. For example, the oil additive may be added to the spray can at the desired concentration after the spray mixture has been prepared. Preferred oil additives include mineral oils or plant-derived oils, such as rapeseed oil, olive oil, or sunflower oil; emulsified vegetable oils; alkyl esters of plant-derived oils, such as methyl derivatives; or animal-derived oils, such as fish oil or tallow. Preferred oil additives include C8-C... 22 Alkyl esters of fatty acids, especially C 12 -C 18Methyl derivatives of fatty acids, such as lauric acid, palmitic acid, and methyl esters of oleic acid (methyl laurate, methyl palmitate, and methyl oleate, respectively). Many oil derivatives are known in the Compendium of Herbicide Adjuvants, 10th edition, Southern Illinois University, 2010.

[0491] These compositions of the invention generally comprise from 0.1% to 99%, particularly from 0.1% to 95% by weight, of the compounds of the invention and from 1% to 99.9% by weight, of formulation aids, which preferably comprise from 0% to 25% by weight of surfactants. Commercial products may preferably be formulated as concentrates, while end users will typically use diluted formulations.

[0492] Application rates vary over a wide range and depend on soil properties, application method, crop species, pests to be controlled, primary climatic conditions, and other factors governed by application method, application time, and target crop. Generally, compounds can be applied at rates ranging from 1 l / ha to 2000 l / ha, particularly from 10 l / ha to 1000 l / ha.

[0493] Preferred formulations may have the following composition (wt%):

[0494] Emulsifiable concentrate :

[0495] Active ingredient: 1% to 95%, preferably 60% to 90%

[0496] Surfactant: 1% to 30%, preferably 5% to 20%

[0497] Liquid carrier: 1% to 80%, preferably 1% to 35%

[0498] dust :

[0499] Active ingredient: 0.1% to 10%, preferably 0.1% to 5%

[0500] Solid carrier: 99.9% to 90%, preferably 99.9% to 99%.

[0501] Suspension concentrate:

[0502] Active ingredient: 5% to 75%, preferably 10% to 50%

[0503] Water: 94% to 24%, preferably 88% to 30%

[0504] Surfactant: 1% to 40%, preferably 2% to 30%

[0505] wettable powder :

[0506] Active ingredient: 0.5% to 90%, preferably 1% to 80%

[0507] Surfactant: 0.5% to 20%, preferably 1% to 15%

[0508] Solid carrier: 5% to 95%, preferably 15% to 90%

[0509] Granules:

[0510] Active ingredient: 0.1% to 30%, preferably 0.1% to 15%.

[0511] Solid carrier: 99.5% to 70%, preferably 97% to 85%

[0512] The following examples further illustrate (but do not limit) the invention.

[0513]

[0514] The combination is thoroughly mixed with these adjuvants and the mixture is thoroughly ground in a suitable grinder to obtain a wettable powder that can be diluted with water to give a suspension of the desired concentration.

[0515] <![CDATA[ Powder for dry seed treatment ]]> a) b) c) Active ingredients 25％ 50％ 75％ Light mineral oil 5％ 5％ 5％ Highly dispersed silica 5％ 5％ - Kaolin 65％ 40％ - talc - 20％

[0516] The combination is thoroughly mixed with the adjuvant and the mixture is thoroughly ground in a suitable grinder to obtain a powder that can be used directly for seed treatment.

[0517]

[0518]

[0519] Emulsions with any required dilution that can be used in plant protection can be obtained by diluting such concentrates with water.

[0520] <![CDATA[ dust ]]> a) b) c) Active ingredients 5％ 6％ 4％ talc 95％ - - Kaolin - 94％ - Mineral packing - - 96％

[0521] A ready-to-use powder is obtained by mixing the mixture with a carrier and grinding the mixture in a suitable grinder. This type of powder can also be used for dry seed dressing.

[0522] <![CDATA[ Extruder granules ]]> Active ingredients 15％ Sodium lignosulfonate 2％ Carboxymethyl cellulose 1％ Kaolin 82％

[0523] The mixture is combined with these additives and ground, and then the mixture is moistened with water. The mixture is extruded and then dried in an air stream.

[0524] <![CDATA[ Coated granules ]]> Active ingredients 8％ Polyethylene glycol (molecular weight 200) 3％ Kaolin 89％

[0525] This finely ground mixture is applied evenly to kaolin moistened with polyethylene glycol in a mixer. This process yields dust-free coated granules.

[0526] suspension concentrate

[0527] Active ingredients 40％ Propylene glycol 10％ Nonylphenol polyethylene glycol ether (15 mol ethylene oxide) 6％ Sodium lignosulfonate 10％ Carboxymethyl cellulose 1％ Silicone oil (in the form of a 75% water emulsion) 1％ water 32％

[0528] The finely ground mixture is tightly blended with adjuvants to obtain a suspension concentrate, from which a suspension concentrate can be diluted with water to obtain a suspension with any desired dilution. Using such dilutions, living plants along with their propagation material can be treated and protected against microbial infection by spraying, pouring, or immersion.

[0529] Flowable concentrate for seed treatment

[0530]

[0531] The finely ground mixture is tightly blended with adjuvants to obtain a suspension concentrate, from which a suspension concentrate can be diluted with water to obtain a suspension with any desired dilution. Using such dilutions, living plants along with their propagation material can be treated and protected against microbial infection by spraying, pouring, or immersion.

[0532] Sustained-release capsule suspension

[0533] 28 parts of the mixture were combined with 2 parts of an aromatic solvent and 7 parts of a toluene diisocyanate / polymethylene-polyphenyl isocyanate mixture (8:1). This mixture was emulsified in a mixture of 1.2 parts of polyvinyl alcohol, 0.05 parts of an antifoaming agent, and 51.6 parts of water until the desired particle size was achieved. 2.8 parts of a 1,6-hexanediamine mixture in 5.3 parts of water were added to this emulsion. The mixture was stirred until polymerization was complete. The resulting capsule suspension was stabilized by adding 0.25 parts of a thickener and 3 parts of a dispersant. This capsule suspension formulation contained 28% of the active ingredient. The diameter of the medium capsule was 8-15 micrometers. The resulting formulation was applied to seeds as an aqueous suspension in a suitable apparatus for this purpose.

[0534] Formulation types include emulsion concentrates (EC), suspension concentrates (SC), suspension emulsions (SE), capsule suspensions (CS), water-dispersible granules (WG), emulsifiable granules (EG), water-in-oil emulsions (EO), oil-in-water emulsions (EW), microemulsions (ME), oil dispersions (OD), oil suspensions (OF), oil-soluble liquids (OL), soluble concentrates (SL), ultra-low volume suspensions (SU), ultra-low volume liquids (UL), technical grade (TK), dispersible concentrates (DC), wettable powders (WP), soluble granules (SG), or any technically feasible formulation in combination with agriculturally acceptable adjuvants.

[0535] Preparation example:

[0536] "Mp" refers to the melting point in °C. The free radical indicates a methyl group. 1 ¹H NMR measurements were recorded on a Brucker 400 MHz spectrometer, and chemical shifts relative to TMS standards are given in ppm. Spectra were measured in deuterated solvents as indicated. These compounds were characterized using any of the following LCMS methods. Characteristic LCMS values ​​obtained for each compound are retention time (“Rt”, recorded in minutes) and the measured molecular ion (M+H). + Or (MH) - .

[0537] LCMS method:

[0538] Method 1:

[0539] Spectra were recorded on a Waters mass spectrometer (SQD single quadrupole mass spectrometer) equipped with an electro-jet source (polarity: positive or negative ion, full scan, capillary voltage: 3.00 kV, cone range: 41 V, source temperature: 150 °C, desolvation temperature: 500 °C, cone gas flow rate: 50 L / Hr, desolvation gas flow rate: 1000 L / Hr, mass range: 110 to 800 Da) and a Waters Class H UPLC: quaternary pump, heated column chamber, and diode array detector. Column: Acquity UPLC HSS T3 C18, 1.8 μm, 30 × 2.1 mm, Temperature: 40 °C, DAD wavelength range (nm): 200 to 400, Solvent gradient: A = water + 5% acetonitrile + 0.1% HCOOH, B = acetonitrile + 0.05% HCOOH; Gradient: 0 min 10% B; 0.2-0.2 min 10%-50% B; 0.2-0.7 min 50%-100% B; 0.7-1.3 min 100% B; 1.3-1.4 min 100%-10% B; 1.4-1.6 min 10% B; Flow rate (mL / min): 0.6.

[0540] Method 2:

[0541] Spectra were recorded on a mass spectrometer (6410 triple quadrupole mass spectrometer) from Agilent Technologies, equipped with an electro-ejector source (polarity: positive or negative ion, MS2 scan, capillary voltage: 4.00 kV, fragmentation voltage: 100 V, desolvation temperature: 350 °C, gas flow rate: 11 L / min, nebulizer gas: 45 psi, mass range: 110 to 1000 Da) and an Agilent 1200 Series HPLC: quaternary pump, heated column chamber, and diode array detector. Column: KINETEX EVO C18, 2.6 μm, 50 × 4.6 mm, temperature: 40 °C, DAD wavelength range (nm): 210 to 400, solvent gradient: A = water + 5% acetonitrile + 0.1% HCOOH, B = acetonitrile + 0.1% HCOOH; gradient: 0 min 10% B, 90% A; 0.9-1.8 min 100% B; 1.8-2.2 min 100%-10% B; 2.2-2.5 min 10% B; flow rate (mL / min) 1.8.

[0542] Example P1: 2-[2-(1-Cyclopropylpyrazole-4-yl)-5-ethylsulfonyl-1-methyl-imidazol-4-yl]-6-(tri-) Preparation of fluoromethoxy)isoindoline-1-one (compound P1)

[0543]

[0544] Step A1: Preparation of methyl 2-amino-5-(trifluoromethoxy)benzoate (intermediate I-1)

[0545]

[0546] Potassium carbonate (6.3 g, 45 mmol) and iodomethane (1.4 mL, 23 mmol) were added to a solution of 2-amino-5-(trifluoromethoxy)benzoic acid (5.0 g, 23 mmol) in N,N-dimethylformamide (50 mL) at room temperature. The reaction mixture was stirred overnight at room temperature. The reaction mixture was quenched with water (300 mL) and extracted with ethyl acetate (3 x 100 mL). The organic layer was dried over sodium sulfate, filtered, and concentrated under vacuum. The crude product was purified by combiflash (silica gel, 0-10% ethyl acetate in cyclohexane) to give methyl 2-amino-5-(trifluoromethoxy)benzoate. LCMS (Method 2): Rt = 1.46 min, m / z = 236 (M+H) + . 1 H NMR (400MHz, CDCl3) δppm: 3.89 (s, 3H), 5.80 (br s, 2H), 6.66 (d, 1H), 7.15 (ddt, 1H), 7.73 (d, 1H).

[0547] Step A2: Preparation of methyl 2-bromo-5-(trifluoromethoxy)benzoate (intermediate I-2)

[0548]

[0549] A solution of sodium nitrite (4.3 g, 62 mmol) in water (22 mL) was added dropwise to an intermediate I-1 (7.3 g, 31 mmol) prepared as described above in hydrobromic acid (48% in water, 73 mL) cooled at 0 °C. The reaction mixture was stirred at 0 °C for 30 min, and then copper bromide (I) (8.0 g, 56 mmol) was added. The reaction mixture was stirred at 0 °C for another 30 min, and then stirred at room temperature for 5 h. The reaction mixture was diluted with water (100 mL) and extracted with ethyl acetate (3 x 200 mL). The combined organic layers were dried over sodium sulfate, filtered, and concentrated under vacuum. The crude product was purified by combiflash (silica gel, 0-8% ethyl acetate in cyclohexane) to give methyl 2-bromo-5-(trifluoromethoxy)benzoate. 1 H NMR (400MHz, CDCl3) δppm: 3.96 (s, 3H), 7.22 (m, 1H), 7.66-7.73 (m, 2H).

[0550] Step A3: Preparation of methyl 2-methyl-5-(trifluoromethoxy)benzoate (intermediate I-3)

[0551]

[0552] In a flask, methyl 2-bromo-5-(trifluoromethoxy)benzoate (intermediate I-2 prepared as described above) (5.3 g, 18 mmol), methylboronic acid (3.3 g, 53 mmol), tripotassium phosphate (11 g, 53 mmol), and tricyclohexylphosphonate (0.50 g, 1.8 mmol) were added, followed by toluene (64 mL) and water (11 mL). The flask was purged with nitrogen for 10 min, then palladium(II) acetate (0.20 g, 0.89 mmol) was added and purging continued for an additional 10 min. The reaction mixture was heated to 100 °C and stirred for 3 h. The reaction mixture was quenched with water (50 mL) and extracted with ethyl acetate (3 x 50 mL). The combined organic layers were dried over sodium sulfate, filtered, and concentrated under vacuum. The crude product was purified by combiflash (silica gel, 100% cyclohexane) to give methyl 2-methyl-5-(trifluoromethoxy)benzoate. 1 H NMR (400MHz, CDCl3) δppm: 2.61 (s, 3H), 3.92 (s, 3H), 7.27-7.30 (m, 2H), 7.78 (s, 1H).

[0553] Step A4: Preparation of methyl 2-(bromomethyl)-5-(trifluoromethoxy)benzoate (intermediate I-4)

[0554]

[0555] At room temperature, N-bromosuccinimide (2.0 g, 11 mmol) and benzoyl peroxide (0.70 g, 2.0 mmol) were added to a solution of methyl 2-methyl-5-(trifluoromethoxy)benzoate (intermediate I-3 prepared as described above) (1.9 g, 8.1 mmol) in tetrachloromethane (65 mL). The reaction mixture was heated to 70 °C and stirred for 3 hours. After cooling to room temperature, the reaction mixture was diluted with ice-cold water (100 mL) and extracted with dichloromethane (3 x 50 mL). The combined organic layers were washed with brine (50 mL), dried over sodium sulfate, filtered, and concentrated under vacuum. The crude product was purified by combiflash (silica gel, 5-10% ethyl acetate in cyclohexane) to give methyl 2-(bromomethyl)-5-(trifluoromethoxy)benzoate. 1 H NMR (400MHz, CDCl3) δppm: 3.97 (s, 3H), 4.95 (s, 2H), 7.50-7.56 (m, 1H), 7.83 (d, 1H), 8.07-8.12 (m, 1H).

[0556] Step B1: Preparation of ethyl 1-methylimidazolium-4-carboxylate (intermediate I-5)

[0557]

[0558] N,N-dimethylformamide (1.23 mL, 15.9 mmol) was added in a single injection to a solution of 1-methylimidazolium-4-carboxylic acid (20.0 g, 159 mmol) in ethanol (200 mL). The mixture was cooled to 0–5 °C. Then, thionyl chloride (34.7 mL, 476 mmol) was added dropwise over 15 minutes at 0–5 °C. The cooling was then removed, and the mixture was stirred from 0–5 °C to 24 °C for one hour. The reaction mixture was stirred at 80 °C for 6 hours under a nitrogen atmosphere. After completion, the reaction mixture was concentrated under vacuum, quenched with a saturated aqueous sodium bicarbonate solution (100 mL), and extracted with ethyl acetate (3 x 200 mL). The combined organic layers were washed with brine, dried over sodium sulfate, filtered, and concentrated under vacuum to give ethyl 1-methylimidazolium-4-carboxylate. This material was used as is in the next step. LCMS (Method 2): Rt = 0.31 min, m / z = 155 (M+H) + .

[0559] Step B2: Preparation of ethyl 2-bromo-1-methyl-imidazolium-4-carboxylate (intermediate I-6)

[0560]

[0561] To a solution of ethyl 1-methylimidazolium-4-carboxylate (intermediate I-5 prepared as described above) (20.0 g, 130 mmol) in tetrahydrofuran (200 mL), N-bromosuccinimide (23.6 g, 130 mmol) and potassium tribasic phosphate (29.0 g, 130 mmol) were added, and the mixture was stirred at room temperature for 16 hours under a nitrogen atmosphere. The reaction mixture was diluted with water (100 mL) and extracted with ethyl acetate (3 x 100 mL). The organic layer was dried over sodium sulfate, filtered, and concentrated under vacuum. The crude product was purified by combiflash (silica gel, 35% ethyl acetate in cyclohexane) to give ethyl 2-bromo-1-methylimidazolium-4-carboxylate as a white solid. LCMS (Method 2): Rt = 0.85 min, m / z = 233 (M+H) + . 1 H NMR (400MHz, CDCl3) δppm: 1.37 (t, 3H) 3.68 (s, 3H) 4.36 (q, 2H) 7.64 (s, 1H).

[0562] Step B3: Preparation of ethyl 2-bromo-5-ethylthio-1-methyl-imidazolium-4-carboxylate (intermediate I-7)

[0563]

[0564] To a solution of N-isopropylpropyl-2-amine (2.4 mL, 17 mmol) in tetrahydrofuran (20 mL), n-butyllithium (2.0 mol / L, 10 mL, 20 mmol in cyclohexane) was added at -78 °C under a nitrogen atmosphere. The resulting solution was stirred at -78 °C for 30 minutes. The solution was then warmed to 0 °C and stirred at 0 °C for 30 minutes. This newly prepared diisopropylaminolithium solution was then added dropwise at -78 °C to a solution of ethyl 2-bromo-1-methyl-imidazolium-4-carboxylate (intermediate I-6 prepared as described above) (2.5 g, 11 mmol) and (ethyl dithioalkyl)ethane (2.6 g, 21 mmol) in tetrahydrofuran (25 mL). The resulting solution was stirred at -78 °C for 30 minutes. The reaction mixture was quenched with a saturated aqueous ammonium chloride solution and extracted with ethyl acetate (2 x 100 mL). The organic layer was washed with brine, dried over sodium sulfate, filtered, and concentrated under vacuum. The crude product was purified by combiflash (silica gel, 20% ethyl acetate in cyclohexane) to give pure ethyl 2-bromo-5-ethylthioalkyl-1-methyl-imidazolium-4-carboxylate as a brown, viscous oil. LCMS (Method 2): Rt = 1.36 min, m / z = 293 (M+H) + . 1 HNMR (400MHz, CDCl3) δppm: 1.21 (t, 3H) 1.40 (t, 3H) 2.92 (q, 2H) 3.71 (s, 3H) 4.40 (q, 2H).

[0565] Step B4: Preparation of ethyl 2-bromo-5-ethylsulfonyl-1-methyl-imidazolium-4-carboxylate (intermediate I-8)

[0566]

[0567] 3-chloroperoxybenzyl acid (8.32 g, 33.8 mmol, 70 wt%) was added to a 0°C cooled solution of ethyl 2-bromo-5-ethylthioalkyl-1-methyl-imidazolium-4-carboxylate (intermediate I-7 prepared as described above) (4.50 g, 15.3 mmol) in acetonitrile (45 mL). The reaction mixture was stirred at room temperature for 4 hours. After completion, the reaction mixture was quenched with 2N sodium hydroxide aqueous solution (50 mL) and water (50 mL), and extracted with ethyl acetate (2 x 100 mL). The combined organic layers were washed with brine (50 mL), dried over sodium sulfate, filtered, and concentrated under vacuum. The crude product was purified by combiflash (silica gel, 30% ethyl acetate in cyclohexane) to give ethyl 2-bromo-5-ethylsulfonyl-1-methyl-imidazolium-4-carboxylate as a viscous oil. LCMS (Method 2): Rt = 1.31 min, m / z = 325 (M+H) + . 1H NMR (400MHz, CDCl3) δppm: 1.35-1.44 (m, 6H) 3.67 (q, 2H) 3.97 (s, 3H) 4.43 (q, 2H).

[0568] Step B5: Ethyl 2-(1-cyclopropylpyrazole-4-yl)-5-ethylsulfonyl-1-methyl-imidazolium-4-carboxylate (middle) Preparation of intermediate I-9

[0569]

[0570] In a microwave-safe vial, cesium carbonate (2.0 g, 5 mmol) and 1-cyclopropyl-4-(4,4,5,5-tetramethyl-1,3,2-dioxoboronyl-2-yl)pyrazole (1.0 g, 5 mmol) were added to a stirred solution of ethyl 2-bromo-5-ethylsulfonyl-1-methyl-imidazolium-4-carboxylate (intermediate I-8 prepared as described above) (0.5 g, 2 mmol) in 1,4-dioxane (9 mL) at room temperature. The reaction mixture was degassed with nitrogen for 15 min, and then tetrakis(triphenylphosphine)palladium (0.2 g, 0.2 mmol) was added under a nitrogen atmosphere. The vial was sealed and transferred to a microwave oven, where it was heated at 110 °C for 30 min under microwave irradiation. The reaction mixture was quenched with water (50 mL) and extracted with ethyl acetate (2 x 50 mL). The combined organic layers were dried over sodium sulfate, filtered, and concentrated under vacuum. The crude product was purified by combiflash (silica gel, 25% ethyl acetate in cyclohexane) to give ethyl 2-(1-cyclopropylpyrazole-4-yl)-5-ethylsulfonyl-1-methyl-imidazolium-4-carboxylate as a viscous substance. LCMS (Method 2): Rt = 1.23 min, m / z = 353 (M+H) + . 1 H NMR (400MHz, CDCl3) δppm: 1.06-1.22(m,4H)1.41(dt,6H)3.63-3.71(m,3H)4.01(s,3H)4.45(q,2H)7.79(s,1H)7.97(s,1H).

[0571] Step B6: 2-(1-Cyclopropylpyrazole-4-yl)-5-ethylsulfonyl-1-methyl-imidazol-4-carboxylic acid (intermediate I-) Preparation of 10)

[0572]

[0573] A solution of lithium hydroxide monohydrate (0.21 g, 4.98 mmol) in water (5 mL) was added to a solution of ethyl 2-(1-cyclopropylpyrazole-4-yl)-5-ethylsulfonyl-1-methyl-imidazolium-4-carboxylic acid (intermediate I-9 prepared as described above) (1.17 g, 3.32 mmol) in tetrahydrofuran (17 mL) at room temperature. The reaction mixture was stirred at room temperature for 3 hours. Lithium hydroxide monohydrate (0.21 g, 4.98 mmol) was added again and the mixture was stirred at room temperature for another 10 hours. After completion, the reaction mixture was quenched with water (50 mL), acidified with 2N hydrochloric acid aqueous solution (20 mL), and extracted with ethyl acetate (3 x 50 mL). The combined organic layers were washed with brine (30 mL), dried over anhydrous sodium sulfate, filtered, and concentrated under vacuum to give 2-(1-cyclopropylpyrazole-4-yl)-5-ethylsulfonyl-1-methyl-imidazolium-4-carboxylic acid as a white solid. Use this material as is in the next step. LCMS (Method 2): Rt = 0.90 min, m / z = 325 (M+H) + .

[0574] Step B7: tert-butylN-[2-(1-cyclopropylpyrazole-4-yl)-5-ethylsulfonyl-1-methyl-imidazol-4-yl] Preparation of carbamate (intermediate I-11)

[0575]

[0576] Triethylamine (0.56 g, 5.43 mmol) was added to a solution of 2-(1-cyclopropylpyrazole-4-yl)-5-ethylsulfonyl-1-methyl-imidazolium-4-carboxylic acid (intermediate I-10 prepared as described above) (1.10 g, 3.39 mmol) in tert-butanol (22 mL) at room temperature. The mixture was heated to 90 °C and stirred for 10 min. Diphenylphosphohydrazine (1.19 mL, 5.43 mmol) was added dropwise over 15 min, and the resulting reaction mixture was stirred at 90 °C for 40 min. The reaction mixture was cooled to room temperature. The reaction mixture was quenched with ice-cold water (50 mL) and extracted with ethyl acetate (3 x 200 mL). The combined organic layers were dried over sodium sulfate, filtered, and concentrated under vacuum. The crude product was purified by combiflash (silica gel, 80% ethyl acetate in cyclohexane) to give tert-butyl N-[2-(1-cyclopropylpyrazole-4-yl)-5-ethylsulfonyl-1-methyl-imidazol-4-yl]carbamate as a white solid. LCMS (Method 2): Rt = 1.35 min, m / z = 396 (M+H) + . 1H NMR (400MHz, CDCl3) δppm: 1.04-1.21 (m, 4H) 1.36 (t, 3H) 1.51 (s, 9H) 3.20 (q, 2H) 3.65 (dt, 1H) 3.87 (s, 3H) 7.77 (s, 1H) 7.90 (s, 1H) 8.06 (s, 1H).

[0577] Step C1: Methyl 2-[[tert-butoxycarbonyl-[2-(1-cyclopropylpyrazole-4-yl)-5-ethylsulfonyl-1-methyl] Preparation of [-imidazolium-4-yl]amino]methyl]-5-(trifluoromethoxy)benzoate (intermediate I-12)

[0578]

[0579] At room temperature, methyl 2-(bromomethyl)-5-(trifluoromethoxy)benzoate (intermediate I-4 prepared as described above) (0.41 g, 1.31 mmol) and cesium carbonate (0.50 g, 1.52 mmol) were added to a stirred solution of tert-butyl N-[2-(1-cyclopropylpyrazole-4-yl)-5-ethylsulfonyl-1-methyl-imidazol-4-yl]carbamate (intermediate I-11 prepared as described above) in acetonitrile (8 mL). The reaction mixture was stirred at 50 °C for 4 hours, then quenched with ice-cold water (50 mL) and extracted with ethyl acetate (3 x 50 mL). The combined organic layers were dried over sodium sulfate, filtered, and concentrated under vacuum. The crude product was purified by combiflash (silica gel, 55% ethyl acetate in cyclohexane) to give a gel-like substance of methyl 2-[[tert-butoxycarbonyl-[2-(1-cyclopropylpyrazole-4-yl)-5-ethylsulfonyl-1-methyl-imidazol-4-yl]amino]methyl]-5-(trifluoromethoxy)benzoate. LCMS (Method 2): Rt = 1.62 min, m / z = 628 (M+H) + .

[0580] Step C2: Methyl 2-[[[2-(1-Cyclopropylpyrazole-4-yl)-5-ethylsulfonyl-1-methyl-imidazol-4-yl] Preparation of [amino]methyl]-5-(trifluoromethoxy)benzoate (intermediate I-13)

[0581]

[0582] 2,2,2-trifluoroacetic acid (1.0 mL, 13.15 mmol) was added dropwise to a solution of methyl 2-[[tert-butoxycarbonyl-[2-(1-cyclopropylpyrazole-4-yl)-5-ethylsulfonyl-1-methyl-imidazol-4-yl]amino]methyl]-5-(trifluoromethoxy)benzoate (intermediate I-12 prepared as described above) (0.55 g, 0.88 mmol) in trifluoromethylbenzene (11 mL) cooled to 0 °C. The reaction mixture was stirred at room temperature for 3 h. The reaction was monitored by TLC. TLC showed the formation of the desired product, along with some starting material. 2,2,2-trifluoroacetic acid (0.67 mL, 8.8 mmol) was added to the reactants and the mixture was stirred at room temperature for another 16 h. The reactants were concentrated under vacuum and quenched with a saturated aqueous solution of sodium bicarbonate (20 mL) and water (10 mL). The aqueous layer was extracted with ethyl acetate (3 x 50 mL), and the combined organic layers were washed with brine (50 mL), dried over sodium sulfate, filtered, and concentrated under vacuum. The crude product was purified by combiflash (silica gel, 55% ethyl acetate in cyclohexane) to give a gel-like substance of methyl 2-[[[2-(1-cyclopropylpyrazole-4-yl)-5-ethylsulfonyl-1-methyl-imidazol-4-yl]amino]methyl]-5-(trifluoromethoxy)benzoate. LCMS (Method 2): Rt = 1.54 min, m / z = 528 (M+H) + .

[0583] Step C3: 2-[[[2-(1-Cyclopropylpyrazole-4-yl)-5-ethylsulfonyl-1-methyl-imidazol-4-yl]amino] Preparation of methyl]-5-(trifluoromethoxy)benzoic acid (intermediate I-14)

[0584]

[0585] A solution of lithium hydroxide monohydrate (0.05 g, 1.14 mmol) in water (1.6 mL) was added to a solution of methyl 2-[[[2-(1-cyclopropylpyrazole-4-yl)-5-ethylsulfonyl-1-methyl-imidazol-4-yl]amino]methyl]-5-(trifluoromethoxy)benzoate (intermediate I-13 prepared as described above) (0.40 g, 0.76 mmol) in tetrahydrofuran (6 mL). The reaction mixture was stirred at room temperature for 16 h. The reaction progress was monitored by TLC and LCMS. LCMS showed the formation of the desired product, along with some of the starting materials. Lithium hydroxide monohydrate (0.05 g, 1.14 mmol) was added to the reactants, and the mixture was stirred at room temperature for another 6 h. After completion, the reaction mixture was quenched with water (20 mL), acidified with 2N hydrochloric acid aqueous solution (10 mL), and extracted with ethyl acetate (3 x 50 mL). The combined organic layers were washed with brine (50 mL), dried over anhydrous sodium sulfate, filtered, and concentrated under vacuum to obtain a gelatinous substance of 2-[[[2-(1-cyclopropylpyrazole-4-yl)-5-ethylsulfonyl-1-methyl-imidazol-4-yl]amino]methyl]-5-(trifluoromethoxy)benzoic acid. This material was used as is in the next step. LCMS (Method 1): Rt = 1.04 min, m / z = 512 (MH) - .

[0586] Step C4: 2-[2-(1-Cyclopropylpyrazole-4-yl)-5-ethylsulfonyl-1-methyl-imidazol-4-yl]-6-(tri-) Preparation of fluoromethoxy)isoindoline-1-one (P1)

[0587]

[0588] Phosphorus trichloride (0.15 mL, 1.558 mmol) was added dropwise to a 0°C cooled solution of 2-[[[2-(1-cyclopropylpyrazole-4-yl)-5-ethylsulfonyl-1-methyl-imidazol-4-yl]amino]methyl]-5-(trifluoromethoxy)benzoic acid (0.40 g, 0.78 mmol) in pyridine (4 mL). The reaction mixture was stirred at 0°C for 45 minutes. The reaction mixture was then stirred at 0 to 10°C for 20 minutes. The reaction mixture was quenched with ice-cold water (30 mL) and extracted with ethyl acetate (2 x 50 mL). The combined organic layers were washed with brine (30 mL), dried over anhydrous sodium sulfate, filtered, and concentrated under vacuum. The crude product was purified by combiflash (silica gel, 80-90% ethyl acetate in cyclohexane) to give a pure compound 2-[2-(1-cyclopropylpyrazol-4-yl)-5-ethylsulfonyl-1-methyl-imidazol-4-yl]-6-(trifluoromethoxy)isoindoline-1-one (compound P1) as a white solid. LCMS (Method 2): Rt = 1.44 min, m / z = 496 (M+H) + .1 H NMR(400MHz, CDCl3)δppm:1.09-1.27(m,4H)1.49(t,3H)3.60-3.74(m,3H)4.00( s,3H)4.94(s,2H)7.47(dd,1H)7.56(d,1H)7.78(s,1H)7.84(s,1H)7.94(s,1H).

[0589] Example P3: 6-[2-(3-cyclopropyl-4,5-dihydroisoxazol-5-yl)-5-ethylsulfonyl-1-methyl-imidazol-] Preparation of [4-yl]-3-(trifluoromethyl)-7H-pyrrolo[3,4-b]pyridin-5-one (compound P3)

[0590]

[0591] Step A1: Preparation of ethyl 2-chloro-5-(trifluoromethyl)pyridine-3-carboxylate

[0592]

[0593] Potassium carbonate (12.25 g, 88.7 mmol) was added to a solution of 2-chloro-5-(trifluoromethyl)pyridine-3-carboxylic acid (10 g, 44.3 mmol) in methyl sulfinylmethane (100 mL). The reaction mixture was stirred at room temperature for 5 minutes. Then iodoethane (10.58 g, 66.5 mmol) was added, and the reaction mixture was stirred at room temperature for 2 hours. The reactants were diluted with ice water, and the product was extracted with ethyl acetate. The organic layer was washed three times with ice water, then once with brine, dried over sodium sulfate, filtered, and concentrated under vacuum to give ethyl 2-chloro-5-(trifluoromethyl)pyridine-3-carboxylic acid ester. This material was used as is in the next step. LCMS (Method 1): Rt = 1.08 min, m / z = 254 (M+H)+. 1 H NMR (400MHz, CDCl3) δppm 1.44 (t, J = 7.15Hz, 3H) 4.46 (q, J = 7.09Hz, 2H) 8.38 (d, J = 2.08Hz, 1H) 8.77 (dd, J = 2.38, 0.67Hz, 1H).

[0594] Step A2: Preparation of ethyl 2-methyl-5-(trifluoromethyl)pyridine-3-carboxylate

[0595]

[0596] In a flask, ethyl 2-chloro-5-(trifluoromethyl)pyridine-3-carboxylate (prepared as described above) (11.1 g, 43.8 mmol), methylboronic acid (8.1 g, 131 mmol), tripotassium phosphate (27.9 g, 131 mmol), and tricyclohexylphosphonane (1.23 g, 4.38 mmol) were added, followed by toluene (111 mL) and water (11 mL). The flask was purged with nitrogen for 10 min, then palladium(II) acetate (0.49 g, 2.19 mmol) was added and purging continued for an additional 5 min. The reaction mixture was heated to 100 °C and stirred for 8 h. The reaction mixture was quenched with water (100 mL) and extracted with ethyl acetate (100 mL). The organic layer was dried over sodium sulfate, filtered, and concentrated under vacuum. The crude product was purified by combiflash (silica gel, 5-10% ethyl acetate in cyclohexane) to give ethyl 2-methyl-5-(trifluoromethyl)pyridine-3-carboxylate. LCMS (Method 1): Rt = 1.04 min, m / z = 234(M+H)+. 1 HNMR (400MHz, CDCl3) δppm 1.45 (t, J = 7.15Hz, 3H) 2.94 (s, 3H) 4.45 (q, J = 7.13Hz, 2H) 8.44 (d, J = 2.20Hz, 1H) 8.86-8.90 (m, 1H).

[0597] Step A3: Preparation of ethyl 2-(bromomethyl)-5-(trifluoromethyl)pyridine-3-carboxylate

[0598]

[0599] At room temperature, N-bromosuccinimide (5.5 g, 30 mmol) and 2,2'-azobis(isobutyronitrile) (0.43 g, 2.6 mmol) were added to a solution of ethyl 2-methyl-5-(trifluoromethyl)pyridine-3-carboxylate (prepared as described above) (6.1 g, 26 mmol) in trifluorobenzene (61 mL). The reaction mixture was heated to 90 °C and stirred for 5 hours, then overnight at 80 °C. After cooling to room temperature, the reaction mixture was diluted with water (60 mL) and stirred for 10 minutes. The organic layers were separated. The aqueous layer was extracted with ethyl acetate (150 mL). The combined organic layers were dried over sodium sulfate, filtered, and concentrated under vacuum. The crude product was purified by combiflash (silica gel, 0–2% ethyl acetate in cyclohexane) to give ethyl 2-(bromomethyl)-5-(trifluoromethyl)pyridine-3-carboxylate. LCMS (Method 1): Rt = 1.11 min, m / z = 312 (M+H)+. 1H NMR (400MHz, CDCl3) δppm: 1.48 (t, J = 7.15Hz, 3H) 4.50 (q, J = 7.21Hz, 2H) 5.08 (s, 2H) 8.52 (d, J = 2.08Hz, 1H) 8.96 (d, J = 1.59Hz, 1H).

[0600] Step B1: Preparation of ethyl 5-ethylsulfonyl-1-methyl-2-vinyl-imidazolium-4-carboxylate

[0601]

[0602] Tributyltin (1.08 mL, 3.50 mmol) was added to a solution of ethyl 2-bromo-5-ethylsulfonyl-1-methyl-imidazolium-4-carboxylate (intermediate I-9 prepared as described in step B4 of Example P1) (1.00 g, 2.92 mmol) in toluene (8 mL), and the solution was degassed with nitrogen for 10 min. Then, [1,1'-bis(diphenylphosphine)ferrocene]dichloropalladium(II) complex (0.0147 g, 0.175 mmol) was added, and the reaction mixture was heated in a microwave at 130 °C for 1 h. The reaction mixture was concentrated under vacuum. The residue was dissolved in ethyl acetate, washed twice with water, and then once with brine. The organic layer was dried over anhydrous sodium sulfate, filtered, and concentrated under vacuum. The crude product was purified by combiflash (silica gel, 50% ethyl acetate in cyclohexane) to give ethyl 5-ethylsulfonyl-1-methyl-2-vinyl-imidazolium-4-carboxylate as a brown oil. LCMS (Method 2): Rt = 0.87 min, m / z = 273(M+H) + . 1 H NMR (400MHz, CDCl3) δppm: 6.61-6.69(m,1H)6.52-6.48(m,1H)5.79(dd,J=11.01,1.25Hz,1H)4.46(q,2H)3.96(s,3H)3.66(q,2H)1.36-1.47(m,6H).

[0603] Step B2: Ethyl 2-(3-cyclopropyl-4,5-dihydroisoxazol-5-yl)-5-ethylsulfonyl-1-methyl-imidazol- Preparation of 4-carbamate

[0604]

[0605] Under nitrogen atmosphere, a drop of trifluoroacetic acid was added to a solution of ethyl 5-ethylsulfonyl-1-methyl-2-vinyl-imidazolium-4-carboxylate (prepared as described above) (0.28 g, 0.925 mmol) in methanol (4.2 mL), followed by diacetoxyiodobenzene (0.36 g, 1.11 mmol), cyclopropaneformaldehyde oxime (0.105 g, 1.11 mmol), and another drop of trifluoroacetic acid. The reaction mixture was stirred at room temperature for 12 hours and then concentrated under vacuum. The crude product was purified by combiflash (silica gel, ethyl acetate in cyclohexane) to give ethyl 2-(3-cyclopropyl-4,5-dihydroisoxazol-5-yl)-5-ethylsulfonyl-1-methyl-imidazolium-4-carboxylate. LCMS (Method 1): Rt = 0.99 min, m / z = 356 (M+H)+. 1 H NMR (400MHz, CDCl3) δppm: 5.61 (dd, J=10.67, 7.65Hz, 1H) 4.43 (qd, J=7.15, 1.63Hz, 2H) 4.03 (s, 3 H)3.88-3.97(m,1H)3.54-3.69(m,2H)3.16(dd,J=16.81,10.79Hz,1H)1.82-1.89(m,1H)1.42(br t,J=7.15Hz,3H)1.39(br t,J=7.40Hz,3H)0.84-1.02(m,4H).

[0606] Step B3: 2-(3-Cyclopropyl-4,5-Dihydroisoxazol-5-yl)-5-ethylsulfonyl-1-methyl-imidazol-4-methyl Preparation of acid (intermediate I-15)

[0607]

[0608] A solution of lithium hydroxide monohydrate (0.71 g, 16 mmol) in water (2 mL) was added to a solution of ethyl 2-(3-cyclopropyl-4,5-dihydroisoxazol-5-yl)-5-ethylsulfonyl-1-methyl-imidazol-4-carboxylic acid (prepared as described above) (2.4 g, 6.4 mmol) in tetrahydrofuran (10 mL) at 0 °C. The reaction mixture was stirred at room temperature for 12 hours. After completion, the reaction mixture was concentrated under vacuum, and the residue was acidified with 1 N hydrochloric acid aqueous solution and poured into ethyl acetate. The organic layer was separated, washed twice with water, then once with brine, dried over anhydrous sodium sulfate, filtered, and concentrated under vacuum to give 2-(3-cyclopropyl-4,5-dihydroisoxazol-5-yl)-5-ethylsulfonyl-1-methyl-imidazol-4-carboxylic acid. This material was used as is in the next step. LCMS (Method 1): Rt = 0.15 min, m / z = 328 (M+H) + .

[0609] Step B4: tert-butylN-[2-(3-cyclopropyl-4,5-dihydroisoxazol-5-yl)-5-ethylsulfonyl-1-methyl- Preparation of imidazole-4-yl]carbamate (intermediate I-16)

[0610]

[0611] Triethylamine (1.0 g, 10 mmol) was added to a solution of 2-(3-cyclopropyl-4,5-dihydroisoxazol-5-yl)-5-ethylsulfonyl-1-methyl-imidazol-4-carboxylic acid (intermediate I-15 prepared as described above) (2.20 g, 6.4 mmol) in tert-butanol (33 mL) at room temperature. The mixture was heated to 90 °C and stirred for 10 min. Diphenylphosphohydrazine (1.19 mL, 5.43 mmol) was added dropwise over 10 min, and the resulting reaction mixture was stirred at 90 °C for 60 min. The reaction mixture was cooled to room temperature, quenched with ice-cold water (100 mL), and the product was extracted with ethyl acetate. The combined organic layers were washed twice with water and once with brine, dried over sodium sulfate, filtered, and concentrated under vacuum. The crude product was purified by combiflash (silica gel, 20-70% ethyl acetate in cyclohexane) to give tert-butyl N-[2-(3-cyclopropyl-4,5-dihydroisoxazol-5-yl)-5-ethylsulfonyl-1-methyl-imidazol-4-yl]carbamate. LCMS (Method 1): Rt = 1.09 min, m / z = 343 [M+H-56] + . 1 HNMR(400MHz, CDCl3)δppm:0.84-1.01(m,4H)1.26-1.40(m,3H)1.52(s,9H)1.80-1.87(m,1H)3.13-3.24 (m,3H)3.81-3.87(m,1H)3.88(s,2H)4.14(d,J=7.09Hz,1H)5.58(dd,J=10.76,8.31Hz,1H)7.77(s,1H).

[0612] Step C1: Ethyl 2-[[tert-butoxycarbonyl-[2-(3-cyclopropyl-4,5-dihydroisoxazol-5-yl)-5-ethyl Preparation of sulfonyl-1-methyl-imidazol-4-yl]amino]methyl]-5-(trifluoromethyl)pyridine-3-carboxylate

[0613]

[0614] At room temperature, 0.80 g (1.91 mmol) of tert-butyl N-[2-(3-cyclopropyl-4,5-dihydroisoxazol-5-yl)-5-ethylsulfonyl-1-methyl-imidazol-4-yl]carbamate (intermediate I-16 prepared as described above) in acetonitrile (20 mL) was added to a stirred solution of tert-butyl N-[2-(3-cyclopropyl-4,5-dihydroisoxazol-5-yl)-5-ethylsulfonyl-1-methyl-imidazol-4-yl]carbamate (intermediate I-4 prepared as described in step A3 of Example P3) (0.41 g, 1.31 mmol) and cesium carbonate (0.50 g, 1.52 mmol). The reaction mixture was stirred at 50 °C for 4 hours, then quenched with ice-cold water (50 mL), and the product was extracted with ethyl acetate (3 x 50 mL). The combined organic layers were dried over sodium sulfate, filtered, and concentrated under vacuum. The crude product was purified by combiflash (silica gel, 55% ethyl acetate in cyclohexane) to give a gel-like substance of methyl 2-[[tert-butoxycarbonyl-[2-(1-cyclopropylpyrazole-4-yl)-5-ethylsulfonyl-1-methyl-imidazol-4-yl]amino]methyl]-5-(trifluoromethoxy)benzoate. LCMS (Method 2): Rt = 1.62 min, m / z = 328 (M+H) + .

[0615] Step C2: Ethyl 2-[[[2-(3-cyclopropyl-4,5-dihydroisoxazol-5-yl)-5-ethylsulfonyl-1-methyl- Preparation of imidazole-4-yl]amino]methyl]-5-(trifluoromethyl)pyridine-3-carboxylate

[0616]

[0617] A solution of ethyl 2-[[[2-(3-cyclopropyl-4,5-dihydroisoxazol-5-yl)-5-ethylsulfonyl-1-methyl-imidazol-4-yl]amino]methyl]-5-(trifluoromethyl)pyridine-3-carboxylate (intermediate I-15 prepared as described above) (1.5 g, 1.9 mmol) in trifluoroacetic acid (5 mL) was stirred for 12 hours. The reaction mixture was then neutralized with a saturated aqueous sodium bicarbonate solution. The aqueous layer was extracted twice with ethyl acetate. The combined organic layers were dried over sodium sulfate, filtered, and concentrated under vacuum to give ethyl 2-[[[2-(3-cyclopropyl-4,5-dihydroisoxazol-5-yl)-5-ethylsulfonyl-1-methyl-imidazol-4-yl]amino]methyl]-5-(trifluoromethyl)pyridine-3-carboxylate. This material was used as is in the next step. LCMS (Method 1): Rt = 1.16 min, m / z = 530(M+H) + .

[0618] Step C3: 2-[[[2-(3-cyclopropyl-4,5-dihydroisoxazol-5-yl)-5-ethylsulfonyl-1-methyl-imidazolium Preparation of [azol-4-yl]amino]methyl]-5-(trifluoromethyl)pyridine-3-carboxylic acid

[0619]

[0620] A solution of lithium hydroxide monohydrate (0.16 g, 3.72 mmol) in water (2 mL) was added to a solution of ethyl 2-[[[2-(3-cyclopropyl-4,5-dihydroisoxazol-5-yl)-5-ethylsulfonyl-1-methyl-imidazol-4-yl]amino]methyl]-5-(trifluoromethyl)pyridine-3-carboxylate (prepared as described above) (0.83 g, 1.49 mmol) in tetrahydrofuran (10 mL). The reaction mixture was stirred at room temperature for 12 hours. After completion, the reaction mixture was concentrated under vacuum, the residue was acidified with 1 N hydrochloric acid aqueous solution, and the product was extracted with ethyl acetate. The organic layer was washed twice with water and once with brine, dried over sodium sulfate, filtered, and concentrated under vacuum to obtain 2-[[[2-(3-cyclopropyl-4,5-dihydroisoxazol-5-yl)-5-ethylsulfonyl-1-methyl-imidazol-4-yl]amino]methyl]-5-(trifluoromethyl)pyridine-3-carboxylic acid. This material was used as is in the next step. LCMS (Method 1): Rt = 1.04 min, m / z = 502 (M+H) + .

[0621] Step C4: 6-[2-(3-cyclopropyl-4,5-dihydroisoxazol-5-yl)-5-ethylsulfonyl-1-methyl-imidazol-] Preparation of 4-yl]-3-(trifluoromethyl)-7H-pyrrolo[3,4-b]pyridin-5-one (P3)

[0622]

[0623] Under nitrogen atmosphere, phosphorus oxychloride (0.28 mL, 2.95 mmol) was added dropwise to a 0°C cooled solution of 2-[[[2-(3-cyclopropyl-4,5-dihydroisoxazol-5-yl)-5-ethylsulfonyl-1-methyl-imidazol-4-yl]amino]methyl]-5-(trifluoromethyl)pyridine-3-carboxylic acid (prepared as described above) (0.78 g, 1.48 mmol) in pyridine (5 mL). The reaction mixture was allowed to reach room temperature and stirred for 2 hours. The reaction mixture was acidified with 1N hydrochloric acid aqueous solution (30 mL), and the product was extracted with ethyl acetate (2 x 30 mL). The combined organic layers were dried over sodium sulfate, filtered, and concentrated under vacuum. The crude product was purified by combiflash (silica gel, 50% ethyl acetate in cyclohexane) to give a solid pure compound 6-[2-(3-cyclopropyl-4,5-dihydroisoxazol-5-yl)-5-ethylsulfonyl-1-methyl-imidazol-4-yl]-3-(trifluoromethyl)-7H-pyrrolo[3,4-b]pyridin-5-one (compound P3). LCMS (Method 2): Rt = 1.35 min, m / z = 484 (M+H)+. 1H NMR(400MHz,DMSO-d6)δppm 9.30(d,J=1.38Hz,1H)8.67(d,J=1.63Hz,1H)5.85(dd,J=10.82,7.07Hz,1H)5.02(d,J=4.38Hz,2H)3.9 1(s,3H)3.49-3.67(m,3H)3.21-3.30(m,1H)1.82-1.89(m,1H)1.27(t,J=7.38Hz,3H)0.79-0.94(m,4H).

[0624] Example P6: 6-[5-ethylsulfonyl-1-methyl-2-(2,2,2-trifluoroethoxy)imidazol-4-yl]-3-(trifluoro Preparation of methyl)-7H-pyrrolo[3,4-b]pyridin-5-one (compound P6)

[0625]

[0626] Step A1: Preparation of ethyl 5-ethylsulfonyl-1-methyl-2-(2,2,2-trifluoroethoxy)imidazolium-4-carboxylate Preparation

[0627]

[0628] Potassium carbonate (6.4 g, 46 mmol) and cuprous iodide (0.44 g, 2.3 mmol) were added to a solution of 2,2,2-trifluoroethanol (7.8 g, 77 mmol) and ethyl 2-bromo-5-ethylsulfonyl-1-methyl-imidazolium-4-carboxylate (intermediate I-8 prepared as described in step B4 of Example P1) (5.0 g, 15 mmol) in pyridine (50 mL) at 0 °C. The reaction mixture was stirred at 16 °C for 16 h. The reaction mixture was then poured into ice-cold water and stirred for 5 min. The aqueous layer was extracted with ethyl acetate (2 x 100 mL), the combined organic layers were washed with water, then with brine, dried over sodium sulfate, filtered, and concentrated under vacuum. The residue was ground with n-pentane, filtered, and dried under vacuum to give ethyl 5-ethylsulfonyl-1-methyl-2-(2,2,2-trifluoroethoxy)imidazolium-4-carboxylate. The crude material was used as is in the next step. LCMS (Method 1): Rt = 1.33 min, m / z = 345(M+H)+.

[0629] Step A2: 5-Ethylsulfonyl-1-methyl-2-(2,2,2-trifluoroethoxy)imidazol-4-carboxylic acid (intermediate I-) 21) Preparation

[0630]

[0631] A solution of lithium hydroxide monohydrate (0.73 g, 17 mmol) in water (2 mL) was added to a solution of ethyl 5-ethylsulfonyl-1-methyl-2-(2,2,2-trifluoroethoxy)imidazolium-4-carboxylic acid (prepared as described above) (2.0 g, 5.8 mmol) in tetrahydrofuran (20 mL) at 0 °C. The reaction mixture was stirred at room temperature for 3 hours. After completion, the reaction mixture was acidified with 2N hydrochloric acid aqueous solution and diluted with water. The aqueous layer was extracted three times with ethyl acetate. The combined organic layers were washed with brine, dried over sodium sulfate, filtered, and concentrated under vacuum to give 5-ethylsulfonyl-1-methyl-2-(2,2,2-trifluoroethoxy)imidazolium-4-carboxylic acid. This material was used as is in the next step. LCMS (Method 1): Rt = 0.95 min, m / z = 317 (M+H) + .

[0632] Step A3: tert-butylN-[5-ethylsulfonyl-1-methyl-2-(2,2,2-trifluoroethoxy)imidazol-4-yl]amino Preparation of carbamate (intermediate I-22)

[0633]

[0634] Triethylamine (0.2 g, 2 mmol) was added to a solution of 5-ethylsulfonyl-1-methyl-2-(2,2,2-trifluoroethoxy)imidazolium-4-carboxylic acid (intermediate I-21 prepared as described above) (0.40 g, 1 mmol) in tert-butanol (8 mL) at room temperature. The mixture was heated to 90 °C and stirred for 10 min. Diphenylphosphohydrazine (0.4 mL, 2 mmol) was added dropwise over 15 min, and the resulting reaction mixture was stirred at 90 °C for 40 min. The reaction mixture was cooled to room temperature, quenched with ice-cold water (100 mL) and brine (40 mL), and the product was extracted with ethyl acetate (3 x 100 mL). The combined organic layers were dried over sodium sulfate, filtered, and concentrated under vacuum. The crude product was purified by combiflash (silica gel, 40% ethyl acetate in cyclohexane) to give tert-butyl N-[5-ethylsulfonyl-1-methyl-2-(2,2,2-trifluoroethoxy)imidazol-4-yl]carbamate. LCMS (Method 1): Rt = 1.10 min, m / z = 288 [M+H-100] + . 1 H NMR (400MHz, CDCl3) δppm 1.26-1.44 (m, 3H) 1.61 (s, 9H) 3.17 (q, J = 7.46Hz, 2H) 3.59 (s, 3H) 4.89 (q, J = 8.07Hz, 2H) 7.85 (s, 1H).

[0635] Step B1: Ethyl 2-[[tert-butoxycarbonyl-[5-ethylsulfonyl-1-methyl-2-(2,2,2-trifluoroethoxy)] Preparation of imidazole-4-yl]amino]methyl]-5-(trifluoromethyl)pyridine-3-carboxylate

[0636]

[0637] At room temperature, 0.60 g, 2 mmol of tert-butyl N-[5-ethylsulfonyl-1-methyl-2-(2,2,2-trifluoroethoxy)imidazol-4-yl]carbamate (intermediate I-22 prepared as described above) in acetonitrile (10 mL) was added to a stirred solution of tert-butyl N-[5-ethylsulfonyl-1-methyl-2-(2,2,2-trifluoroethoxy)imidazol-3-carbamate (intermediate I-4 prepared as described in step A3 of Example P3) (0.60 g, 2 mmol) and cesium carbonate (0.80 g, 2 mmol). The reaction mixture was stirred at 50 °C for 24 hours, then quenched with ice-cold water (30 mL), and the product was extracted with ethyl acetate (3 x 50 mL). The combined organic layers were washed with brine, dried over sodium sulfate, filtered, and concentrated under vacuum. The crude product was purified by combiflash (silica gel, 30% ethyl acetate in cyclohexane) to give ethyl 2-[[tert-butoxycarbonyl-[5-ethylsulfonyl-1-methyl-2-(2,2,2-trifluoroethoxy)imidazol-4-yl]amino]methyl]-5-(trifluoromethyl)pyridine-3-carboxylate. LCMS (Method 1): Rt = 1.24 min, m / z = 619 (M+H) + .

[0638] Step B2: Ethyl 2-[[[5-Ethylsulfonyl-1-methyl-2-(2,2,2-trifluoroethoxy)imidazol-4-yl]amino Preparation of 5-(trifluoromethyl)pyridine-3-carboxylate

[0639]

[0640] Trifluoroacetic acid (1 mL) was added to a solution of ethyl 2-[[tert-butoxycarbonyl-[5-ethylsulfonyl-1-methyl-2-(2,2,2-trifluoroethoxy)imidazol-4-yl]amino]methyl]-5-(trifluoromethyl)pyridine-3-carboxylate (prepared as described above) (0.60 g, 1 mmol) in trifluoromethylbenzene (10 mL). The reaction mixture was stirred for 12 hours and then concentrated under vacuum. Water (50 mL) was added and the solution was neutralized with a saturated aqueous sodium bicarbonate solution (30 mL). The aqueous layer was extracted with ethyl acetate (2 × 50 mL). The combined organic layers were dried over sodium sulfate, filtered, and concentrated under vacuum to give ethyl 2-[[[5-ethylsulfonyl-1-methyl-2-(2,2,2-trifluoroethoxy)imidazol-4-yl]amino]methyl]-5-(trifluoromethyl)pyridine-3-carboxylate as a solid. This material was used as is in the next step. LCMS (Method 2): Rt = 1.55 min, m / z = 519(M+H) + .

[0641] Step B3: 2-[[[5-Ethylsulfonyl-1-methyl-2-(2,2,2-trifluoroethoxy)imidazol-4-yl]amino]methyl Preparation of 5-(trifluoromethyl)pyridine-3-carboxylic acid

[0642]

[0643] A solution of lithium hydroxide monohydrate (0.051 g, 1.16 mmol) in water (0.5 mL) was added to a solution of ethyl 2-[[[5-ethylsulfonyl-1-methyl-2-(2,2,2-trifluoroethoxy)imidazol-4-yl]amino]methyl]-5-(trifluoromethyl)pyridine-3-carboxylic acid (prepared as described above) (0.120 g, 0.231 mmol) in tetrahydrofuran (5 mL). The reaction mixture was stirred overnight at room temperature. After completion, the reaction mixture was concentrated under vacuum, the residue was acidified with 1N hydrochloric acid aqueous solution, and the product was extracted twice with ethyl acetate (2 x 50 mL). The combined organic layers were washed with water, then with brine, dried over sodium sulfate, filtered, and concentrated under vacuum to give 2-[[[5-ethylsulfonyl-1-methyl-2-(2,2,2-trifluoroethoxy)imidazol-4-yl]amino]methyl]-5-(trifluoromethyl)pyridine-3-carboxylic acid. Use this material as is in the next step. LCMS (Method 1): Rt = 1.10 min, m / z = 491(M+H) + .

[0644] Step B4: 6-[5-ethylsulfonyl-1-methyl-2-(2,2,2-trifluoroethoxy)imidazol-4-yl]-3-(trifluoro Preparation of methyl)-7H-pyrrolo[3,4-b]pyridin-5-one (P6)

[0645]

[0646] Under nitrogen atmosphere, phosphorus oxychloride (0.038 mL, 0.408 mmol) was added dropwise to a 0°C cooled solution of 2-[[[5-ethylsulfonyl-1-methyl-2-(2,2,2-trifluoroethoxy)imidazol-4-yl]amino]methyl]-5-(trifluoromethyl)pyridine-3-carboxylic acid (prepared as described above) (0.100 g, 0.204 mmol) in pyridine (1 mL). The reaction mixture was stirred at this temperature for 1 hour. The reaction mixture was poured into ice-cold water (30 mL), acidified with 1N hydrochloric acid aqueous solution (30 mL), and the product was extracted with ethyl acetate (2 x 30 mL). The combined organic layers were washed with brine, dried over sodium sulfate, filtered, and concentrated under vacuum. The crude product was purified by combiflash (silica gel, 30-100% ethyl acetate in cyclohexane) to give a pure compound 6-[5-ethylsulfonyl-1-methyl-2-(2,2,2-trifluoroethoxy)imidazol-4-yl]-3-(trifluoromethyl)-7H-pyrrolo[3,4-b]pyridin-5-one (compound P6) as a brown solid. LCMS (Method 2): Rt = 1.41 min, m / z = 473 (M+H)+. 1H NMR (400MHz, DMSO-d6) δppm 1.08-1.50 (m, 3H) 3.52-3.55 (m, 2H) 3.57 (s, 3H) 4.93 (s, 2H) 5.08 (q, J = 8.67Hz, 2H) 8.61 (d, J = 1.50Hz, 1H) 9.23 (s, 1H).

[0647] Example P16: 6-[2-(3-chloropyrazol-1-yl)-5-ethylsulfonyl-1-methyl-imidazol-4-yl]-3-(trifluoromethyl) Preparation of 7H-pyrrolo[3,4-b]pyridin-5-one (compound P16)

[0648]

[0649] Step A1: Preparation of ethyl 2-(3-chloropyrazol-1-yl)-5-ethylsulfonyl-1-methyl-imidazol-4-carboxylate

[0650]

[0651] At room temperature, N,N'-dimethylethane-1,2-diamine (0.542 g, 6.15 mmol), potassium carbonate (1.70 g, 12.3 mmol), and 3-chloro-1H-pyrazole (3.47 g, 33.8 mmol) were added to a solution of ethyl 2-bromo-5-ethylsulfonyl-1-methyl-imidazolium-4-carboxylate (intermediate I-9 prepared as described in step B4 of Example P1) in N,N-dimethylformamide (100 mL), followed by the addition of cuprous iodide (0.586 g, 3.08 mmol). The reaction mixture was stirred at 120 °C for 16 hours. Water was then added and the aqueous layer was extracted with ethyl acetate (3 x 100 mL). The combined organic layers were washed with water, dried over sodium sulfate, and concentrated under vacuum. The crude product was purified by combiflash (silica gel, 0-25% ethyl acetate in cyclohexane) to give ethyl 2-(3-chloropyrazol-1-yl)-5-ethylsulfonyl-1-methyl-imidazol-4-carboxylate, a pale yellow semi-solid. LCMS (Method 1): Rt = 1.09 min, m / z = 347 (M+H)+. 1 H NMR (400MHz, CDCl3) δppm 1.43(td,J=7.31,2.02Hz,6H)3.67(q,J=7.46Hz,2H)4.11-4.17(m,3H)4.46(q,J=7.13Hz,2H)6.47(d,J=2.69Hz,1H)8.12(d,J=2.69Hz,1H).

[0652] Step A2: 2-(3-chloropyrazol-1-yl)-5-ethylsulfonyl-1-methyl-imidazol-4-carboxylic acid (intermediate I-37) Preparation

[0653]

[0654] A solution of lithium hydroxide monohydrate (0.889 g, 21 mmol) in water (19.6 mL) was added to a solution of ethyl 2-(3-chloropyrazol-1-yl)-5-ethylsulfonyl-1-methyl-imidazol-4-carboxylic acid (prepared as described above) (4.90 g, 14.1 mmol) in tetrahydrofuran (73.5 mL) at room temperature. The reaction mixture was stirred at room temperature for 16 hours. After completion, the reaction mixture was quenched with water (100 mL), acidified with 2N hydrochloric acid aqueous solution (20 mL), and the product was extracted with ethyl acetate (3 x 100 mL). The combined organic layers were washed with brine, dried over sodium sulfate, filtered, and concentrated under vacuum. The crude material was washed twice with n-pentane and dried to give 2-(3-cyclopropyl-4,5-dihydroisoxazol-5-yl)-5-ethylsulfonyl-1-methyl-imidazol-4-carboxylic acid as a white solid. This material was used as is in the next step. LCMS (Method 1): Rt = 0.92 min, m / z = 319(M+H) + . 1 H NMR(400MHz,DMSO-d6)δppm 1.28 (t, J = 7.40Hz, 3H) 3.67 (q, J = 7.34Hz, 2H) 3.83 (s, 3H) 6.80 (d, J = 2.69Hz, 1H) 8.41 (d, J = 2.57Hz, 1H) 13.27-14.12 (m, 1H).

[0655] Step A3: tert-butylN-[2-(3-chloropyrazol-1-yl)-5-ethylsulfonyl-1-methyl-imidazol-4-yl]amino Preparation of formate ester (intermediate I-36)

[0656]

[0657] Triethylamine (2.10 g, 20.6 mmol) was added to a solution of 2-(3-chloropyrazol-1-yl)-5-ethylsulfonyl-1-methyl-imidazol-4-carboxylic acid (intermediate I-37 prepared as described above) (4.10 g, 12.9 mmol) in tert-butanol (82 mL) at room temperature. The mixture was heated to 90 °C and stirred for 10 min. Diphenylphosphohydrazine (4.53 mL, 20.6 mmol) was added dropwise over 15 min, and the resulting reaction mixture was stirred at 90 °C for 40 min. The reaction mixture was cooled to room temperature, quenched with ice-cold water (100 mL) and brine (40 mL), and the product was extracted with ethyl acetate (3 x 100 mL). The combined organic layers were dried over sodium sulfate, filtered, and concentrated under vacuum. The crude product was purified by combiflash (silica gel, 40% ethyl acetate in cyclohexane) to give tert-butyl N-[2-(3-chloropyrazol-1-yl)-5-ethylsulfonyl-1-methyl-imidazol-4-yl]carbamate. LCMS (Method 2): Rt = 1.37 min, m / z = 388 (MH) -. 1 H NMR (400MHz, CDCl3) δppm 1.37 (t, J = 7.40Hz, 3H) 1.56 (s, 9H) 3.22 (d, J = 7.46Hz, 2H) 4.04 (s, 3H) 6.41 (d, J = 2.81Hz, 1H) 8.23 ​​(d, J = 2.69Hz, 1H).

[0658] Step B1: Ethyl 2-[[tert-butoxycarbonyl-[2-(3-chloropyrazol-1-yl)-5-ethylsulfonyl-1-methyl-imidazolium] Preparation of [azol-4-yl]amino]methyl]-5-(trifluoromethyl)pyridine-3-carboxylate

[0659]

[0660] At room temperature, 1.00 g, 2.56 mmol of tert-butyl N-[2-(3-chloropyrazol-1-yl)-5-ethylsulfonyl-1-methyl-imidazol-4-yl]carbamate (intermediate I-36 prepared as described above) in acetonitrile (20 mL) was added to a stirred solution of tert-butyl N-[2-(3-chloropyrazol-1-yl)-5-(trifluoromethyl)pyridine-3-carbamate (intermediate I-4 prepared as described in step A3 of Example P3) (1.04 g, 3.33 mmol) and cesium carbonate (1.25 g, 3.85 mmol). The reaction mixture was stirred at 50 °C for 9 hours, then quenched with ice-cold water (30 mL), and the product was extracted with ethyl acetate (3 x 50 mL). The combined organic layers were washed with brine (20 mL), dried over sodium sulfate, filtered, and concentrated under vacuum to obtain ethyl 2-[[tert-butoxycarbonyl-[2-(3-chloropyrazol-1-yl)-5-ethylsulfonyl-1-methyl-imidazol-4-yl]amino]methyl]-5-(trifluoromethyl)pyridine-3-carboxylate. This material was used as is in the next step.

[0661] Step B2: Ethyl 2-[[[2-(3-chloropyrazol-1-yl)-5-ethylsulfonyl-1-methyl-imidazol-4-yl]amino] Preparation of methyl]-5-(trifluoromethyl)pyridine-3-carboxylate

[0662]

[0663] Ethyl 2-[[tert-Butoxycarbonyl-[2-(3-chloropyrazol-1-yl)-5-ethylsulfonyl-1-methyl-imidazol-4-yl]amino]methyl]-5-(trifluoromethyl)pyridine solution was prepared at 0 °C by adding 2.10 g (3.38 mmol) of the 3-carboxylate salt (prepared as described above) from trifluoromethylbenzene (42 mL) to trifluoroacetic acid (3.88 mL, 50.7 mmol). The reaction mixture was stirred at room temperature for 3 h, then trifluoroacetic acid (1.29 mL, 16.9 mmol) was added and the mixture was stirred for 16 h. After completion, the reaction mixture was concentrated under vacuum. Water (20 mL) was added to the residue, and the solution was neutralized with saturated sodium bicarbonate aqueous solution (30 mL). The aqueous layer was extracted with ethyl acetate (3 x 50 mL). The combined organic layers were washed with brine (50 mL), dried over sodium sulfate, filtered, and concentrated under vacuum. The crude product was purified by combiflash (silica gel, 40% ethyl acetate in cyclohexane) to give a semi-solid ethyl 2-[[[2-(3-chloropyrazol-1-yl)-5-ethylsulfonyl-1-methyl-imidazol-4-yl]amino]methyl]-5-(trifluoromethyl)pyridine-3-carboxylate. LCMS (Method 2): Rt = 1.51 min, m / z = 521 (M+H) + . 1 H NMR (400MHz, CDCl3) δppm 1.28-1.39(m,3H)1.46(t,J=7.15Hz,3H)3.18(q,J=7.46Hz,2H)3.94(s,3H)4.47(q,J=7.09Hz,2H)5.11(s,2H)6.40(d,J=2.69Hz,1H)6.75(br s,1H)8.06(d,J=2.69Hz,1H)8.47(d,J=1.96Hz,1H)8.96(d,J=1.47Hz,1H).

[0664] Step B3: 2-[[[2-(3-chloropyrazol-1-yl)-5-ethylsulfonyl-1-methyl-imidazol-4-yl]amino]methyl Preparation of 5-(trifluoromethyl)pyridine-3-carboxylic acid

[0665]

[0666] A solution of lithium hydroxide monohydrate (0.16 g, 3.84 mmol) in water (4 mL) was added to a solution of 2-[[[2-(3-chloropyrazol-1-yl)-5-ethylsulfonyl-1-methyl-imidazol-4-yl]amino]methyl]-5-(trifluoromethyl)pyridine-3-carboxylic acid (prepared as described above) (1.00 g, 1.92 mmol) in tetrahydrofuran (15 mL) at room temperature. The reaction mixture was stirred at room temperature for 5 hours. After completion, the reaction mixture was quenched with water (20 mL), acidified with 2N hydrochloric acid aqueous solution (10 mL), and the product was extracted with ethyl acetate (3 x 50 mL). The combined organic layers were washed with brine, dried over sodium sulfate, filtered, and concentrated under vacuum to give 2-[[[2-(3-chloropyrazol-1-yl)-5-ethylsulfonyl-1-methyl-imidazol-4-yl]amino]methyl]-5-(trifluoromethyl)pyridine-3-carboxylic acid as a white solid. Use this material as is in the next step. LCMS (Method 1): Rt = 1.41 min, m / z = 493 (M+H) + . 1 H NMR (400MHz, DMSO-d6) δppm 1.17 (t, J = 7.27Hz, 3H) 3.24-3.41 (m, 2H) 3.69 (s, 3H) 5.02 (br d,J=5.01Hz,2H)6.65-6.70(m,1H)6.73(d,J=2.69Hz,1H)8.29(d,J=2.69 Hz, 1H) 8.49 (d, J = 1.96 Hz, 1H) 9.11 ( d, J = 1.34 Hz, 1H) 13.39-14.75 ( m, 1H).

[0667] Step B4: 6-[2-(3-chloropyrazol-1-yl)-5-ethylsulfonyl-1-methyl-imidazol-4-yl]-3-(trifluoromethyl) Preparation of 7H-pyrrolo[3,4-b]pyridin-5-one (P16)

[0668]

[0669] Under nitrogen atmosphere, phosphorus oxychloride (0.328 mL, 3.49 mmol) was added dropwise to a 0°C cooled solution of 2-[[[2-(3-chloropyrazol-1-yl)-5-ethylsulfonyl-1-methyl-imidazol-4-yl]amino]methyl]-5-(trifluoromethyl)pyridine-3-carboxylic acid (prepared as described above) (0.860 g, 0.948 mmol) in pyridine (8.6 mL). The reaction mixture was stirred at this temperature for 45 minutes, then poured into ice-cold water (30 mL) and extracted with ethyl acetate (2 x 50 mL). The combined organic layers were washed with brine (30 mL), dried over sodium sulfate, filtered, and concentrated under vacuum. The crude product was purified by combiflash (silica gel, 70-80% ethyl acetate in cyclohexane) to give a pure compound 6-[2-(3-chloropyrazol-1-yl)-5-ethylsulfonyl-1-methyl-imidazol-4-yl]-3-(trifluoromethyl)-7H-pyrrolo[3,4-b]pyridin-5-one (compound P16) as a yellow solid. LCMS (Method 1): Rt = 1.07 min, m / z = 475 (M+H)+. 1 H NMR (400MHz, CDCl3) δppm 1.41-1.58(m,3H)3.62(q,J=7.46Hz,2H)4.17(s,3H)5.04(s,2H)6.48(d,J=2.69Hz,1H)8.09(d,J=2.69Hz,1H)8.44(s,1H)9.10(s,1H).

[0670] Table P: Examples of compounds having formula (I)

[0671]

[0672]

[0673]

[0674]

[0675]

[0676] Table I: Examples of Intermediates

[0677]

[0678]

[0679]

[0680]

[0681]

[0682]

[0683]

[0684]

[0685]

[0686]

[0687] The activity of the compositions according to the invention can be significantly broadened and adapted to general conditions by adding other insecticidal, acaricidal, and / or fungicidal ingredients. Mixtures of compounds of Formula I with other insecticidal, acaricidal, and / or fungicidal ingredients can also have additional unexpected advantages, which can be described more broadly as synergistic activity. For example, better plant tolerance, reduced phytotoxicity, control of insects at different developmental stages, or better behavior during their production (e.g., during grinding or mixing, during storage, or during use).

[0688] Here, the appropriate active ingredients are representative of the following categories of active ingredients: organophosphorus compounds, nitrophenol derivatives, thiourea, juvenile hormones, formamidin, benzophenone derivatives, ureas, pyrrole derivatives, carbamates, pyrethroids, chlorinated hydrocarbons, acylurea, pyridylmethylene amino derivatives, macrolides, neonicotinoids, and Bacillus thuringiensis preparations.

[0689] The following mixtures of compounds having Formula I and active ingredients are preferred (the abbreviation "TX" means "a compound selected from the group consisting of compounds described in Tables A-1 to A-48, C-1 to C-24, D-1 to D-12, E-1 to E-12 and Table P of the present invention"):

[0690] The auxiliary agent is selected from the following group of substances: petroleum (alias) (628) + TX;

[0691] Insect control active substances selected from abamectin + TX, miticide + TX, acetamiprid + TX, acetamiprid + TX, flufenoxuron + TX, acynonapyr + TX, bispyrifos + TX, afralanar + TX, pyrethroid + TX, α-cypermethrin + TX, lambda-cyhalothrin + TX, sulfadiazine + TX, methamidophos + TX, triazophos + TX, chlorpyrifos + TX, benzoyl permethrin + TX, Benzpyrimoxan + TX, β-cypermethrin + TX, β-cypermethrin + TX, bifenazate + TX, bifenthrin + TX, chlorfenapyr + TX, bio-allethrin + TX, S-bio-allethrin + TX, bio-benzylfenoxuron + TX, and more. Triflufenoxam + TX, Broflanilide + TX, Broflufenoxam + TX, Bromothion-Ethyl + TX, Thiamethoxam + TX, Butanil + TX, Thiamethoxam + TX, Carbaryl + TX, Sevin + TX, Thiamethoxam + TX, Bataan + TX, CAS No.: 1632218-00-8+TX, CAS No.: 1808115-49-2+TX, CAS No.: 2032403-97-5+TX, CAS No.: 2044701-44-0+TX, CAS No.: 2128706-05-6+TX, CAS No.: 2095470-94-1+TX, CAS No.: 2377084-09-6+TX, CAS No.: 14 45683-71-5+TX, CAS No.: 2408220-94-8+TX, CAS No.: 2408220-91-5+TX, CAS No.: 1365070-72-9+TX, CAS No.: 2171099-09-3+TX, CAS No.: 2396747-83-2+TX, CAS No.: 2133042-31-4+TX, CAS No.: 2133042-44-9+TX, CAS No.: 1445684-82-1+TX, CAS No.: 1445684-82-1+TX, CAS No.: 1922957-45-6+TX, CAS No.: 1922957-46-7+TX, CAS CAS Nos: 1922957-47-8+TX, 1922957-48-9+TX, 2415706-16-8+TX, 1594624-87-9+TX, 1594637-65-6+TX, 1594626-19-3+TX, 1990457-52-7+TX, 1990457-55-0+TX, 1990457-57-2+TX, 1990457-77-6+TX, 1990457-66-3+TX, 1990457-85-6+TXCAS No.: 2220132-55-6+TX, CAS No.: 1255091-74-7+TX, Chlorantraniliprole +TX, Chlordane +TX, Bromoxynil +TX, Cyprodinil +TX, Clenbuterol +TX, Cloethocarb +TX, Thiamethoxam +TX, 2-Chlorophenyl N-methylcarbamate (CPMC) +TX, Benzoate +TX, Bromoxynil +TX, Cyclobutrifluram +TX, Pyrethroids +TX, Ethoxyfen +TX, Cyclobutrifluram +TX, Cyprodinil +TX, Cyclobutrifluram +TX, Fluorochlor Cypermethrin + TX, Cyhalodiamide + TX, Trifluralin + TX, Cypermethrin + TX, Phenylebin + TX, Cyproflanilide + TX, Cyromazine + TX, Deltamethrin + TX, Acaricide + TX, Chlorimuron + TX, Dibrom + TX, Dichlorvos + TX, Flufenoxuron + TX, Diflubenzuron + TX, Difenoconazole + TX, Difenoconazole + TX, Difenoconazole + TX, Fipronil + TX, Emafenoxam (or Emafenoxam benzoate) + TX, D-cyclohexylpyridinium +TX, ε-momfluorothrin+TX, ε-methoxybenzylfluthrin+TX, cypermethrin+TX, ethion +TX, acetamiprid +TX, etoxazole +TX, phosmet +TX, quinfenoxam +TX, pendimethalin +TX, fenmezoditiaz +TX, fenitrothion +TX, methyl parathion +TX, fenthion +TX, fenoxycarb +TX, cypermethrin +TX, fenpyroximate +TX, fensodium +TX, fenthion +TX, cypermethrin +TX, flumetoquinone +TX, flupyradifurone +TX, pyrimethanil +TX, fluazaindolizine +TX, pyrimethanil +TX, flufenoxuron +TX, flufenoxuron +TX, fluchlordiniliprole +TX, flucitrinate +TX, flufenoxuron +TX, flufenoxuron +TX, flufenoxuron +TX, pyrimethanil +TX, trifluralin +TX, butenpyram +TX, fluhexafon +TX, flupyridaben +TX, flupyradifurone +TX, flupentiofenox +TX, flupyrflufenoxuron +TX, flupyrflufenoxuron +TXFlupyrimin + TX, fluralaner + TX, lambda-cyhalothrin + TX, fluxametamide + TX, thiazophos + TX, γ-trifluorocypermethrin + TX, Gossyplure, TM+TX, imidacloprid +TX, chlorfenapyr +TX, benzylfentanyl +TX, heptafluthrin +TX, thiamethoxam +TX, flufenoxuron +TX, imidacloprid +TX, imidacloprid +TX, indazapyroxamet +TX, indoxacarb +TX, iodomethacin +TX, iprodione +TX, isocycloseram +TX, isopyram +TX, ivermectin +TX, κ-bifenthrin +TX, κ-heptafluthrin +TX, lambda-cyhalothrin +TX, rapamycin +TX, lotilanar +TX Chlorfenapyr + TX, Cyfluthrin + TX, Metformin + TX, Mefenoxam + TX, Metformin + TX, Methoxyfenozide + TX, Methoxyfenozide + TX, Mefenoxam + TX, Mefenoxam + TX, Acaricide + TX, Momfluorothrin + TX, Dimethoate + TX, Nicofluprole + TX; Acetaminophen + TX, Nitrothiamethoxam + TX, Omethoate + TX, Cypermethrin + TX, Oxazosulfyl + TX, Parathion-ethyl + TX, Permethrin + TX, Difenoconazole + TX, Calcium oxychloride + TX, Piperazine + TX, Pyrimethanil-ethyl + TX, Pyrimethanil-methyl + TX, Polyhexene Virus + TX, propargite + TX, profenofos + TX, fenfluroxyfen + TX, chlorfenapyr + TX, acetamiprid + TX, propoxur + TX, fenthion + TX, protrifenbute + TX, pyflubumide + TX, pymetrozine + TX, pyrazophos + TX, pyrafluprole + TX, pyridaben + TX, acetamiprid + TX, pyrifluquinazon + TX, pyrimethanil + TX, pyrimethanil + TX, pyrazophos + TX, pyridaben + TX, fenfluroxyfen + TX, pyrimethanil + TX, pyrimethanil + TX, pyrimethanil + TX, pyrimethanil + TX, pyrimethanil + TX, pyrimethanil + TX, pyrimethanil + TX, pyrimethanil + TX, pyrimethanil + TX, pyrimethanil + TX, pyrimethanil + TX , Flufenoxam + TX, Ethyl spinosad + TX, Spinosad + TX, Spiropidion + TX, Spirotetramethrin + TX, Spiropidone + TX, Sulfadiazine + TX, Tebufenozide + TX, Pyridaben + TX, Tebupirimiphos + TX, Heptamethrin + TX, Dimethoate + TX, Tetrachlorfenapyr + TX, Tetradiphon + TX, Pyrethroid + TX, Tetrafluthrin + TX, Acaricide + TX, Flufenoxuron + TX, θ-Cypermethrin + TX, Thiamethoxam + TX, Thiamethoxam + TX, Cypermethrin + TX, Thiamethoxam + TX, Dichlorvos + TX, Thiamethoxam + TX, Dichlorvos + TX, Thiamethoxam + TX, Dichlorvos + TX, Methion + TX, Pyridaben + TXTioxazafen+TX, acetamiprid+TX, toxaphene+TX, tetrabromopyr+TX, tetrafluorobenzylpyr+TX, pymetrozine+TX, triazophos+TX, trichlorfon+TX, cypermethrin+TX, trichlorfon+TX, triflumezopyrim+TX, tyclopyrazoflor+TX, ζ-cypermethrin+TX, seaweed extract and fermented products derived from glycoyl +TX, seaweed extract and fermented products derived from glycoyl (including urea+TX, amino acids+TX, potassium and molybdenum, and EDTA chelated manganese)+TX, seaweed extract and fermented plant products+TX, seaweed extract and fermented plant products (including plant hormones+TX, vitamins+TX, EDTA chelated copper+TX, zinc+TX, and iron+TX), azadirachtin+TX, Bacillus aizawai+TX, Bacillus chitinosa Bacillus chitinosporus AQ746 (NRRL Registry No. B-21618) + TX, Bacillus sturdier + TX, Bacillus kurstaki + TX, Bacillus mycosis fungoides AQ726 (NRRL Registry No. B-21664) + TX, Bacillus pumilus (NRRL Registry No. B-30087) + TX, Bacillus pumilus AQ717 (NRRL Registry No. B-21662) + TX, Bacillus species AQ178 (ATCC Registry No. 53522) + TX, Bacillus species AQ175 (ATCC Registry No. 55608) + TX, Bacillus species AQ177 (ATCC Registry No. 55609) + TX, Bacillus subtilis (unspecified) + TX, Bacillus subtilis AQ153 (ATCC Registry No. 55614) +TX, Bacillus subtilis AQ30002 (NRRL Registry No. B-50421) +TX, Bacillus subtilis AQ30004 (NRRL Registry No. B-50455) +TX, Bacillus subtilis AQ713 (NRRL Registry No. B-21661) +TX, Bacillus subtilis AQ743 (NRRL Registry No. B-21665) +TX, Bacillus thuringiensis AQ52 (NRRL Registry No. B-21619) +TX, Bacillus thuringiensis BD#32 (NRRL Registry No. B-21530) +TX, Bacillus thuringiensis Kurstaki subsp. BMP 123+TX, Beauveria bassiana +TX, D-limonene +TX, Granulovirus +TX, Harpin +TX, Cotton bollworm nucleopolyhedrovirus +TX, Gramineae nucleopolyhedrovirus +TX, Tobacco budworm nucleopolyhedrovirus +TX, Australian cotton bollworm nucleopolyhedrovirus +TX, Metarhizium species +TX,Muscodor albus 620 (NRRL Registry No. 30547) +TX, Muscodor roseus A3-5 (NRRL Registry No. 30548) +TX, neem-based products +TX, *Paecilomyces rosenbergii* +TX, *Paecilomyces lilacinus* +TX, *Paecilomyces szawa* +TX, *Paecilomyces punctata* +TX, *Paecilomyces mycoides* +TX, *Paecilomyces thornei* +TX, *Paecilomyces* +TX, p-cymene +TX, diamondback moth granulovirus +TX, diamondback moth nucleopolyhedrovirus +TX, polyhedrovirus +TX, pyrethrum +TX, QRD 420 (terpene blend) +TX, QRD 452 (terpene blend) +TX, QRD 460 (terpene blend) + TX, *Saponaria spp.* + TX, *Rhodococcus spherulites* AQ719 (NRRL registry number B-21663) + TX, *Fall Armyworm* nucleopolyhedrovirus + TX, *Streptomyces flavus* (NRRL registry number 30232) + TX, *Streptomyces* species (NRRL registry number B-30145) + TX, terpene blend + TX, and *Verticillium* species;

[0692] Algicide selected from the following groups of substances: bethoxazin [CCN]+TX, copper dioctanoate (IUPAC name) (170)+TX, copper sulfate (172)+TX, 2-tert-butylamino-4-cyclopropylamino-6-methylthio-s-triazine [CCN]+TX, dichlone (1052)+TX, dichlorophenol (232)+TX, fentin (295)+TX, fentin (347)+TX, quicklime [CCN]+TX, sodium mancozeb (566)+TX, quinoclamine (714)+TX, quinonamid (1379)+TX, simazine (730)+TX, tin triphenylacetate (IUPAC name) (347) and tin triphenyl hydroxide (IUPAC name) (347)+TX;

[0693] The anthelmintic is selected from the group of substances consisting of: abamectin (1)+TX, chlorfenapyr (1011)+TX, cyclobutyral+TX, doxorubicin (alias) [CCN]+TX, emamectin (291)+TX, emamectin benzoate (291)+TX, irinotecan (alias) [CCN]+TX, ivermectin (alias) [CCN]+TX, milbemycin oxime (alias) [CCN]+TX, moxicillin (alias) [CCN]+TX, piperazine [CCN]+TX, slakine (alias) [CCN]+TX, spinosad (737) and thiophanate (1435)+TX;

[0694] Bird killers selected from the following groups of substances: chloralose (127) + TX, isodrin (1122) + TX, fenthion (346) + TX, pyridine-4-amine (IUPAC name) (23) and strychnine (745) + TX;

[0695] Bactericides selected from the following groups of substances: 1-hydroxy-1H-pyridine-2-thione (IUPAC name) (1222)+TX, 4-(quinoxalo-2-ylamino)benzenesulfonamide (IUPAC name) (748)+TX, 8-hydroxyquinoline sulfate (446)+TX, bromonitrile (97)+TX, copper dioctanoate (IUPAC name) (170)+TX, copper hydroxide (IUPAC name) (169)+TX, cresol [CCN]+TX, dichlorophenol (232)+TX, dipyrithione (1105)+TX, doxycycline (1112)+TX, fenaminosulfonate (1144)+TX, formaldehyde (404)+TX, mercaptophenone ( (Alternative names) [CCN]+TX, Kasugamycin (483)+TX, Kasugamycin hydrochloride hydrate (483)+TX, Di(dimethyldithiocarbamate) nickel (IUPAC name) (1308)+TX, Nitropyrin (580)+TX, Octhilinone (590)+TX, Oxytetracycline (606)+TX, Oxytetracycline (611)+TX, Potassium hydroxyquinoline sulfate (446)+TX, Probenazole (658)+TX, Streptomycin (744)+TX, Streptomycin sesquisulfate (744)+TX, Phthalate (766)+TX, and Thimerosal (alternative name) [CCN]+TX;

[0696] Biological reagents, selected from the following groups of substances: Cotton Brown Leaf Roller GV (alias) (12)+TX, *Agrobacterium radiata* (alias) (13)+TX, *Amblyseius spp.* (alias) (19)+TX, Celery Noctuid Moth NPV (alias) (28)+TX, *Anagrus atomus* (alias) (29)+TX, *Aphelinus adominalis* (alias) (33)+TX, Cotton Aphid Parasitic Wasp (Aphidius colemani) (alias) (34)+TX, Aphidoletes aphidimyza (alias) (35)+TX, Alfalfa Silver-striped Noctuid Moth NPV (alias) (38)+TX, *Bacillus firmus* (alias) (48)+TX, *Bacillus sphaericus* Neide)(scientific name)(49)+TX, Bacillus thuringiensis Berliner)(scientific name)(51)+TX, Bacillus thuringiensis subsp. aizawai)(scientific name)(51)+TX, Bacillus thuringiensis subsp. israelensis)(scientific name)(51)+TX, Bacillus thuringiensis subsp. japonensis)(scientific name)(51)+TX, Bacillus thuringiensis subsp. kurstaki)(scientific name)(51)+TX, Bacillus thuringiensis subsp. truncatella)(scientific name)(51)+TX, Bacillus thuringiensis subsp.tenebrionis (scientific name) (51)+TX, Beauveria bassiana (synonym) (53)+TX, Beauveria brongniartii (synonym) (54)+TX, Chrysoperla carnea (synonym) (151)+TX, Cryptolaemus montrouzieri (synonym) (178)+TX, Codling moth GV (synonym) (191)+TX, Dacnusa sibirica (synonym) (212)+TX, Diglyphusisaea (synonym) (254)+TX, Encarsia formosa (scientific name) (293)+TX, Eretmocerus eremicus (alias) (300)+TX, Grainworm NPV (alias) (431)+TX, Heterorhabditis bacteriophora and H. megidis (alias) (433)+TX, Hippodamia convergens (alias) (442)+TX, Leptomastixdactylopii (alias) (488)+TX, Macrophorus caliginosus (alias) (491)+TX, Cabbage moth NPV (alias) (494)+TX, Metaphycus helvolus (alias) (522)+TX, Metarhizium anisopliae var. acridum (scientific name) (523)+TX, Metarhizium anisopliae var. anisopliae (scientific name) (523)+TX, Neodiprionsertifer NPV and Neodiprionsertifer (N.lecontei)NPV (synonyms) (575)+TX, Species of the genus *Lecontei* (synonyms) (596)+TX, *Paecilomyces fumosoroseus* (synonyms) (613)+TX, *Phytoseiulus persimilis* (synonyms) (644)+TX, *Spodopteraexigua multicapsid nuclear polyhedrosis virus* (scientific name) (741)+TX, *Steinernema bibionis* (synonyms) (742)+TX, *Steinernema carpocapsae* (synonyms) (742)+TX, *Steinernema glaseri* (synonyms) (742)+TX, *Steinernema rubescens* (synonyms) (742)+TX, *Steinernema glaseri* (synonyms) (742)+TX, *Steinernema rubescens* riobrave)(synonyms)(742)+TX, Steinernema riobravis)(synonyms)(742)+TX, Steinernema scapterisci)(synonyms)(742)+TX, Steinernema spp.)(synonyms)(742)+TX, Trichogramma spp.(synonyms)(826)+TX, Typhlodromus occidentalis(synonyms)(844) and Verticillium lecanii(synonyms)(848)+TX;

[0697] Soil disinfectant, selected from the following group of substances: iodomethane (IUPAC name) (542) and bromomethane (537) + TX;

[0698] Chemical sterilizing agents are selected from the following groups of substances: apholate [CCN]+TX, bisazir [CCN]+TX, busulfan [CCN]+TX, diflubenzuron (250)+TX, dimatif [CCN]+TX, hemel [CCN]+TX, hempa [CCN]+TX, metepa [CCN]+TX, methyl thiophanate... Methiotepa [CCN]+TX, methylapholate [CCN]+TX, morzid [CCN]+TX, penfluron (alias) [CCN]+TX, tepa [CCN]+TX, thiohempa (alias) [CCN]+TX, thiotepa (alias) [CCN]+TX, tratamine (alias) [CCN], and urethaneimine (alias) [CCN]+TX;

[0699] Insect pheromones are selected from the following groups of substances: (E)-dec-5-en-1-yl acetate and (E)-dec-5-en-1-ol (IUPAC name) (222)+TX, (E)-tetadecarbon-4-en-1-yl acetate (IUPAC name) (829)+TX, (E)-6-methylheptane-2-en-4-ol (IUPAC name) (541)+TX, (E,Z)-tetradecane-4,10-dien-1-yl acetate (IUPAC name) (779)+TX, (Z)-dodecane-7-en-1-yl acetate (IUPAC name) (285)+TX, (Z)-hexadecane-11-enal (IUPAC name) (436)+TX, (Z)-hexadecane-11-en-1-yl acetate (IUPAC name) (437)+T X, (Z)-hexadec-13-en-11-yn-1-yl acetate (IUPAC name) (438)+TX, (Z)-eicosero-13-en-10-one (IUPAC name) (448)+TX, (Z)-tetradec-7-en-1-al (IUPAC name) (782)+TX, (Z)-tetradec-9-en-1-ol (IUPAC name) (783)+TX, (Z)-tetradec-9-en-1-yl acetate (IUPAC name) (784)+TX, (7E,9Z)-dodec-7,9-dien-1-yl acetate (IUPAC name) (283)+TX, (9Z,11E)-tetradec-9,11-dien-1-yl acetate (IUPAC name) (780)+TX, (9Z,12E)-tetradec-9,12-Dien-1-ylacetate (IUPAC name) (781)+TX, 14-Methyloctadec-1-ene (IUPAC name) (545)+TX, 4-Methylnon-5-ol and 4-Methylnon-5-one (IUPAC name) (544)+TX, alpha-multistriatin (alias) [CCN]+TX, brevicomin (alias) [CCN]+TX, codlelure (alias) [CCN]+TX, codlelure (alias) [CCN]+TX, codlelure (alias) mone)(alias)(167)+TX, cuelure)(alias)(179)+TX, disparlure)(277)+TX, dodecano-8-en-1-yl acetate (IUPAC name))(286)+TX, dodecano-9-en-1-yl acetate (IUPAC name))(287)+TX, dodecano-8+TX, 10-dien-1-yl acetate (IUPAC name))(284)+TX, dominicalure(alias)[CCN]+TX, ethyl 4-methyloctanoate (IUPA) C Name)(317)+TX, Eugenol (Alias) [CCN]+TX, Frontalin (Alias) [CCN]+TX, Gossyplure (Alias) (420)+TX, Grandlure (421)+TX, Grandlure I (Alias) (421)+TX, Grandlure II (Alias) (421)+TX, Grandlure III (Alias) (421)+TX, Grandlure IV (Alias) (421)+TX, Hexalure [CCN]+TX, ipsdienol (alias) [CCN]+TX, ipsenol (alias) [CCN]+TX, japonilure (alias) (481)+TX, lineatin (alias) [CCN]+TX, litlure (alias) [CCN]+TX, looplure (alias) [CCN]+TX, medlure (alias) [CCN]+TX, megatomoic acid (alias) [CCN]+TX, methyl eugenol (alias) (540)+TX, muscalure (563)+TX, octadec-2,13-dien-1-yl acetate (IUPAC name) (588)+TX, octadec-3,13-Dien-1-ylacetate (IUPAC name) (589)+TX, Orfralure (alias) [CCN]+TX, Oryctalure (alias) (317)+TX, Ostramone (alias) [CCN]+TX, Siglure (CCN)+TX, Sordidin (alias) (736)+TX, Sulcatol (Alias) [CCN]+TX, tetradec-11-en-1-yl acetate (IUPAC name) (785)+TX, Mediterranean fruit fly attractant (839)+TX, Mediterranean fruit fly attractant A (alias) (839)+TX, Mediterranean fruit fly attractant B1 (alias) (839)+TX, Mediterranean fruit fly attractant B2 (alias) (839)+TX, Mediterranean fruit fly attractant C (alias) (839) and trunc-call (alias) [CCN]+TX;

[0700] Insect repellents selected from the group consisting of the following substances: 2-(octylthio)ethanol (IUPAC name) (591)+TX, butopyronoxyl (933)+TX, butoxy (polypropylene glycol) (936)+TX, dibutyl adipate (IUPAC name) (1046)+TX, dibutyl phthalate (1047)+TX, dibutyl succinate (IUPAC name) (1048)+TX, DEET [CCN]+TX, dimethyl carbate [CCN]+TX, dimethyl phthalate [CCN]+TX, ethylhexanediol (1137)+TX, hexourea [CCN]+TX, methoquin-butyl (1276)+TX, methylneodecanamide [CCN]+TX, oxamate [CCN], and picaridin [CCN]+TX;

[0701] Molluscicides selected from the group consisting of the following substances: di(tributyltin)oxide (IUPAC name) (913)+TX, bromoacetamide [CCN]+TX, calcium arsenate [CCN]+TX, chlorpyrifos (999)+TX, copper acetylacetate [CCN]+TX, copper sulfate (172)+TX, triphenyltin (347)+TX, ferric phosphate (IUPAC name) (352)+TX, metaldehyde (518)+TX, cypermethrin (530)+TX, niclosamide (576)+TX, niclosamide-ethanolamine (576)+TX, pentachlorophenol ( 623)+TX, sodium pentachlorophenoxide (623)+TX, tazimcarb (1412)+TX, thiamethoxam (799)+TX, tributyltin oxide (913)+TX, trifenmorph (1454)+TX, trimethacarb (840)+TX, triphenyltin acetate (IUPAC name) (347) and triphenyltin hydroxide (IUPAC name) (347)+TX, pyriprole [394730-71-3]+TX;

[0702] Nematicides selected from the following groups of substances: AKD-3088 (compound code) + TX, 1,2-dibromo-3-chloropropane (IUPAC / Chemical Abstracts name) (1045) + TX, 1,2-dichloropropane (IUPAC / Chemical Abstracts name) (1062) + TX, 1,2-dichloropropane and 1,3-dichloropropene (IUPAC name) (1063) + TX, 1,3-dichloropropene (233) + TX, 3,4-dichlorotetrahydrothiophene 1,1-dioxide (IUPAC / Chemical Abstracts name) Abstract Name)(1065)+TX, 3-(4-chlorophenyl)-5-methylrhodanine (IUPAC name) (980)+TX, 5-methyl-6-thio-1,3,5-thiadiazin-3-ylacetic acid (IUPAC name) (1286)+TX, 6-isopentenylaminopurine (synonym) (210)+TX, avermectin (1)+TX, acetaminophen [CCN]+TX, basil (15)+TX, aldicarb (16)+TX, aldicarb (863)+TX, AZ 60541 (compound code) + TX, benclothiazide [CCN] + TX, benomyl (62) + TX, butylpyridaben (synonym) + TX, chlorpyrifos (109) + TX, carbofuran (118) + TX, carbon disulfide (945) + TX, thiocarbofuran (119) + TX, chloropicrin (141) + TX, chlorpyrifos (145) + TX, [unclear text - possibly a compound code] Viagra (999) + TX, Cyclobutrazol + TX, Cytokinin (alias) (210) + TX, Dazomet (216) + TX, DBCP (1045) + TX, DCIP (218) + TX, Diamidafos (1044) + TX, Diamidafos (1051) + TX, Diclophos (alias) + TX, Dimethoate (262) + TX, Dolactin (alias) [ [CCN]+TX, Emamectin (291)+TX, Emamectin Benzoate (291)+TX, Irinokine (alias) [CCN]+TX, Phosphate (312)+TX, Dibromoethane (316)+TX, Phosphate (326)+TX, Fenpyrad (alias)+TX, Fonsodium (1158)+TX, Thiazolium (408)+TX, Butylthionine (1196)+TX, Fenpyroxene Aldehyde (synonyms) [CCN]+TX, GY-81 (research code) (423)+TX, phosmet [CCN]+TX, iodomethane (IUPAC name) (542)+TX, isamidophos (1230)+TX, chlorpyrifos (1231)+TX, ivermectin (synonyms) [CCN]+TX, kinetin (synonyms) (210)+TX, methyl pymetrozine (1258)+TX,Vibrio (519)+TX, Vibrio potassium salt (alias) (519)+TX, Vibrio sodium salt (519)+TX, Methyl bromide (537)+TX, Methyl isothiocyanate (543)+TX, Milbexime (alias) [CCN]+TX, Moxifloxacin (alias) [CCN]+TX, Myrothecium verrucaria composition (alias) (565)+TX, NC-184 (compound code)+TX, chlorpyrifos (602)+TX, phorate (636)+TX, phosphamidon (639)+TX, phosmet [CCN]+TX, chlorpyrifos (alias)+TX, silachlor (alias) [CCN]+TX, spinosad (737)+TX, tert-butylcarbate (synonym)+TX, terbufos (773)+TX, tetrachlorothiophene (IUPAC / Chemical Abstracts name) (1422)+TX, thiafenox (synonym)+TX, phosmet (1434)+TX, triazophos (820)+TX, triazophos (synonym)+TX, xylenol [CCN]+TX, YI-5302 (compound code) and zeatin (synonym) (210)+TX, fluensulfone [318290-98-1]+TX, fluopyram+TX;

[0703] The nitration inhibitor is selected from the group consisting of potassium ethyl xanthate [CCN] and nitrapyrin (580) + TX;

[0704] Plant activator selected from the following group of substances: acibenzolar (6)+TX, acibenzo-S-methyl (6)+TX, probenazole (658) and Reynoutria sachalinensis extract (synonym) (720)+TX;

[0705] Rodenticide selected from the group consisting of the following substances: 2-isovaleryl indan-1,3-dione (IUPAC name) (1246) + TX, 4-(quinoxalo-2-ylamino)benzenesulfonamide (IUPAC name) (748) + TX, α-chlorool [CCN] + TX, aluminum phosphide (640) + TX, antagonist (880) + TX, arsenic trioxide (882) + TX, barium carbonate (891) + TX, daridin (912) + TX, bromadiolone (89) + TX, and bromodiphenyl ether. Bromadiolone (including α-bromadiolone) + TX, bromadiolone (92) + TX, calcium cyanide (444) + TX, chloralose (127) + TX, chlorpyrifos (140) + TX, cholecalciferol (synonym) (850) + TX, chlorpyrifos (1004) + TX, cyproheptadine (1005) + TX, bromadiolone (175) + TX, pyrimidine (1009) + TX, cyproheptadine (246) + TX, thiamethoxam (249) + TX, bromadiolone (273) + TX, calciferol (301) + T X, fluoroacetamide (357) + TX, fluoroacetamide (379) + TX, fluoroacetidine (1183) + TX, fluoroacetidine hydrochloride (1183) + TX, γ-HCH (430) + TX, HCH (430) + TX, hydrogen cyanide (444) + TX, iodomethane (IUPAC name) (542) + TX, lindane (430) + TX, magnesium phosphide (IUPAC name) (640) + TX, methyl bromide (537) + TX, phosmet (1318) + TX, phosmet ( 1336)+TX, Phosphine (IUPAC name) (640)+TX, Phosphine [CCN]+TX, Warfarin (1341)+TX, Potassium Arsenite [CCN]+TX, Warfarin (1371)+TX, Onion Glycoside (1390)+TX, Sodium Arsenite [CCN]+TX, Sodium Cyanide (444)+TX, Sodium Fluoroacetate (735)+TX, Strychnine (745)+TX, Thallium Sulfate [CCN]+TX, Warfarin (851) and Zinc Phosphide (640)+TX;

[0706] Synergists selected from the group consisting of the following substances: 2-(2-butoxyethoxy)ethyl piperitate (IUPAC name) (934)+TX, 5-(1,3-benzodioxane-5-yl)-3-hexylcyclohex-2-enone (IUPAC name) (903)+TX, farnesol with nerolidol (alias) (324)+TX, MB-599 (research code) (498)+TX, MGK 264 (research code) (296)+TX, piperonyl butoxide (649)+TX, piperonal (1343)+TX, propyl isomer (1358)+TX, S421 (research code) (724)+TX, sesamex (1393)+TX, sesasmolin (1394) and sulfoxide (1406)+TX;

[0707] Animal repellents selected from the following groups of substances: 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 (422)+TX, cypermethrin (530)+TX, pyridine-4-amine (IUPAC name) (23)+TX, silane (804)+TX, trimethacarb (840)+TX, zinc naphthenate [CCN], and zinc thiram (856)+TX;

[0708] The antiviral agent is selected from the following group of substances: Imanin (also known as CCN) and Ribavirin (also known as CCN) + TX;

[0709] The wound protectant is selected from the following group of substances: mercuric oxide (512) + TX, octhilinone (590) and methyl thiophanate (802) + TX;

[0710] Bioactive substances selected from 1,1-bis(4-chloro-phenyl)-2-ethoxyethanol + TX, 2,4-dichlorophenylbenzenesulfonate + TX, 2-fluoro-N-methyl-N-1-naphthylacetamide + TX, 4-chlorophenylphenyl sulfone + TX, acetamiprid + TX, aldicarb + TX, cypermethrin + TX, phosmet + TX, methamidophos + TX, ammonium oxalate + TX, amitraz + TX, dicofol + TX, arsenic trioxide + TX, azobenzene + TX, azophos + TX, benomyl + TX, benzyl benzoate + TX, bifenthrin + TX, bromopyr + TX, and bromopyr + TX. Bromothion + TX, Bromodifen + TX, Thiamethoxam + TX, Butanone + TX, Butanone Sulfonate + TX, Butylpyridinium + TX, Calcium Polysulfide + TX, Camphene Octadec + TX, Chlorfenapyr + TX, Trithion + TX, Acaricide + TX, Dimethoate + TX, Acaricide + TX, Acaricide + TX, Acaricide Hydrochloride + TX, Dichlorvos + TX, Acaricide + TX, Dichlorvos + TX, Ethyl Acetate + TX, Chlormebuform + TX, Diflubenzuron + TX, Propyl Acetate + TX, Chlorpyrifos + TX, Ciprofloxacin I + TX, Ciprofloxacin II + TX, Ciprofloxacin + TX, Clofenac + TX, Phoxim + TX, Clomid + TX, phosmet + TX, thiophanate-methyl + TX, phosmet + TX, DCPM + TX, DDT + TX, phosmet + TX, phosmet-O + TX, phosmet-S + TX, phosmet-S + TX, phosmet-S-methyl + TX, demeton-S-methylsulfon + TX, phosmet + TX, dichlorvos + TX, dichlorvos + TX, chlorpyrifos + TX, methylflufenoxam + TX, dinex + TX, dinex-diclexine + TX, diclexine-4 + TX, diclexine- 6+TX, chlorpyrifos +TX, amyl nitrate +TX, nitroglycerin +TX, nitrate +TX, dichlorvos +TX, sulfadiazine +TX, disulfiram +TX, DNOC +TX, dofenapyn +TX, dofenapyn +TX, phosmet +TX, phosmet +TX, phenoxyacetic acid +TX, fenpyrad +TX, fenpyroximate +TX, fenpyroximate +TX, fenpyroximate +TX, fenpyroximate +TX, fenpyroximate +TX, fentrifanil +TX, flufenoxuron +TX, flufenoxuron +TX, fenpyroximate ...Benzyl ether + TX, cetylcyclopropane carboxylate + TX, methamidophos + TX, jasmine ester I + TX, jasmine ester II + TX, iodophos + TX, lindane + TX, propiconazole + TX, phosmet + TX, dithiamethoxam + TX, methiophene + TX, chlorfenapyr + TX, methyl bromide + TX, methamidophos + TX, milbemime + TX, propanil + TX, phosmet + TX, methamidophos + TX, moxifloxacin + TX, naled + TX, 4-chloro-2-(2-chloro-2-methyl-propyl)-5-[(6-iodo-3-pyridyl)methoxy]pyridazine-3-one + TX, flufenoxuron + TX, nicotinamide + TX, cyanamide + TX, cyanamide 1:1 zinc chloride complex +TX, Omethoate +TX, Sulfonate +TX, Phosphate +TX, pp'-DDT +TX, Parathion +TX, Permethrin +TX, Fenthion +TX, Phosphate +TX, Phosphamidon +TX, Phosphamidon +TX, Polychloroterpenes +TX, Polynactins +TX, Prochloraz +TX, Carbendazim +TX, Prochloraz +TX, Ethiazophos +TX, Phosphate +TX, Pyrethrin I +TX, Pyrethrin II +TX, Pyrethrin +TX, Pyridaben +TX, Pyrazophos +TX, Pyrimethanil +TX, Pyrimethanil +TX, Quinalphos +TX, Quintiofos +TX, R-149 2+TX, glyphosate+TX, rotenone+TX, octamethrin+TX, chlorpyrifos+TX, silachlor+TX, thiophanate-methyl+TX, SSI-121+TX, sufil+TX, fipronil+TX, thiophanate-methyl+TX, sulfur+TX, flufenoxam+TX, t-flufenoxam+TX, TEPP+TX, terbufos+TX, tetrachlorfon+TX, chlorfenapyr+TX, thiafenoxam+TX, chlorpyrifos+TX, methyl methamidophos+TX, chlorpyrifos+TX, thiamethoxam+TX, chlorpyrifos+TX, fenpyroxetine+TX, triazophos+TX, trichlorfon+TX, trichlorfon+TX, chlorpyrifos+TX, fenpyroxetine+TX, vanil iprole)+TX, cybutanol+TX, copper dioctanoate+TX, copper sulfate+TX, cybutryne+TX, dichloronaphthoquinone+TX, dichlorophenol+TX, cybutanol+TX, triphenyltin+TX, quicklime+TX, sodium mancozeb+TX, cybutanol+TX, cybutanol+TX, cybutanol+TX, cybutanol+TX, simazine+TX, triphenyltin acetate+TX, triphenyltin hydroxide+TX, cypermethrin+TX, piperazine+TX, thiophanate-methyl+TX, chloralose+TX, phosmet+TX, pyridine-4-amine+TX, strychnine+TX, 1-hydroxy-1H-pyridine-2-thione+TX, 4-(quinoxalo-2-ylamino)benzenesulfonamide+TX, 8-hydroxyquinoline sulfate+TX, bromonitrile+TX, copper hydroxide+TXCresol + TX, Dipyridamole + TX, Doxorubicin + TX, Sodium Dichlorophenate + TX, Formaldehyde + TX, Mercuroquine + TX, Kasugamycin + TX, Kasugamycin Hydrochloride Hydrate + TX, Di(Dimethyldithiocarbamate) Nickel + TX, Trichloromethylpyridine + TX, Octethiazoline + TX, Oxytetracycline + TX, Potassium Hydroxyquinoline Sulfate + TX, Thiamethoxam + TX, Streptomycin + TX, Streptomycin Sesquisulfate + TX, Leaf Blight + TX, Thimerosal + TX, Cotton Brown Leaf Roller GV + TX, Agrobacterium radiata + TX, Amblyseius species + TX, Celery Noctuid moth NPV + TX, Protoceratops spp. + TX, Short-spurred Aphids + TX, Cotton Aphid Parasitic Wasp + TX, Aphid Gall Moth + TX, Alfalfa Silver-striped Noctuid moth NPV + TX, Bacillus spheroides + TX, Beauveria bassiana + TX, common lacewing + TX, *Cryptocoryne mongolica* + TX, codling moth GV + TX, *Siberian chastes parasitic wasp* + TX, pea leafminer wasp + TX, *Encarsia formosa* + TX, *Aphidius spp.* + TX, *Heterotrophic nematode* and *Heterotrophic nematode* + TX, *Spotted long-legged ladybug* + TX, *Citrus citrus scale parasitic wasp* + TX, mirid bug + TX, *Calophyllum noctuid moth* NPV + TX, *Broad-stalked flea wasp* + TX, *Metarhizium anisopliae* + TX, *Metarhizium anisopliae* microsporum variety + TX, *Neopyrhinus cerana* NPV and *Neopyrhinus rubescens* NPV + TX, *Stereophora* species + TX, *Paecilomyces flavus* + TX, *Physeieus chiaretus* + TX, hairy nematode + TX, *Stereophora stylosa* + TX, *Stereophora stylosa* + TX, *Nematophora griseus* + TX, *Stereophora stylosa ... riobravis+TX, *Strombus stearothermiae* +TX, *Strombus stearothermiae* species +TX, *Trichogramma* species +TX, *Vibrio vulnificus* +TX, *Verticillium clavatum* +TX, azirphosphazine +TX, bis(aziridine)methylaminophosphonate sulfide +TX, busulfan +TX, dimeltifol +TX, hexamethylmelamine +TX, hexamethylphosphine +TX, methylthiophosphine +TX, methylthiophosphine +TX, methylazirphosphazine +TX, styramine +TX, flufenoxuron +TX, thiophosphine +TX, thiophosphine +TX, tratamine +TX, urethaneimine +TX, (E)-dec-5-en-1-ylacetate and (E)-dec-5-en-1-ol +TX, (E)-tetrate-4-en-1-yl acetate +TX, (E)-6-methylhept-2-en-4-ol +TX, (E,Z)-tetradecane-4,10-dien-1-yl acetate +TX, (Z)-dodecane-7-en-1-yl acetate +TX, (Z)-hexadecane-11-enal +TX, (Z)-hexadecane-11-en-1-yl acetate +TX, (Z)-hexadecane-13-en-11-ynyl acetate +TX, (Z)-eicosode-13-en-10-one +TX, (Z)-tetradecane-7-en-1-al +TX, (Z)-tetradecane-9-en-1-ol +TX(Z)-Tetradecano-9-en-1-yl acetate + TX, (7E,9Z)-Dodeca-7,9-dien-1-yl acetate + TX, (9Z,11E)-Tetradecano-9,11-dien-1-yl acetate + TX, (9Z,12E)-Tetradecano-9,12-dien-1-yl acetate + TX, 14-Methyloctadecano-1-ene + TX, 4-Methylnon-5-ol and 4-Methylnon-5-one + TX, α-polystyrin + TX, western pine bark beetle pheromone + TX, dodecadienol + TX, cyproterone + TX, cyclohexane + TX, cyclohexane + TX, dodecano-8-en-1-yl acetate + TX, dodecano- -9-en-1-yl acetate + TX, dodecano-8 + TX, 10-dien-1-yl acetate + TX, dominicalure + TX, ethyl 4-methyloctanoate + TX, eugenol + TX, Southern pine bark beetle pheromone + TX, attractant ene mixture + TX, attractant ene mixture I + TX, attractant ene mixture II + TX, attractant ene mixture III + TX, attractant ene mixture IV + TX, hexane attractant + TX, bark beetle dienol + TX, small beetle enol + TX, scarab beetle sex pheromone + TX, trimethyldioxane + TX, litlure + TX, white armyworm sex pheromone + TX, attractant ester + TX, megatomoic Acid + TX, Insecticidal Ether + TX, Insecticidal Enzyme + TX, Octadec-2,13-dien-1-yl Acetate + TX, Octadec-3,13-dien-1-yl Acetate + TX, Hecombi + TX, Coconut Beetle Aggregating Pheromone + TX, Filacon + TX, Insecticidal Ring + TX, Sordidin + TX, Fungicidal Entrainer + TX, Tetradecano-11-en-1-yl Acetate + TX, Mediterranean Fruit Fly Attractant + TX, Mediterranean Fruit Fly Attractant A + TX, Mediterranean Fruit Fly Attractant B1 + TX, Mediterranean Fruit Fly Attractant B2 + TX, Mediterranean Fruit Fly Attractant C + TX, Trunc-Call + TX, 2-(Octylthio)-ethanol + TX, DEET + TX, Butoxy(polypropylene glycol) + TX, Dibutyl Adipate + TX, dibutyl phthalate + TX, dibutyl succinate + TX, DEET + TX, mosquito repellent + TX, dimethyl phthalate + TX, ethylhexanediol + TX, hexane + TX, methylquinoline + TX, methylneodecanamide + TX, oxaloate + TX, picaridin + TX, 1-dichloro-1-nitroethane + TX, 1,1-dichloro-2,2-di(4-ethylphenyl)-ethane + TX, 1,2-dichloropropane and 1,3-dichloropropene + TX, 1-bromo-2-chloroethane + TX, 2,2,2-trichloro-1-(3,4-dichloro-phenyl)ethyl acetate + TX, 2,2-dichlorovinyl-2-ethylsulfinyl ethyl methyl phosphate + TX, 2-(1,3-dithiopentane-2-yl)phenyl dimethyl carbamate + TX,2-(2-Butoxyethoxy)ethyl thiocyanate + TX, 2-(4,5-dimethyl-1,3-dioxolane-2-yl)phenylmethylcarbamate + TX, 2-(4-chloro-3,5-dimethylmethyloxy)ethanol + TX, 2-chlorovinyl diethyl phosphate + TX, 2-imidazolinone + TX, 2-isovaleryl indan-1,3-dione + TX, 2-methyl(prop-2-ynyl)aminophenylmethylcarbamate + TX, 2-cyanothioethyl laurate + TX, 3-bromo-1-chloroprop-1-ene + TX, 3-methyl-1-phenylpyrazole-5-yldimethylamino Carbamate + TX, 4-methyl(prop-2-ynyl)amino-3,5-xylylmethylcarbamate + TX, 5,5-dimethyl-3-oxocyclohex-1-enyldimethylcarbamate + TX, asethion + TX, acrylonitrile + TX, aldrin + TX, chlorpyrifos + TX, α-decanoic acid + TX, aluminum phosphide + TX, chlorpyrifos + TX, neonicotinoid + TX, ethyl phosphide + TX, methyl pyridinium + TX, Bacillus thuringiensis δ-endotoxin + TX, barium hexafluorosilicate + TX, barium polysulfide + TX Cypermethrin + TX, Bayer 22 / 190 + TX, Bayer 22408 + TX, β-cyhalothrin + TX, β-cypermethrin + TX, bioethanomethrin + TX, permethrin + TX, bis(2-chloroethyl) ether + TX, borax + TX, bromophenylenephos + TX, bromo-DDT + TX, cypermethrin + TX, chlorpyrifos + TX, butathiofos + TX, butyl phosphate + TX, calcium arsenate + TX, calcium cyanide + TX, carbon disulfide + TX, carbon tetrachloride + TX, batamethrin hydrochloride + TX Cevadine + TX, Borneol + TX, Chlordane + TX, Decachlorophenone + TX, Chloroform + TX, Chloropicrin + TX, Chloronitrile Oxime + TX, Chlorprazophos + TX, Cis-resmethrin + TX, Cismethrin + TX, Clocythrin (another name) + TX, Copper Acetate Arsenite + TX, Copper Arsenate + TX, Copper Oleate + TX, Coumithoate + TX, Cryolite + TX, CS 708+TX, benzoylphos +TX, fenitrothion +TX, pyrethrum +TX, cypermethrin +TX, d-methoxyfenozide +TX, DAEP +TX, dazomet +TX, decarbofuran +TX, chlorpyrifos +TX, isochlorpyrifos +TX, chlorpyrifos +TX, dicresyl +TX, cyclopyrronium +TX, dieldrin +TX, diethyl-5-methylpyrazol-3-yl phosphate +TX, dior +TX, tetrafluoromethrin +TX, dimethoate +TX,Benzylpyrethrin + TX, Methyl chlorpyrifos + TX, Difenoconazole + TX, Pronitrophenol + TX, Pentylnitrophenol + TX, Diphenoxyethanol + TX, Benzylphos + TX, Phosphate + TX, Thiamethoxam + TX, DSP + TX, Ecstatone + TX, EI 1642 + TX, EMPC + TX, EPBP + TX, Etaphos + TX, Ethyl formate + TX, Dibromoethane + TX, Dichloroethane + TX, Ethylene oxide + TX, EXD + TX, Fenoxacrim + TX, Ethyl carbendazim + TX, Fenitrothion + TX, Fenoxacrim + TX, Cypermethrin + TX, Fonsophos + TX, Ethyl thion + TX, Flucofuron + TX, Butylphosphide + TX, Phosphate + TX, Butylphosphide + TX, Furazolidone + TX, Pyrethroids +TX, Biguanide Octyl Salt +TX, Biguanide Octyl Acetate +TX, Sodium Tetrathiocarbonate +TX, Benzylfentanyl +TX, HCH +TX, HEOD +TX, Heptachlor +TX, Phosphate +TX, HHDN +TX, Hydrogen Cyanide +TX, Quinoline +TX, IPSP +TX, Chlorpyrifos +TX, Carbochlor +TX, Isofenphos +TX, Isofenphos +TX, Transplanting Agent +TX, Isoprothiolane +TX, Oxadiazon +TX, Juvenile Hormone I +TX, Juvenile Hormone II +TX, Juvenile Hormone III +TX, Chlorpentine +TX, Acetaminophen +TX, Lead Arsenate +TX, Bromobenzyl + TX, Acetaminophen + TX, Thiazolium + TX, m-isopropylphenyl methyl carbamate + TX, Magnesium phosphide + TX, Azoxystrobin + TX, Methyl phosphonate + TX, Phosphorus + TX, Mercurous chloride + TX, Methyl sulfoxide + TX, Potassium phosphonate + TX, Sodium phosphonate + TX, Methylsulfonyl fluoride + TX, Butenyl phosphonate + TX, Methoprene + TX, Permethrin + TX, Methoxydextrin + TX, Methyl isothiocyanate + TX, Methyl chloroform + TX, Dichloromethane + TX, Pyrimethanil + TX, Miperazine + TX, Naphthalene + TX, NC-1 70+TX, Nicotine+TX, Nicotine Sulfate+TX, Nitrothiazide+TX, Protonicine+TX, O-5-Dichloro-4-iodophenyl O-ethyl ethyl thiophosphonate+TX, O,O-Diethyl O-4-methyl-2-oxo-2H-benzopyran-7-yl thiophosphonate+TX, O,O-Diethyl O-6-methyl-2-propylpyrimidin-4-yl thiophosphonate+TX, O,O,O',O'-Tetrapropyl dithiopyrophosphate+TX, Oleic Acid+TX, p-Dichlorobenzene+TX, Methyl parathionine+TX, Pentachlorophenol+TX, Pentachlorophenyl Laurate+TX, pH 60-38+TX, fenthion+TX, parachlorpyrifos+TX, phosphine+TX, methyl phoxim+TX, methamidophos+TX, polychlorinated dicyclopentadiene isomer+TX, potassium arsenite+TX, potassium thiocyanate+TX, precocious pruning agent I+TX, precocious pruning agent II+TX,Precocious Pruning Agent III + TX, Aminopyrimidine Phosphate + TX, Procymidone + TX, Mancozeb + TX, Propyridaben + TX, Pyraclostrobin + TX, Pyrethrum + TX, Quassia Extract + TX, Quinalphos-Methyl + TX, Phoxim + TX, Iodophos + TX, Benzylfuran + TX, Rotenone + TX, Thiamethoxam + TX, Rianodine + TX, Sabadilla + TX, Octylphosphide + TX, Ketoconazole + TX, SI-0009 + TX, Thiamethoxam + TX, Sodium Arsenite + TX, Sodium Cyanide + TX, Sodium Fluoride + TX, Sodium Hexafluorosilicate + TX, Sodium Pentachlorophenolate + TX, Sodium Selenate + TX, Sodium Thiocyanate + TX, Sulfobenzyl Oxide (su 1, ... X, tebufenozide + TX, veratrine + TX, veratrine + TX, XMC + TX, zetamethrin + TX, zinc phosphide + TX, pyraclostrobin + TX, chlorpyrifos + TX, tetrafluoromethrin + TX, bis(tributyltin)oxide + TX, bromoacetamide + TX, ferric phosphate + TX, niclosamide-ethanolamine + TX, tributyltin oxide + TX, pyrmorpholine + TX, serotonin + TX, 1,2-dibromo-3-chloropropane + TX, 1,3-dichloropropene + TX, 3,4-dichlorotetrahydrothiophene 1,1-dioxide + TX, 3-(4-chlorophenyl)-5-methylrhodanine + TX, 5-methyl-6-thio-1,3,5-thiadiazin-3-ylacetic acid + TX, 6-isopentenyl Aminopurine +TX, anisiflupurin +TX, phenylchlorothiazide +TX, cytokinin +TX, DCIP +TX, furfural +TX, isoamylphosphine +TX, kinetin +TX, *Lysimachia christinae* composition +TX, tetrachlorothiophene +TX, xylenol +TX, zeatin +TX, potassium ethyl xanthate +TX, aramidoylbenzene +TX, aramidoylbenzene-S-methyl +TX, Polygonum cuspidatum extract +TX, α-chlorool +TX, antagonist +TX, barium carbonate +TX, dimethomorph +TX, bromadiolone +TX, bromadiolone +TX, bromadiolone +TX, bromadiolone +TX, chlorpyrifos +TX, cholecalciferol +TX, chlorpyrifos +TX, cymoxanil +TX, cymoxanil +TX, cymoxanil +TX, cymoxanil +TX, cymoxanil +TXFiberam + TX, Fiberam + TX, Calcium alcohol + TX, Fluorine + TX, Fluoroacetamide + TX, Fluorine + TX, Fluorine hydrochloride + TX, Fiberam + TX, Rat parathion + TX, Phosphate + TX, Rat chlorpyrifos + TX, Rat chlorpyrifos + TX, Rat chlorpyrifos + TX, Onion glycoside + TX, Sodium fluoroacetate + TX, Thallium sulfate + TX, Fiberam + TX, 2-(2-butoxyethoxy)ethyl piperine + TX, 5-(1,3-benzodioxane-5-yl)-3-hexylcyclohex-2-enone + TX, Farnesol with nerolidol + TX, Synergistic alkyne + TX, MGK 264+TX, Piperyl Butyl Ether+TX, Synergistic Aldehyde+TX, Propyl Isomer+TX, S421+TX, Synergistic Powder+TX, Sesamin+TX, Sulfoxide+TX, Anthraquinone+TX, Copper Naphthenate+TX, Copper Oxide+TX, Dicyclopentadiene+TX, Ciprofloxacin+TX, Zinc Naphthenate+TX, Zinc Ferroxetine+TX, Imanin+TX, Ribavirin+TX, Chlorindolehydrazine+TX, Mercuric Oxide+TX, Methyl Thiophanate+TX, Azaconazole+TX, Bifenthrin+TX, Fenoxacillin+TX, Cycloconazole+TX, Difenoconazole+TX, Tebuconazole+TX, Fluorocyclic Azoxystrobin + TX, cyproconazole + TX, fluquinazole + TX, flusilazole + TX, tebuconazole + TX, furazolidone + TX, hexaconazole + TX, imazalil + TX, imazalil + TX, tebuconazole + TX, cyproconazole + TX, paclobutrazol + TX, isoprothiolane + TX, tebuconazole + TX, prothioconazole + TX, pyrifenoxam + TX, prochloraz + TX, propiconazole + TX, pyraclostrobin + TX, simeconazole + TX, tebuconazole + TX, flufenoxuron + TX, triadimefon + TX, triadimefon + TX Fluopyram + TX, tebuconazole + TX, pyrimidinol + TX, chlorophenylpyrimidinol + TX, fluphenylpyrimidinol + TX, bupirimate + TX, dimethirimol + TX, ethirimol + TX, dodecyl morpholine + TX, fenpropidin + TX, butyl morpholine + TX, spirocyclam + TX, tridemorpholine + TX, azoxystrobin + TX, azoxystrobin + TX, pyrimethanil + TX, seed dressing + TX, fludioxonil + TX, benalaxyl+TX, furaxyl+TX, metalaxyl+TX, R-metalaxyl+TX, furazolidone+TX, oxadixyl+TX, carbendazim+TX, debacarb+TX, tebuconazole+TX, thiabendazole+TX, chlozolinate+TX, dichlozoline+TX, myclozoline+TX, procymidone+TXVinclozoline + TX, boscalid + TX, carbendazim + TX, methomyl + TX, flutolanil + TX, oxadiazon + TX, oxychloride + TX, penthiopyrad + TX, thifluzamide + TX, doxycycline + TX, biguanidine + octylamine + TX, azoxystroburin + TX, ethoxystroburin + TX, fluopyram + TX, fluopyram + TX, ethoxystroburin + TX, azoxystroburin + TX, fenoxystroburin + TX, azoxystroburin + TX, azoxystroburin + TX, azoxystroburin + TX, azoxystroburin + TX, azoxystroburin + TX, pyraclostroburin +TX, azoxystrobin +TX, ferrous sulfate +TX, mancozeb +TX, mancozeb +TX, mancozeb +TX, methyl mancozeb +TX, mancozeb +TX, captan +TX, captan +TX, fenvalerate +TX, fenvalerate +TX, fenvalerate +TX, methyl thiophanate +TX, Bordeaux mixture +TX, copper oxide +TX, mancozeb +TX, quinoline copper +TX, phthalimide +TX, chlorpyrifos +TX, isoprothiolane +TX, chlorpyrifos +TX, methyl thiophanate +TX, fenpyroximate +TX, benomyl +TX, blasticidin +TX, chloroneb +TX, chlorothalonil +TX, cyclobutr +TX, cymoxanil +TX, cyclobutr ifluram+TX, diclocymet+TX, diclomezine+TX, dicloran+TX, diethofencarb+TX, dimethomorph+TX, flumorph+TX, dithianon+TX, ethaboxam+TX, etridiazole+TX, oxadiazon+TX, fenamidone+TX, fenoxanil+TX, ferimzone+TX, fluazinam+TX Flumetylsulforim + TX, fluopicolide + TX, fluoxytioconazole + TX, flusulfamide + TX, fluoxetine + TX, cyclophosphamide + TX, fosetyl-aluminium + TX, hymexazol + TX, propineb + ​​TX, cyazofamid + TX, methasulfocarb + TX, benomyl + TX, pencycuron + TX, phthalide + TX, polyoxins + TXPropamocarb + TX, Pyrafenoxam + TX, Proquinazid + TX, Pyroquilon + TX, Pyriofenone + TX, Quinoxal + TX, Pentachloronitrobenzen + TX, Thiamethoxam + TX, Triazol + TX, Tricyclazole + TX, Azoxystrobin + TX, Enteromycin + TX, Valamid + TX, Zoxamide + TX, Mandipropamid + TX, Flubeneteram + TX, Isopyrazam + TX, Fluoxetine Sedaxane + TX, Benzylfluopyram + TX, Fluopyram + TX, 3-Difluoromethyl-1-methyl-1H-pyrazole-4-carboxylic acid (3',4',5'-trifluoro-biphenyl-2-yl)-amide + TX, Isoflucypram + TX, Isothiazine + TX, Dipymetitrone + TX, 6-Ethyl-5,7-dioxo-pyrrolo[4,5][1,4]dithia[1,2-c]isothiazolidin-3-carboxynitrile + TX, 2-(Difluoromethyl)-N-[3-ethyl-1,1-dimethyl-indan-4-yl]pyridine-3-carboxamide + TX, 4-(2,6-difluorophenyl)-6-methyl-5-phenyl-pyridazine 3-Formonitrile + TX, (R)-3-(difluoromethyl)-1-methyl-N-[1,1,3-trimethylindan-4-yl]pyrazole-4-carboxamide + TX, 4-(2-bromo-4-fluoro-phenyl)-N-(2-chloro-6-fluoro-phenyl)-2,5-dimethyl-pyrazole-3-amine + TX, 4-(2-bromo-4-fluorophenyl)-N-(2-chloro-6-fluorophenyl)-1,3-dimethyl-1H-pyrazole-5-amine + TX, fluindapyr + TX, jiaxiangjunzhi + TX, lvbenmixianan + TX, dichlobentiazox + TX, mandestrob In addition to TX, the following are also listed: 3-(4,4-difluoro-3,4-dihydro-3,3-dimethylisoquinoline-1-yl)quinolone + TX, 2-[2-fluoro-6-[(8-fluoro-2-methyl-3-quinolinyl)oxy]phenyl]prop-2-ol + TX, oxathiapiprolin + TX, N-[6-[[[(1-methyltetrazol-5-yl)-phenyl-methylene]amino]oxymethyl]-2-pyridyl]tert-butyl carbamate + TX, piraziflumid + TX, inpyrfluxam + TX, trolprocarb + TX, chlorfluazuron + TX, and ipfentrifluconazole + TX.2-(difluoromethyl)-N-[(3R)-3-ethyl-1,1-dimethyl-indan-4-yl]pyridine-3-carboxamide + TX, N'-(2,5-dimethyl-4-phenoxy-phenyl)-N-ethyl-N-methyl-formamidin + TX, N'-[4-(4,5-dichlorothiazol-2-yl)oxy-2,5-dimethyl-phenyl]-N-ethyl-N-methyl-formamidin + TX, [2-[3-[2-[1-[2-[3,5-bis(difluoromethyl)pyrazole-1-yl]acetyl]-4-piperidinyl]thiazol-4-yl]-4,5-dihydroisoxazol-5-yl]-3-chloro-phenyl]methanesulfonate + TX, N-[6-[[(Z)-[(1-methyltetrazole-5-yl)- [Phenylene-methylene]amino]oxymethyl]-2-pyridyl]carbamate butyl-3-yne ester + TX, N-[[5-[4-(2,4-dimethylphenyl)triazol-2-yl]-2-methyl-phenyl]methyl]carbamate methyl ester + TX, 3-chloro-6-methyl-5-phenyl-4-(2,4,6-trifluorophenyl)pyridazine + TX, pyridachlometyl + TX, 3-(difluoromethyl)-1-methyl-N-[1,1,3-trimethylindan-4-yl]pyrazole-4-carboxamide + TX, 1-[2-[[1-(4-chlorophenyl)pyrazole-3-yl]oxymethyl]-3-methyl-phenyl]-4-methyl-tetrazol-5-one + TX, 1-methyl-4-[3- Methyl-2-[[2-methyl-4-(3,4,5-trimethylpyrazol-1-yl)phenoxy]methyl]phenyl]tetrazole-5-one+TX, aminopyrifen+TX, azoxystrobin+TX, indazolesulfonamide+TX, fluopyram-aniline+TX, (Z,2E)-5-[1-(4-chlorophenyl)pyrazol-3-yl]oxy-2-methoxyimino-N,3-dimethyl-pent-3-enamine+TX, florylpicoxamid+TX, fenpicoxamid+TX, metarylpicoxamid+TX, isobutylethoxyquinoline+TX, ipflufenoquin+TX, quinofum Elin+TX, Isoprothiamethoxam+TX, N-[2-[2,4-dichloro-phenoxy]phenyl]-3-(difluoromethyl)-1-methyl-pyrazole-4-carboxamide+TX, N-[2-[2-[2-chloro-4-(trifluoromethyl)phenoxy]phenyl]-3-(difluoromethyl)-1-methyl-pyrazole-4-carboxamide+TX, Benzothiamethoxam+TX, Cyazofamid+TX, 5-amino-1,3,4-thiadiazole-2-thiol zinc salt (2:1)+TX, Fluopyram+TX, Flufenoxadiazam+TX, Flufenoxadiazam+TX, Fluopyram+TX, Pyrapropoyne+TX, Piperazon (picarbutrazox)+TX2-(difluoromethyl)-N-(3-ethyl-1,1-dimethyl-indane-4-yl)pyridine-3-carboxamide + TX, 2-(difluoromethyl)-N-((3R)-1,1,3-trimethylindane-4-yl)pyridine-3-carboxamide + TX, 4-[[6-[2-(2,4-difluorophenyl)-1,1-difluoro-2-hydroxy-3-(1,2,4-triazol-1-yl)propyl]-3-pyridyl]oxy]benzonitrile + TX, metyltetraprole + TX, 2-(difluoromethyl)-N-((3R)-1,1,3-trimethylindane-4-yl) α-(1,1-dimethylethyl)-α-[4'-(trifluoromethoxy)[1,1'-diphenyl]-4-yl]-5-pyrimidinemethanol+TX, fluoxapiprolin+TX, enoxastrobin+TX, 4-[[6-[2-(2,4-difluorophenyl)-1,1-difluoro-2-hydroxy-3-(1,2,4-triazol-1-yl)propyl]-3-pyridyl]oxy]benzonitrile+TX, 4-[[6-[2-(2,4-difluorophenyl)-1,1-difluoro-2-hydroxy-3-(1,2,4-triazol-1-yl)propyl]-3-pyridyl]oxy]benzonitrile+TX, 4-[[6-[2-(2,4-difluorophenyl)-1,1-difluoro-2-hydroxy-3-] -(5-thioalkyl-1,2,4-triazol-1-yl)propyl]-3-pyridyl]oxy]benzonitrile + TX, 4-[[6-[2-(2,4-difluorophenyl)-1,1-difluoro-2-hydroxy-3-(5-thio-4H-1,2,4-triazol-1-yl)propyl]-3-pyridyl]oxy]benzonitrile + TX, anti-dampness ester + TX, eugenol + TX, kasugamycin + TX, thiamethoxam + TX, thiamethoxam + TX, metronidazole zinc + TX, amectotractin + TX, iprodione + TX, octochlor + TX; N'-[5-bromo-2-methyl-6-[(1S)-1 [-methyl-2-propoxy-ethoxy]-3-pyridyl]-N-ethyl-N-methyl-formamidin + TX, N'-[5-bromo-2-methyl-6-[(1R)-1-methyl-2-propoxy-ethoxy]-3-pyridyl]-N-ethyl-N-methyl-formamidin + TX, N'-[5-bromo-2-methyl-6-(1-methyl-2-propoxy-ethoxy)-3-pyridyl]-N-ethyl-N-methyl-formamidin + TX, N'-[5-chloro-2-methyl-6-(1-methyl-2-propoxy-ethoxy)-3-pyridyl]-N-ethyl-N-methyl-formamidin + TX,N'-[5-bromo-2-methyl-6-(1-methyl-2-propoxy-ethoxy)-3-pyridyl]-N-isopropyl-N-methyl-formamidinium + TX (these compounds can be prepared by the method described in WO2015 / 155075); N'-[5-bromo-2-methyl-6-(2-propoxypropoxy)-3-pyridyl]-N-ethyl-N-methyl-formamidinium + TX (this compound can be prepared by the method described in IPCOM000249876D); N-isopropyl-N'-[5-methoxy-2-methyl-4-(2,2,2-trifluoro-1-hydroxy-1-phenyl-ethyl)phenyl]-N-methyl N-methylformamidinium + TX, N'-[4-(1-cyclopropyl-2,2,2-trifluoro-1-hydroxy-ethyl)-5-methoxy-2-methyl-phenyl]-N-isopropyl-N-methylformamidinium + TX (these compounds can be prepared by the method described in WO2018 / 228896); N-ethyl-N'-[5-methoxy-2-methyl-4-[(2-trifluoromethyl)oxetane-2-yl]phenyl]-N-methylformamidinium + TX, N-ethyl-N'-[5-methoxy-2-methyl-4-[(2-trifluoromethyl)tetrahydrofuran-2-yl]phenyl]-N-methylformamidinium + TX (these compounds can be prepared by the method described in WO2018 / 228896); (Prepared by the method described in 2019 / 110427); N-[(1R)-1-benzyl-3-chloro-1-methyl-but-3-enyl]-8-fluoro-quinoline-3-carboxamide + TX, N-[(1S)-1-benzyl-3-chloro-1-methyl-but-3-enyl]-8-fluoro-quinoline-3-carboxamide + TX, N-[(1R)-1-benzyl-3,3,3-trifluoro-1-methyl-propyl]-8-fluoro-quinoline-3-carboxamide + TX, N-[(1S)-1-benzyl-3,3,3-trifluoro-1-methyl-propyl]-8-fluoro-quinoline-3-carboxamide + TX, N-[(1R)-1-benzyl-1,3-dimethyl-butyl]-7,8-difluoro-quinoline-3-carboxamide + TX, N-[(1S)-1 [-benzyl-1,3-dimethyl-butyl]-7,8-difluoro-quinoline-3-carboxamide + TX, 8-fluoro-N-[(1R)-1-[(3-fluorophenyl)methyl]-1,3-dimethyl-butyl]quinoline-3-carboxamide + TX, 8-fluoro-N-[(1S)-1-[(3-fluorophenyl)methyl]-1,3-dimethyl-butyl]quinoline-3-carboxamide + TX, N-[(1R)-1-benzyl-1,3-dimethyl-butyl]-8-fluoro-quinoline-3-carboxamide + TX, N-[(1S)-1-benzyl-1,3-dimethyl-butyl]-8-fluoro-quinoline-3-carboxamide + TX, N-((1R)-1-benzyl-3-chloro-1-methyl-but-3-enyl)-8-fluoro-quinoline-3-carboxamide + TXN-((1S)-1-benzyl-3-chloro-1-methyl-but-3-enyl)-8-fluoro-quinoline-3-carboxamide + TX (these compounds can be prepared by the method described in WO 2017 / 153380); 1-(6,7-dimethylpyrazolo[1,5-a]pyridin-3-yl)-4,4,5-trifluoro-3,3-dimethyl-isoquinoline + TX, 1-(6,7-dimethylpyrazolo[1,5-a]pyridin-3-yl)-4,4,6-trifluoro-3,3-dimethyl-isoquinoline + TX, 4,4-difluoro-3,3-dimethyl -1-(6-methylpyrazolo[1,5-a]pyridin-3-yl)isoquinoline + TX, 4,4-difluoro-3,3-dimethyl-1-(7-methylpyrazolo[1,5-a]pyridin-3-yl)isoquinoline + TX, 1-(6-chloro-7-methyl-pyrazolo[1,5-a]pyridin-3-yl)-4,4-difluoro-3,3-dimethyl-isoquinoline + TX (these compounds can be derived from WO4) Prepared by the method described in 2017 / 025510); 1-(4,5-dimethylbenzimidazol-1-yl)-4,4,5-trifluoro-3,3-dimethyl-isoquinoline + TX, 1-(4,5-dimethylbenzimidazol-1-yl)-4,4-difluoro-3,3-dimethyl-isoquinoline + TX, 6-chloro-4,4-difluoro-3,3-dimethyl-1-(4-methylbenzimidazol-1-yl)isoquinoline + TX, 4,4-difluoro-1-(5-fluoro-4-methyl-benzimidazol-1-yl)-3,3-dimethyl-isoquinoline + TX, 3-(4,4-difluoro-3,3-dimethyl-1-isoquinoline)-7,8-dihydro-6H-cyclopentadien[e]benzimidazol + TX (these compounds can be prepared by WO Prepared by the method described in 2016 / 156085); N-methoxy-N-[[4-[5-(trifluoromethyl)-1,2,4-oxadiazol-3-yl]phenyl]methyl]cyclopropaneformamide + TX, N,2-dimethoxy-N-[[4-[5-(trifluoromethyl)-1,2,4-oxadiazol-3-yl]phenyl]methyl]propionamide + TX, N-ethyl-2-methyl-N-[[4-[5-(trifluoromethyl)-1,2,4-oxadiazol-3-yl]phenyl]methyl]propionamide + TX, 1-methoxy-3-methyl 1-[[4-[5-(trifluoromethyl)-1,2,4-oxadiazol-3-yl]phenyl]methyl]urea + TX, 1,3-dimethoxy-1-[[4-[5-(trifluoromethyl)-1,2,4-oxadiazol-3-yl]phenyl]methyl]urea + TX, 3-ethyl-1-methoxy-1-[[4-[5-(trifluoromethyl)-1,2,4-oxadiazol-3-yl]phenyl]methyl]urea + TX, N-[[4-[5-(trifluoromethyl)-1,2,4-oxadiazol-3-yl]phenyl]methyl]propionamide + TX,4,4-Dimethyl-2-[[4-[5-(trifluoromethyl)-1,2,4-oxadiazol-3-yl]phenyl]methyl]isoxazolidine-3-one + TX, 5,5-Dimethyl-2-[[4-[5-(trifluoromethyl)-1,2,4-oxadiazol-3-yl]phenyl]methyl]isoxazolidine-3-one + TX, 1-[[4-[5-(trifluoromethyl)-1,2,4-oxadiazol-3-yl]phenyl]methyl]pyrazole-4-carboxylic acid ethyl ester + TX, N,N-Dimethyl-1-[[4-[5-(trifluoromethyl)-1,2,4-oxadiazol-3-yl]phenyl]methyl]-1,2,4-triazol-3-amine + TX. The compounds in this paragraph can be derived from WO 2017 / 055473, WO 2017 / 055469,Prepared by the methods described in WO 2017 / 093348 and WO 2017 / 118689; 2-[6-(4-chlorophenoxy)-2-(trifluoromethyl)-3-pyridyl]-1-(1,2,4-triazol-1-yl)prop-2-ol + TX (this compound can be prepared by the method described in WO 2017 / 029179); 2-[6-(4-bromophenoxy)-2-(trifluoromethyl)-3-pyridyl]-1-(1,2,4-triazol-1-yl)prop-2-ol + TX (this compound can be prepared by the method described in WO 2017 / 029179); 3-[2-(1-chlorocyclopropyl)-3-(2-fluorophenyl)-2-hydroxypropyl]imidazolium-4-formonitrile + TX (this compound can be prepared by WO 2017 / 093348 and WO 2017 / 118689); Prepared by the method described in WO 2016 / 156290); 3-[2-(1-chlorocyclopropyl)-3-(3-chloro-2-fluoro-phenyl)-2-hydroxy-propyl]imidazolium-4-carboxynitrile + TX (this compound can be prepared by the method described in WO 2016 / 156290); methyl 2-amino-6-methyl-pyridine-3-carboxylic acid (4-phenoxyphenyl) ester + TX (this compound can be prepared by WO 2016 / 156290) Prepared by the method described in WO 2014 / 006945); 2,6-dimethyl-1H,5H-[1,4]dithiobenzo[2,3-c:5,6-c']bipyrrole-1,3,5,7(2H,6H)-tetraone + TX (this compound can be prepared by the method described in WO 2011 / 138281); N-methyl-4-[5-(trifluoromethyl)-1,2,4-oxadiazol-3-yl]thiobenzamide + TX; N-methyl-4-[5-(trifluoromethyl)-1,2,4-oxadiazol-3-yl]benzamide + TX; (Z,2E)-5-[1-(2,4-dichlorophenyl)pyrazol-3-yl]oxy-2-methoxyimino-N,3-dimethyl-pent-3-enamide + TX (this compound can be prepared by the method described in WO 2014 / 006945); Prepared by the method described in WO 2018 / 153707); N'-(2-chloro-5-methyl-4-phenoxy-phenyl)-N-ethyl-N-methyl-formamidin + TX; N'-[2-chloro-4-(2-fluorophenoxy)-5-methyl-phenyl]-N-ethyl-N-methyl-formamidin + TX (this compound can be prepared by the method described in WO 2016 / 202742); 2-(difluoromethyl)-N-[(3S)-3-ethyl-1,1-dimethyl-indan-4-yl]pyridine-3-carboxamide + TX (this compound can be prepared by the method described in WO 2014 / 095675); (5-methyl-2-pyridyl)-[4-[5-(trifluoromethyl)-1,2,4-oxadiazol-3-yl]phenyl]methyl ketone + TX,(3-Methylisoxazol-5-yl)-[4-[5-(trifluoromethyl)-1,2,4-oxadiazol-3-yl]phenyl]methyl ketone + TX (these compounds can be prepared by the method described in WO 2017 / 220485); 2-oxo-N-propyl-2-[4-[5-(trifluoromethyl)-1,2,4-oxadiazol-3-yl]phenyl]acetamide + TX (this compound can be prepared by the method described in WO 2018 / 065414); 1-[[5-[5-(trifluoromethyl)-1,2,4-oxadiazol-3-yl]-2-thienyl]methyl]pyrazole-4-carboxylic acid ethyl ester + TX (this compound can be prepared by WO 2017 / 220485) Prepared by the method described in WO 2018 / 158365); 2,2-difluoro-N-methyl-2-[4-[5-(trifluoromethyl)-1,2,4-oxadiazol-3-yl]phenyl]acetamide + TX, N-[(E)-methoxyiminomethyl]-4-[5-(trifluoromethyl)-1,2,4-oxadiazol-3-yl]benzamide + TX, N-[(Z)-methoxyiminomethyl]-4-[5-(trifluoromethyl)-1,2,4-oxadiazol-3-yl]benzamide + TX, N-[N-methoxy-C-methyl-carbonimino]-4-[5-(trifluoromethyl)-1,2,4-oxadiazol-3-yl]benzamide + TX (these compounds can be prepared by the method described in WO 2018 / 202428);

[0711] Microorganisms, including: Acinetobacter lwoffii + TX, Acremonium alternatum + TX + TX, Acremonium cephalosporium + TX + TX, Acremonium diospyri + TX, Acremonium obclavatum + TX, and Adoxophyes orana granulovirus (AdoxGV). +TX, Agrobacterium radiobacter strain K84 (Galltrol- )+TX, Alternaria alternate+TX, Alternaria cassia+TX, Alternaria destruens +TX, Ampelomyces quisqualis +TX, Aspergillus flavus AF36 +TX, Aspergillus flavus NRRL 21882 +TX, Aspergillus species +TX, Aureobasidium pullulans +TX, Azospirillum +TX, ( +TX、TAZO +TX, Azotobacter +TX, Chroocuccum +TX, Bionatural Blooming Cysts Bacillus amyloliquefaciens +TX, Bacillus cereus +TX, Bacillus chitinosporus strain CM-1 +TX, Bacillus strain AQ746 +TX, Bacillus licheniformis strain HB-2 (Biostart) TM )+TX, Bacillus licheniformis strain 3086 ( +TX、Green )+TX, Bacillus circulans+TX, Bacillus firmus ( +TX、BioNem- +TX、 Bacillus mesori (strain I-1582+TX), Bacillus macerans+TX, Bacillus marismortui+TX, Bacillus megaterium+TX, Bacillus mycoides (strain AQ726+TX), Bacillus papillae (Milky Spore) )+TX, Bacillus pumilus spp. species+TX, Bacillus pumilus strain GB34 (Yield) )+TX, Bacillus pumilus strain AQ717+TX, Bacillus pumilus strain QST 2808 ( +TX、Ballad )+TX, Bacillus spahericus +TX, Bacillus spp. species +TX, Bacillus strain AQ175+TX, Bacillus strain AQ177+TX, Bacillus strain AQ178+TX, Bacillus subtilis strain QST 713 ( +TX、 +TX、 )+TX, Bacillus subtilis strain QST 714 +TX, Bacillus subtilis strain AQ153+TX, Bacillus subtilis strain AQ743+TX, Bacillus subtilis strain QST3002+TX, Bacillus subtilis strain QST3004+TX, Bacillus subtilis variant Bacillus amyloliquefaciens strain FZB24 ( +TX、 Bacillus thuringiensis Cry 2Ae+TX, Bacillus thuringiensis Cry 1Ab+TX, Bacillus thuringiensis aizawai GC 91 +TX, Bacillus thuringiensis israelensis ( +TX、 +TX、 +TX, Bacillus thuringiensis kurstaki ( +TX、 +TX、 +TX、 +TX, Scutella +TX、Turilav +TX、 +TX、Dipel +TX、 +TX、 +TX, Bacillus thuringiensis kurstaki BMP 123 +TX, Bacillus thuringiensis Kurstak subspecies HD-1 (Bioprotec- )+TX, Bacillus thuringiensis strain BD#32+TX, Bacillus thuringiensis strain AQ52+TX, Bacillus thuringiensis var. aizawa ( +TX、 )+TX, bacterial species ( +TX、 +TX、 +TX, bacteriophage of Clavipacter michiganensis +TX、 +TX, Beauveria bassiana ( +TX、Brocaril )+TX, Beauveria bassiana GHA (Mycotrol) +TX、Mycotrol +TX、 )+TX, Beauveria branniartii ( +TX, Schweizer +TX、 )+TX, Beauveria spp. species+TX, Botrytis cineria+TX, Bradyrhizobium japonicum slow-growing rhizobium of soybean +TX, Brevibacillus brevis, Bacillus thuringiensistenebrionis +TX, BtBooster+TX, Burkholderiacepacia (bacterium cepacia) +TX、 +TX、Blue Burkholderia gladii +TX, Burkholderia gladioli +TX, Burkholderia spp. +TX, Canadian thistle fungus (CBHCanadian) Candida butyri +TX, Candida famata +TX, Candida fructus +TX, Candida glabrata +TX, Candida guilliermondii +TX, Candida melibiosica +TX, Candida oleophila strain O +TX, Candida parapsilosis +TX, Candida pelliculosa +TX, Candida pulcherrima +TX, Candida reukaufii +TX, Candida saitoana (Bio- +TX、 )+TX, Candida sake+TX, Candida spp.+TX, Candida tenius+TX, Cedecea dravisae+TX, Cellulomonas flavigena+TX, Chaetomium cochliodes (Nova- +TX, Chaetomium globosum (Nova- )+TX, Chromobacterium subtsugae strain PRAA4-1T +TX, Cladosporium cladosporioides+TX, Cladosporium oxysporum+TX, Cladosporium chlorocephalum+TX, Cladosporium spp.+TX, Cladosporium tenuissimum+TX, Clonastachys rosea +TX, Colletotrichum acutatum +TX, Coniothyrium minitans (Cotans )+TX, Coniothyrium spp.+TX, Cryptococcus albidus +TX, Cryptococcus humicola +TX, Cryptococcus infirmo-miniatus +TX, Cryptococcus laurentii +TX, Cryptoophlebia leucotreta granulovirus +TX, Cupriavidus campinensis+TX, Cydia pomonella granulovirus (CYD- )+TX, codling moth granulovirus ( +TX, Madex +TX、Madex Max / )+TX、Cylindrobasidium laeve +TX, Cylindrocladium +TX, Debaryomyceshansenii +TX, Drechslera hawaiinensis +TX, Enterobacter cloacae +TX, Enterobacteriaceae +TX, Entomophthora virulenta +TX, Epicoccum nigrum +TX, Epicoccum purpurascens +TX, Epicoccum species +TX, Filobasidium floriforme +TX, Fusarium argentis +TX, Fusarium chlamydosporium +TX, Fusarium oxysporum ( / Biofox )+TX, Fusarium moniliformes+TX, Fusarium species+TX, Galactomyces geotrichum+TX, Gliocladium catenulatum ( +TX、 )+TX, Gliocladium roseum +TX, species of the genus Gliocladium +TX, Green broom mold +TX, Particulate Virus +TX, Halobacillus halophilus +TX, Halobacillus litoralis +TX, Halobacillus trueperi +TX, species of Halomonas +TX, Halomonas subglacialis +TX, Halovibrio variabilis +TX, Hansenula polysaccharide in grape juice +TX, Helicobacter pylori nucleopolyhedrovirus +TX, Grainworm nucleopolyhedrovirus +TX, isoflavones - gentianin +TX, Klebsiella lemonis +TX, Klebsiella species +TX, Lagenidium giganteum +TX, Lecanicillium longisporum +TX, Lecanicillium muscarium +TX, Gypsy moth nucleopolyhedrovirus +TX, Halophilic sea cocci +TX, Meira geulakonigii +TX, Metarhizium anisopliae +TX, Destruxin )+TX, Metschnikowia fruticola +TX, Metschnikowia pulcherrima+TX, Microdochium dimerum +TX, Micromonospora coerulea (sky blue) +TX, Microsphaeropsis ochracea +TX, Muscodor albus (foul-smelling white fungus) 620 +TX, Muscodor roseus strain A3-5+TX, mycorrhiza species (Mycorrhizae spp.). +TX, Root )+TX, *Varicocephala var. verrucae* strain AARC-0255 +TX, BROS +TX, Ophiostoma piliferum strain D97 +TX, Paecilomyces farinosus +TX, Paecilomyces fuchsia ( +TX、 )+TX, Paecilomyces lilacinus (Biostat) )+TX, Paecilomyces lilacinus strain 251 (MeloCon )+TX, Bacillus polymyxa +TX, Pantotheca acuminata (BlightBan C9- )+TX, Pantotheca species+TX, Pasteurella species +TX, Pasteuria nishizawae +TX, Penicillium globosum +TX, Penicillium billai ( +TX、 )+TX, Short Dense Penicillium +TX, Commonly Present Penicillium +TX, Grayish Yellow Penicillium +TX, Purple-producing Penicillium +TX, Penicillium species +TX, Pure Green Penicillium +TX, Phlebiopsis gigantean +TX, Phosphate-solubilizing bacteria +TX, Phytophthora cryptica +TX, Phytophthora palmatum +TX, Pichia aberrant +TX, Pichia guilermondii +TX, Pichia membranaceus +TX, Pichia nail +TX, Pichia trunk +TX, Pseudomonas aeruginosa +TX, Pseudomonas aureofasciens (Spot-Less) )+TX, Pseudomonas cepacia +TX, Pseudomonas aeruginosa +TX, Pseudomonas corrugate +TX, BlightBan strain A506 )+TX, *Pseudomonas reactans*+TX, *Pseudomonas* species+TX, *Bio- )+TX, Pseudomonas aeruginosa +TX, Pseudomonas fluorescens +TX, Pseudozyma flocculosa strain PF-A22 UL (Sporodex )+TX, Puccinia canaliculata+TX, Puccinia thlaspeos (Wood) )+TX, Pythium paroecandrum +TX, Pythium oligomastoides ( +TX、 )+TX, Pythium spp.+TX, Rhanella aquatilis+TX, Rhanella species+TX, Rhizobia ( +TX、 )+TX, Rhizoctonia+TX, Rhodococcus globerulus strain AQ719+TX, Rhodosporidium diobovatum+TX, Rhodosporidium toruloides+TX, Rhodotorula spp.+TX, Rhodotorula glutinis+TX, Rhodotorula graminis+TX, Rhodotorula mucilagnosa+TX, Rhodotorula rubra+TX, Saccharomyces cerevisiae+TX, Salinococcus roseus+TX, Sclerotinia minor+TX, Sclerotinia minor +TX, *Scytalidium* spp. species +TX, *Scytalidium uredinicola* +TX, *Spodoptera exigua* nuclear polyhedrosis virus (Spod- +TX、 )+TX, Serratia marcescens+TX, Serratia plymuthica+TX, Serratia spp.+TX, Sordaria fimicola+TX, Spodoptera littoralis nucleopolyhedrovirus +TX, *Sporobolomyces roseus* +TX, *Stenotrophomonas maltophilia* +TX, *Streptomyces ahygroscopicus* +TX, *Streptomyces albaduncus* +TX, *Streptomyces exfoliates* +TX, *Streptomyces galbus* +TX, *Streptomyces griseoplanus* +TX, *Streptomyces griseoviridis* +TX, Streptomyces lydicus +TX, Streptomyces lidiflora WYEC-108 +TX, Streptomyces violaceus +TX, Tilletiopsis minor +TX, Tilletiopsis spp. +TX, Trichoderma asperellum (T34) +TX, Trichoderma gamsii +TX, Trichoderma atroviride +TX, Trichoderma hamatum TH 382+TX, Trichoderma harzianum rifai +TX, Trichoderma harzianum T-22 (Trianum- +TX, PlantShield +TX、 +TX、Trianum- )+TX, Trichoderma harzianum T-39 +TX, *Trichoderma inhamatum* +TX, *Trichoderma koningii* +TX, *Trichoderma* spp. LC 52 +TX, Trichoderma lignorum +TX, Trichoderma longibrachiatum +TX, Trichoderma polysporum (Binab) )+TX, Trichoderma taxi+TX, Trichoderma virens+TX, Trichoderma virens (formerly known as Gliocladium virens GL-21) +TX, Trichoderma viride +TX, Trichoderma viride strain ICC 080 +TX, Trichosporon pullulans +TX, Trichosporon spp. +TX, Trichothecium spp. +TX, Trichothecium roseum +TX, Typhula phacorrhiza strain 94670 +TX, Typhula phacorrhiza strain 94671 +TX, Ulocladium atrum +TX, Ulocladium oudemansii (Botry- )+TX, Ustilago maydis +TX, various bacteria and micronutrient supplements (Natural) )+TX, various fungi (Millennium) )+TX, Verticillium chlamydosporium+TX, Verticillium lecanii ( +TX、 )+TX、Vip3Aa20 +TX, Virgibaclillus marismortui +TX, Xanthomonas praecox pv. Poae +TX, Burkholderia foetida +TX, Nematophyte pathogens;

[0712] Plant extracts, including: pine oil +TX, Plasma Neem +TX、 +TX、 +TX、Molt- +TX, Plant IGR ( +TX、 )+TX, rapeseed oil (Lilly Miller) )+TX, Chenopodium ambrosioides near ambrosioides +TX, chrysanthemum extract +TX, Neem oil extract +TX, Labiatae essential oil +TX, clove-rosemary-peppermint and thyme oil extracts (Garden insect) )+TX, betaine +TX, garlic +TX, lemongrass oil +TX, Neem oil +TX, Catnip (Nepeta cataria) (catnip oil) +TX, Nepeta catarina +TX, Nicotine +TX, Oregano oil +TX, Pedaliaceae oil +TX, Pyrethrum +TX, Saponaria saponaria +TX, Reynoutria sachalinensis ( +TX、 )+TX, Rotenone (Eco )+TX, Rutaceae plant extracts +TX, soybean oil (Ortho) )+TX, Tea Tree Oil (Timorex) )+TX, thyme oil+TX, MMF+TX, +TX, a blend of rosemary-sesame-peppermint-thyme and cinnamon extracts (EF) )+TX, a blend of clove-rosemary and peppermint extracts (EF) )+TX, clove-peppermint-garlic oil and mint blend (Soil) )+TX, Kaolin +TX, storage glucan of brown algae

[0713] Pheromones, including: 3M Sprayable Blackheaded Fireworm Pheromones +TX, codling moth pheromone (Paramount dispenser-(CM) / Isomate C-) )+TX, Grape Leafroller Pheromones (3M MEC-GBM Sprayable) )+TX, leafroller pheromone (3M MEC–LR Sprayable) +TX, housefly pheromone (Muscamone) (Snip7 Fly) +TX, Starbar Premium Fly )+TX, Pear Fruit Moth Pheromones (3M oriental fruitmoth sprayable) +TX, Peachtree Borer pheromone (Isomate- )+TX, Tomato Pinworm pheromone (3M Sprayable) )+TX, Entostat powder (an extract from palm trees) (Exosex) (E+TX,Z+TX,Z)-3+TX,8+TX,11-tetradecanetrienyl acetate +TX, (Z+TX,Z+TX,E)-7+TX,11+TX,13-hexadecanetrienal +TX, (E+TX,Z)-7+TX,9-dodecadien-1-yl acetate +TX, 2-methyl-1-butanol +TX, calcium acetate +TX +TX、 +TX、Check- +TX, Lavandulylsenecioate;

[0714] Macrobial agents include: Aphelinus abdominalis + TX, and Aphidius ervi (Aphelinus- )+TX, Acerophagus papaya+TX, two-spotted ladybug (Adalia bipunctata) (Adalia- )+TX, Ladybug +TX, Ladybug +TX, Agniaspis citricola +TX, Agniaspis fuscicollis +TX, Amblyseius andersoni ( +TX、Andersoni- +TX, Amblyseius californicus ( +TX、 )+TX, Amblyseius cucumeris ( +TX, Bugline )+TX, Amblyseius fallacis +TX, Amblyseius swirskii (Bugline) +TX、Swirskii- +TX, Amblyseius womersleyi +TX, Whitefly Wasp (Amitushesperidum) +TX, Primitive Plum-winged Wasp (Anagrus atomus) +TX, Dark-bellied Long-corded Jumping Wasp (Anagyrus fusciventris) +TX, Kama Long-corded Jumping Wasp (Anagyrus kamali) +TX, Anagyrus loecki +TX, White Scale Long-corded Jumping Wasp (Anagyrus pseudococci) +TX, Red Wax Scale (Anicetus benefices) +TX, Golden Wasp (Anisopteromalus calandrae) +TX, Woodland Flower Bug (Anthocoris nemoralis) (Anthocoris- )+TX, Short-span Aphid Wasp ( +TX、 )+TX, Aphelinus asychis +TX, Aphidius colemani (cotton aphid parasitoid wasp) +TX, Aphidius ervi +TX, Aphidius gifuensis +TX, Aphidius matricariae (Aphipar- +TX, Aphidoletes aphidimyza +TX, Aphid-eating gall midge +TX, Aphytis lingnanensis +TX, Aphytis melinus +TX, Aprostocetus hagenowii +TX, Atheta coriaria +TX, species of the genus *Bombus* spp. +TX, European bumblebee (*Bombus terrestris*) (Natupol) )+TX, European bumblebee ( +TX、 )+TX, Cephalonomia stephanoderis+TX, Black-backed Ladybug (Chilocorus nigritus+TX), Common Lacewing (Chrysoperla carnea) +TX, common lacewing +TX, Red Lacewing (Chrysoperla rufilabris) +TX, Cirrospilus ingenuus +TX, Four-banded Chrysalis Wasp (Cirrospilus quadristriatus) +TX, White-spotted Orange Wasp (Citrostichus phyllocnistoides) +TX, Closterocerus chamaeleon +TX, Closterocerus spp. +TX, Coccidoxenoides perminutus +TX, Coccophagus cowperi +TX, Coccophagus lycimnia +TX, Cotesia flavipes +TX, Cotesia plutellae +TX, Cryptolaemus montrouzieri ( +TX、 )+TX, Japanese square-headed beetle (Cybocephalus nipponicus)+TX, Siberian mammillary wasp (Dacnusa sibirica)+TX, Siberian mammillary wasp (Dacnusa sibirica) +TX, the pea leafminer wasp (Diglyphus isaea) +TX, Ladybug (Delphastus catalinae) +TX, Delphastus pusillus+TX, Diachasmimorpha krausii+TX, Diachasmimorpha longicaudata+TX, Diaparsis jucunda+TX, Diaphorencyrtus aligarhensis+TX, Diglyphus isaea+TX, Diglyphus isaea (Pea Leafminer Fly) +TX、 )+TX, Siberian Dacnusa sibirica ( +TX、 )+TX, Diversinervus spp. species+TX, Encarsia citrina+TX, Encarsia formosa (Encarsia +TX、 +TX、En- +TX, Eretmocerus eremicus (a type of wasp) +TX, Encarsia guadeloupae +TX, Encarsia haitiensis +TX, Episyrphus balteatus +TX, Eretmoceris siphonini+TX, Eretmocerus californicus+TX, Eretmocerus eremicus( +TX、Eretline )+TX, Aphidius chinensis +TX, Eretmocerushayati +TX, Eretmocerus mundus +TX、Eretline )+TX, Eretmocerus siphonini+TX, Four-spotted ladybug (Exochomus quadripustulatus+TX), Gall midge (Feltiella acarisuga) +TX, Feltiella acarisuga (a type of mosquito that feeds on mites) +TX, Alishan leafminer wasp (Fopius arisanus) +TX, Fopius ceratitivorus +TX, Formononetin (Wirless) +TX, the slender-waisted thrips (Franklinothripsvespiformis) +TX, Galendromus occidentalis +TX, Goniozus legneri +TX, Habrobracon hebetor +TX, Harmonia axyridis +TX, Heterorhabditis spp. (Lawn) )+TX, Heterorhabditis bacteriophora (NemaShield) +TX、 +TX、Terranem- +TX、 +TX、 +TX、B- +TX、 +TX、 )+TX, Heterorhabditis megidis (Nemasys) +TX、BioNem +TX, Exhibitline +TX、Larvanem- )+TX, Hippodamia convergens+TX, Hypoaspis aculeifer (Aculeifer- +TX、Entomite- +TX, Hypoaspis miles (Hypoline) +TX、Entomite- )+TX, Black Gall Bee (Lbalialeucospoides)+TX, Lecanoideus floccissimus+TX, Lemophagus errabundus+TX, Tricolor Gall Bee (Leptomastidea abnormis)+TX, Leptomastix dactylopii +TX, Leptomastix epona +TX, Lindorus lophanthae +TX, Lipolexis oregmae +TX, Lucilia caesar +TX, Lysiphlebustestaceipes +TX, Macrorolophus caliginosus (Mirical- +TX、Macroline +TX、 )+TX, Mesoseiulus longipes+TX, Yellow Broad-stalked Flying Wasp (Metaphycus flavus+TX), Metaphycus lounsburyi+TX, Horned-veined Brown Flyfly (Micromusangulatus) +TX, Yellow Flowerwing Flying Bee (Microterys flavus) +TX, Muscidifurax raptorellus and Spalangia cameroni +TX, Neodryinustyphlocybae+TX, Neoseiulus californicus+TX, Neoseiulus cucumeris +TX, Neoseiulus fallacis +TX, Nesideocoris tenuis ( +TX、 +TX, Bronze Black Fly (Ophyraaenescens) +TX, Orius insidiosus (Thripor- +TX、Oriline )+TX, hairless small flower bug (Orius laevigatus) (Thripor- +TX、Oriline +TX, Large Flower Bug (Orius majusculus) (Oriline) +TX, Small Black Flower Stink Bug (Orius strigicollis)(Thripor- )+TX, Pauesia juniperorum+TX, Pediobius foveolatus+TX, Phasmarhabditis hermaphrodita +TX, Phymastichus coffea+TX, Phytoseiulus macropilus+TX, Chilean phytoseiulus persimilis ( +TX, Phytoline +TX, Podisus maculiventris +TX, Pseudacteon curvatus+TX, Pseudacteon obtusus+TX, Pseudacteon tricuspis+TX, Pseudaphycus maculipennis+TX, Pseudleptomastix mexicana+TX, Psyllaephagus pilosus+TX, Psyttalia concolor (complex)+TX, Quadrastichus spp.+TX, Rhyzobius lophanthae+TX, Rodolia cardinalis+TX, Rumina decollate+TX, Semielacher petiolatus+TX, Sitobion a...

Claims

1. A compound having the formula IF: in G1 is N and G2 is CH; or both G1 and G2 are CH. R2 is a C1-C6 haloalkyl or C1-C6 haloalkoxy; R4 is a C1-C6 alkyl group; and R3 is selected from the group consisting of: cyclopropyl; C1-C6 haloalkoxy; phenyl that may be monosubstituted by cyanocyclopropyl; C-linked pyrimidinyl; N-linked pyrazolyl that may be monosubstituted by chloro, cyclopropyl, or trifluoromethyl; C-linked pyrazolyl that is N-substituted by cyclopropyl, -CHF2, -CH2CHF2, -CH2CF3, -(CH2)-cyclopropyl, or -(CH2)-cyanocyclopropyl; and C-linked dihydroisoxazole that may be monosubstituted by cyclopropyl; Or its chemically acceptable salt for agricultural use.

2. The compound having the formula IF according to claim 1, wherein... R2 is CF3, CF2CF3, or OCF3; and R4 is either methyl or ethyl.

3. The compound having the formula IF according to claim 1, wherein... R2 is CF3 or OCF3; and R4 is a methyl group.

4. The compound having the formula IF according to any one of claims 1 to 3, wherein R3 is selected from -OCH2CF3; 3-chloro-pyrazole-1-yl; 3-cyclopropyl-pyrazole-1-yl; 4-(1-cyanocyclopropyl)phenyl; 3-(1-cyanocyclopropyl)phenyl; pyrimidin-5-yl; pyrimidin-2-yl; 1-cyclopropylpyrazole-4-yl; cyclopropyl; 1-difluoromethylpyrazole-4-yl; 1-(2,2-difluoroethyl)pyrazole-4-yl; 1-(2,2,2-trifluoroethyl)pyrazole-4-yl; 3-cyclopropyl-4,5-dihydro-isoxazole-5-yl; 3-trifluoromethyl-pyrazole-1-yl; 4-trifluoromethyl-pyrazole-1-yl; 1-(cyclopropylmethyl)pyrazole-4-yl and 1-(1-cyanocyclopropylmethyl)pyrazole-4-yl.

5. The compound having the formula IF according to claim 1, wherein the compound is selected from the group consisting of: 2-[2-(1-Cyclopropylpyrazole-4-yl)-5-ethylsulfonyl-1-methyl-imidazol-4-yl]-6-(trifluoromethoxy)isoindoline-1-one (compound P1); 6-[2-(1-Cyclopropylpyrazole-4-yl)-5-ethylsulfonyl-1-methyl-imidazol-4-yl]-3-(trifluoromethyl)-7H-pyrrolo[3,4-b]pyridin-5-one (compound P2); 6-[2-(3-Cyclopropyl-4,5-dihydroisoxazol-5-yl)-5-ethylsulfonyl-1-methyl-imidazol-4-yl]-3-(trifluoromethyl)-7H-pyrrolo[3,4-b]pyridin-5-one (compound P3); 1-[[4-[5-ethylsulfonyl-1- Methyl-4-[5-oxo-3-(trifluoromethyl)-7H-pyrrolo[3,4-b]pyridin-6-yl]imidazol-2-yl]pyrazole-1-yl]methyl]cyclopropionitrile (compound P4); 6-[2-[1-(2,2-difluoroethyl)pyrazole-4-yl]-5-ethylsulfonyl-1-methyl-imidazol-4-yl]-3-(trifluoromethyl)-7H-pyrrolo[3,4-b]pyridin-5-one (compound P5); 6-[5-ethylsulfonyl-1-methyl-2-(2,2,2-trifluoroethoxy)imidazol-4-yl]-3-(trifluoromethyl)-7H-pyrrolo[3,4-b]pyridin-5-one (compound P6); 2-(5-ethylsulfonyl-1-methyl- 2-Pyrimidin-5-yl-imidazol-4-yl)-6-(trifluoromethoxy)isoindoline-1-one (compound P7); 6-(5-ethylsulfonyl-1-methyl-2-pyrimidin-5-yl-imidazol-4-yl)-3-(trifluoromethyl)-7H-pyrrolo[3,4-b]pyridin-5-one (compound P8); 6-[2-[1-(cyclopropylmethyl)pyrazole-4-yl]-5-ethylsulfonyl-1-methyl-imidazol-4-yl]-3-(trifluoromethyl)-7H-pyrrolo[3,4-b]pyridin-5-one (compound P9); 6-[5-ethylsulfonyl-1-methyl-2-[1-(2,2,2-trifluoroethyl)pyrazole-4-yl]imidazol-4-yl]-3-( (trifluoromethyl)-7H-pyrrolo[3,4-b]pyridin-5-one (compound P10); 2-(5-ethylsulfonyl-1-methyl-2-pyrimidin-2-yl-imidazol-4-yl)-6-(trifluoromethoxy)isoindoline-1-one (compound P11); 6-(5-ethylsulfonyl-1-methyl-2-pyrimidin-2-yl-imidazol-4-yl)-3-(trifluoromethyl)-7H-pyrrolo[3,4-b]pyridin-5-one (compound P12); 6-[2-[1-(difluoromethyl)pyrazol-4-yl]-5-ethylsulfonyl-1-methyl-imidazol-4-yl]-3-(trifluoromethyl)-7H-pyrrolo[3,4-b]pyridin-5-one (compound P13).6-[5-ethylsulfonyl-1-methyl-2-[4-(trifluoromethyl)pyrazol-1-yl]imidazol-4-yl]-3-(trifluoromethyl)-7H-pyrrolo[3,4-b]pyridin-5-one (compound P14); 6-[2-(3-cyclopropylpyrazol-1-yl)-5-ethylsulfonyl-1-methyl-imidazol-4-yl]-3-(trifluoromethyl)-7H-pyrrolo[3,4-b]pyridin-5-one (compound P15); 6-[2-(3-chloropyrazol-1-yl)-5-ethylsulfonyl-1-methyl-imidazol] [-4-yl]-3-(trifluoromethyl)-7H-pyrrolo[3,4-b]pyridin-5-one (compound P16); 6-(2-cyclopropyl-5-ethylsulfonyl-1-methyl-imidazol-4-yl)-3-(trifluoromethyl)-7H-pyrrolo[3,4-b]pyridin-5-one (compound P17); 1-[4-[5-ethylsulfonyl-1-methyl-4-[5-oxo-3-(trifluoromethyl)-7H-pyrrolo[3,4-b]pyridin-6-yl]imidazol-2-yl]phenyl]cyclopropionitrile (compound P18).

6. A composition comprising an effective amount of an insecticidal, acaricidal, nematicidal, or molluscicidal compound having the formula IF as defined in any one of claims 1 to 5, or an agriculturally chemically acceptable salt thereof, and optionally, an adjuvant or diluent.

7. A method for combating and controlling insects, the method comprising applying to insects, insect habitats, or insect-vulnerable plants an insecticidal effective amount of a compound having the formula IF as defined in any one of claims 1-5, or an agriculturally chemically acceptable salt thereof, or a composition as defined in claim 6.

8. A method for protecting plant propagation material from insect attack, the method comprising treating the propagation material or the site where the propagation material is planted with the composition according to claim 6.

9. A compound having the formula XVII-a in X, R2, G1, G2, R1, R3, R4, R5, R6, and R7 are defined as follows under formula IF as described in claim 1; and R a It is hydrogen, C1-C6 alkyl, benzyl or phenyl.

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